CN108623562A - A kind of quinolinone alkaloid class compound and its preparation method and application - Google Patents

A kind of quinolinone alkaloid class compound and its preparation method and application Download PDF

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CN108623562A
CN108623562A CN201710180878.1A CN201710180878A CN108623562A CN 108623562 A CN108623562 A CN 108623562A CN 201710180878 A CN201710180878 A CN 201710180878A CN 108623562 A CN108623562 A CN 108623562A
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aliphatic
base
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amino
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邵长伦
林永成
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Ocean University of China
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Ocean University of China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/62—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms three- or four-membered rings or rings with more than six members
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Abstract

The present invention relates to a kind of quinolinone alkaloid class compounds, or non-equal amount of mixture, geometric isomer, solvate, pharmaceutically acceptable salt or the prodrug of its tautomer, stereoisomer, racemic modification, enantiomter, and the pharmaceutical composition comprising the compound.The invention also discloses this kind of compound and its pharmaceutical compositions as drug, especially as agricultural insecticidal, sterilization, herbicide drug purposes.

Description

A kind of quinolinone alkaloid class compound and its preparation method and application
Technical field
The invention belongs to agriculture fields, and more particularly to quinolinone alkaloid class compound and its pharmaceutical composition and Quinolinone alkaloid class compound and its pharmaceutical composition as agricultural insecticidal, sterilization, herbicide purposes.
Background technology
Patent WO 2004048378, which discloses a kind of quinolinone compounds, has immunoregulatory activity.
Eur. (1997) Pat. Appl., EP 811613, which discloses compound as follows, has antibacterial activity.
PCT Int. Appl. (2002), WO 2002070515, which disclose compound as follows, has antitumor activity.
Chinese patent CN 2009100183228 discloses following piperazine Nino acid（penicinoline）Compound represented conduct Insecticide.
Chinese patent CN 2009100183213 discloses following piperazine Nino peace (penicinotam) compound represented conduct Insecticide.
The present invention studies the activity of its derivative disclosed in patent CN 2009100183228 on the basis of piperazine Nino acid compound, It was found that the insecticidal effect of piperazine Nino acid derivative better than piperazine Nino acid, in addition to this, also has agricultural sterilization and weeding well Effect.
Invention content
The present invention provides a kind of quinolinone alkaloid class compound, or its pharmaceutical composition, and its is used in agriculture field In preparing the application in insecticide, fungicide, herbicide.Its quinolinone alkaloid class compound, tautomer, solid Non- equal amount of mixture, geometric isomer, solvate, the pharmaceutically acceptable salt of isomers, racemic modification, enantiomter Or the solvate of its salt.It is characterized in that compound has the following structure:, Wherein A, B are five yuan or hexa-atomic aromatic ring, hetero-aromatic ring, carbon heterocyclic;N=1,2,3, or 4;K=1,2,3 or 4;Y is O Or NR5; “" indicate singly-bound or be not present;R1, R2, R3, R4, R5Shown in being defined as follows：
Each R1, R4 R8Can be identical or different, separate is hydrogen, deuterium, halogen, hydroxyl, amino, nitro, cyanogen Base, alkyl, halogenated alkyl, alkoxy, alkylamino, alkyl acyl, hydroxy alkoxy base, Hydroxyalkylamino, hydroxyl alkane Acyl group, halogenated alkoxy, halogenated alkylamino, ohaloalkanoyl, aminoalkoxy, naphthenic base, cycloalkyl oxy, ring Alkyl amino, cycloalkanoyl, alkenyl, alkenylalkoxy, alkenyl alkylamino, alkenyl alkanoyl, alkynyl, alkynyl alkane Oxygroup, alkynyl alkylamino, alkynyl alkanoyl, aryl, aryloxy group, aroyl, fragrant amino, alkoxy aryl, aryl Alkylamino, heteroaryl, heteroaryloxy, 4-hetaroylpyrazol, heteroaryl amino, heteroarylalkoxy, heteroarylalkylamino are miscellaneous Ring group alkanoyl, Heterocyclylalkyl, heterocycle oxygroup, heterocyclylamino group, heterocyclylacyl, heterocyclylalkoxy, heterocycle Base alkylamino, heterocycle alkanoyl, azido alkoxy, condensed-bicyclic base condense miscellaneous bicyclic group, condensed-bicyclic base fat Fat race, condensed miscellaneous bicyclic group aliphatic, condensed-bicyclic base oxygroup, condensed miscellaneous bicyclic group oxygroup, condensed-bicyclic base amino, Miscellaneous bicyclic group amino is condensed, condensed-bicyclic base alkoxy condenses miscellaneous bicyclic group alkoxy, and condensed-bicyclic base alkylamino is thick Miscellaneous bicyclic group alkylamino is closed, condensed-bicyclic base oxygroup alkoxy condenses miscellaneous bicyclic group oxygroup alkoxy, condensed-bicyclic base ammonia Base alkoxy, condenses miscellaneous bicyclic group aminoalkoxy, and condensed-bicyclic base-C (=O)-, condensed-bicyclic base-C (=O) O- are condensed Miscellaneous bicyclic group-C (=O)-condenses miscellaneous bicyclic group-C (=O) O-, condensed-bicyclic base amino-C (=O)-, condenses miscellaneous bicyclic group ammonia Base-C (=O)-, condensed-bicyclic base-C (=O) N (R6)-, condenses miscellaneous bicyclic group-C (=O) N (R6)-, spiral shell bicyclic group, spiral shell are miscellaneous double Ring group, spiral shell bicyclic group aliphatic, the miscellaneous bicyclic group aliphatic of spiral shell, spiral shell bicyclic group oxygroup, the miscellaneous bicyclic group oxygroup of spiral shell, spiral shell are bicyclic Base amino, the miscellaneous bicyclic group amino of spiral shell, spiral shell bicyclic group alkoxy, the miscellaneous bicyclic group alkoxy of spiral shell, spiral shell bicyclic group alkylamino, spiral shell Miscellaneous bicyclic group alkylamino, spiral shell bicyclic group oxygroup alkoxy, the miscellaneous bicyclic group oxygroup alkoxy of spiral shell, spiral shell bicyclic group aminoalkoxy, The miscellaneous bicyclic group aminoalkoxy of spiral shell, spiral shell bicyclic group-C (=O)-, spiral shell bicyclic group-C (=O) O-, the miscellaneous bicyclic group-C of spiral shell (=O)-, Miscellaneous bicyclic group-the C of spiral shell (=O) O-, spiral shell bicyclic group amino-C (=O)-, the miscellaneous bicyclic group amino-C of spiral shell (=O)-, spiral shell bicyclic group-C (= O)N(R6Miscellaneous bicyclic group-the C of)-, spiral shell (=O) N (R6)-, R7R6N-, -C(=O)NR6R7, -OC(=O)NR6R7, -OC(=O)OR6, -N(R6)C(=O)NR6R7, -N(R6)C(=O)OR7, -N(R6)C(=O)-R7, R6R7N-S(=O)t-, R6S(=O)t-, R6S(= O)tN(R7)-, R7R6N- alkyl, R6S(=O)tAlkyl, R6R7N-C (=O)-alkyl, R7R6N- alkoxies, R6S(=O)tAlkane Oxygroup, R6R7N-C (=O)-alkoxy, aryl-(CH2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle- (CH2)p-G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(=O), S(=O)2,C(= O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O)N(R6)-, -(R6)N-S(=O)t-, - OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is each independently 0, l, 2,3 or 4;Or it is wherein fragrant Base-(CH2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle-(CH2)p-G-(CH2)m, or naphthenic base- (CH2)p-G-(CH2)mCan F, Cl, Br, I, alkyl, alkenyl, alkynyl, alkoxy or cyanogen be selected from by one or more The substituent group of base replaces.
Each R2, R3, R5Can be identical or different, separate is hydrogen, deuterium, alkyl, halogenated alkyl, alkyl acyl Base, hydroxyalkanoyl, ohaloalkanoyl, naphthenic base, cycloalkanoyl, alkenyl, alkenyl alkanoyl, alkynyl, alkynyl Alkanoyl, aryl, aroyl, heteroaryl, 4-hetaroylpyrazol, heterocycle alkanoyl, Heterocyclylalkyl, heterocyclylacyl, Heterocycle alkanoyl, azido alkyl, condensed-bicyclic base condense miscellaneous bicyclic group, and condensed-bicyclic base-C (=O)-is condensed miscellaneous Bicyclic group-C (=O)-, condensed-bicyclic base amino-C (=O)-, condensed miscellaneous bicyclic group amino-C (=O)-, spiral shell bicyclic group, spiral shell are miscellaneous Bicyclic group, spiral shell bicyclic group aliphatic, the miscellaneous bicyclic group aliphatic of spiral shell, spiral shell bicyclic group-C (=O)-, the miscellaneous bicyclic group-C of spiral shell (=O)-, Spiral shell bicyclic group amino-C (=O)-, the miscellaneous bicyclic group amino-C of spiral shell (=O)-,-C (=O) NR6R7, R6R7N-S(=O)t-, R6S(= O)t-, R7R6N- alkyl, R6S(=O)tAlkyl, R6R7N-C (=O)-alkyl, aryl-(CH2)p-G-(CH2)m, heteroaryl- (CH2)p-G-(CH2)m, heterocycle-(CH2)p-G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(=O), S(=O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O) N(R6)-, -(R6)N-S(=O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m are each independently 0, l, 2,3 or 4;Or aryl-(CH therein2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle- (CH2)p-G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)mCan F, Cl, Br, I, cyanogen be selected from by one or more Base, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, carbocylic radical, the substituent group substitution of heterocycle.
R8Can be identical or different, it is each independently hydrogen, R6R7NC(=O)-, R6OC(=O)-, R6C(=O)-, R6R7NS(=O)-, R6OS(=O)-, R6S(=O)-, R6R7NS(=O)2-, R6OS(=O)2-, R6S(=O)2, aliphatic, halogen Fat subsitutes race, hydroxyl group aliphatic, amino aliphatic, alkoxy aliphatic, alkylamino aliphatic, alkylthio group aliphatic, Aromatic yl aliphat, heteroaryl aliphatic, heterocycle aliphatic, naphthenic base aliphatic, aryloxy group aliphatic, heterocyclyloxy Base aliphatic, cycloalkyl oxy aliphatic, fragrant amino aliphatic, heterocyclylamino group aliphatic, cycloalkyl amino aliphatic, Aryl, heteroaryl, heterocycle or carbocylic radical.
Each R6And R7It independently is hydrogen, deuterium, aliphatic, halogenated aliphatic, hydroxyl group aliphatic, amino aliphatic, alkane Oxygroup aliphatic, alkylamino aliphatic, alkylthio group aliphatic, aromatic yl aliphat, heteroaryl aliphatic, heterocycle fat Race, naphthenic base aliphatic, aryloxy group aliphatic, heterocycle oxygroup aliphatic, cycloalkyl oxy aliphatic, fragrant amino fat Fat race, heterocyclylamino group aliphatic, cycloalkyl amino aliphatic, aryl, heteroaryl, heterocycle or naphthenic base；Work as R6With R7It is connected on the same nitrogen-atoms, R6, R7Substituted or non-substituted 3-8 membered rings can be randomly formed with nitrogen-atoms, are condensed Bicyclic or spiral shell is bicyclic;The hetero atom in heterocycle, heteroaryl, condensed miscellaneous bicyclic group, the miscellaneous bicyclic group of spiral shell involved in above-mentioned group For the 1-5 hetero atom in N, O, S, Se.
Above-mentioned R1, R2, R3, R4, R5, R6, R7, R8Group can appoint by hydroxyl, methylol, carboxyl, acetyl ammonia Base, alkyl (such as methyl, ethyl, propyl), alkoxy (such as methoxyl group, ethyoxyl, tert-butoxy), alkylamino, naphthenic base, Alkenyl, alkynyl, trifluoromethyl, trifluoroacetyl group, sulfydryl, halogen, nitro, amino, azido (- N3), guanidine radicals, Cyano, tertbutyloxycarbonyl (- Boc), carbonyl (- C=O), oxo (=O) is thio (=S), sulfonyl, aryl, heteroaryl, One or more of heterocycle replaces.
In some embodiments, compound of the present invention is general formula III-VI compounds represented or general formula III- The stereoisomer geometric isomer of compound shown in VI, tautomer, nitrogen oxides, raceme, hydrate, solvation Object, metabolite, pharmaceutically acceptable salt or prodrug：
, wherein T1, T2, T3, T4Separate is CR1Or N, wherein T1, T2, T3, T4At most there are two can contain N; V1, V2, V3, V4 Separate is CR4, NR9, O or S;Y is O or NR5; X1, X2, X3, X4, X5Separate is CR4Or N; “" indicate singly-bound or be not present;Each R1, R2, R3, R4, R5, R9As follows:
Each R1, R4Can be identical or different, it is separate be H, D, F, Cl, Br, I, hydroxyl, amino, nitro, Cyano, C1-C20 alkyl, C1-C20 halogenated alkyls, C1-C20 alkoxies, C1-C20 alkylaminos, C1-C20 alkyl acyls, Hydroxyl C1-C20 alkoxies, hydroxyl C1-C20 alkylaminos, hydroxyl C1-C20 alkanoyls, C1-C20 halogenated alkoxies, C1- The halogenated alkylaminos of C20, C1-C20 ohaloalkanoyls, C1-C20 aminoalkoxies, C3-C10 naphthenic base, C3-C10 naphthenic base Oxygroup, C3-C10 cycloalkyl aminos, C3-C10 cycloalkanoyls, C2-C8 alkenyls, C2-C8 alkynyls, C6-C10 aryl, C6-C10 aryloxy group, C6-C10 aroyls, C6-C10 fragrant aminos, C6-C10 aryl C1-C6 alkoxies, C6-C10 aryl alkane Amino, C5-C12 heteroaryls, C5-C12 heteroaryloxies, C5-C12 4-hetaroylpyrazols, C5-C12 heteroaryl amino, C5-C12 are miscellaneous Aryl C1-C6 alkoxies, C5-C12 heteroaryl C1-C6 alkylaminos, C4-C12 heterocycle C1-C6 alkanoyls, C4-C12 heterocycles Alkyl, C4-C12 heterocycle oxygroups, C4-C12 heterocyclylamino groups, C4-C12 heterocyclylacyls, C4-C12 heterocycles C1-C6 Alkoxy, C4-C12 heterocycle C1-C6 alkylaminos, C4-C12 heterocycle C1-C6 alkanoyls, R7R6N-, -C(=O)NR6R7, -OC(=O)NR6R7, -OC(=O)OR6, -N(R6)C(=O)NR6R7, -N(R6)C(=O)OR7, -N(R6)C(=O)-R7, R6R7N-S(=O)t-, R6S(=O)t-, R6S(=O)tN(R7)-, R7R6N- C1-C6 alkyl, R6S(=O)t- C1-C6 alkyl, R6R7N-C (=O)-C1-C6 alkyl, R7R6N- C1-C6 alkoxies, R6S(=O)t- C1-C6 alkoxies, R6R7N-C(=O)- C1-C6 alkoxies, C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m-, C4-C12 Heterocycle-(CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(= O), S(=O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O)N(R6)-, - (R6)N-S(=O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is each independently 0, l, 2,3 Or 4;Or wherein C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m-, C4-C12 Heterocycle-(CH2)p-G-(CH2)m, or C3-C1 naphthenic base-(CH2)p-G-(CH2)mCan F be selected from by one or more, The substituent group of Cl, Br, I, alkyl, alkenyl, alkynyl, alkoxy or cyano replaces;
Each R2, R3, R5, R9Can be identical or different, it is each independently H, D, C1-C20 alkyl, C1-C20 alkyl halides Base, C1-C20 alkyl acyls, C1-C20 hydroxyalkanoyls, C1-C20 ohaloalkanoyls, C3-C10 naphthenic base, C3-C10 Cycloalkanoyl, C2-C8 alkenyls, C2-C8 alkenyl alkanoyls, C2-C8 alkynyls, C2-C8 alkynyl alkanoyls, C6-C10 virtues Base, C6-C10 aroyls, C5-C12 heteroaryls, C5-C12 4-hetaroylpyrazols, C4-C12 heterocycle alkanoyls, C4-C12 are miscellaneous Naphthenic base, C4-C12 heterocyclylacyls, C4-C12 heterocycle C1-C6 alkanoyls, C5-C12 condensed-bicyclic bases, C5-C12 are thick Close miscellaneous bicyclic group ,-C (=O) NR6R7, R6R7N-S(=O)t-, R6S(=O)t-, R7R6N-C1-C6 alkyl, R6S(=O)t-C1- C6 alkyl, R6R7N-C (=O)-C1-C6 alkyl, C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p- G-(CH2)m, C4-C12 heterocycles-(CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)m, wherein G It is O, S, NR8, S(=O), S(=O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6) C(=O)N(R6)-, -(R6)N-S(=O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is respectively independent Ground is 0, l, 2,3 or 4;Or wherein C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G- (CH2)m, C4-C12 heterocycles-(CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)mIt can be by one It is a or multiple selected from F, Cl, Br, I, cyano, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, carbocyclic ring Base, the substituent group substitution of heterocycle.
