CN109320452B - Quinoline derivatives and its preparation method and application - Google Patents

Quinoline derivatives and its preparation method and application Download PDF

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Publication number
CN109320452B
CN109320452B CN201710637588.5A CN201710637588A CN109320452B CN 109320452 B CN109320452 B CN 109320452B CN 201710637588 A CN201710637588 A CN 201710637588A CN 109320452 B CN109320452 B CN 109320452B
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base
compound
aryl
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CN109320452A (en
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李义涛
李法霖
陈涛
徐俊星
姚文强
林健
刘新烁
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Dongguan dongyangguang pesticide R & D Co., Ltd
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Dongguan Dongyang Guangke Research and Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen 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
    • A01N43/34—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
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • 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
    • C07D401/02—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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a kind of quinoline derivatives, and the composition comprising the analog derivative.The present invention also provides the method for preparing the analog derivative and analog derivative prevention or treatment disinfect pathogens, the purposes for killing pest.

Description

Quinoline derivatives and its preparation method and application
Technical field
The present invention relates to for prevent and treat plant pathogenic fungi, kill pest quinoline derivatives and its nitrogen oxides and Salt.
Background technique
To ornamental crops, vegetable crop, field crop, cereal crops and the prejudicial phytopathogen of fruit tree crop, pest It can cause the significant decrease of yield, so as to cause the cost increase of consumer.And the now agriculture long-time due to pesticide uses, Disease, pest on crop are substantially reduced existing pesticide control effect to which create drug resistances, in order to improve prevention and treatment effect Fruit, it is necessary to improve the amount of application of pesticide, this causes environment and severely compromises.
To solve the problems, such as economy and environment, need to continually develop the new compound for providing sterilization, insecticidal activity.
Summary of the invention
The present invention provides a kind of quinoline derivatives, and the composition comprising this analog derivative, the quinoline derivatives And combinations thereof for prevent and treat plant pathogenic fungi, kill pest.
Specifically:
On the one hand, the present invention provides a kind of alloisomerism of compound as shown in formula (I) compound represented or formula (I) Body, nitrogen oxides and its salt:
Wherein:
R1For hydrogen, C1-6Alkyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl ,-COR6Or-SO2R7；R1Optionally by one or It is multiple to be selected from A1Substituent group replace；
Wherein, R6For C1-6Alkyl, C2-8Alkenyl, C2-8Alkynyl, C3-10Naphthenic base, C6-12Aryl, 3-10 circle heterocyclic ring base, 5-10 Unit's heteroaryl ,-OR8Or-NRnRm；
Wherein, R7For C1-6Alkyl, C3-10Naphthenic base, C6-12Aryl, 5-10 unit's heteroaryl or-NRnRm；
Wherein, R8For C1-6Alkyl, C2-8Alkenyl, C2-8Alkynyl, C3-10Naphthenic base, 3-10 circle heterocyclic ring base, 5-10 unit's heteroaryl, C6-12Aryl or C6-12Aryl-C1-6Alkyl；
Wherein, each RnAnd RmIt independently is hydrogen, C1-6Alkyl, C3-10Naphthenic base, C6-12Aryl or 5-10 unit's heteroaryl；
Or Rn、Rm3-10 circle heterocyclic ring base is formed with connected nitrogen-atoms；
R2For hydrogen or C1-6Alkyl；
R3For C1-6Alkyl, halogenated C1-6Alkyl, C2-8Alkenyl or C1-6Alkoxy；
R2And R3A is optionally selected from by one or more2Substituent group replace；
Or R2With R3It is optionally formed C together3-6Alkylidene；
R4aFor hydrogen, halogen, cyano, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, C1-6Alkyl-carbonyl, C1-6Alkoxy Carbonyl or C1-6Alkyl acyloxy；
R4bFor hydrogen, halogen, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, C1-6Alkyl-carbonyl, C1-6Alkoxy carbonyl or C1-6Alkyl acyloxy；
R4cFor hydrogen, halogen, C1-6Alkyl, halogenated C1-6Alkyl or C1-6Alkoxy；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen；
L1For-NR9-、-O-、-S-、-SO-、-SO2-、-CH2Or-(C=O)-；
L2For-SO2-、-CR10R11Or-CR12R13-CR14R15-；
Or L1With L2It is formed together-CR9a=N-；
Wherein, R9And R9aIt is each independently hydrogen, C1-6Alkyl, C6-12Aryl, C1-6Alkyl-carbonyl, C6-12Aryl carbonyl, C1-6Alkyl sulphonyl or C6-12Aryl sulfonyl；
Wherein, R10、R11、R12、R13、R14And R15It is each independently hydrogen, halogen, hydroxyl, nitro, cyano, C1-6Alkyl, Halogenated C1-6Alkyl or C1-6Alkoxy；R10、R11、R12、R13、R14And R15A is optionally selected from by one or more3Substituent group take Generation；
Condition are as follows: L1For-CH2, L2For-CR10R11Or-CR12R13-CR14R15, R10、R11、R12、R13、R14And R15Respectively It independently is hydrogen or C1-6Alkyl, R2And R3It is not simultaneously-CH3；
Or R10And R11、R12And R13、R14And R15The carbon atom being optionally connected with them is formed together 3-10 circle heterocyclic ring Base ,-(C=O)-or
Wherein, each R16It independently is C1-6Alkyl, C6-12Aryl-C1-6Alkyl, C2-8Alkenyl or C2-8Alkynyl；
R5For C1-6Alkyl, C2-8Alkenyl, C2-8Alkynyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl, 5-10 unit's heteroaryl, 5- 10 unit's heteroaryl-C1-6Alkyl, C3-10Naphthenic base, C3-10Naphthenic base-C1-6Alkyl, 3-10 circle heterocyclic ring base, C3-8Cycloalkenyl, C1-6Alkane Acyloxy, halogenated C1-6Alkyl acyloxy, C1-6Alkyl amino, C6-12Arylamino, C3-8Cycloalkyl amino or 5-10 member heteroaryl Base amino；R5Optionally A is selected from by 1,2,3,4,5,6,7,8,9 or 104Substituent group replace；
Wherein, A1、A2、A3And A4It is each independently halogen, cyano, nitro, oxo (=O), C1-6Alkyl, halogenated C1-6 Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C3-10Naphthenic base, C2-8Alkenyl, C2-8Alkynyl, C6-12Aryl, halogenated C6-12Aryl, C1-6Alkyl-substituted C6-12Aryl, halogenated C1-6Alkyl-substituted C6-12Aryl, C1-6The C that alkoxy replaces6-12It is aryl, halogenated C1-6The C that alkoxy replaces6-12Aryl, 3-10 circle heterocyclic ring base, 5-10 unit's heteroaryl, C1-6Alkyl-carbonyl, C6-12Aryl carbonyl or C1-6Alkyl acyloxy；
Condition is that formula (I) compound represented of the present invention does not include the chloro- 6- of compound 5- ((4- chlorobenzyl) oxygen) -2,3- Dimethyl quinoline -4- yl acetate, the chloro- 6- of 7- ((4- chlorobenzyl) oxygen) -2,3- dimethyl quinoline -4- yl acetate, 2,3- bis- Methyl -6- ((4- (trifluoromethoxy) benzyl) oxygen) -7- (trifluoromethyl) quinolyl-4 acetic acid esters, 2- ethyl -3,5,7- front three Base -6- ((4- (trifluoromethoxy) benzyl) oxygen) quinolyl-4 methyl carbonate and 2- ethyl -3,5,7- trimethyl -6- (3- (5- (trifluoromethyl) pyridine -2- base) propoxyl group) quinolyl-4 methyl carbonate.