Wherein each R8Can be identical or different, it is each independently H, D, R6R7NC(=O)-, R6OC(=O)-, R6C(= O)-, R6R7NS(=O)-, R6OS(=O)-, R6S(=O)-, R6R7NS(=O)2-, R6OS(=O)2-, R6S(=O)2-, C1-C3 Aliphatic, C1-C3 halogenated aliphatics, C1-C3 hydroxyl group aliphatics, C1-C3 amino aliphatic, C1-C3 alkoxy C 1-C3 fat Fat race, C1-C3 alkylamino C1-C3 aliphatic, C1-C3 alkylthio group C1-C3 aliphatic, C6-C10 aryl C1-C3 aliphatic, C5-C9 heteroaryl C1-C3 aliphatic, C4-C10 heterocycle C1-C3 aliphatic, C3-C10 naphthenic base C1-C3 aliphatic, C6- C10 aryloxy group C1-C3 aliphatic, C4-C10 heterocycle oxygroup C1-C3 aliphatic, C3-C10 cycloalkyl oxies C1-C3 fat Race, C6-C10 fragrant amino C1-C3 aliphatic, C4-C10 heterocyclylamino group C1-C3 aliphatic, C3-C10 cycloalkyl aminos C1- C3 aliphatic, C6-C10 aryl, C5-C10 heteroaryls, C4-C10 heterocycles or C3-C10 naphthenic base.
Wherein each R6And R7It independently is H, D, C1-C3 aliphatic, C1-C3 halogenated aliphatics, C1-C3 hydroxy aliphatics Race, C1-C3 amino aliphatic, C1-C3 alkoxy C 1-C3 aliphatic, C1-C3 alkylamino C1-C3 aliphatic, C1-C3 alkane Sulfenyl C1-C3 aliphatic, C6-C10 aryl C1-C3 aliphatic, C5-C9 heteroaryl C1-C3 aliphatic, C4-C10 heterocycles C1-C3 aliphatic, C3-C10 naphthenic base C1-C3 aliphatic, C6-C10 aryloxy group C1-C3 aliphatic, C4-C10 heterocyclyloxies Base C1-C3 aliphatic, C3-C10 cycloalkyl oxy C1-C3 aliphatic, C6-C10 fragrant amino C1-C3 aliphatic, C4-C10 are miscellaneous Ring group amino C1-C3 aliphatic, C3-C10 cycloalkyl amino C1-C3 aliphatic, C6-C10 aryl, C5-C10 heteroaryls, C4-C10 heterocycles or C3-C10 naphthenic base；Work as R6And R7It is connected on the same nitrogen-atoms, R6, R7It can be arbitrary with nitrogen-atoms Ground forms substituted or non-substituted 3-8 membered rings.
Above-mentioned R1, R2, R3, R4, R5, R6, R7, R8, R9Group can appoint by hydroxyl, methylol, carboxyl, acetyl Amino, alkyl (such as methyl, ethyl, propyl), alkoxy (such as methoxyl group, ethyoxyl, tert-butoxy), alkylamino, cycloalkanes Base, alkenyl, alkynyl, trifluoromethyl, trifluoroacetyl group, sulfydryl, halogen, nitro, amino, azido (- N3), guanidine Base, cyano, tertbutyloxycarbonyl (- Boc), carbonyl (- C=O), oxo (=O) is thio (=S), sulfonyl, and aryl is miscellaneous Aryl, the substitution of one or more of heterocycle.
In other embodiments, each R in compound of the present invention1, R4Can be identical or different, respectively solely Vertical is H, D, F, Cl, Br, I, hydroxyl, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, Butyl, tertiary butyl, C5H11, C6H13, C8H17, trifluoromethyl, hydroxymethyl, amino methyl, methoxyl group, ethyoxyl, Tert-butoxy, methylamino, ethylamino, isopropylamino, 3- hydroxyl-propyls, acetyl group, trifluoroacetyl group, cyano-acetamide Base, methylamino acetyl group, propiono, iso-propionyl, 2- hydroxypropanoyls, 2- aminopropionyls, 2- chlorine propionos, 2- bromine propionos, valeryl, caproyl, heptanoyl group, methacrylyl, phenyl, benzoyl, p-nitrophenyl, To methyl benzoyl, fluoro benzoyl, p-benzoyl base, to methoxybenzoyl base, 2,4- dimethyl benzenes Formoxyl, azidobenzoyl, benzyl, p-chlorobenzyl, vinyl, acrylic, allyl, n-butene base, Isobutenyl, n-pentene base, isopentene group, cyclopropyl, ring propiono, ring valeryl, cyclohexanoyl, 3- pyridine first Acyl group, naphthalene, phenethyl imidazole radicals, pyridyl group, pyrrole radicals, oxazolyls, isoxazolyl, triazol radical, tetrazole Base, furyl, thienyl, thiazolyl, piperidyl, piperazinyl, indyl, carbazyl, benzofuranyl tetrahydrochysene furan It mutters base, THP trtrahydropyranyl, pyrimidine bases, purine bases ,-N (CH3)2,-C (C=O) NH-C1-C4 alkyl ,-OC (C= O)-NH-C1-C4 alkyl ,-OC (O=O) O-C1-C4 alkyl ,-NHC (=O) NH-C1-C4 alkyl ,-NHC (=O) O-C1- C4 alkyl ,-NHC (=O)-C1-C4 alkyl, C1-C4 alkyl-NH-S (=O)2, C1-C4 alkyl S (=O)2, C1-C4 alkane Base S (=O)2NH-, phenyl-(CH2)P-G-(CH2)m, difluorophenyl-(CH2)P-G-(CH2)m, thiazolyl-(CH2)p-G- (CH2)m, pyridyl group-(CH2)p-G-(CH2)m, phenylethyl, cyclohexyl-(CH2)p-G-(CH2)m, wherein G is O, S, S(=O), S (=O)2, C(=O);P and m is each independently 0,1,2 or 3;Or wherein C6-C10 aryl- (CH2)P-G-(CH2)mCan by one or more be selected from F, Cl, Br, I, methyl, ethyl, propyl, acetenyl, The substituent group of propinyl, butynyl, methoxyl group, ethyoxyl or cyano replaces;Or above-mentioned R1, R4It is welcome by F, Cl, Br, I, hydroxyl, hydroxyl, methylol, carboxyl, acetylamino, C1-C6 alkyl（Such as methyl, ethyl, propyl）, C1-C6 alkoxies, C1-C6 alkylaminos, trifluoromethyl, trifluoroacetyl group, sulfydryl, nitro, amino, azido（- N3）, guanidine radicals, cyano, tertbutyloxycarbonyl（-Boc）, carbonyl（-C=O）, oxo（=O）, thio（=S）, sulfonyl, benzene One or more of base replaces.
In some embodiments, each R in compound of the present invention2, R3, R5, R9Can be identical or different, respectively From being independently H, D, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, C5H11, C6H13, C8H17, three Methyl fluoride, hydroxymethyl, amino methyl, 3- hydroxyl-propyls, acetyl group, trifluoroacetyl group, Cyanoacetyl, methyl Glycyl, propiono, iso-propionyl, 2- hydroxypropanoyls, 2- aminopropionyls, 2- chlorine propionos, 2- bromines third Acyl group, valeryl, caproyl, heptanoyl group, methacrylyl, phenyl, benzoyl, p-nitrophenyl, to methyl Benzoyl, fluoro benzoyl, p-benzoyl base, to methoxybenzoyl base, 2,4- dimethylbenzoyls, Between azidobenzoyl, benzyl, p-chlorobenzyl, vinyl, acrylic, allyl, n-butene base, isobutenyl, N-pentene base, isopentene group, cyclopropyl, ring propiono, ring valeryl, cyclohexanoyl, 3- picolinoyls, naphthalene, Phenethyl imidazole radicals, pyridyl group, pyrrole radicals, oxazolyls, isoxazolyl, triazol radical, tetrazole base, furyl, Pyranose, thienyl, thiazolyl, piperidyl, piperazinyl, indyl, carbazyl, benzofuranyl tetrahydrofuran Base, THP trtrahydropyranyl, pyrimidine bases, purine bases, pentose base, hexose base ,-(C=O) NH-C1-C4 alkyl, C1-C4 alkyl-NH-S (=O)2, C1-C4 alkyl S (=O)2, phenyl-(CH2)P-G-(CH2)m, difluorophenyl-(CH2)P- G-(CH2)m, thiazolyl-(CH2)p-G-(CH2)m, pyridyl group-(CH2)p-G-(CH2)m, phenylethyl, cyclohexyl- (CH2)p-G-(CH2)m, wherein G is O, S, S (=O), S (=O)2, C(=O);P and m are each independently 0,1,2 Or 3;Or wherein C6-C10 aryl-(CH2)P-G-(CH2)mCan F, Cl, Br, I, first be selected from by one or more The substituent group of base, ethyl, propyl, acetenyl, propinyl, butynyl, methoxyl group, ethyoxyl or cyano replaces; Or above-mentioned R2, R3, R5, R9It is welcome by F, Cl, Br, I, hydroxyl, hydroxyl, methylol, carboxyl, acetyl ammonia Base, C1-C6 alkyl (such as methyl, ethyl, propyl), C1-C6 alkoxies, C1-C6 alkylaminos, trifluoromethyl, trifluoroacetyl Base, sulfydryl, nitro, amino, azido (- N3), guanidine radicals, cyano, tertbutyloxycarbonyl (- Boc), carbonyl (- C=O), Oxo (=O), thio (=S), sulfonyl, the substitution of one or more of phenyl.
In some embodiments, structure or following one of the compound of the present invention including but not limited to following one The tautomer of structure, non-equal amount of mixture, geometric isomer, the solvent of stereoisomer, racemic modification, enantiomter The solvate of compound, pharmaceutically acceptable salt or its salt, or prodrug：
。
General formula I-VI compounds show excellent activity to a variety of germs in agriculture field, to pest evil mite, weeds Also show that preferable activity.Therefore, technical scheme of the present invention further includes that general formula I-VI compounds are used as in agriculture field Prepare the purposes of insecticide, fungicide, herbicide.
The example of disease referenced below is only used for illustrating the present invention, but never limits the present invention.
General formula I-VI compounds can be used for preventing following disease：Oomycetes diseases, such as downy mildew (cucumber downy mildew, rape Downy mildew, downy mildew, beet downy mildew, downy mildew of sugarcane, tobacco downy mildew, pea downy mildew, sponge gourd downy mildew, wax gourd Downy mildew, muskmelon downy mildew, cabbage downy mildew, downy mildew of spinach, radish downy mildew, downy mildew of garpe, onion mildew), white rust Bacterium (white rust of colza, cabbage white blister), samping off (damping off by rape samping off, Tobacco seedling diseases, tomato samping off, capsicum Disease, eggplant samping off, cucumber samping off, cotton seedling samping off), (capsicum pythium rot, sponge gourd pythium rot, wax gourd are continuous rotten for pythium rot Disease), epidemic disease (broad bean epidemic disease, Cucumber Blight, pumpkin epidemic disease, wax gourd epidemic disease, watermelon epidemic disease, muskmelon blight, capsicum epidemic disease, leek Epidemic disease, garlic epidemic disease, Cotton blight), late blight (late blight of potato, tomato late blight) etc.；Fungi Imperfecti disease, such as droop (sweet potato droop, cotton wilt, sesame droop, castor-oil plant droop, tomato wilt, Kidney bean droop, cucumber are withered Disease, sponge gourd droop, pumpkin droop, wax gourd droop, watermelon blight, Muskmelon Fusarium wilt, capsicum wilt, broad bean are withered Disease, rape droop, soybean Fusariuming disease), root rot (Fusarium solani, eggplant root rot, Kidney bean root rot, cucumber root rot, Balsam pear root rot, cotton black root rot, root rot of Vicia faba), damping-off (cotton seedling blight, sesame damping-off, capsicum damping-off, Huang Melon damping-off, Chinese cabbage damping-off), anthracnose (anthracnose of sorghum, cotton anthracnose, bluish dogbane anthracnose, jute anthracnose, flax Anthracnose, anthracnose of tobacco, mulberry anthracnose, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, balsam pear charcoal Subcutaneous ulcer disease, cucurbita pepo anthracnose, wax gourd anthracnose, watermelon anthrax, muskmelon anthracnose, lichee anthracnose), verticillium wilt (cotton yellow Wither disease, sunflower verticillium wilt, tomato verticillium wilt, capsicum verticillium wilt, eggplant verticillium wilt), scab (cucurbita pepo scab, wax gourd Scab, muskmelon scab), gray mold (cotton boll gray mold, bluish dogbane gray mold, graw mold of tomato, Botrytis cinerea, Kidney bean ash Mildew, celery gray mold, spinach gray mold, Kiwi berry gray mold), (cotton brown spot, jute brown spot, beet are brown for brown spot Pinta, the cercospora brown spot of peanut, capsicum brown spot, wax gourd brown spot, soybean brown spot, septorial brown spot of sunflower, pea brown spot, broad bean Brown spot), black spot (flax vacation black spot, alternaria stem rot of colza, sesame black spot, sunflower black spot, castor-oil plant black spot, kind Eggplant black spot, capsicum black spot, eggplant black spot, Kidney bean black spot, cucumber black spot, celery black spot, carrot black rot, Black rot of carrot, melanose or canker of apple, the cercospora black spot of peanut), spot blight (spotted wilt of tomato, capsicum spot blight, celery septoria disease), Early blight (early blight of tomato, capsicum early blight, eggplant early blight, target, early blight of celery), ring spot (soybean Ring spot, sesame ring spot, Kidney bean ring spot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, muskmelon Leaf blight), base rot disease (tomato base rot disease, Kidney bean base rot disease) and other (Helminthosporium carbonum, bluish dogbane waist folding disease, rice blasts Disease, the black sheath disease of chestnut, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem wilt, soybean diplostomiasis, the big spot of muskmelon The red leaf spot of disease, Peanut Web Blotch Disease, tea, pepper white star disease, wax gourd leaf spot, celery black rot, spinach heartrot, bluish dogbane leaf mold Disease, bluish dogbane spot disease, jute stem blight, purple spot of soybean, Alternaria sesami, castor-oil plant graywall, dark brown leaf spot, eggplant are brown It is rotten that color justifies star disease, Kidney bean red spot disease, balsam pear Leucoplakia, watermelon spot disease, jute withered rotten disease, sunflower root stem rot, Kidney bean charcoal Disease, soybean target spot disease, eggplant stick spore leaf spot, Leaf Spot Caused by Corynespora cassiicola on Cucumber, leaf muld of tomato, eggplant leaf mold, broad bean red spot etc.) Deng；Load fungus diseases, as rust is (stripe rust of wheat, the stem rust of wheat, wheat leaf rust, Peanut Rust, rust of sunflower, sweet Sugarcane rust, leek rust, rust of onion, chestnut rust, soybean rust), smut (maize head smut, corn smut, sorghum silk Smut, sorghum loose smut, covered kernel smut of kaoliang, high beam column smut, chestnut kernel smut, smut of sugarcane, Bean rust disease) And other (such as wheat sharp eyespots, rice sheath blight disease) etc.；Sac fungus disease, such as powdery mildew (wheat powdery mildew, rape white powder Disease, sesame powdery mildew, sunflower powdery mildew, beet powdery mildew, eggplant powdery mildew, powdery mildew of pea, sponge gourd powdery mildew, pumpkin are white Powder disease, Pumpkin powdery mildew, wax gourd powdery mildew, melon powdery mildew, uncinula necator, broad bean powdery mildew), sclerotiniose (flax bacterium Core disease, sclerotinia sclerotiorum, soybean sclerotinia crown rot, peanut sclerotiniose, tobacco sclerotiniose, capsicum sclerotiniose, eggplant sclerotiniose, Kidney bean bacterium Core disease, pea sclerotiniose, cucumber timberrot, balsam pear sclerotiniose, wax gourd sclerotinia, watermelon sclerotiniose, celery sclerotiniose), black star Sick (scab of apple, pear scab) etc..Particularly, to corn rust, rice blast, tomato black spot and cucumber downy mildew Disease still has good control effect at lower doses.
General formula I-VI compounds can be used for preventing following pest：Coleoptera (Coleoptera) (beetle)：Bean weevil belongs to kind It is (Acanthoscelides spp.) (curculionid), acanthoscelides obtectus (Acanthoscelides obtectus) (common pea weevil), white The narrow lucky fourth (Agrilus planipennis) (emerald ash borer, Agrilus planipennis) of wax, acupuncture needle Eimeria kind (Agriotes spp.) (acupuncture needle Worm), anoplophora glabripennis (Anoplophora glabripennis) (Asia psacotheahilaris), Anthonomusgrandis belong to kind an of (Anthonomus Spp.) (Culculionidae), Mexican anthonomusgrandis (Anthonomus grandis) (bollworm), cocoon bee belong to kind an of (Aphidius Spp.), weevil belongs to kind of (Apion spp.) (curculionid), sugarcane cockchafer belongs to kind of (Apogonia spp.) (grub), black suede cockchafer (Atacnius sprctulus) (smaller velvety chafer), Atomaria linearis (Atomaria linearis) (small beet beetle (pygmy mangold beetle), cucumber beetle belong to kind of (an Aulacophore spp.), beet as (Bothynoderes Punctiventris) (beet root curculionid), bean weevil belong to kind of (Bruchus spp.) (curculionid), pea weevil (Bruchus Pisorum) (pea weevil), Cacoesia belong to kind of (a Cacoesia spp.), Callosobruchus maculatus (Callosobruchus Maculatus) (southern cowpea curculionid), pineapple bug (Carpophilus hemipteras) (dried-frait beetle), beet tortoise First (Cassida vittata), day bovine kind (Ccrostcrna spp.), Ccrotoma belong to kind of (a Ccrotoma spp.) (gold Trichomonad (chrysomcids)), beans chrysomelid (Cerotoma trifur cata) (the chrysomelid worm of beans), ceutorhynchus kind (Ceutorhynchus spp.) (curculionid), Chinese cabbage seed tortoise are as (Ceutorhynchus assimilis) (Chinese cabbage weevil (cabbage seedpod weevil)), turnip tortoise is as (Ceutorhynchus napi) (cabbage curculionid (cabbage Curculio)), phyllotreta kind (Chaetocnema spp.) (chrysomonad), Colaspis belong to kind of (a Colaspis spp.) (soil Beetle), Conoderus scalaris, Conoderus stigmosus, Lee is as (Conotrachelus nenuphar) (plum Bore weevil), Cotinus nitidis (Green june beetle (Green June beetle)), asparagus scotellaris (Crioceris Asparagi) (asparagus beetle), rusty grain beetle (Cryptolestes ferrugincus) (rust paddy beetle (rusty Grainbeetle)), Cryptolestes pusillus (Cryptolestes pusillus) (flat ostomatid), Cryptolestes turcicus Grouville (Cryptolestes turcicus) (Turkey paddy beetle (Turkish grain beetle)), Ctenicera belong to kind (Ctenicera spp.) (nematode), Curculio kind (Curculio spp.) (curculionid), round end rhinoceros cockchafer belong to kind (Cyclocephala spp.) (grub), close withe are as (Cylindrocpturus adspersus) (sunflower grass curculionid (sunflower stem weevil)), mango leaf-cutting is as (Deporaus marginatus) (mango leaf-cutting curculionid (mango Leaf-cutting weevil)), lader beetle stupid (Dermestes lardarius) (lader beetle is stupid), white abdomen skin it is stupid (Dermestes maculates) (white abdomen skin is stupid), chrysomelid category kind of (Diabrotica spp.) (chrysomelid), mexican bean ladybird (Epilachna varivcstis) (Mexico beans beetle), moth stem weevil (raustinus cubae), pale rootstock as (Hylobius pales) (pales weevil (pales weevil)), Phytonomus kind (Hypera spp.) (curculionid), alfalfa leaf As (Hypera postica) (alfalfa weevil), Hyperdoes belong to kind of (Hyperdoes spp.) (Argentinian stem weevil (Hyperodes weevil)), the small stupid category kind of coffee berry small stupid (Hypothenemus hampei) (coffee berry beetle), tooth (Ips spp.) (spine shin is small stupid (engravers)), lasioderma serricorne (Lasioderma serricorne) (cigarette beetle), Ma Ling Potato beetle (Leptinotarsa decemlineata) (Colorado potato beetle), Liogenys fuscus, The stupid category kind of Liogenys suturalis, rice water weevil (Lissorhoptrus oryzophilus) (rice water weevil), powder (Lyctus spp.) (the stupid stupid beetle of moth/powder (powder post beetles) of wood), Maecolaspis joliveti, Megascelis belongs to kind of (a Megascelis spp.), corn click beetle (Melanotus communis), nitidulid category kind (Meligethes spp.), rape nitidulid (Meligethes aeneus) (brevitarsis (blossom beetle)), May Chafer (Melolontha melolontha) (typical European chafer), Oberea brevis, linear cylinder longicorn (Oberea Linearis), paddy is sawed in coconut palm moth rhinoceros cockchafer (Oryctes rhinoceros) (date palm beetle (date palm beetle)), trade Steal (Oryzaephilus mercator) (market saw-toothed grain beetle (merchant grain beetle)), saw-toothed grain beetle (Oryzaephilus surinamensis) (sawtooth paddy beetle (sawtoothcd grain bcctlc)), beak weevil belong to kind (Otiorhynchus spp.) (curculionid), black angle scotellaris (Oulema melanopus) (cereal leaf beetle (cereal Leafbeetle)), Oulema oryzae (Oulema oryzae), the short beak of rose as belong to kind of (Pantomorus spp.) (curculionid), It eats phyllobranchia cockchafer and belongs to kind of (a Phyllophaga spp.) (May/June chafer), Phvllophaga cuyabana, yellow item are jumped First belongs to kind of (Phyllotreta spp.) (chrysomonad), apple tiger as belonging to kind of (a Phynchites spp.), Japan popillia flavosellata fairmaire (large space between muscles length is stupid for (Popillia japonica) (Japanese beetle), large space between muscles stupid (Prostephanus truncates) (larger grain borer)), paddy stupid (Rhizopertha dominica) (the small moth of paddy (lesser grain Borer)), root gill cockchafer belongs to kind of (Rhizotrogus spp.) (European chafer (an Eurpoean chafer)), Rhynchophorus Kind (Rhynchophorus spp.) (curculionid), small stupid category kind (Scolytus spp.) (the stupid moth of wood), Shenophorus belong to kind (Shenophorus spp.) (grain weevil), pea leaf are as (Sitona lincatus) (pealeaf weevil (pca leaf Weevil)), Sitophilus kind (Sitophilus spp.) (grain weevil first), grain weevil (Sitophilus granaries) (paddy worm (granary weevil)), rice weevil (Sitophilus oryzae) (rice weevil first (rice weevil)), medicinal material ostomatid (Stegobium paniceum) (Stegobium paniceum (drugstore beetle)), (face Tribolium kind (Tribolium spp.) Curculionid), red flour beetle (Tribolium castaneum) (red flour beetle (red flour beetle)), miscellaneous quasi- paddy moistens (Tribolium confusum) (confused flour beetle (confused flour beetle)), the stupid (Trogoderma of piebald skin Variabile) (warehouse skin is stupid (warehouse beetle)) and Zabrus tenebioides.
Dermaptera (Dcrmaptcra) (earwig).
Neuroptera (Dictyoptera) (cockroach)：Groton bug (Blattella germanica) (Groton bug (German cockroach)), oriental cockroach (Blatta orientalis) (oriental cockoach), Pennsylvania wood Lian (Parcoblatta pennylvanica), American cockroach (Periplaneta americana) (America roach consumptive disease (American Cockroach)), Australian cockroach (Periplaneta australoasiae) (Australian cockroach (Australian Cockroach)), periplaneta brunnea (Pcriplancta brunnca) (periplaneta brunnea (brown cockroach)), dark brown are big Lian (Periplaneta fuliginosa) (Peroplaneta fluligginosa (smokybrown cockroach)), the green blattaria of sugarcane (Pyncoselus suninamensis) (sugarcane Lian (Surinam cockroach)) and long hair blattaria (Supella Longipalpa) (brown band blattaria (brownbanded cockroach)).
Diptera (Diptera) (fly)：Latent fly (the Agromyza of Aedes kind (Aedes spp.) (mosquito), alfalfa Frontella) ((Agromyza spp.) is (latent for (alfalfa dive fly (alfalfa blotch leafminer)), Hippelates kind Leaf fly), (add by trypetid (Anastrepha suspensa) by Anastrepha kind (Anastrepha spp.) (drosophila), Caribbean Strangle than press trypetid (Caribbean fruit fly)), Anopheles kind (Anopheles spp.) (mosquito), Bactrocera kind (Batrocera spp.) (drosophila), melonfly (Bactrocera cucurbitae) (melon fly), citrus fruit fly (Bactrocera dorsalis) (oriental fruit fly), small Anastrepha kind (Ceratitis spp.) (drosophila), the small item in Mediterranean Trypetid (Ceratitis capitata) (medfly), Chrysops kind (Chrysops spp.) (deer horsefly), Callitroga's kind (Cochliomyia spp.) (screw worm fly larva), Ying uranotaenia kind (Contarinia spp.) (Ying mosquitos), Culex kind (Culex Spp.) (mosquito), Ye Ying uranotaenias kind (Dasineura spp.) (Ying mosquitos), You Cai Ye Ying mosquitos (Dasineura brassicae) (volume Xin Cai Ying mosquitos), Delia kind (Delia spp.), delia platura (Delia platura) (root maggot (seedcorn Maggot)), Drosophila kind (Drosophila spp.) (vinegar fly), Fannia kind (Fannia spp.) (housefly), anthomyia canicularis (Fannia canicularis) (Fannia canicularis (little house fly)), anthomyia scalaris (Fannia scalaris) (ash Abdomen latrine fly), big horse botfly (Gasterophilus intestinalis) (horse botfly), Gracillia perseae, Haematobia irritans (Haematobia irritans) (horn fly), Hylemyia kind (Hylemyia spp.) (root maggot (root maggot)), heel fly (Hypoderma lineatum) (common heel fly (common cattle grub)), Liriomyza kind (Liriomyza Spp.) (Liriomyza), wild cabbage liriomyza bryoniae (Liriomyza brassica) (snake Liriomyza (serpentine Leafminer)), sheep hippoboscid (Melophagus ovinus) (sheepked), fly belong to kind of (Musca spp.) (housefly (muscid fly)), face fly (Musca autumnalis) (face fly (face fly)), housefly (Vusca Domestica) (housefly (house fly)), Oestrus ovis (Oestrus ovis) (sheep nose fly (sheep bot fly)), Europe Frit fly (Oscinella frit) (Oscinella frit), beet spring fly (Pegomyia betae) (spinach leaf miner (beet Leafminer)), wheat fly belongs to kind of (a Phorbia spp.), carrot fly (Psila rosae) (carrot rust fly (carrotrust fly)), cherry fruit fly (Rhagoletis cerasi) (cherry fruit fly (cherry fruit fly)), apple Fruit fly (Rhagoletis pomonella) (apple maggots (apple maggot)), wheat midge (Sitodiplosis Mosellana) (orange wheat flower mosquito (orange wheat blossom midge)), tatukira (stomoxys Calcitruns) (tatukira (stable fly)), the gadfly belong to kind of (Tahanus spp.) (horse botfly) and big uranotaenia kind (Tipula Spp.) (daddy-longlegs).