In some embodiments, R1For hydrogen, C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl ,-COR6Or- SO2R7；R1A is optionally selected from by one or more1Substituent group replace；Or further R1Optionally by 1,2,3,4,5 or 6 It is a to be selected from A1Substituent group replace；
Wherein, R6For C1-4Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-8Naphthenic base, C6-10Aryl, 3-8 circle heterocyclic ring base, 5-10 member Heteroaryl ,-OR8Or-NRnRm；
Wherein, R7For C1-4Alkyl, C3-8Naphthenic base, C6-10Aryl, 5-10 unit's heteroaryl or-NRnRm；
Wherein, R8For C1-4Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-8Naphthenic base, C6-10Aryl or C6-10Aryl-C1-4Alkyl；
Wherein, each RnAnd RmIt independently is hydrogen, C1-4Alkyl or C6-10Aryl；
Or Rn、Rm3-10 circle heterocyclic ring base is formed with connected nitrogen-atoms；
R2For hydrogen or C1-4Alkyl；
R3For C1-4Alkyl, halogenated C1-4Alkyl, C2-6Alkenyl or C1-4Alkoxy；
R2And R3A is optionally selected from by one or more2Substituent group replace；Or further R2And R3Optionally by 1, 2,3,4,5 or 6 are selected from A2Substituent group replace；
Or R2With R3It is optionally formed C together3-6Alkylidene；
R4aFor hydrogen, halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, C1-4Alkyl-carbonyl, C1-4Alkane Epoxide carbonyl or C1-4Alkyl acyloxy；
R4bFor hydrogen, halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl or C1-4Alkyl acyloxy；
R4cFor hydrogen, halogen, C1-4Alkyl, halogenated C1-4Alkyl or C1-4Alkoxy；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen；
Wherein, A1And A2It is each independently halogen, cyano, nitro, oxo (=O), C1-4Alkyl, C1-4Alkoxy, C3-8 Naphthenic base, C1-4Alkyl-carbonyl or C1-6Alkyl acyloxy.
In other embodiments, R1For C6-10Aryl-C1-4Alkyl ,-COR6Or-SO2R7；R1Optionally by one or It is multiple to be selected from A1Substituent group replace；Or further R1Optionally A is selected from by 1,2,3,4,5 or 61Substituent group replace；
Wherein, R6For C1-4Alkyl, C6-10Aryl, 5-10 unit's heteroaryl ,-OR8Or-NRnRm；
Wherein, R7For C1-4Alkyl, C6-10Aryl or-NRnRm；
Wherein, R8For C1-4Alkyl or C6-10Aryl；
Wherein, each RnAnd RmIt independently is hydrogen, C1-4Alkyl or C6-10Aryl；
R2For hydrogen or C1-4Alkyl；
R3For C1-4Alkyl, halogenated C1-4Alkyl, C2-6Alkenyl or C1-4Alkoxy；
R2And R3A is optionally selected from by one or more2Substituent group replace；Or further R2And R3Optionally by 1, 2,3,4,5 or 6 are selected from A2Substituent group replace；
Or R2With R3It is optionally formed C together3-6Alkylidene；
R4aFor hydrogen, halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or C1-4Alkoxy carbonyl；
R4bFor hydrogen, halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or C1-4Alkoxy carbonyl；
R4cFor hydrogen, halogen, C1-4Alkyl, halogenated C1-4Alkyl or C1-4Alkoxy；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen；
Wherein, A1And A2It is each independently halogen, cyano, nitro, oxo (=O) or C1-4Alkyl.
Also in some embodiments, R1For following subformula:
R2For hydrogen ,-CH3、-CH2CH3Or-C (CH3)3；
R3For-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-CHF2Or-CF3；
Or R2With R3It is formed together-(CH2CH2CH2)-or-(CH2CH2CH2CH2)-；
R4aFor hydrogen, fluorine, chlorine, bromine, cyano, nitro ,-CH3、-CH2CH3、-CF3、-OCH3Or-C (=O) OCH3；
R4bFor hydrogen, fluorine, chlorine, bromine ,-CH3、-CH2CH3、-CHF2、-CF3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-C (= O)OCH3；
R4cFor hydrogen, fluorine, chlorine, bromine ,-CH3、-CF3Or-OCH3；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen.
In some embodiments, L1For-NR9-、-O-、-S-、-SO2-、-CH2Or-(C=O)-；
L2For-SO2-、-CR10R11Or-CR12R13-CR14R15-；
Or L1With L2It is formed together-CR9a=N-；
Wherein, R9And R9aIt is each independently hydrogen, C1-4Alkyl, C6-10Aryl, C1-4Alkyl-carbonyl, C6-10Aryl carbonyl, C1-4Alkyl sulphonyl or C6-10Aryl sulfonyl；
Wherein, R10、R11、R12、R13、R14And R15It is each independently hydrogen, halogen, hydroxyl, nitro, cyano, C1-4Alkyl, Halogenated C1-4Alkyl or C1-4Alkoxy；R10、R11、R12、R13、R14And R15A is optionally selected from by one or more3Substituent group take Generation；Or further R10、R11、R12、R13、R14And R15Optionally A is selected from by 1,2,3,4,5 or 63Substituent group replace；
Condition are as follows: L1For-CH2, L2For-CR10R11Or-CR12R13-CR14R15, R10、R11、R12、R13、R14And R15Respectively It independently is hydrogen or C1-6Alkyl, R2And R3It is not simultaneously-CH3；
Or R10And R11、R12And R13、R14And R15The carbon atom being optionally connected with them is formed together 3-6 circle heterocyclic ring Base ,-(C=O)-or
Wherein, each R16It independently is C1-4Alkyl, C6-10Aryl-C1-4Alkyl, C2-6Alkenyl or C2-6Alkynyl；
R5For C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl, 5-10 unit's heteroaryl, 5-10 unit's heteroaryl-C1-4Alkane Base, C3-8Naphthenic base, C3-8Naphthenic base-C1-4Alkyl, 3-8 circle heterocyclic ring base, C3-6Cycloalkenyl, C1-4Alkyl acyloxy, halogenated C1-4Alkane Acyloxy, C1-4Alkyl amino, C6-10Arylamino, C3-8Cycloalkyl amino or 5-10 unit's heteroaryl amino；R5Optionally by 1, 2,3,4,5,6,7,8,9 or 10 are selected from A4Substituent group replace；
Wherein, A3And A4It is each independently halogen, cyano, nitro, oxo (=O), C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, halogenated C1-4Alkoxy, C3-8Naphthenic base, C2-6Alkenyl, C2-6Alkynyl, C6-10Aryl, halogenated C6-10Aryl, C1-4Alkane The C that base replaces6-10Aryl, halogenated C1-4Alkyl-substituted C6-10Aryl, C1-4The C that alkoxy replaces6-10Aryl, halogenated C1-4Alcoxyl The C that base replaces6-10Aryl, 3-8 circle heterocyclic ring base, 5-10 unit's heteroaryl, C1-4Alkyl-carbonyl, C6-10Aryl carbonyl or C1-4Alkyl acyl Oxygroup.
In other embodiments, L1For-NR9Or-O-；
Wherein, R9For hydrogen, C1-4Alkyl, C6-10Aryl, C1-4Alkyl-carbonyl, C6-10Aryl carbonyl, C1-4Alkyl sulphonyl or C6-10Aryl sulfonyl.
In other embodiments, L2For-SO2-、-CR10R11Or-CR12R13-CR14R15-；
Wherein, R10、R11、R12、R13、R14And R15It is each independently hydrogen, halogen, hydroxyl, C1-4Alkyl or halogenated C1-4Alkane Base.
In other embodiments, R10And R11、R12And R13Or R14And R15The carbon atom being optionally connected with them Be formed together 3-6 circle heterocyclic ring base ,-C (=O)-or
Wherein, each R16It independently is C1-4Alkyl, C6-10Aryl-C1-4Alkyl, C2-6Alkenyl or C2-6Alkynyl.
Also in other embodiments, L1With L2It is formed together-CH=N-.
In some embodiments, R5For C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl, 5-10 unit's heteroaryl, 5- 10 unit's heteroaryl-C1-4Alkyl, C3-8Naphthenic base, C3-8Naphthenic base-C1-4Alkyl, 3-8 circle heterocyclic ring base, C1-4It is alkyl acyloxy, halogenated C1-4Alkyl acyloxy, C1-4Alkyl amino, C6-10Arylamino, C3-8Cycloalkyl amino or 5-10 unit's heteroaryl amino；R5Optionally Ground is selected from A by 1,2,3,4 or 54Substituent group replace；
Wherein, A4For fluorine, chlorine, bromine, cyano, nitro, oxo (=O), C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, Halogenated C1-4Alkoxy, C2-6Alkenyl, C2-6Alkynyl, C6-10Aryl, halogenated C6-10Aryl, C1-4Alkyl-substituted C6-10It is aryl, halogenated C1-4Alkyl-substituted C6-10Aryl, C1-4The C that alkoxy replaces6-10Aryl, halogenated C1-4The C that alkoxy replaces6-10Aryl, 5-10 Unit's heteroaryl, C1-4Alkyl-carbonyl, C6-10Aryl carbonyl or C1-4Alkyl acyloxy.
Also in some embodiments, L1For-NH- or-O-.
In other embodiments, L1For following subformula:
In some embodiments, L2For-SO2,-C (=O)-,-CH2-、-CHF-、-CF2-、-C(CH3)2-、-C (CF3)2-、-CH2CH2Or-C (=O) CH2-。
In other embodiments, L2For following subformula:
In some embodiments, R5For-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3。
In other embodiments, R5For following subformula:
In some embodiments, the present invention provides a kind of compound as shown in formula (II) compound represented or formula (II) Stereoisomer, nitrogen oxides and its salt:
Wherein: R1、R2、R3、R4a、R4b、R4cAnd R9With meaning as described in the present invention；
R5aFor C1-6Alkyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl, 5-10 unit's heteroaryl, C3-10Naphthenic base or 3-10 member Heterocycle；R5aOptionally A is selected from by 1,2,3,4,5 or 64aSubstituent group replace；
A4aFor halogen, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C2-6Alkenyl or C2-6Alkynes Base.
In some embodiments, R5aFor C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl, 5-10 unit's heteroaryl, C3-8Naphthenic base or 3-8 circle heterocyclic ring base；R5aOptionally A is selected from by 1,2,3,4,5 or 64aSubstituent group replace；
A4aFor halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, halogenated C1-4Alkoxy, C2-4Alkenyl or C2-4Alkynes Base.
In other embodiments, R5aFor-CH3、-CH2CH3、-CH2CH2CH3, phenyl, benzyl, phenethyl, furyl, Thienyl, pyrazolyl, imidazole radicals, isoxazolyl, pyridyl group, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, piperidyl, piperazine Base or morpholinyl；R5aOptionally A is selected from by 1,2,3,4,5 or 64aSubstituent group replace；
A4aFor fluorine, chlorine, bromine, iodine ,-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH (CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2CF3、-CH(CF3)2、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH (CH3)2、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3,-CH=CH2,-CH=CH-CH3Or-CH2- CH=CH2。
In other embodiments, R5aFor following subformula:
In some embodiments, the present invention provides a kind of chemical combination as shown in formula (III) compound represented or formula (III) Stereoisomer, nitrogen oxides and its salt of object:
Wherein, R1、R2、R3、R4a、R4bAnd R4cWith meaning as described in the present invention；
R5bFor C1-6Alkyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl or 5-10 unit's heteroaryl；R5bFor optionally by 1,2, 3,4 or 5 are selected from A4bSubstituent group replace；
A4bFor halogen, cyano, nitro, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy or halogenated C1-6Alkoxy.
In some embodiments, R5bFor C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl or 5-10 unit's heteroaryl； R5bTo be optionally selected from A by 1,2,3,4 or 54bSubstituent group replace；
A4bFor halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or halogenated C1-4Alkoxy.
In other embodiments, R5bFor-CH3、-CH2CH3, phenyl, naphthalene, benzyl, phenethyl, furyl, thiophene Base or pyridyl group；R5bTo be optionally selected from A by 1,2,3,4 or 54bSubstituent group replace；
A4bFor fluorine, chlorine, bromine, iodine ,-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH (CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2CF3、-CH(CF3)2、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH (CH3)2、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3Or-OCH2CF3。
In other embodiments, R5bFor following subformula:
In some embodiments, the present invention provides a kind of compound as shown in formula (IV) compound represented or formula (IV) Stereoisomer, nitrogen oxides and its salt:
Wherein, R1、R2、R3、R4a、R4bAnd R4cWith meaning as described in the present invention；
X is 0 or 1；
R22、R33、R44And R55It is each independently hydrogen, halogen, hydroxyl, nitro, cyano, C1-6Alkyl, halogenated C1-6Alkyl or C1-6Alkoxy；R22、R33、R44And R55A is optionally selected from by one or more3aSubstituent group replace；Or further R22、 R33、R44And R55Optionally A is selected from by 1,2,3,4,5,6,7,8,9 or 103aSubstituent group replace；
Or R22And R33、R44And R55The carbon atom being optionally connected with them is formed together 3-10 circle heterocyclic ring base ,-(C= O)-or
Wherein, each R16With meaning as described in the present invention；
R5cFor C1-6Alkyl, C2-8Alkenyl, C2-8Alkynyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl, 5-10 unit's heteroaryl, 5- 10 unit's heteroaryl-C1-6Alkyl, C3-10Naphthenic base, C3-10Naphthenic base-C1-6Alkyl, 3-10 circle heterocyclic ring base, C3-8Cycloalkenyl, C1-6Alkane Acyloxy, halogenated C1-6Alkyl acyloxy, C1-6Alkyl amino, C6-12Arylamino, C3-8Cycloalkyl amino or 5-10 member heteroaryl Base amino；R5Optionally A is selected from by 1,2,3,4,5,6,7,8,9 or 104cSubstituent group replace；
Wherein, A3aAnd A4cIt is each independently halogen, cyano, nitro, oxo (=O), C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C3-10Naphthenic base, C2-8Alkenyl, C2-8Alkynyl, C6-12Aryl, halogenated C6-12Aryl, C1-6Alkane The C that base replaces6-12Aryl, halogenated C1-6Alkyl-substituted C6-12Aryl, C1-6The C that alkoxy replaces6-12Aryl, halogenated C1-6Alcoxyl The C that base replaces6-12Aryl, 3-10 circle heterocyclic ring base, 5-10 unit's heteroaryl, C1-6Alkyl-carbonyl, C6-12Aryl carbonyl or C1-6Alkyl acyl Oxygroup；
Condition are as follows: formula (IV) compound represented of the present invention do not include formula 1), formula 2), formula 3), formula 4) and formula 5) shown in Compound,
Formula 1)Formula 1) the corresponding title of compound represented are as follows: 5- chloro- 6- ((4- chlorine Benzyl) oxygen) -2,3- dimethyl quinoline -4- yl acetate；
Formula 2)Formula 2) the corresponding title of compound represented are as follows: 7- chloro- 6- ((4- chlorine Benzyl) oxygen) -2,3- dimethyl quinoline -4- yl acetate；
Formula 3)Formula 3) the corresponding title of compound represented are as follows: 2,3- dimethyl- 6- ((4- (trifluoromethoxy) benzyl) oxygen) -7- (trifluoromethyl) quinolyl-4 acetic acid esters；
Formula 4)Formula 4) the corresponding title of compound represented are as follows: ethyl -3 2-, 5,7- trimethyl -6- ((4- (trifluoromethoxy) benzyl) oxygen) quinolyl-4 methyl carbonate；
Formula 5)Formula 5) the corresponding title of compound represented are as follows: ethyl -3 2-, 5,7- trimethyl -6- (3- (5- (trifluoromethyl) pyridine -2- base) propoxyl group) quinolyl-4 methyl carbonate.