Semiptera (Hemiptera) (stinkbug)：Quasi- acrosternumhilare (Acrosternum hilare) (acrosternumhilare (green stink Bug)), america valley cinchbug (Blissus leucopterus) (chinch bug (chinch bug)), potato person of outstanding talent fleahopper (Calocoris norvegicus) (potato fleahopper (potato mirid)), cimex hemipterus (Cimex hemipterus) (cimex hemipterus (tropical bed bug)), bedbug (Cimex lectularius) (bedbug (bed hug)), Daghertus The black wing red stinkbug of fasciatus, Dichelops furcatus, cotton (Dysdercus suturellus) (red cotton bug (cotton Stainer)), Edessa meditabunda, Europe Eurygasterspp (Eurygaster maura) (paddy worm (cereal bug)), Euschistus heros, brown smelly stinkbug (Euschistus servus) (brown stinkbug (brown stink bug)), iS-One angle fleahopper (Helopeltis antonii), tea angle fleahopper (Helopeltis theivora) (tea blight plantbug), stinkbug category Kind (Lagynotomus spp.) (stinkbug), big Leptocorisa spp (Leptocorisa oratorius), different Leptocorisa spp (Leptocorisa varicornis), Lygus Hahn kind (Lygus spp.) (fleahopper (plant bug)), lygushesperus (Lygus hesperus) (western tarnished plant bug), the graceful powder stinkbug (Maconellicoccus of the rose of Sharon Hirsutus), Neurocolpus longirostris, green rice bug (Nezara viridula) (southern green Stink bug), Phytocoris kind (PhyLocoris spp.) (fleahopper), California plant fleahopper (Phytocoris Californicus), Phytocoris relativus, Piezodorus guildingi, four line fleahoppers (Poecilocapsus lineatus)(fourlined plant bug)、Psallus vaccinicola、Pseudacysta Perseae, Scaptocoris castanea and Triatoma kind (Triatoma spp.) (cone nose worm of sucking blood (bloodsuckingconenose bug)/hunt stinkbug (kissing bug)).
Homoptera (Homoptera) (aphid, a red-spotted lizard, aleyrodid, leafhopper)：Acyrthosiphum pisim (Acrythosiphonpisum) (pea Aphid (pea aphid)), adelgid kind (Adelges spp.) (adelgids), wild cabbage aleyrodid (Aleurodes Proletella) (cabbage aleyrodid), Aleurodicus dispersus (Aleurodicus disperses), velvet aleyrodid (Aleurothrixus flccosus) (whitefly in bt cotton (woolly whitefly)), white wheel armored scale belong to kind an of (Aluacaspis Spp.), Amrasca bigutella bigutella, froghopper belong to kind of (Aphrophora spp.) (leafhopper (leafhopper)), California red scale (Aonidiella aurantii) (California red a red-spotted lizard (California red Scale)), Aphis kind (Aphis spp.) (aphid), cotten aphid (Aphis gossypii) (cotton aphid), apple aphid (Aphis pomi) (apple aphid), eggplant are without net aphid (Aulacorthitm solani) (digitalis aphid (foxglove Aphid)), Aleyrodes kind (Bemisia spp.) (aleyrodid), Bemisia argentifolii (Bemisia argentifolii), sweet potato whitefly (Bemisia tabaci) (sweetpotato whitefly), Diuraphis noxia (Brachycolus noxius) (Russian aphid (Russian aphid)), asparagus tubule aphid (Brachycorynclia asparagi) (asparagus aphid (asparagus Aphid)), Brevennia rehi, brevicoryne brassicae (Brevicoryne brassicae) (cabbage aphid), lecanium belong to kind (Ceroplastes spp.) (a red-spotted lizard), ceroplastes rubens (Ceroplastes rubens) (red wax scale), snow armored scale belong to kind (Chionaspis spp.) (a red-spotted lizard), Aspidiotus belong to kind of (Chrysomphalus spp.) (a red-spotted lizard), soft wax a red-spotted lizard belongs to kind an of (Coccus Spp.) (a red-spotted lizard), the pink bad aphid (Dysaphis plantaginea) (rosy apple aphid) of apple, green jassids belong to kind (Empoasca spp.) (leafhopper) apple aphid (Eriosoma lanigerum) (woolly apple aphid), blows cotton a red-spotted lizard (Icerya purchasi) (cottony cushion scale), mango yellow line leafhopper (Idioscopus nitidulus) (mango leafhopper), small brown rice planthopper (Laodelphax striatellus) (smaller brown planthopper), Lepidosaphes shimer kind (Lepidosaphes spp.), long tube Aphis kind (Macrosiphum spp.), root of Beijing euphorbia Macrosiphus spp (Macrosiphum euphorbiae) (potato aphid (potato aphid)), grain aphid (Macrosiphum Granarium) (Britain's wheat aphid (English grain aphid)), rose aphid (Macrosiphum rosae) (rose Aphid (rose aphid)), four line leafhopper (Macrosteles quadrilineatus) (Aster tataricus leafhopper (aster Leafhopper)), Mahanarva frimbiolata, Acyrthosiphon dirhodum (Metopolophium dirhodum) (rose Wheat aphid (rose grain aphid)), Midis longicornis, black peach aphid (Myzus persicae) (black peach aphid (green Peach aphid)), rice green leafhopper belong to kind of (Nephotettix spp.) (leafhopper), rice green leafhopper (Nephotettix Cinctipes) (greenery cicada (green leafhopper)), brown paddy plant hopper (Nilaparvata lugens) (brown Planthopper), chaff piece armored scale (Parlatoria pergandii) (chaff scale), ebony armored scale (Parlatoria Ziziphi) (ebony scale), popcorn wing plant hopper (Peregrinus maidis) (corn delphacid), froghopper category Kind (Philaenus spp.) (spittle insects), grape phylloxera (Phylloxera vitifoliae) (grape Phylloxera), Physokermes piceae (Physokermes piceae) (spruce bud scale), stern line mealybug belong to kind (Planococcus spp.) (mealybug), mealybug belong to kind of (Pseudococcus spp.) (mealybug), the clean mealybug of pineapple (Pscudococcus brcvipcs) (pinc apple mcalybug), theatre armored scale (Quadraspidiotus Perniciosus) (san jose scale (San Jose scale)), aphid a red-spotted lizard belong to kind of (Rhapalosiphum spp.) (aphid), jade Rice tree louse (Rhapalosiphum maida) (corn leaf aphids (corn leaf aphid)), rhopalosiphum padi (Rhapalosiphum padi) (oatbird-cherry aphid), pearl lecanium belong to kind of (Saissetia spp.) (a red-spotted lizard), olive Pearl lecanium (Saissetia oleae) (black a red-spotted lizard), green bugs (Schizaphis graminum) (green bugs (gr Eenbug)), grain aphid (Sitobion avenge) (Britain's wheat aphid), white backed planthopper (Sogatella furcifera) (white-backed planthopper), variegation Aphis kind (Therioaphis spp.) (aphid), line lecanium belong to kind (Toumeyella spp.) (a red-spotted lizard), sound Aphis kind (Toxoptera spp.) (aphid), white powder Pediculus kind (Trialeurodes Spp.) (aleyrodid), Trialeurodes vaporariorum Westwood (Trialeurodes vaporariorum) (greenhouse whitefly (greenhouse Whitefly)), knot wing trialeurodes vaporariorum (Trialeurodes abutiloneus) (bandedwing whitefly), sharp armored scale category The sharp clam (Unaspis yanonensis) (arrow a red-spotted lizard (arrowhead scale)) of kind of (Unaspis spp.) (a red-spotted lizard), arrow and Zulia entreriana。
Hymenoptera (Hymenoptera) (ant, wasp and honeybee)：It is Myrmecina kind (Acromyrrmex spp.), new Boundary cabbage sawfly (Athalia rosae), leaf ant belong to kind of (Atta spp.) (an Ieafcutting ants), black ant belongs to kind (Camponotus spp.) (carpented ant (carpenter ant)), Diprion kind (Diprion spp.) (sawfly (sawfly)), ant belongs to kind of (Formica spp.) (ant), Argentine ant (Iridomyrmex humilis) (Argentineant), Monomorium subspecies (Monomorium ssp.), MonomoriumMayr (Monomorium minumum) (little Black ant), kitchen ant (Monomorium pharaonis) (little red ant (Pharaoh ant)), Neodiprion kind (Neodiprion spp.) (sawfly), Pogonomyrmex kind (Pogonomyrmex spp.) (harvester ant), hornet belong to kind (Polistes spp.) (wasp (paper wasp)), Solenopsis kind (Solenopsis spp.) (fiery ant), odorous antenna (Tapoinoma sessile) (odorous antenna (odorous house ant)), Tetramorium kind (Tetranomorium spp.) (Pavement Ant (pavement ant)), Vespula kind (Vespula spp.) (yellow jacket (yellow jacket)) and carpenter bee Belong to kind of (Xylocopa spp.) (carpenter bee (a carpenter bee)).
Isoptera (Isoptera) (termite)：Formosanes belong to kind of (a Coptotcrmcs spp.), bent jaw termite (Coptotermes curvignathus), French termite (Coptotermes frenchii), coptotermes formosanus (Coptotermes Formosanus) (Formosan subterranean termite), angle Cryptotermes kind (Cornitermes spp.) (proboscis Termite (nasute termite)), sand Cryptotermes kind (Cryptotermes spp.) (dry-wood termite), different Cryptotermes kind (Heterotermes spp.) (desert Soil termites (desert subterranean termite)), golden yellow different termite ((IIeterotermes aureus), kalotermitid belong to kind of (Kalotermes spp.) (dry-wood termite), principal columns of a hall Cryptotermes kind (Incistitermes spp.) (dry-wood termite), Macrotermes kind (Macrotermes spp.) (cultivation termite (fungus Growing termite)), edge kalotermitid belong to kind ((Marginitermes spp.) (dry-wood termite), saw a Cryptotermes kind (Microcerotermes spp.) (careless termite (harvester termite)), the small termite (Microtermes of rice and kernel Obesi), former angle Cryptotermes kind (Procornitermes spp.), Reticulitermes kind (Reticulitermes spp.) (dwell by soil Termite), Reticulitermes banyulensis, meadow reticulitermes flavipe (Reticulitermes grassei), yellow limb dissipate it is white Ant (Reticulitermes flavipes) (east Soil termites), U.S. little Huang reticulitermes flavipes (Reticulitermes Hageni), west reticulitermes flavipe (Reticulitermes hesperus) (west Soil termites), Sang Te reticulitermes flavipes (Reticulitermes santonensis), the northern reticulitermes flavipe that dwells (Reticulitermes speratus), U.S. black shin reticulitermes flavipe (Reticulitermes tibialis), U.S. small black reticulitermes flavipe (Reticulitermes virginicus), proboscis reticulitermes flavipe Belong to kind of (Schedorhinotermes spp.) and ancient Cryptotermes kind (Zootermopsis spp.) (rotten wood termite).
Lepidoptera (Lepidoptera) (moth and butterfly)：Achoea janata, Adoxophyessp kind (Adoxophyes Spp.), adoxophyes moth (Adoxophyes orana), tiger belong to kind of (Agrotis spp.) (cutworm), small cutworm ((Agrotis ipsilon) (black cutworm), cotton leaf ripple noctuid (Alabama argillacea) (cotton leafworm (cotton leafworm))、Amorbia cuneana, Amyelosis transitella(navel orangeworm)、 Anacamptodes defectaria, sliver gelechiid (Anarsia lineatella) (peach twig borer), jute bridge Night high (Anomis sabulijera) (jute looper), Anticarsia (Anticarsia gemmatalis) (velvetbean caterpillar), fruittree leafroller (Archips argyrospila) (fruit tree Leafroller), rose leaf roller (Archips rosana) (rose leaf roller), volume moth belong to kind an of (Ar Gyrotaenia spp.) (tortricid moths), tangerine Argyrotaenia spp (Argyrotaenia citrana) (citrus leaf-roller (orange tortrix)), Autographa gamma, Bonagota cranaodcs, rice leaf roller (Borbo Cinnara) (rice leaf folder), cotton leaf lyonetid (Bucculatrix thurberiella) (cotton Leafperforator), thin moth belongs to kind of (Caloptilia spp.) (leaf miner), Capua reticulana, peach fruit moth (Carposina niponensis) (peach fruit moth (peach fruit moth)), straw borer spp kind (Chilo spp.), mango Chlumetia transversa (Chlumetia transversa) (mango shoot borer), rose Choristoneura spp (Choristoneura Rosaceana) (oblique banded leaf roller), Noctua kind (Chrysodeixis spp.), cnaphalocrocis are wild Snout moth's larva (Cnaphalocerus medinalis) (meadow leaf roller (grass leafroller)), beans Pier kind (Colias Spp.), lichee litchi (Conpomorpha cramerella), the stupid moth (Cossus cossus) of fragrance wood (the stupid moth of wood), Crambus Fabricius kind (Crambus spp.) (Sod webworms), Lee's Grapholita spp (Cydia funebrana) (Li Guoe (plum Fruit moth)), oriental fruit months (Cydia molesta) (east heart-eating worm (oriental fruit moth)), pea Eat into pod high (Cydia nignicana) (pea moth), the stupid moth of apple (Cydia pomonella) (codling moth (codling moth)), Darna diducta, Diaphania kind (Diaphania spp.) (stem borer (stem borer)), Snout moth's larva belongs to kind of (Diatr aea spp.) (stem borer (a stalk bor er)), small sugarcane borer (Diatraea saccharalis) (sugarcane borer), Diatraea grandiosella (Diatraea graniosella) (southwester corn Borer), Earias kind (Earias spp.) (bollworm), earias insulana (Earias insulata) (Egyptian Bollworm), earias fabia (Earias vit.ella) (rough northern bollworm), Ecdytopopha Aurantianum, South America maize seedling phycitid (Elasmopalpus lignosellus) (lesser cornstalk borer), Shallow brown apple moth (Epiphysias postruttana) (light brown apple moth), meal moth belong to kind (Ephestia spp.) (powder snout moth's larva), meal moth (Ephestia cautella) (almond moth), tobacco powder sp (Ephestia elutella) (tobacco snout moth's larva (tobbaco moth)), Mediterranean flour moth (Ephestia kuehniella) (Mediterranean flour moth), Epimeces belong to kind of (an Epimeces spp.), night steinernema (Epinotia Aporema), Erionota thorax (Linne) (Erionota thrax) (banana skipper), ligustrum fine tortricidae (Eupoecilia Ambiguella) (grape berry moth (grape berry moth)), original cutworm (Euxoa auxiliaris) (army Cutworm), Agrotis kind (Feltia spp.) (cutworm), angle sword Noctua kind (Gortyna spp.) (stem borer), Fruit moth (Grapholita molesta) (peach (apricot) sub- heart-eating worm (oriental fruit moth)), treble cut snout moth are eaten into east (Hedylepta indicata) (bean pyralid (bean leaf webber)), green Eimeria kind (Helicoverpa spp.) (noctuid), bollworm (Helicoverpa armigera) (cotton bollworm), paddy reality noctuid (Helicoverpa Zea) (corn borer ridge (snout moth's larva ridge worm/bollworm)), Heliothis kind (Heliothis spp.) (noctuid), tobacco budworm (Heliothis virescens) (tobacco budworm), Hellula undalis (Hellula undalis) (cabbage Webworm), Indarbela belongs to kind of (Indarbela spp.) (a root moth), the stupid moth (Keiferia of tomato Lycopersicella) (tomato pinworm), the white wing open country snout moth's larva of eggplant (Leucinodes orbonalis) (eggplant Fruit borer), pear leaf blister moth (Leucoptera malifoliella), thin moth belong to kind of (a Lithocollectis spp.), Grape olethreutid (Lobesia botrana) (grape fruit moth), Loxagrotis belong to kind an of (Loxagrotis Spp.) (noctuid), beans white line cutworm (Loxagrotis albicosta) (western bean cutworm), gypsymoth (Lymantria dispar) (gypsy moth), apple leaf miner (Lyonetiaclerkella) (apple leaf miner (apple Leafminer)), oil palm bag moth (Mahasena corbetti) (oil palm bagworm), Malacosoma kind (Malacosoma spp.) (tent caterpillars), lopper worm (Mamestra brassicae) (dish march moth (cabbage armyworm)), beanpod open country snout moth's larva (Maruca testulalis) (beans open country snout moth's larva), bag moth (Metisa plana) (knot Grass-and-insect painting), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato moths (small tomato borer)), 3 water snout moth's larva (Nymphula depunctalis) (rice leaf roller (rice Caseworm)), winter looper (Operophthera brumata) (winter moth), European corn borer (Ostrinia Nubilalis) (European corn borer (European corn borer)), Oxydia vesulia, the brown volume moth (Pandemis of boundary Cerasana) (common glucose leaf roller (common currant tortrix)), apple brown bortrix (Pandemis heparana) (brown apple tortrix), African Bodhidharma swallowtail butterfly (Papilio demodocus), Pectinophora gossypiella (Pectinophora Gossypiella) (pink bollworm (pink bollworm)), boundary Noctua kind (Peridroma spp.) (cutworm), variegated Tiger (Peridroma saucia) (variegated cutworm), coffee leafminer (Perileucoptera Coffeella) (white coffee leafminer), phthorimaea operculella (Phthorimaea operculella) (potato tuber moth), citrus leaf lyonetid (Phyllocnisitis citrella), thin moth belong to kind (Phyllonorycter spp.) (leaf miner), cabbage butterfly (Pieris rapae) (external cabbage caterpillar (imported Cabbageworm)), head is by green noctuid (Plathypena scabra), India paddy spot moth (Plodia interpunctella) (Indian meal moth), diamond-back moth (Plutella xylostella) (diamondback moth), grape berry moth (Polychrosis viteana) (grape berry moth), tangerine fruit ermine moth (Prays endocarps), olive ermine moth (Prsys oleae) (olive moth), mythimna separata belong to kind of (Pseudaletia spp.) (noctuid), Pseudaletia Unipunctata (armyworm), soybean noctuid (Pseudoplusia includens) (soybean looper), looper (Rachiplusia nu), yellow rice borer (Scirpophaga incertulas), moth stem night high category kind (Sesamia spp.) (moth Stem worm), Sesamia inferens (Sesamia inferens) (pink rice stemborer), powder stems moth (Sesamia Nonagrioides), the brown slug moth of copper stain (Setora nitens), gelechiid (Sitotroga cerealella) (Angoumois Grain moth), pilleriana (Sparganothis pilleriana), Spodoptera kind (Spodoptera Spp.) night is coveted on (armyworm), beet armyworm (Spodoptera exigua) (beet armyworm (beet armyworm)), meadow Moth (Spodoptcra fugipcrda) (autumn armyworm (fall armyworm)), southern spodoptera (Spodoptera Oridania) (root is eaten into for (southern armyworm (southern armyworm)), emerging Noctua kind (Synanthedon spp.) Worm), Thecla basilides, Thermisia gemmatalis, casemaking clothes moth (Tineola bisselliella) (webbing Clothes moth), cabbage looper (Trichoplusia ni) (cabbage looper), Liriomyza brponiae (Tuts Absoluta), Yponomeuta kind (Yponomeuta spp.), the stupid moth of coffee leopard (Zeuzeracoffeae) (red branch ) and Zeuzera pyrina (the stupid moth of pears leopard (leopard moth)) borer.