In some embodiments, x is 0 or 1；
R22、R33、R44And R55It is each independently hydrogen, halogen, hydroxyl, C1-4Alkyl, halogenated C1-4Alkyl or C1-4Alkoxy； R22、R33、R44And R55A is optionally selected from by one or more3aSubstituent group replace；Or further R22、R33、R44And R55 Optionally A is selected from by 1,2,3,4,5,6,7,8,9 or 103aSubstituent group replace；
Or R22And R33、R44And R55The carbon atom being optionally connected with them is formed together 3-8 circle heterocyclic ring base ,-(C= O)-or
Wherein, each R16With meaning as described in the present invention；
R5cFor C1-4Alkyl, C6-10Aryl, C6-10Aryl-C1-4Alkyl, 5-10 unit's heteroaryl, 5-10 unit's heteroaryl-C1-4Alkane Base, C3-8Naphthenic base, C3-8Naphthenic base-C1-4Alkyl, 3-8 circle heterocyclic ring base, C3-6Cycloalkenyl, C1-4Alkyl acyloxy, halogenated C1-4Alkane Acyloxy, C1-4Alkyl amino, C6-10Arylamino, C3-6Cycloalkyl amino or 5-10 unit's heteroaryl amino；R5Optionally by 1, 2,3,4,5,6,7 or 8 are selected from A4cSubstituent group replace；
Wherein, A3aAnd A4cIt is each independently halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, Halogenated C1-4Alkoxy, C3-8Naphthenic base, C2-6Alkenyl, C2-6Alkynyl, C6-10Aryl, halogenated C6-10Aryl, C1-4It is alkyl-substituted C6-10Aryl, halogenated C1-4Alkyl-substituted C6-10Aryl, C1-4The C that alkoxy replaces6-10Aryl, halogenated C1-4What alkoxy replaced C6-10Aryl, 5-10 unit's heteroaryl, C1-4Alkyl-carbonyl, C6-10Aryl carbonyl or C1-4Alkyl acyloxy.
In other embodiments, x is 0 or 1；
R22、R33、R44And R55It is each independently hydrogen, fluorine, chlorine, bromine, iodine ,-CH3、-CH2CH3、-CH2CH2CH3、-CH (CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2CF3Or-CH (CF3)2；R22、 R33、R44And R55A is optionally selected from by one or more3aSubstituent group replace；Or further R22、R33、R44And R55Optionally Ground is selected from A by 1,2,3,4,5,6,7,8,9 or 103aSubstituent group replace；
Or R22And R33、R44And R55The carbon atom being optionally connected with them is formed together (C=O)-or
Wherein, each R16It independently is-CH3、-CH2CH3、-CH2CH2CH3, benzyl or-CH2- CH=CH2；
R5cFor-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3, phenyl, naphthalene, benzyl, phenethyl, furan Mutter base, thienyl, imidazole radicals, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl group, benzoxazolyl, Benzo isoxazolyl, benzothiazolyl, benzisothia oxazolyl, benzofuranyl, benzothienyl, benzimidazolyl, benzopyrene Oxazolyl, quinoline, isoquinolin, 2- picolyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, Cvclopropvlmethvl, ethylene oxide Base, morpholinyl, piperidyl, piperazinyl, CH3C (=O) O-, CH3CH2C (=O) O-, CF3C (=O) O-, CF3CH2C (=O) O-, CF3CF2C (=O) O-, methylamino, ethylamino, dimethylamino, diethylamino, N- methyl-N-ethylamino, phenyl Amino, cyclopropylamino, Cyclobutylamino, clopentylamino, hexamethylene alkylamino, 2-aminopyridine, 3- aminopyridine or 4- ammonia Yl pyridines；R5Optionally A is selected from by 1,2,3,4,5 or 64cSubstituent group replace；
Wherein, A3aAnd A4cIt is each independently fluorine, chlorine, bromine, iodine, cyano, nitro ,-CH3、-CH2CH3、-CH2CH2CH3、- CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2CF3、-CH(CF3)2、- OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3, cyclopropyl Base, cyclobutyl, cyclopenta, cyclohexyl ,-CH=CH2,-CH=CH-CH3、-CH2- CH=CH2, phenyl, naphthalene, 4- chlorphenyl, 2- fluorophenyl, 3,5- dichlorophenyl, 3,5- difluorophenyl, 3,4,5- trifluorophenyl, 2,3,4- trifluorophenyl, 2- aminomethyl phenyl, 3- aminomethyl phenyl, 4- aminomethyl phenyl, 2,3- 3,5-dimethylphenyl, 2,4- 3,5-dimethylphenyl, 2,5- 3,5-dimethylphenyl, 3,4- dimethyl Phenyl, 2- trifluoromethyl, 3- trifluoromethyl, 4- trifluoromethyl, 2- methoxyphenyl, 3- methoxyphenyl, 4- methoxyphenyl, 2- Trifluoromethoxyphen-l, 3- Trifluoromethoxyphen-l, 4- Trifluoromethoxyphen-l, phenyl, naphthalene, benzyl Base, phenethyl, furyl, thienyl, imidazole radicals, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl group, CH3C (=O)-, CH3CH2C (=O)-, phenylcarbonyl group, CH3C (=O) O- or CH3CH2C (=O) O.
In other embodiments, R22、R33、R44And R55It is each independently hydrogen, fluorine, chlorine, bromine ,-CH3Or-CF3。
In other embodiments, R22And R33Or R44And R55The carbon atom being optionally connected with them is formed together- (C=O)-,
R5cFor-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3；
Or R5cFor following subformula:
Also in some embodiments, the present invention provides with the compound of one of flowering structure or has following structure compound Stereoisomer, nitrogen oxides and its salt, but be not limited to these compounds:
On the other hand, the present invention provides a kind of composition, and it includes the compound of the present invention as active material.
In some embodiments, it is living to further include acceptable surface in Pesticide Science for composition of the present invention Property agent and carrier.
Also in some embodiments, composition of the present invention includes other active materials, wherein other active matters Matter is fungicide, bactericidal drug, insecticide, acaricide, nematicide, arthropodicides, herbicide or plant growth regulating One of agent is a variety of.
On the other hand, the present invention provides application of the composition comprising the compounds of this invention in agricultural.
In some embodiments, the present invention provides the composition comprising the compounds of this invention and is used as fungicide in agricultural Purposes.
Also in other embodiments, composition of the present invention offer comprising the compounds of this invention is used as in agricultural kills The purposes of worm agent.
Also in some embodiments, the present invention provides composition the answering in other field comprising the compounds of this invention With.
On the other hand, the present invention provides a kind of method of prevention and treatment plant pathogenic fungi, pest, and the method includes with having The compounds of this invention processing plant of effect amount or soil.
Detailed description of the invention book
Definition and general terms
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference It is bright.
Unless otherwise stated, following definition used herein should be applied.For purposes of the present invention, chemical element with The periodic table of elements CAS editions, and " Handbook of Chemistry and Physics ", the 75th edition, 1994 is consistent.In addition, organic chemistry General Principle can join It examines " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito:1999, With " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry March, John Description in Wiley&Sons, New York:2007, entire contents are incorporated herein by reference.
Term " optional " or " optionally " refer to the event then described or situation can with but not necessarily occur, that is, this is retouched It states and includes the case where the case where wherein event or situation occur and do not occur.For example, " optionally by 1,2,3 or 4 ... It is replaced " include the case where replaced group substituent group described in 1 or 2 or 3 or 4 and the group not The case where being replaced by the substituent group.Further, when the group is replaced by 1 substituent group described above, the substituent group Between be mutually indepedent, that is, 1 or more the substituent group can be mutually different, be also possible to identical.
As described in the invention, the compound of the present invention can be optionally replaced one or more substituent groups, such as General formula compound above, or as example special inside embodiment, subclass, and a kind of compound that the present invention is included. In general, term " substitution " indicates one or more hydrogen atoms in given structure replaced specific substituent group.Unless its He shows that an optional substituent group can replace at various substitutable position of that group at aspect.When given knot More than one position can be replaced one or more substituent groups selected from specific group, then substituent group can be identical in structure formula Or differently replace at various locations.Wherein, " one or more substituent groups " indicates one or more substitution Base, the number of specific substituent group by be substituted group can the number of substituted position determined.The substituent group can be, But it is not limited to, deuterium, oxo (=O), halogen, cyano, nitro, hydroxyl, sulfydryl, carboxyl, amino, fragrant amino, aminoalkyl, alkane Base, alkyl oxy, alkyl sulfenyl, alkenyl, alkynyl, hydroxy alkyl, halogenated alkyl, carbocylic radical, heterocycle, aryl, heteroaryl ,-C (=O) R ,-ORa,-C (=O) ORa,-OC (=O) Ra、-SO2Ra、-NRbRc、-CONRbRc、-SO2NRbRc、-C(NRbRc)=NRd Or=NRd；Wherein, R, Ra、Rb、RcAnd RdIndependent is hydrogen, cyano, amino, alkyl, alkylamino, fragrant amino, alkyl sulfide Base, alkoxy, aryloxy group, hydroxyl, sulfydryl, alkyl, halogenated alkyl, carbocylic radical, heterocycle, aryl, heteroaryl, alkyl sulfonyl Base, amino-sulfonyl, hydroxy alkyl, aminoalkyl, alkyl acyl or aminoacyl.Wherein, each alkane ammonia in the substituent group Base, fragrant amino, alkoxy, aryloxy group, hydroxyl, sulfydryl, alkyl, halogenated alkyl, carbocylic radical, heterocycle, aryl, heteroaryl, alkane Base sulfonyl, amino-sulfonyl, hydroxy alkyl, aminoalkyl, alkyl acyl, aminoacyl and alkyl sulfenyl have institute of the present invention The meaning of description, and can be further by monosubstituted or identical or different polysubstituted of substituent group described in the invention.
In addition, it is necessary to explanation, unless otherwise explicitly point out, in the present invention used by describing mode " each ... independently be " and " ... be each independently " and " ... independently be " can be interchanged, and shall be understood in a broad sense, both may be used To refer among the different groups, does not influence mutually, can also indicate in phase between expressed specific option between the same symbol In same group, do not influenced mutually between expressed specific option between the same symbol.
It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It is special It does not point out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term “C1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C3Alkyl, C4Alkyl, C5Alkyl and C6Alkyl."C1-4Alkyl " refers in particular to Methyl, ethyl, the C being individually disclosed3Alkyl (i.e. propyl, including n-propyl and isopropyl), C4Alkyl (i.e. butyl, including positive fourth Base, isobutyl group, sec-butyl and tert-butyl).
Terminology used in the present invention " alkyl " or " alkyl group " are indicated containing 1 to 20 carbon atom, the straight chain of saturation Or branch univalent hydrocarbyl group, wherein the alkyl group can be optionally by one or more substitutions described in the invention Replaced base.Unless otherwise detailed instructions, alkyl group contains 1-20 carbon atom.In some embodiments, alkyl group Contain 1-12 carbon atom；In other embodiments, alkyl group contains 1-6 carbon atom；In other embodiment In, alkyl group contains 1-4 carbon atom；In other embodiments, alkyl group contains 1-3 carbon atom.Term “C1-6Alkyl " indicates the alkyl group comprising 1-6 carbon atom.
The example of alkyl group includes, but is not limited to, methyl (Me ,-CH3), ethyl (Et ,-CH2CH3), n-propyl (n- Pr、-CH2CH2CH3), isopropyl (i-Pr ,-CH (CH3)2), normal-butyl (n-Bu ,-CH2CH2CH2CH3), isobutyl group (i-Bu ,- CH2CH(CH3)2), sec-butyl (s-Bu ,-CH (CH3)CH2CH3), tert-butyl (t-Bu ,-C (CH3)3), n-pentyl (- CH2CH2CH2CH2CH3), 2- amyl (- CH (CH3)CH2CH2CH3), 3- amyl (- CH (CH2CH3)2), 2- methyl -2- butyl (- C (CH3)2CH2CH3), 3- methyl -2- butyl (- CH (CH3)CH(CH3)2), 3- methyl-1-butyl (- CH2CH2CH(CH3)2), 2- first Base -1- butyl (- CH2CH(CH3)CH2CH3), n-hexyl (- CH2CH2CH2CH2CH2CH3), 2- hexyl (- CH (CH3) CH2CH2CH2CH3), 3- hexyl (- CH (CH2CH3)(CH2CH2CH3)), 2- methyl -2- amyl (- C (CH3)2CH2CH2CH3), 3- first Base -2- amyl (- CH (CH3)CH(CH3)CH2CH3), 4- methyl -2- amyl (- CH (CH3)CH2CH(CH3)2), 3- methyl -3- penta Base (- C (CH3)(CH2CH3)2), 2- methyl -3- amyl (- CH (CH2CH3)CH(CH3)2), 2,3- dimethyl -2- butyl (- C (CH3)2CH(CH3)2), 3,3- dimethyl -2- butyl (- CH (CH3)C(CH3)3), n-heptyl, n-octyl, etc..