Mallophaga ((Mallophaga) poultry louse (chewing lice))：Sheep poultry louse (Bovicola ovis) (sheep Biting louse), fire menopon gallinae (Menacanthus stramineus) (chick poultry louse (chicken body )) and shaft louse (Menopon gallinea) (common henhouse (common hen house)) louse.
Orthoptera (Orthoptera) (grasshopper, locust and cricket)：Blackspot arna Zhong (Anabrus simplex) (Mo Men Katydid (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket (mole cricket)), Asiatic migrotory locust (Locusta migratoria), grasshopper belong to kind of (Melanoplus spp.) (grasshopper), guiding principle wing spinelet Zhong (Microcentrum Retinerve) (angle wing katydid (angular winged katydid)), Pterophylla belong to kind an of (Pterophylla Spp.) (katydid), chistocerca gregaria, fork-tail katydid (Scudderia furcata) (fork-tail shrubbery tree Zhong (fork tailed bush katydid)) and black angle oncus locust (Valanga nigricorni).
Anoplura (Phthiraptera) (sucks lice (sucking louse))：Pediculus of sucking blood kind (Haematopinus Spp.) (ox louse and pig lice), sheep jaw lice (Linognathus ovillus) (sheep lice (sheep louse)), head louse (Pediculus humanus capitis) (body louse), pediculus humanus corporis (Pediculus humanus humanus) (body louse) and the moon Lice (Pthirus pubis) (crab louse (crab louse)).
Siphonaptera (Siphonaptera) (flea)：Ctenocephalides canis (Ctenocephal ides canis) (dog flea), Ctenocephalides felis (Ctenocephalides felis) (cat flea) and Pulex irritans (Pulex irritans) (human flea).
Thysanoptera (thrips)：Cigarette brown thrip (Frankliniella fusca) (tobacco thrip), western classical architecture (Frankliniella occidentalis) (western flower thrips), Frankliniella shultzei, prestige Lian Si flower thrips (Frankliniella williamsi) (corn thrips (corn thrip)), greenhouse thrips (IIeliothrips haemorrhaidalis)(greenhouse thrip)、Riphiphorothrips cruentatus、 Hard Thrips kind (Scirtothrips spp), campanulaceae thrips (Scirtothrips cirri) (citrus thrip), tea are yellow Thrips (Scirtothrips dorsalis) (yellow tea thrips), Taeniothrips rhopalantennalis With Thrips kind (Thrips spp.).
Thysanoptera (Thysanura) (moth (bristletail))：Silverfish belongs to kind of (Lepisma spp.) (stupid worm (silverfish)) belong to kind of (Thermobia spp.) (a special mess fish) with special mess silverfish.
Acarina (Acarina) (mite (mite) and cicada (tick))：Wu Shi bee shields mite (Acarapsis woodi) (honeybee gas Pipe endoparasitism mite (tracheal mite of honeybee)), Tyroglyphus kind (Acarus spp.) (food mites), Acarus siro (Acarus siro) (paddy mite (grain mite)), mango bud mite (Aceria mangiferae) (mango bud mite), Peronium Eriophyes kind (Aculops spp.), Aculops lycopersici (Aculops lycopersici) (tomato russet Mite), Aculops pelekasi, tangerine peronium goitre mite (Aculus pelekassi), Si Shi thorn goitre mites (Aculus Schlechtendali) (apple pierces goitre mite (apple rust mite)), lone star tick (Amblyomma amcricanum) (lone star tick), Boophilus kind (Boophilus spp.) (tick), oval short hairs tick (Brevipalpus Obovatus) (privet mite), purplish red short hairs mite (Brevipalpus phoenicis) (red and black flat Mite), fat tick belongs to kind of (Demodex spp.) (a mange mites), Dermacentor kind (Dermacentorspp.) (hard tick), U.S. Continent dog tick (Dermacentor variabilis) (american dog tick), dermatophagoides pteronyssinus (Dermatophagoides Pteronyssinus) (house dust mite), Eotetranychus kind (Eotetranycus spp.), Eotetranychus carpini (Eotetranychus carpini) (yellow spider mite (yellow spider mite)), Epitrimerus kind (Epitimerus Spp.), Eriophyes kind (Eriophyes spp.), Isodesspp kind (work;Odes spp.) (tick), Panonychus citri category kind ((Metatetranycus spp.), notoedres cati (Notoedres cati), Oligonychus kind (Oligonychus spp.), coffee Coffee unguiculus mite (Oligonychus coffee), ilex Oligonychus (Oligonychus ilicus) (southernred mi Te), Panonychus citri belongs to kind of (a Panonychus spp.), Jie-Li enzyme-SQ (Panonychus cirri) (orange spider (citrus Red mite)), panonychus ulmi (Panonychus ulmi) (European red spider (European red mite)), tangerine wrinkle leaf Pierce goitre (Phyllocoptruta oleivora) (citrus rust mite), Polyphagotarsonemus latus Banks (Polyphagotarsonemun latus) (broad mite (broad mite)), brown dog tick (Rhipicephalus Sanguineus) (brown dog tick (brown dog tick)), root mite belong to kind of (Rhizoglyphus spp.) (root mite (bulb Mite)), itch mite (Sarcoptes scabiei) (itch mite), avocado apical cap goitre mite (Tegolophus Perseaflorae), Tetranychus kind (Tetranychus spp.), T.urticae Koch (Tetranychus urticae) (2 spiders Spider mite (twospotted spider mite)) and Di Shi watts of mite (Varroa destructor) (honeybee mite).
Nematoda (nematode)：Aphelenchoides kind (Aphelenchoides spp.) (bud and leaf and Bursaphelenchus xylophilus (bud And leaf ＆ pine wood nematode)), thorn Turbatrix kind (Belonolaimus spp.) (sting Nematodes), small loop wire Eimeria kind (Criconemella spp.) (ring nematodes), heart worm (Dirofilaria immitis) (dog heartworm), Ditylenchus kind (Ditylenchus spp.) (stem and bulb line Worm), spine rubber-insulated wire Eimeria kind (Heterodera spp.) (cyst nematode), corn cyst nematode (Heterodera Zeae) (corn cyst nematode), Hirschmanniella kind (Hirschmanniella spp.) (root nematodes), Tie Turbatrix kind (Hoplolaimus spp.) (lance nematodes), Meloidogyne kind (Meloidogyne Spp.) (root-knot nematode), Meloidogyne incognita ((Meloidogyne incognita) (root-knot nematode), Onchocerca caecutiens (Onchocerca volvulus) (hook-tail worm), Pratylenchus kind (PraLylenchus spp.) (rotten nematode (lesion nematode)), perforation line Eimeria kind (Radopholus spp.) (similes thorne (burrowing )) and banana reniform nematode (Rotylenchus reniformis) (kidney-shaped nematode) nematode.
Symphyla (comprehensive insects)：Kahikatea worm (Scutigerella immaculata).
Particularly, to cotten aphid, diamondback moth and tobacco budworm, still there is good control effect at lower doses.
General formula I-VI compounds can be used for preventing following weeds:Grassy weed, such as barnyard grass, lady's-grass, green bristlegrass, wild swallow Wheat, bromegrass, india lovegrass, amur foxtail, eleusine indica, annual bluegrass, Bermuda grass, reed, wheatgrass, speedwell, wild broomcorn millet, cogongrass and reed Deng；Sedge weed, such as difformed galingale herb, brown fringe nutgrass flatsedge and the rhizome of nutgrass flatsedge；Commelianaceae weeds, such as dayflower；Broad leaved weed, As volume stem smartweed, lamb's-quarters, artemisia annua, argy wormwood, Amaranthus retroflexus, sowthistle, chenopodium glaucum linn, small lamb's-quarters, lamb's-quarters, cane lamb's-quarters, sarson, wolf are purple Grass, vetch, summer cypress, field thistle, cottonsedge-like thistle herb, water pepper, field bindweed, hemp, meadow pine, pivots storage, chickweed, salsola collina, wild mint, Clover, dawrf mallow, Hairy Bittercress, clearvers, wartwort, shepherd's purse, purslane, motherwort, black nightshade, Ageratum conyzoides, Siberian cocklebur, one hundred days Grass, piemarker, flowerofanhour root or herb, clearvers, Descurainia sophia, beggar-ticks, acalypha copperleaf, wartwort, humid euphorbia, shamrock, alfalfa, vegetation Sweet-scented osmanthus, ivy glorybind, erect hypecoum, rice crock, curled dock and pale persicaria etc..
Meanwhile general formula I-VI compounds have hypotoxicity to many beneficial insects and acarid, mammal, fish, bird, and And there is no phytotoxicity.
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family The environment that poultry and breeding stock and the mankind often go is from there is the injury of pest, mite.
To obtain ideal effect, the dosage of compound changes because of various factors, such as compound used therefor, the work protected in advance Object, the type of harmful organism, gradient of infection, weather conditions, application method, the dosage form of use.
The compound dosage of 10 grams -5 kilograms of per hectare can provide sufficient prevention.
It is typically beneficial using the composition containing one or more general formula I-VI compounds in order to be applied to agricultural 's.
Therefore, another technical solution of the invention further includes a kind of desinsection, sterilization, Herbicidal combinations, contains conduct The general formula I-VI compounds of active component and agriculturally acceptable carrier, the weight percentage of active component is in composition 0.5-90%.
" pharmaceutically acceptable salt " used in the present invention refers to the organic salt and inorganic salts of the compound of the present invention.Medicine Acceptable salt is known to us in fields on, such as document：S. M. Berge et al., describe pharmaceutically acceptable salts in detail in J. Pharmaceutical Sciences, 66:1-19,1977. recorded.The salt that pharmaceutically acceptable nontoxic acid is formed is including but not limited to ammonia Base group, which reacts the inorganic acid salt to be formed, a hydrochloride, hydrobromate, phosphate, sulfate, perchlorate, and organic Hydrochlorate, such as acetate, oxalates, maleate, tartrate, citrate, succinate, malonate, or These salt are obtained by other methods described in the books or literature such as ion-exchange.Other pharmaceutically acceptable salt packets It includes:Adipate, alginates, ascorbate, aspartate, benzene sulfonate, benzoate, bisulphate, Borate, butyrate, camphor hydrochlorate, camsilate, cyclopentyl propionate, digluconate, dodecyl sulphur Hydrochlorate, esilate, formates, fumarate, gluceptate, glycerophosphate, gluconate, half Sulfate, enanthate, caproate, hydriodate, 2- hydroxy-ethanesulfonate salts, lactobionate, lactate, lauric acid Salt, lauryl sulfate, malate, malonate, mesylate, 2- naphthalene sulfonates, nicotinate, nitrate, Oleate, palmitate, pamoate, pectate, persulfate, 3- phenylpropionic acid salt, picrate, pivalic acid Salt, propionate, stearate, rhodanate, tosilate, undecylate, valerate, etc..By appropriate The obtained salt of alkali include alkali metal, alkaline-earth metal, ammonium and N+(C1-C4 alkyl)4Salt.The present invention is also intended to contemplate any The compound of the group of included N is formed by quaternary ammonium salt.Water-soluble or oil-soluble or dispersion product can be turned by quaternary ammonium With obtaining.Alkali or alkaline earth metal salt includes sodium, lithium, potassium, calcium, magnesium, etc..Pharmaceutically acceptable salt is further Including appropriate, nontoxic ammonium, the amine cation that quaternary ammonium salt and gegenions are formed, such as halide, hydroxide, carboxylic Compound, hydrosulphate, phosphoric acid compound, nitric acid compound, C1-C8 azochlorosulfonate acid compounds and aromatic sulphonic acid compound.
The salt of part of compounds of the present invention can be as follows the salt of particular compound illustrate, but simultaneously Do not limit the present invention.