Term " alkenyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one carbon- Carbon sp2Double bond, wherein the alkenyl group can optionally replaced one or more substituent groups described in the invention, It includes the positioning of " cis " and " tans ", or the positioning of " E " and " Z ".In some embodiments, alkenyl group includes 2-8 A carbon atom；In other embodiments, alkenyl group includes 2-6 carbon atom；In other embodiment, alkenyl base Group includes 2-4 carbon atom.The example of alkenyl group includes, but is not limited to, vinyl (- CH=CH2), allyl (- CH2CH =CH2), allyl (- CH=CHCH3) etc..
Term " alkynyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one carbon- Tri- key of carbon sp, wherein the alkynyl group can be optionally replaced one or more substituent groups described in the invention.? In some embodiments, alkynyl group includes 2-8 carbon atom；In other embodiments, alkynyl group includes 2-6 carbon Atom；In other embodiment, alkynyl group includes 2-4 carbon atom.The example of alkynyl group includes, but and unlimited In acetenyl, propinyl etc..
Term " naphthenic base " refers to containing 3-12 ring carbon atom, the nonaromatic saturation monocycle of unit price or multivalence, Bicyclic or three-ring system.In some embodiments, naphthenic base includes 3-10 ring carbon atom；In other embodiments, Naphthenic base includes 3-8 ring carbon atom；In other embodiment, naphthenic base includes 3-6 ring carbon atom.Group of naphthene base Example include, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc..The group of naphthene base is optional Replaced one or more substituent groups described in the invention.
Term " cycloalkenyl " refers to containing 3-12 ring carbon atom, the unsaturated nonaromatic monocycle in part, bicyclic Or three-ring system.In some embodiments, cycloalkenyl includes 3-10 ring carbon atom；In other embodiments, cyclenes Base includes 3-8 ring carbon atom；In other embodiment, cycloalkenyl includes 3-6 ring carbon atom.The reality of cycloalkenyl groups Example includes, but is not limited to, cyclopropanyl, cyclobutane base, cyclopentenyl, cyclohexenyl group etc..The cycloalkenyl groups can appoint Replaced the substituent groups described in the invention by one or more of choosing.
Term " aryl " indicates a containing 6-14 annular atom or 6-12 annular atom or 8-12 annular atom or 6-10 The monocycle of annular atom, bicyclic and tricyclic aryl group, wherein having one or more attachment points and molecule in the aroma system Rest part be connected.Term " aryl " can be used interchangeably with term " aromatic rings " or " aromatic ring ".The aryl group includes Aromatic rings and aromatic rings or aromatic rings and it is nonaromatic it is carbocyclic fused made of ring system.The example of aryl group can wrap Include phenyl, naphthalene, anthryl, 1,2,3,4- tetralyl, 2,3- dihydro -1H- indenyl, two rings [4,2,0] octyl- 1 (6), 2,4- tri- Alkenyl.The aryl group can be substituted or non-substituted, and wherein substituent group can be, but be not limited to, fluorine, chlorine, bromine, oxygen Generation (=O), cyano, nitro, carboxyl, hydroxyl, amino, amino methyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, first Base sulfonyl, amino-sulfonyl, acetyl group, methoxyl group, phenoxy group, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, just Butyl, tert-butyl, cyclopropyl, cyclopenta, cyclohexyl, tetrahydrofuran base, tetrahydro-thienyl, nafoxidine base, imidazole radicals, imidazoles Quinoline base, piperidyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrole radicals, phenyl, pyridyl group, pyrimidine radicals ,-C (=NH) NH2Or trifluoromethyl etc..
Term " heterocycle " and " heterocycle " are used interchangeably here, all refer to the saturation comprising 3-12 annular atom or portion Divide unsaturated monocyclic, bicyclic or tricyclic system, wherein at least one annular atom is selected from nitrogen, sulphur and oxygen atom, and the heterocycle Any one ring is all nonaromatic in system.Unless otherwise stated, heterocycle can be carbon-based or nitrogen base, and-CH2Base Group can optionally be substituted by-C (=O)-.The sulphur atom of ring can optionally be oxidized to S- oxide.The nitrogen-atoms of ring can To be optionally oxidized to N- oxygen compound.In some embodiments, heterocycle is 5-12 former molecular heterocycle；? In other embodiments, heterocycle is 5-8 former molecular heterocycle；In other embodiment, heterocycle 5-7 A molecular heterocycle of original；Also in some embodiments, heterocycle is 5-6 former molecular heterocycle.Heterocycle is also It can be bicyclic heterocyclic radical；In some embodiments, heterocycle is 7-12 former molecular bicyclic heterocyclic radical；At other In embodiment, heterocycle is 7-10 former molecular bicyclic heterocyclic radical；In other embodiment, heterocycle is 8-10 A molecular bicyclic heterocyclic radical of original.
The example of heterocycle includes, but are not limited to: Oxyranyle, azelidinyl, oxetanylmethoxy, pyrrolidinyl, Pyrazolidinyl, dihydrothiophene, 1,3- dioxy cyclopenta, 1,3- dioxocyclohex base, 1,4- dioxocyclohex base, two sulphur cyclopenta, THP trtrahydropyranyl, tetrahydro thiapyran base, piperidyl, 1,2- dihydropyridine base, morpholinyl, thio-morpholinyl, hexahydropyrimidine base, 1,6- Dihydro-pyrimidin base, 1,2- dihydro-pyrimidin base, 1,2- dihydro pyrazine base, 1,3- oxazines alkyl, piperazinyl, oxazolidinyl, dioxanes Base, dithianyl, thiophene oxane base, high piperazine base, homopiperidinyl, oxepane alkyl, thia cycloheptyl alkyl, 2- oxa- -5- nitrogen Miscellaneous bicyclic [2.2.1] hept- 5- base.- CH in heterocycle2Group includes, but are not limited to 2- oxygen by-C (=the O)-example replaced For pyrrolidin-1-yl, oxo -1,3- thiazolidinyl, 2- oxo oxazolidine -3- base, 2- oxo-piperidine -1- base, 3- oxomorpholin Base, 2- oxypiperazin -1- base, 3,5- dioxy piperazine piperidinyl, -1 (2H)-base of 2- oxo tetrahydropyrimidine and 2- oxo-dihydro pyrimidine -1 (2H)-base.The example that sulphur atom is oxidized in heterocycle includes, but are not limited to sulfolane base, 1,1- dioxothiomorpholinyl With 1,1- dioxo -1,2- thio-morpholinyl.The heterocyclyl groups can be substituted or non-substituted, and wherein substituent group can It to be, but is not limited to, fluorine, chlorine, bromine, oxo (=O), cyano, nitro, carboxyl, hydroxyl, amino, amino methyl, aminoacyl Base, methylamino, phenylamino, hydroxymethyl, methyl sulphonyl, amino-sulfonyl, acetyl group, methoxyl group, phenoxy group, trifluoro methoxy Base, methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, cyclopropyl, cyclopenta, cyclohexyl, tetrahydrofuran base, tetrahydro thiophene Pheno base, nafoxidine base, imidazole radicals, imidazolinyl, piperidyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrole Cough up base, phenyl, pyridyl group, pyrimidine radicals ,-C (=NH) NH2Or trifluoromethyl etc..
In some embodiments, heterocycle is the 5-6 molecular heterocycle of original, is referred to comprising 5 or 6 annular atoms Saturation or the unsaturated monocycle in part, wherein at least one annular atom are selected from nitrogen, sulphur and oxygen atom.5-6 former molecular miscellaneous The example of ring group includes, but are not limited to: pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidine Base, tetrahydrofuran base, dihydrofuryl, tetrahydro-thienyl, oxazolidinyl, piperidyl, 1,2- dihydropyridine base, morpholinyl, sulphur For morpholinyl, hexahydropyrimidine base, 1,6- dihydro-pyrimidin base, 1,2- dihydro-pyrimidin base, 1,2- dihydro pyrazine base, 1,3- oxazines alkane Base, piperazinyl, 1,2,3,6- tetrahydro pyridyl, 1,2,3,4- tetrahydro pyridyl, 1,2,3,4- tetrahydro-pyrimidine base, 2,5- dihydros- 1H- pyrrole radicals etc..- CH in 5-6 former molecular heterocycle2Group can be replaced by-C (=O)-, or in which sulphur it is former Son can be oxidized to S- oxide.Also, described 5-6 former molecular heterocyclyl groups can optionally by one or Replaced multiple substituent groups described in the invention.
Monocycle of term " heteroaryl " expression containing 5-12 annular atom or 5-10 annular atom or 5-6 annular atom, Bicyclic and three-ring system, wherein at least one ring are aromatic, and at least one ring includes one or more nitrogen, sulphur and oxygen Hetero atom, wherein thering are one or more attachment points to be connected with molecule rest part in the heteroaryl system.Term " heteroaryl " can To be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl includes hetero-aromatic ring and aromatic rings, hetero-aromatic ring With hetero-aromatic ring or hetero-aromatic ring and nonaromatic carbocyclic ring or it is heterocyclic fused made of ring system.In some embodiments, 5-10 A molecular heteroaryl of original includes 1,2,3 or 4 hetero atom for being independently selected from oxygen, sulphur and nitrogen.In some embodiments, miscellaneous Aryl is 7-12 former molecular heteroaryl, and it includes the hetero atoms that 1,2,3 or 4 is independently selected from O, S and N；7-12 former Molecular heteroaryl can be single ring systems, be also possible to the bicyclic system comprising two rings.In other embodiments, Heteroaryl is 7-10 former molecular heteroaryl, and it includes the hetero atoms that 1,2,3 or 4 is independently selected from oxygen, sulphur and nitrogen；7-10 A molecular heteroaryl of original can be single ring systems, be also possible to the bicyclic system comprising two rings.The heteroaryl groups It can be substituted or non-substituted, wherein substituent group can be, but be not limited to, fluorine, chlorine, bromine, oxo (=O), cyano, nitre Base, carboxyl, hydroxyl, amino, amino methyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methyl sulphonyl, amino sulphur Acyl group, acetyl group, methoxyl group, phenoxy group, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, cyclopropyl Base, cyclopenta, cyclohexyl, tetrahydrofuran base, tetrahydro-thienyl, nafoxidine base, imidazole radicals, imidazolinyl, piperidyl, piperazine Base, morpholinyl, thienyl, thiazolyl, furyl, pyrrole radicals, phenyl, pyridyl group, pyrimidine radicals, guanidine radicals (- NHC (=NH) NH2) ,-N=C=S ,-C (=NH) NH2Or trifluoromethyl etc..
The example of heteroaryl groups includes, but is not limited to, furyl, imidazole radicals (such as 1H- imidazoles -1- base), isoxazole Base, oxazolyl (such as 2- oxazolyl) pyrrole radicals, 1,3,4- oxadiazoles base, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine Base, 4- pyrimidine radicals, 5- pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), thiazolyl (such as 2- thiazolyl), 2- thienyl, 3- thienyl, Pyrazolyl (such as 4- pyrazolyl, 1H- pyrazol-1-yl), pyrazinyl, cyanuro 1,3,5, triazolyl, tetrazole radical；Also include with Under it is bicyclic, but it is bicyclic to be not limited to these: benzopyrrole base, 6,7- dihydro-thiophene [3,2-c] and pyridine -5 (4H)-base, 1, 3- dioxoisoindolin -2- base, pyrimido imidazole radicals, benzimidazolyl, benzofuranyl, dihydro benzo furyl, benzo Thienyl, indyl (such as 1H- indoles -1- base), isoindoline -2- base, benzo [d] thiazol-2-yl, indazolyl (such as 1H- Yin Azoles -1- base etc.), quinolyl (such as 2- quinolyl, 3- quinolyl, 4- quinolyl), isoquinolyl (such as 1- isoquinolyl, 3- isoquinoline Quinoline base or 4- isoquinolyl), 5,6,7,8- tetrahydric quinoline group, 3,4- dihydro -2H- pyrans simultaneously [3,2-b] pyridyl group, 2,3- bis- Hydrogen-[1,4] dioxin simultaneously [2,3-b] pyridyl group, 2,3- dihydrobenzo [b] [1,4] dioxin base, 6,7- dihydro -5H- pentamethylene And [3,2-b] pyridyl group, 2,3 dihydro furan [3,2-b] pyridine, quinoline ketone group, dihydroquinoline ketone group etc..
Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, wherein alkyl group tool There is meaning as described in the present invention.In some embodiments, alkoxy base contains 1-6 carbon atom；In other implementations In scheme, alkoxy base contains 1-4 carbon atom；In other embodiment, it is former that alkoxy base contains 1-3 carbon Son.The alkoxy base can be optionally replaced one or more substituent groups described in the invention.Alkoxy base Example include, but is not limited to, methoxyl group (MeO ,-OCH3), ethyoxyl (EtO ,-OCH2CH3), 1- propoxyl group (n-PrO, n- Propoxyl group ,-OCH2CH2CH3), etc..
Term " alkyl-carbonyl " indicates that alkyl group is connected by carbonyl (- C (=O) -) with molecule rest part, wherein Alkyl group has meaning as described in the present invention.The alkylcarbonyl-residues can be optionally by one or more institutes of the present invention Replaced the substituent group of description.The example of alkyl-carbonyl includes, but is not limited to ,-C (=O) CH3,-C (=O) CH2CH3,-C (=O) CH2CH2CH3, etc..
Term " aryl carbonyl " indicates that aryl group is connected by carbonyl (- C (=O) -) with molecule rest part, wherein Aryl group has meaning as described in the present invention.The arylcarbonyl group can be optionally by one or more institutes of the present invention Replaced the substituent group of description.The example of aryl carbonyl includes, but is not limited to,Deng Deng.
Term " alkoxy carbonyl " indicates that alkoxy base is connected by carbonyl (- C (=O) -) with molecule rest part, In, alkoxy base has meaning as described in the present invention.The alkoxycarbonyl groups can be optionally one or more Replaced substituent group described in the invention.The example of alkoxy carbonyl includes, but is not limited to ,-C (=O) OCH3,-C (= O)OCH2CH3,-C (=O) OCH2CH2CH3Etc..
Term " alkyl acyloxy " indicates that alkyl group is connected by acyloxy (- C (=O) O-) with molecule rest part, Wherein, alkyl group has meaning as described in the present invention.Selected alkyl acyloxy group can be optionally one or more Replaced substituent group described in the invention.The example of alkyl acyloxy includes, but is not limited to, CH3C (=O) O-, CH3CH2C (=O) O-), CH3CH2CH2C (=O) O- etc..