。
" solvate " of the present invention refers to that one or more solvent molecules are formed by association with the compound of the present invention Object.The solvent of solvate is formed including but not limited to, water, isopropanol, ethyl alcohol, methanol, dimethyl sulfoxide, acetic acid Ethyl ester, acetic acid, ethylaminoethanol.Term " hydrate " refers to that solvent molecule is that water is formed by associated matter.
The solvate of part of compounds or the solvate of its salt of the present invention can use the specific chemical combination listed as follows The salt of object illustrates, but is not limited to the present invention：
。
The use form of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, hang Floating agent etc.：The selection of types of compositions depends on specific application.
Composition is prepared in a known way, such as optionally in the presence of surfactant, by with solvent medium And/or solid diluent or dissolving active material.
Available solid diluent or carrier are for example：Silica, kaolin, bentonite, talcum, diatomite, white clouds Stone, calcium carbonate, magnesia, chalk, clay, synthetic silicate, Attagel, sepiolite.
Than water, available liquid diluent be for example aromatic organic solvent (mixture of dimethylbenzene or alkylbenzene, Chlorobenzene etc.), paraffin (petroleum distillate), alcohols (methanol, propyl alcohol, butanol, octanol, glycerine), esters (ethyl acetate, Sucrose Acetate Ester etc.), ketone (cyclohexanone, acetone, acetophenone, isophorone, ethylpentyl ketone etc.), amides (N, N- dimethyl formyl Amine, N-Methyl pyrrolidone etc.).
Available surfactant be alkylsulfonate, alkylaryl sulfonates, polyoxyethylene alkylphenol, sorbierite it is poly- Sodium, calcium, triethylamine or the triethanolamine salt of ethylene oxide ester, lignosulfonates etc..
Composition can also contain special additive for specific purpose, for example, adhesive for example Arabic gum, polyvinyl alcohol, Polyvinylpyrrolidone etc..
In above-mentioned composition the concentration of active constituent can according to active constituent, its use purpose, environmental condition and use Preparation type and change in OK range.In general, the concentration range of active constituent is 1-90%, preferably 5-50%.
It can be with general formula I- if desired, can be added into compositionThe other active components of compound compatibility, such as Other acaricide/insecticide, fungicide, plant growth regulator, antibiotic, herbicide, fertilizer.
The preparation method of several dosage forms is exemplified below：
The preparation of suspending agent：Active component content is 5%-35% in common prescription.Using water as medium, by active compound, dispersant, help Suspension and antifreeze etc. are added in sand mill, are ground, suspending agent is made.
The preparation of aqueous emulsion：Active compound, solvent and emulsifier are added together, make to be dissolved into homogeneous oil phase.By water, antifreeze Etc. being mixed, become uniform water phase.Under high velocity agitation, water phase is added to oil phase or oil phase is added to water phase, formed The aqueous emulsion of favorable dispersibility.The aqueous emulsion active component content of the present invention is generally 5%-15%.To prepare emulsifiable concentrate, this hair Bright compound is dissolvable in water one or several kinds of mixed solvents, adds emulsifier to enhance the dispersion effect of compound in water Fruit.
The preparation of wettable powder：It is by recipe requirements, active compound, various surfactants and solid diluent etc. is fully mixed It closes, to get to the wettable powder product of predetermined content (such as 10%-40%) after ultra-fine pulverizer disintegrating.It is suitable to prepare In the wettable powder of sprinkling, the compound of the present invention can be with finely ground solid powder such as clay, inorganic silicate, carbonic acid Salt and wetting agent, adhesive and/or dispersant composition mixture.
The preparation of water-dispersible granules：Active compound and powdered solid diluents, wetting spreader-sticker and adhesive etc. are mixed It closes and crushes, after adding water kneading, be added in the comminutor equipped with 10 to 100 mesh screens and be granulated, then again through drying, screening (pressing screen cloth scope).Also active compound, dispersant, disintegrant and wetting agent and solid diluent can be added in sand mill, is with water Suspending agent is made in medium milling, then carries out spray drying granulation, and it is 20% -30% granular product to be typically formulated content.
Specific implementation mode
Following specific examples is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.(except as otherwise note It is bright outer, raw materials used to be commercially available).
Embodiment
Embodiment 1.1- (3- aminopropyls) -4- oxygen -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates
Step（1）4- oxyquinoline -3- Ethyl formates
It weighs aniline (0.011 mol) and diethyl ethoxymethylenemalonate (0.012 mol) is added in 20 mL ethyl alcohol, 90oC is heated three hours, is cooled to room temperature, the phenetole of 40 mL is added, 100o30 min are heated under C, are cooled to room temperature, instead After answering, ice water is added, ethyl acetate extracts (100 mL × 2), merging organic phase, organic phase saturated common salt water washing, Anhydrous sodium sulfate is dried, filtering, and organic phase concentration, residue obtains 4- hydroxyls -2- hydrogen-quinoline -3- formic acid second through silica gel column chromatography Ester (66% yield)；
Step（2）4- chloroquinoline -3- Ethyl formates
It weighs 4- oxyquinoline -3- Ethyl formates (7.3 mmol) to be dissolved in 100 mL dioxane, trichlorine oxygen is then added After phosphorus (7.4 mmol) mixing, 80oC is heated one hour, is after reaction poured into ice water reaction solution, is used saturated sodium carbonate Solution adjusts pH to neutrality, and ethyl acetate extracts (100 mL × 2), merges organic phase, organic phase saturated common salt water washing, nothing Aqueous sodium persulfate is dried, filtering, and organic phase concentration, residue obtains 4- chloroquinoline -3- Ethyl formates through silica gel column chromatography（58% production Rate）；
Step（3）The bromo- 4- chloroquinolines -3- Ethyl formates of 2-
It weighs 4- chloroquinoline -3- Ethyl formates (4.7 mmol) to be dissolved in chloroform (20 mL), peroxide benzene first is added in room temperature thereto It is stirred at room temperature 4 hours after sour (6.8 mmol), tribromo oxygen phosphorus (6.9 mmol) is added toward reaction solution stirs 1 hour afterwards, reaction knot Reaction solution is poured into ice water after beam, with saturated sodium carbonate solution tune pH value to neutrality, ethyl acetate extracts (100 mL × 2), Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration, residue is through column layer Analyse (EtOAc: PET = 1 :60) the bromo- 4- chloroquinolines -3- Ethyl formates of 2- (62% yield) are obtained;
Step（4）2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formates
Weigh the bromo- 4- chloroquinolines -3- Ethyl formates of 2- (3.2 mmol) and (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) boric acid (3.3 mmol) is dissolved in Isosorbide-5-Nitrae-dioxane (15 mL) and water (6 mL), thereto be added potassium carbonate (6.5 mmol) and Palladium (0.3 mmol), reaction solution is 50oIt is stirred 3 hours under C, reaction solution is poured into ice water after reaction, uses acetic acid Ethyl ester extracts (100 mL × 2).Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying is filtered, had Machine mutually concentrates, and residue obtains 2- (1- (tertbutyloxycarbonyl) -1 through column chromatographyHPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formates (43% yield)；
Step（5）4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates
By 2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) -4- chloroquinoline -3- Ethyl formates (1.7 mmol) are dissolved in acetic acid (10 mL), ethyl alcohol (6 mL) are warming up to 75 after water (5 ml)oC reacts 18 hours, and vacuum distillation removes acetic acid, ethyl alcohol, gained Residue is diluted with water, and is adjusted to neutrality with unsaturated carbonate potassium solution, ethyl acetate extracts (100 mL × 2), merges organic phase, has Machine mutually uses saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration.Residue obtains 4- oxos -2- through column chromatography (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates (36% yield)；
Step（6）1- (3- aminopropyls) -4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates
By 4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates（1.2 mmol）With 3- N-Propyl Bromides -1- Amine（0.9 mmol）It is dissolved in DMSO (10 mL), potassium carbonate (6.5 mmol) is added thereto, reaction solution is stirred at room temperature 1 Hour, reaction solution is poured into ice water after reaction, is extracted with ethyl acetate (100 mL × 2).Merge organic phase, organic phase With saturated common salt water washing, anhydrous sodium sulfate drying is filtered, and organic phase concentration, residue obtains 1- (3- aminopropyls)-through column chromatography 4- oxos -2- (1HPyrroles -2- bases)-Isosorbide-5-Nitrae-dihydroquinoline -3- Ethyl formates (25%, yield).
ESI-MS (m/z): 340.16 [M+H]+。
Embodiment 2.1- (3- hydroxypropyls) -4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates
By 4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- Ethyl formates (1.2 mmol) and 3- N-Propyl Bromides -1- Alcohol (0.9 mmol) is dissolved in DMSO (10 mL), potassium carbonate (6.5 mmol) is added thereto, reaction solution is stirred at room temperature 1 Hour, reaction solution is poured into ice water after reaction, is extracted with ethyl acetate (100 mL × 2).Merge organic phase, organic phase With saturated common salt water washing, anhydrous sodium sulfate drying is filtered, and organic phase concentration, residue obtains 1- (3- hydroxypropyls)-through column chromatography 4- oxos -2- (1HPyrroles -2- bases)-Isosorbide-5-Nitrae-dihydroquinoline -3- Ethyl formates (25%, yield).
ESI-MS (m/z): 341.14 [M+H]+。
Embodiment 3.7- (3- fluorophenoxies) -4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- formic acid fourths Ester
Step（1）7- (3- fluorophenoxies) -4- oxyquinoline -3- butyl formates
Weigh 3- (3- fluorophenoxies) aniline (0.011 mol) and (E) -2- (ethoxymeyhylene) malonic acid 1- butyl 3- ethyls Ester (0.012 mol) is added in 20 mL ethyl alcohol, 90oC is heated three hours, is cooled to room temperature, and the phenetole of 40 mL is added, 100o30min is heated under C, is cooled to room temperature, after reaction, ice water is added, ethyl acetate extracts (100 mL × 2), merges Organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration, residue is through silica gel column layer Analyse (EtOAc: PET = 1:30) 7- (3- fluorophenoxies) -4- oxyquinoline -3- butyl formates (66% yield) are obtained;
Step（2）7- (3- fluorophenoxies) -4- chloroquinoline -3- butyl formates
Weigh 7- (3- fluorophenoxies) -4- oxyquinoline -3- butyl formates（7.3 mmol）It is dissolved in 100 mL dioxane, Then phosphorus oxychloride is added（7.4 mmol）After mixing, 80oC is heated one hour, and reaction solution is poured into ice water after reaction In, pH is adjusted to neutrality with saturated sodium carbonate solution, and ethyl acetate extracts (100 mL × 2), merges organic phase, and organic phase is used full And brine It, anhydrous sodium sulfate drying, filtering, organic phase concentration, residue obtain 7- (3- fluorobenzene oxygen through silica gel column chromatography Base) -4- chloroquinoline -3- butyl formates (58% yield);
Step（3）The chloro- 7- of the bromo- 4- of 2- (3- fluorophenoxies) quinoline -3- butyl formates
It weighs 7- (3- fluorophenoxies) -4- chloroquinoline -3- butyl formates (4.7 mmol) and is dissolved in tetrahydrofuran (20 mL), room Temperature is stirred at room temperature 4 hours after benzoyl hydroperoxide (6.8 mmol) is added thereto, and tribromo oxygen phosphorus (6.9 is added toward reaction solution Mmol it) stirs 1 hour, after reaction pours into reaction solution in ice water, with saturated sodium carbonate solution tune pH value to neutrality, second afterwards Acetoacetic ester extracts (100 mL × 2), merges organic phase, organic phase saturated common salt water washing, and anhydrous sodium sulfate drying is filtered, Organic phase concentrates, and residue obtains the bromo- 4- of 2- chloro- 7- (3- fluorophenoxies) quinoline -3- butyl formates (62% yield) through column chromatography;
Step（4）2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) the chloro- 7- of -4- (3- fluorophenoxies) quinoline -3- butyl formates
Weigh the bromo- 4- of 2- chloro- 7- (3- fluorophenoxies) quinoline -3- butyl formates (3.2 mmol) and (1- (tertbutyloxycarbonyl) - 1HPyrroles -2- bases) boric acid (3.3 mmol) is dissolved in Isosorbide-5-Nitrae-dioxane (15 mL), potassium carbonate (6.5 is added thereto Mmol) and palladium (0.3 mmol), reaction solution is 50oIt is stirred 3 hours under C, reaction solution is poured into ice water after reaction In, it is extracted with ethyl acetate (100 mL × 2).Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate is done Dry, filtering, organic phase concentration, residue is through column chromatography (EtOAc: PET = 1:30) 2- (1- (tertbutyloxycarbonyl) -1 are obtainedH- Pyrroles -2- bases) the chloro- 7- of -4- (3- fluorophenoxies) quinoline -3- butyl formates (43% yield)；
Step（5）7- (3- fluorophenoxies) -4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- butyl formates
By 2- (1- (tertbutyloxycarbonyl) -1HPyrroles -2- bases) the chloro- 7- of -4- (3- fluorophenoxies) quinoline -3- butyl formates (1.7 Mmol) it is dissolved in acetic acid (10 mL), ethyl alcohol (6 mL), water（5 mL）After be warming up to 75oC reacts 18 hours, and vacuum distillation removes second Acid, ethyl alcohol, gained residue are diluted with water, and neutrality is adjusted to unsaturated carbonate potassium solution, and ethyl acetate extracts (100 mL × 2), Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, filtering, organic phase concentration.Residue is through column layer Analyse to obtain 7- (3- fluorophenoxies) -4- oxos -2- (1HPyrroles -2- bases) -1,4- dihydroquinoline -3- butyl formates (36% yield).
ESI-MS (m/z): 421.15 [M+H]+。
Biological activity determination
Embodiment 4
Bactericidal activity test method bibliography Liu, Qing-Ai; Shao, Chang-Lun; Gu, Yu-Cheng; Blum, Mathias; Gan, Li-She; Wang, Kai-Ling; Chen, Min; Wang, Chang-Yun. Antifouling and Fungicidal Resorcylic Acid Lactones from the Sea Anemone- Derived Fungus Cochliobolus lunatus. Journal of Agricultural and Food Chemistry (2014), 62 (14), 3183-3191. is using metalaxyl and mandipropamid as positive drug.
Active testing data
DCRs indicates disease control rate in table（%）；" ++++" DCR is indicated between 90-100%, " +++ " indicates DCR in 80-90% Between, " ++ " indicates DCR between 60-80%, and "+" indicates DCR between 30-60%, and " 0 " indicates that no control, "-" indicate not It is tested under the concentration.
Active testing shows：The agriculture pathogenic activity of the compounds of this invention prevention is better than positive drug or suitable with positive drug, Show preferable application value.
Embodiment 5
Insecticidal activity is tested
Test parallel testing three times, the disease and insect of test is respectively cotton aphid (Aphis gossypii), diamondback moth larvae (Plutella xylost) and heliothis virescens larvae (Heliothis virescens).The initial concentration of test sample is 500 ppm, when test, are diluted with water as 100 ppm, each sample are added separately in 96 orifice plates, each larva cultivates 5-9 It.
The compound that the present invention tests is diluted with water to two concentration of 500 ppm and 100 ppm, respectively to above-mentioned orifice plate 0.5 ml is added.
Active testing data
" ++++" lethality is indicated between 90-100%, " +++ " indicates lethality between 80-90%, and " ++ " indicates lethality Between 70-80%, "+" indicates lethality between 50-70%.
It is apparent that active testing shows that the compounds of this invention has cotton aphid, diamondback moth larvae and heliothis virescens larvae Killing activity, therefore can be used as microbial pesticide insecticide, and raw material can be mass produced, application prospect is wide It is wealthy.
Embodiment 6
Activity of weeding test reference document Yang, Zihui; Chen, Aiyu; Hu, Aixi; Ye, Jiao. Synthesis, crystal structure and herbicidal activity of n-(thiazol-2-yl)-2- (4-aryloxyphenoxy) propionamides. Youji Huaxue (2017), 37 (1), 149-156. Yi oxazoles Acyl grass amine is positive drug.
Preventive effect grade scale：0 is invalid, and 100% is to kill weeds completely or seriously inhibit.Compound test agent Amount is 1000 g/hm2。
Active testing data（Inhibiting rate/%, 1000 g/hm2）
" ++++" inhibiting rate is indicated between 80-100%, " +++ " indicates inhibiting rate between 50-80%, and " ++ " indicates inhibiting rate Between 30-50%, "+" indicates inhibiting rate between 5-30%.
Active testing shows：The compounds of this invention is notable to youth-and-old-age, piemarker, green bristlegrass and barnyard grass fragmentation effect, part Compound activity is better than positive drug or suitable with positive drug, shows preferable application value.

Claims (10)

1. the quinolinone alkaloid class compound of a kind of Formulas I and Formula II structure, tautomer, stereoisomer, racemic The solvent of body, the non-equal amount of mixture of enantiomter, geometric isomer, solvate, pharmaceutically acceptable salt or its salt Compound, it is characterised in that compound has the following structure：, Middle A, B are five yuan or hexa-atomic aromatic ring, hetero-aromatic ring, carbon heterocyclic；N=1,2,3, or 4；K=1,2,3 or 4；Y be O or NR5; “" indicate singly-bound or be not present; R1, R2, R3, R4, R5Shown in being defined as follows：
Each R1, R4Can be identical or different, it is separate be hydrogen, deuterium, halogen, hydroxyl, amino, nitro, cyano, Alkyl, halogenated alkyl, alkoxy, alkylamino, alkyl acyl, hydroxy alkoxy base, Hydroxyalkylamino, hydroxyalkanoyl, Halogenated alkoxy, halogenated alkylamino, ohaloalkanoyl, aminoalkoxy, naphthenic base, cycloalkyl oxy, naphthenic base ammonia Base, cycloalkanoyl, alkenyl, alkenylalkoxy, alkenyl alkylamino, alkenyl alkanoyl, alkynyl, alkynyl alkoxy, Alkynyl alkylamino, alkynyl alkanoyl, aryl, aryloxy group, aroyl, fragrant amino, alkoxy aryl, aryl alkane amino, Heteroaryl, heteroaryloxy, 4-hetaroylpyrazol, heteroaryl amino, heteroarylalkoxy, heteroarylalkylamino, heterocycle alkane acyl Base, Heterocyclylalkyl, heterocycle oxygroup, heterocyclylamino group, heterocyclylacyl, heterocyclylalkoxy, heterocycle alkylamino, Heterocycle alkanoyl, azido alkoxy, condensed-bicyclic base condense miscellaneous bicyclic group, and condensed-bicyclic base aliphatic condenses Miscellaneous bicyclic group aliphatic, condensed-bicyclic base oxygroup condense miscellaneous bicyclic group oxygroup, and condensed-bicyclic base amino condenses miscellaneous bicyclic Base amino, condensed-bicyclic base alkoxy condense miscellaneous bicyclic group alkoxy, and condensed-bicyclic base alkylamino condenses miscellaneous bicyclic group Alkylamino, condensed-bicyclic base oxygroup alkoxy, condensed miscellaneous bicyclic group oxygroup alkoxy, condensed-bicyclic base aminoalkoxy, Miscellaneous bicyclic group aminoalkoxy is condensed, condensed-bicyclic base-C (=O)-, condensed-bicyclic base-C (=O) O- condense miscellaneous bicyclic group-C (=O)-, miscellaneous bicyclic group-C (=O) O-, condensed-bicyclic base amino-C (=O)-are condensed, miscellaneous bicyclic group amino-C (=O)-is condensed, Condensed-bicyclic base-C (=O) N (R6)-, condenses miscellaneous bicyclic group-C (=O) N (R6)-, spiral shell bicyclic group, the miscellaneous bicyclic group of spiral shell, spiral shell are bicyclic Base aliphatic, the miscellaneous bicyclic group aliphatic of spiral shell, spiral shell bicyclic group oxygroup, the miscellaneous bicyclic group oxygroup of spiral shell, spiral shell bicyclic group amino, spiral shell are miscellaneous Bicyclic group amino, spiral shell bicyclic group alkoxy, the miscellaneous bicyclic group alkoxy of spiral shell, spiral shell bicyclic group alkylamino, the miscellaneous bicyclic group alkane ammonia of spiral shell Base, spiral shell bicyclic group oxygroup alkoxy, the miscellaneous bicyclic group oxygroup alkoxy of spiral shell, spiral shell bicyclic group aminoalkoxy, the miscellaneous bicyclic group of spiral shell Aminoalkoxy, spiral shell bicyclic group-C (=O)-, spiral shell bicyclic group-C (=O) O-, the miscellaneous bicyclic group-C of spiral shell (=O)-, the miscellaneous bicyclic group-of spiral shell C (=O) O-, spiral shell bicyclic group amino-C (=O)-, the miscellaneous bicyclic group amino-C of spiral shell (=O)-, spiral shell bicyclic group-C (=O) N (R6)-, spiral shell Miscellaneous bicyclic group-C (=O) N (R6)-, R7R6N-, -C(=O)NR6R7, -OC(=O)NR6R7, -OC(=O)OR6, -N(R6)C(=O) NR6R7, -N(R6)C(=O)OR7, -N(R6)C(=O)-R7, R6R7N-S(=O)t-, R6S(=O)t-, R6S(=O)tN(R7)-, R7R6N- alkyl, R6S(=O)tAlkyl, R6R7N-C (=O)-alkyl, R7R6N- alkoxies, R6S(=O)tAlkoxy, R6R7N-C (=O)-alkoxy, aryl-(CH2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle-(CH2)p- G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(=O), S(=O)2,C(=O), -C (=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O)N(R6)-, -(R6)N-S(=O)t-, -OS(= O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is each independently 0, l, 2,3 or 4;Or wherein aryl- (CH2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle-(CH2)p-G-(CH2)m, or naphthenic base- (CH2)p-G-(CH2)mCan F, Cl, Br, I, alkyl, alkenyl, alkynyl, alkoxy or cyanogen be selected from by one or more The substituent group of base replaces;
R2, R3, R5Can be identical or different, separate is hydrogen, deuterium, alkyl, halogenated alkyl, alkyl acyl, hydroxyl Base alkanoyl, ohaloalkanoyl, naphthenic base, cycloalkanoyl, alkenyl, alkenyl alkanoyl, alkynyl, alkynyl alkanoyl, Aryl, aroyl, heteroaryl, 4-hetaroylpyrazol, heterocycle alkanoyl, Heterocyclylalkyl, heterocyclylacyl, heterocycle alkane Acyl group, azido alkyl, condensed-bicyclic base condense miscellaneous bicyclic group, and condensed-bicyclic base-C (=O)-condenses miscellaneous bicyclic group-C (=O)-, condensed-bicyclic base amino-C (=O)-, condensed miscellaneous bicyclic group amino-C (=O)-, spiral shell bicyclic group, the miscellaneous bicyclic group of spiral shell, Spiral shell bicyclic group aliphatic, the miscellaneous bicyclic group aliphatic of spiral shell, spiral shell bicyclic group-C (=O)-, the miscellaneous bicyclic group-C of spiral shell (=O)-, spiral shell is bicyclic Base amino-C (=O)-, the miscellaneous bicyclic group amino-C of spiral shell (=O)-,-C (=O) NR6R7, R6R7N-S(=O)t-, R6S(=O)t-, R7R6N- alkyl, R6S(=O)tAlkyl, R6R7N-C (=O)-alkyl, aryl-(CH2)p-G-(CH2)m, heteroaryl- (CH2)p-G-(CH2)m, heterocycle-(CH2)p-G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(=O), S(=O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O) N(R6)-, -(R6)N-S(=O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m are each independently 0, l, 2,3 or 4;Or aryl-(CH therein2)p-G-(CH2)m, heteroaryl-(CH2)p-G-(CH2)m, heterocycle- (CH2)p-G-(CH2)m, or naphthenic base-(CH2)p-G-(CH2)mCan F, Cl, Br, I, cyanogen be selected from by one or more Base, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, carbocylic radical, the substituent group substitution of heterocycle;
R8Can be identical or different, it is each independently hydrogen, R6R7NC(=O)-, R6OC(=O)-, R6C(=O)-, R6R7NS(= O)-, R6OS(=O)-, R6S(=O)-, R6R7NS(=O)2-, R6OS(=O)2-, R6S(=O)2, aliphatic, halogenated aliphatic Race, hydroxyl group aliphatic, amino aliphatic, alkoxy aliphatic, alkylamino aliphatic, alkylthio group aliphatic, aryl fat Fat race, heteroaryl aliphatic, heterocycle aliphatic, naphthenic base aliphatic, aryloxy group aliphatic, heterocycle oxygroup fat Race, cycloalkyl oxy aliphatic, fragrant amino aliphatic, heterocyclylamino group aliphatic, cycloalkyl amino aliphatic, aryl, Heteroaryl, heterocycle or carbocylic radical;
Each R6And R7It independently is hydrogen, deuterium, aliphatic, halogenated aliphatic, hydroxyl group aliphatic, amino aliphatic, alkoxy Aliphatic, alkylamino aliphatic, alkylthio group aliphatic, aromatic yl aliphat, heteroaryl aliphatic, heterocycle aliphatic, Naphthenic base aliphatic, aryloxy group aliphatic, heterocycle oxygroup aliphatic, cycloalkyl oxy aliphatic, fragrant amino aliphatic, Heterocyclylamino group aliphatic, cycloalkyl amino aliphatic, aryl, heteroaryl, heterocycle or naphthenic base;Work as R6And R7It is connected in On the same nitrogen-atoms, R6, R7Can be randomly formed 3-8 substituted or non-substituted membered rings with nitrogen-atoms, condensed-bicyclic or Spiral shell is bicyclic;The hetero atom in heterocycle, heteroaryl, condensed miscellaneous bicyclic group, the miscellaneous bicyclic group of spiral shell involved in above-mentioned group is independent 1-5 hetero atom of the ground in N, O, S, Se;
Above-mentioned R1, R2, R3, R4, R5, R6, R7, R8Group can appoint by hydroxyl, methylol, carboxyl, acetylamino, alkane Base (such as methyl, ethyl, propyl), alkoxy (such as methoxyl group, ethyoxyl, tert-butoxy), alkylamino, naphthenic base, alkenyl, Alkynyl, trifluoromethyl, trifluoroacetyl group, sulfydryl, halogen, nitro, amino, azido (- N3), guanidine radicals, cyano, Tertbutyloxycarbonyl (- Boc), carbonyl (- C=O), oxo (=O) is thio (=S), sulfonyl, aryl, heteroaryl, heterocycle One or more of base replaces.
2. compound according to claim 1 is general formula III-VI compounds represented, or general formula III-VI shownization It closes the stereoisomer geometric isomer of object, tautomer, nitrogen oxides, raceme, hydrate, solvate, be metabolized production Object, pharmaceutically acceptable salt or prodrug：
, wherein T1, T2, T3, T4Separate is CR1Or N, wherein T1, T2, T3, T4At most there are two can contain N; V1, V2, V3, V4Respectively It is independently CR4, NR9, O or S;Y is O or NR5; X1, X2, X3, X4, X5Separate is CR4Or N; “" table Show singly-bound or is not present;Each R1, R2, R3, R4, R5, R9As follows：
Each R1, R4Can be identical or different, it is separate be H, D, F, Cl, Br, I, hydroxyl, amino, nitro, Cyano, C1-C20 alkyl, C1-C20 halogenated alkyls, C1-C20 alkoxies, C1-C20 alkylaminos, C1-C20 alkyl acyls, Hydroxyl C1-C20 alkoxies, hydroxyl C1-C20 alkylaminos, hydroxyl C1-C20 alkanoyls, C1-C20 halogenated alkoxies, C1- The halogenated alkylaminos of C20, C1-C20 ohaloalkanoyls, C1-C20 aminoalkoxies, C3-C10 naphthenic base, C3-C10 naphthenic base Oxygroup, C3-C10 cycloalkyl aminos, C3-C10 cycloalkanoyls, C2-C8 alkenyls, C2-C8 alkynyls, C6-C10 aryl, C6-C10 aryloxy group, C6-C10 aroyls, C6-C10 fragrant aminos, C6-C10 aryl C1-C6 alkoxies, C6-C10 aryl alkane Amino, C5-C12 heteroaryls, C5-C12 heteroaryloxies, C5-C12 4-hetaroylpyrazols, C5-C12 heteroaryl amino, C5-C12 are miscellaneous Aryl C1-C6 alkoxies, C5-C12 heteroaryl C1-C6 alkylaminos, C4-C12 heterocycle C1-C6 alkanoyls, C4-C12 heterocycles Alkyl, C4-C12 heterocycle oxygroups, C4-C12 heterocyclylamino groups, C4-C12 heterocyclylacyls, C4-C12 heterocycles C1-C6 Alkoxy, C4-C12 heterocycle C1-C6 alkylaminos, C4-C12 heterocycle C1-C6 alkanoyls, R7R6N-, -C(=O)NR6R7, -OC(=O)NR6R7, -OC(=O)OR6, -N(R6)C(=O)NR6R7, -N(R6)C(=O)OR7, -N(R6)C(=O)-R7, R6R7N-S(=O)t-, R6S(=O)t-, R6S(=O)tN(R7)-, R7R6N- C1-C6 alkyl, R6S(=O)t- C1-C6 alkyl, R6R7N-C (=O)-C1-C6 alkyl, R7R6N- C1-C6 alkoxies, R6S(=O)t- C1-C6 alkoxies, R6R7N-C(=O)- C1-C6 alkoxies, C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m-, C4-C12 Heterocycle-(CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(= O), S(=O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O)N(R6)-, - (R6)N-S(=O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is each independently 0, l, 2,3 Or 4;Or wherein C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m-, C4-C12 Heterocycle-(CH2)p-G-(CH2)m, or C3-C1 naphthenic base-(CH2)p-G-(CH2)mCan F be selected from by one or more, The substituent group of Cl, Br, I, alkyl, alkenyl, alkynyl, alkoxy or cyano replaces;
R2, R3, R5, R9For H, D, C1-C20 alkyl, C1-C20 halogenated alkyls, C1-C20 alkyl acyls, C1-C20 hydroxyls Base alkanoyl, C1-C20 ohaloalkanoyls, C3-C10 naphthenic base, C3-C10 cycloalkanoyls, C2-C8 alkenyls, C2-C8 Alkenyl alkanoyl, C2-C8 alkynyls, C2-C8 alkynyl alkanoyls, C6-C10 aryl, C6-C10 aroyls, C5-C12 heteroaryls Base, C5-C12 4-hetaroylpyrazols, C4-C12 heterocycle alkanoyls, C4-C12 Heterocyclylalkyls, C4-C12 heterocyclylacyls, C4- C12 heterocycle C1-C6 alkanoyls, C5-C12 condensed-bicyclic bases, C5-C12 condense miscellaneous bicyclic group ,-C (=O) NR6R7, R6R7N-S(=O)t-, R6S(=O)t-, R7R6N-C1-C6 alkyl, R6S(=O)t- C1-C6 alkyl, R6R7N-C(=O)-C1-C6 Alkyl, C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m, C4-C12 heterocycles- (CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)m, wherein G is O, S, NR8, S(=O), S(= O)2,C(=O), -C(=O)N(R6)-, -OC(=O)N(R6)-, -OC(=O)-, -N(R6)C(=O)N(R6)-, -(R6)N-S(= O)t-, -OS(=O)t, or-OS (=O)tN(R6)-;T is l or 2;P and m is each independently 0, l, 2,3 or 4;Or Person wherein C6-C10 aryl-(CH2)p-G-(CH2)m, C5-C12 heteroaryls-(CH2)p-G-(CH2)m, C4-C12 heterocycles- (CH2)p-G-(CH2)m, or C3-C10 naphthenic base-(CH2)p-G-(CH2)mCan F, Cl, Br be selected from by one or more, I, cyano, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, carbocylic radical, the substituent group substitution of heterocycle;
Wherein each R8Can be identical or different, it is each independently H, D, R6R7NC(=O)-, R6OC(=O)-, R6C(=O)-, R6R7NS(=O)-, R6OS(=O)-, R6S(=O)-, R6R7NS(=O)2-, R6OS(=O)2-, R6S(=O)2, C1-C3 fat Race, C1-C3 halogenated aliphatics, C1-C3 hydroxyl group aliphatics, C1-C3 amino aliphatic, C1-C3 alkoxy Cs 1-C3 fat Race, C1-C3 alkylamino C1-C3 aliphatic, C1-C3 alkylthio group C1-C3 aliphatic, C6-C10 aryl C1-C3 aliphatic, C5-C9 heteroaryl C1-C3 aliphatic, C4-C10 heterocycle C1-C3 aliphatic, C3-C10 naphthenic base C1-C3 aliphatic, C6- C10 aryloxy group C1-C3 aliphatic, C4-C10 heterocycle oxygroup C1-C3 aliphatic, C3-C10 cycloalkyl oxies C1-C3 fat Race, C6-C10 fragrant amino C1-C3 aliphatic, C4-C10 heterocyclylamino group C1-C3 aliphatic, C3-C10 cycloalkyl aminos C1- C3 aliphatic, C6-C10 aryl, C5-C10 heteroaryls, C4-C10 heterocycles or C3-C10 naphthenic base;
Wherein each R6And R7It independently is H, D, C1-C3 aliphatic, C1-C3 halogenated aliphatics, C1-C3 hydroxyl group aliphatics, C1-C3 amino aliphatic, C1-C3 alkoxy C 1-C3 aliphatic, C1-C3 alkylamino C1-C3 aliphatic, C1-C3 alkylthio groups C1-C3 aliphatic, C6-C10 aryl C1-C3 aliphatic, C5-C9 heteroaryl C1-C3 aliphatic, C4-C10 heterocycles C1-C3 Aliphatic, C3-C10 naphthenic base C1-C3 aliphatic, C6-C10 aryloxy group C1-C3 aliphatic, C4-C10 heterocycle oxygroups C1- C3 aliphatic, C3-C10 cycloalkyl oxy C1-C3 aliphatic, C6-C10 fragrant amino C1-C3 aliphatic, C4-C10 heterocycles Amino C1-C3 aliphatic, C3-C10 cycloalkyl amino C1-C3 aliphatic, C6-C10 aryl, C5-C10 heteroaryls, C4- C10 heterocycles or C3-C10 naphthenic base；Work as R6And R7It is connected on the same nitrogen-atoms, R6, R7It can arbitrary landform with nitrogen-atoms At substituted or non-substituted 3-8 membered rings;
Above-mentioned R1, R2, R3, R4, R5, R6, R7, R8, R9Group can appoint by hydroxyl, methylol, carboxyl, acetyl ammonia Base, alkyl (such as methyl, ethyl, propyl), alkoxy (such as methoxyl group, ethyoxyl, tert-butoxy), alkylamino, naphthenic base, Alkenyl, alkynyl, trifluoromethyl, trifluoroacetyl group, sulfydryl, halogen, nitro, amino, azido（-N3）, guanidine radicals, Cyano, tertbutyloxycarbonyl（-Boc）, carbonyl（-C=O）, oxo（=O）, thio（=S）, sulfonyl, aryl, heteroaryl, One or more of heterocycle replaces.
3. according to compound described in claim 1-2, wherein each R1, R4Can be identical or different, it is separate be H, D, F, Cl, Br, I, hydroxyl, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, C5H11, C6H13, C8H17, trifluoromethyl, hydroxymethyl, amino methyl, methoxyl group, ethyoxyl, tert-butoxy, first Amino, ethylamino, isopropylamino, 3- hydroxyl-propyls, acetyl group, trifluoroacetyl group, Cyanoacetyl, methylamino Acetyl group, propiono, iso-propionyl, 2- hydroxypropanoyls, 2- aminopropionyls, 2- chlorine propionos, 2- bromine propionos, Valeryl, caproyl, heptanoyl group, methacrylyl, phenyl, benzoyl, p-nitrophenyl, to toluyl Base, fluoro benzoyl, p-benzoyl base, to methoxybenzoyl base, 2,4- dimethylbenzoyls are folded Nitrogen base benzoyl, benzyl, p-chlorobenzyl, vinyl, acrylic, allyl, n-butene base, isobutenyl, just Pentenyl, isopentene group, cyclopropyl, ring propiono, ring valeryl, cyclohexanoyl, 3- picolinoyls, naphthalene, Phenethyl imidazole radicals, pyridyl group, pyrrole radicals, oxazolyls, isoxazolyl, triazol radical, tetrazole base, furyl, Thienyl, thiazolyl, piperidyl, piperazinyl, indyl, carbazyl, benzofuranyl tetrahydrofuran base, tetrahydrochysene pyrrole It mutters base, pyrimidine bases, purine bases ,-N (CH3)2,-C (C=O) NH-C1-C4 alkyl ,-OC (C=O)-NH-C1-C4 alkane Base ,-OC (O=O) O-C1-C4 alkyl ,-NHC (=O) NH-C1-C4 alkyl ,-NHC (=O) O-C1-C4 alkyl ,-NHC (= O)-C1-C4 alkyl, C1-C4 alkyl-NH-S (=O)2, C1-C4 alkyl S (=O)2, C1-C4 alkyl S (=O)2NH-, benzene Base-(CH2)P-G-(CH2)m, difluorophenyl-(CH2)P-G-(CH2)m, thiazolyl-(CH2)p-G-(CH2)m, pyridyl group- (CH2)p-G-(CH2)m, phenylethyl, cyclohexyl-(CH2)p-G-(CH2)m, wherein G is O, S, S (=O), S (= O)2, C(=O);P and m is each independently 0,1,2 or 3;Or wherein C6-C10 aryl-(CH2)P-G-(CH2)mIt can be with F, Cl, Br, I, methyl, ethyl, propyl, acetenyl, propinyl, butynyl, methoxy are selected from by one or more The substituent group of base, ethyoxyl or cyano replaces;Or above-mentioned R1, R4It is welcome by F, Cl, Br, I, hydroxyl, hydroxyl Base, methylol, carboxyl, acetylamino, C1-C6 alkyl（Such as methyl, ethyl, propyl）, C1-C6 alkoxies, C1-C6 alkane Amino, trifluoromethyl, trifluoroacetyl group, sulfydryl, nitro, amino, azido（-N3）, guanidine radicals, cyano, tertiary fourth oxygen Carbonyl（-Boc）, carbonyl（-C=O）, oxo（=O）, thio（=S）, sulfonyl, the substitution of one or more of phenyl;
According to compound described in claim 1-2, wherein each R2, R3, R5, R9Can be identical or different, separate is H, D, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, C5H11, C6H13, C8H17, trifluoromethyl, hydroxyl first Base, amino methyl, 3- hydroxyl-propyls, acetyl group, trifluoroacetyl group, Cyanoacetyl, methylamino acetyl group, third Acyl group, iso-propionyl, 2- hydroxypropanoyls, 2- aminopropionyls, 2- chlorine propionos, 2- bromine propionos, valeryl, Caproyl, heptanoyl group, methacrylyl, phenyl, benzoyl, p-nitrophenyl, to methyl benzoyl, fluorine Benzoyl, p-benzoyl base, to methoxybenzoyl base, 2,4- dimethylbenzoyls, triazobenzene first Acyl group, benzyl, p-chlorobenzyl, vinyl, acrylic, allyl, n-butene base, isobutenyl, n-pentene base, Isopentene group, cyclopropyl, ring propiono, ring valeryl, cyclohexanoyl, 3- picolinoyls, naphthalene, phenethyl miaow Oxazolyl, pyridyl group, pyrrole radicals, oxazolyls, isoxazolyl, triazol radical, tetrazole base, furyl, pyranose, Thienyl, thiazolyl, piperidyl, piperazinyl, indyl, carbazyl, benzofuranyl tetrahydrofuran base, tetrahydrochysene pyrrole It mutters base, pyrimidine bases, purine bases, pentose base, hexose base ,-(C=O) NH-C1-C4 alkyl, C1-C4 alkyl- NH-S(=O)2, C1-C4 alkyl S (=O)2, phenyl-(CH2)P-G-(CH2)m, difluorophenyl-(CH2)P-G-(CH2) m-, Thiazolyl-(CH2)p-G-(CH2)m, pyridyl group-(CH2)p-G-(CH2)m, phenylethyl, cyclohexyl-(CH2)p-G- (CH2)m, wherein G is O, S, S (=O), S (=O)2, C(=O);P and m is each independently 0,1,2 or 3;Or Person wherein C6-C10 aryl-(CH2)P-G-(CH2)mCan F, Cl, Br, I, methyl, second be selected from by one or more The substituent group of base, propyl, acetenyl, propinyl, butynyl, methoxyl group, ethyoxyl or cyano replaces;Or it is above-mentioned R2, R3, R5, R9It is welcome by F, Cl, Br, I, hydroxyl, methylol, carboxyl, acetylamino, C1-C6 alkyl （Such as methyl, ethyl, propyl）, C1-C6 alkoxies, C1-C6 alkylaminos, trifluoromethyl, trifluoroacetyl group, sulfydryl, nitre Base, amino, azido（-N3）, guanidine radicals, cyano, tertbutyloxycarbonyl（-Boc）, carbonyl（-C=O）, oxo（=O）, sulphur Generation（=S）, sulfonyl, the substitution of one or more of phenyl.
4. according to compound described in claim 1-2, structure or following one structure including but not limited to following one it is mutual Non- equal amount of mixture, geometric isomer, solvate, the medicine of tautomeric, stereoisomer, racemic modification, enantiomter The solvate of acceptable salt or its salt on, or prodrug：
。
5. the solvate of claim 1-4 any one of them solvate or salt is selected from:Monohydrate, dihydrate, three Hydrate, a methanol solvate, diformazan alcohol adduct, an acetonitrile close object, diacetonitrile closes object, an acetone closes object, two acetone close object, partly rich Horse hydrochloride-hydrate, fumarate dihydrate, one ethanolates of fumarate;It is preferred that monohydrate, fumaric acid monocalcium salt Close object, one ethanolates of fumarate.
6. claim 1-4 any one of them pharmaceutically acceptable salts are selected from:Hydrochloride, sulfate, phosphate, oxalic acid Salt, maleate, methane sulfonates, succinate, citrate, fumarate, glucuronate salt, formates, acetate, Succinate.
7. a kind of pharmaceutical composition, it includes according to a kind of compound of claim 1-6 any one of them or several compounds Or the non-equal amount of mixture of its tautomer, stereoisomer, racemic modification, enantiomter, geometric isomer, solvation Any one or a few in the solvate of object, pharmaceutically acceptable salt or its salt is as active component;Wherein, it combines The weight percentage of active component is 0.1-99% in object.
8. the pharmaceutical composition described in claim 7, it is characterised in that:The pharmaceutical composition also include it is at least one other Agriculture field is used to prepare the drug of insecticide, fungicide, herbicide;It is specifically including but not limited to, parathion, DDVP, enemy Hundred worms, pyrethroid, dormant oil emulsion, Furadan, sevin, Spanon, camptothecine, Bordeaux mixture, difenoconazole, hundred bacterium Clearly, hymexazol, Fluoxastrobin, Mancozeb, glyphosate, paraquat, chlorine pyrazothion, Acetochlor etc..
9. compound or its tautomer, its stereoisomer, its racemic modification described in any one of claim 1-6, The non-equal amount of mixture of its enantiomter, its geometric isomer, its solvate, its pharmaceutically acceptable salt or its salt Pharmaceutical composition described in any one of solvate or claim 7-8 is preparing agricultural bacteriocide, Insecticides (tech) ＆ Herbicides (tech) Purposes.
10. the preparation method of compound described in claim 1 is following reaction scheme：
Wherein R1, R2, R3, R4, A, B, Y, n, k, “" definition with any of the above-described place of the present invention to R1, R2, R3, R4, A, B, Y, n, k, “" definition.
CN201710180878.1A 2017-03-24 2017-03-24 A kind of quinolinone alkaloid class compound and its preparation method and application Pending CN108623562A (en)

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CN114989064A (en) * 2022-06-16 2022-09-02 辽宁中医药大学 Novel pyrrole alkaloid compound in purslane and extraction and separation method thereof
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Publication number Priority date Publication date Assignee Title
US11345681B1 (en) 2020-06-05 2022-05-31 Kinnate Biopharma Inc. Inhibitors of fibroblast growth factor receptor kinases
CN113735769A (en) * 2021-09-26 2021-12-03 太原理工大学 Quinolinone alkaloid derivative containing acylhydrazone structure at 3-position and preparation method and application thereof
CN113735769B (en) * 2021-09-26 2023-02-28 太原理工大学 Quinolinone alkaloid derivative containing acylhydrazone structure at 3-position and preparation method and application thereof
US11820747B2 (en) 2021-11-02 2023-11-21 Flare Therapeutics Inc. PPARG inverse agonists and uses thereof
WO2023156323A1 (en) * 2022-02-17 2023-08-24 Syngenta Crop Protection Ag Herbicidal quinolone derivatives
CN114989064A (en) * 2022-06-16 2022-09-02 辽宁中医药大学 Novel pyrrole alkaloid compound in purslane and extraction and separation method thereof
CN114989064B (en) * 2022-06-16 2023-05-05 辽宁中医药大学 Novel pyrrole alkaloid compound in purslane and extraction and separation method thereof

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Application publication date: 20181009