Term " naphthenic base-alkyl " indicates that group of naphthene base is connected by alkyl with molecule rest part, wherein naphthenic base Group and alkyl group have meaning as described in the present invention.The cycloalkyl-alkyl-radical can be optionally by one or more Replaced a substituent group described in the invention.Naphthenic base-alkyl example includes, but is not limited to,Etc..
Term " aryl-alkyl " indicates that aryl group is connected by alkyl with molecule rest part, wherein aryl group with Alkyl group has meaning as described in the present invention.The aryl-alkyl group can be optionally by one or more present invention Replaced described substituent group.The example of aryl-alkyl includes, but is not limited to, benzyl, phenethyl etc..
Term " heteroaryl-alkyl " indicates that heteroaryl groups are connected by alkyl with molecule rest part, wherein heteroaryl Group and alkyl group have meaning as described in the present invention.The heteroaryl-alkyl-group can be optionally by one or more Replaced a substituent group described in the invention.The example of heteroaryl-alkyl includes, but is not limited to,Etc..
Term " halogenated C1-6Alkoxy " or " halogenated C6-12Aryl " respectively indicates alkoxy base or aryl group by one Or replaced multiple halogen groups, such example is included, but is not limited to ,-OCF3、Etc..
“C1-6Alkyl-substituted C6-12Aryl ", " halogenated C1-6Alkyl-substituted C6-12Aryl ", " C1-6What alkoxy replaced C6-12Aryl " or " halogenated C1-6The C that alkoxy replaces6-12Aryl " respectively indicates aryl group by one or more alkyl, halogenated Replaced alkyl, alkoxy or halogenated alkoxy, such example is included, but is not limited to,Etc..
Term " alkyl amino ", " arylamino ", " cycloalkyl amino " or " heteroaryl amino " respectively indicates amino group Replaced one or two alkyl group, aryl group, group of naphthene base or heteroaryl groups.Such example includes, but It is not limited to, N- methylamino, N- ethylamino, N, N- dimethylamino, N, N- lignocaine, N- phenylamino, N- cyclopropylamino, 6- Picoline -2- amino, etc..
Term " hetero atom " refers to O, S, N, P and Si, the form including any oxidation state of N, S and P；Primary, secondary, tertiary amine and season The form of ammonium salt；Or the substituted form of hydrogen in heterocycle on nitrogen-atoms, for example, N is (as in 3,4- dihydro-2 h-pyrrole base N), NH (as the NH in pyrrolidinyl) or NR (NR in pyrrolidinyl replaced as N-).
Term " halogen " refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
No matter term " sulfonyl " is single use or is used in conjunction with other terms, be expressed as-SO2-。
" acceptable salt " of the invention includes the salt of sour addition and the salt of alkali addition, and suitable alkali is alkali metal and alkaline earth gold The hydroxide of category, carbonate, bicarbonate, especially sodium, potassium, magnesium and calcium salt and ammonium, there is (C1-C4)-alkyl base The primary, secondary and tertiary amine of group, (C1-C4Mono-, two- and tri-alkanolamine, choline and the choline chloride of)-alkanol.
Salt can be a kind of salt with inorganic acid addition, and inorganic acid can be hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, Or the salt with organic acid addition, organic acid can be formic acid, carbonic acid and alkanoic acid such as acetic acid, trifluoroacetic acid, trichloroacetic acid and third Acid and glycolic, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturation or single insatiable hunger and/or two Unsaturated C6-C20Fatty acid, alkylsurfuric acid monoesters, alkyl sulfonic acid be (linear or branched alkyl group with 1-20 carbon atom Sulfonic acid), aryl sulfonic acid or aryl disulfonic (aromatic group with one or two sulfonic acid group, such as phenyl and naphthalene), Alkyl phosphonic acid (phosphonic acids of the linear or branched alkyl group with 1-20 carbon atom), arylphosphonic acid or aryl di 2 ethylhexyl phosphonic acid (have one A or two phosphonyl groups aromatic group, such as phenyl and naphthalene), wherein the alkyl and aryl group can take with other Dai Ji, such as p-methyl benzenesulfonic acid, salicylic acid, PAS, 2- phenoxy benzoic acid, Aspirin etc..
The composition and preparation of the compounds of this invention
The invention further relates to the compositions comprising a kind of the compounds of this invention I.This kind of composition especially further include as Auxiliary agent defined in lower.
Suitable auxiliary agent is solvent, liquid-carrier, solid carrier or filler, surfactant, dispersing agent, emulsifier, profit Humectant, adjuvant, solubilizer, penetration enhancer, protective colloid, adhesive, thickener, moisturizer, expellent, attractant, Feeding stimulants, compatilizer, fungicide, antifreezing agent, defoaming agent, colorant, tackifier and adhesive.
Suitable solvent and liquid-carrier are water and organic solvent, arrive high boiling mineral oil fractions as in, such as kerosene, Diesel oil；The oil of plant or animal origin；Aliphatic series, cyclic annular and aromatic hydrocarbons, such as toluene, paraffin, naphthane, alkylated naphthalene；Alcohol Class, such as ethyl alcohol, propyl alcohol, butanol, benzylalcohol, cyclohexanol；Glycols；DMSO；Ketone, such as cyclohexanone；Esters, such as lactate, Carbonic ester, aliphatic ester, gamma-butyrolacton；Fatty acid；Phosphonate ester；Amine；Amides, such as N-Methyl pyrrolidone, fatty acid Dimethylformamide；And their mixture.
Suitable solid carrier or filler are mine soil, such as silicate, silica gel, talcum, kaolin, lime stone, lime, white Chalk, clay, dolomite, diatomite, bentonite, calcium sulfate, magnesium sulfate, magnesia；Polysaccharide, such as cellulose, starch；Fertilizer, Such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas；The product of plant origin, such as flour, bark powder, wood powder and shuck powder, And their mixture.
Suitable surfactant is surface reactive material, such as anion, cation, nonionic and amophoteric surface active Agent, block polymer, polyelectrolyte and their mixture.Such surfactant may be used as emulsifier, dispersing agent, Solubilizer, wetting agent, penetration enhancer, protective colloid or adjuvant.
Suitable anionic surfactant be sulfonic acid, sulfuric acid, phosphoric acid, the alkali metal of carboxylic acid, alkaline-earth metal or ammonium salt with And their mixture.The example of sulfonate is alkylaryl sulfonates, diphenyl sulfonate, alpha-alkene sulfonate, lignin sulphur Hydrochlorate, the sulfonate of fatty acid and oil, the sulfonate of ethoxylated alkylphenol, the sulfonate of alkoxylate aryl phenol, condensation naphthalene Sulfonate, the sulfonate of dodecyl-and tridane, the sulfonate of naphthalene and alkylnaphthalene, sulfosuccinate or sulfo group Succinamate.The example of sulfate is the sulfuric acid of the sulfate of fatty acid and oil, the sulfate of ethoxylated alkylphenol, alcohol The sulfate of salt, the sulfate of ethoxylated alcohol or aliphatic ester.Phosphatic example is phosphate ester.The example of carboxylate is Alkyl carboxylate and carboxylation alcohol or alkylphenol ethoxylate.
Suitable nonionic surfactant is alcoxylates, the fatty acid amide that N- replaces, amine oxide, esters, Glycosyl surfactant active, polymeric surfactant and its mixture.The example of alcoxylates is that all 1-50 as has already been work as Measure the compound of alkoxylated alcohol, alkyl phenol, amine, amide, aryl phenol, fatty acid or aliphatic ester.It can be by ethylene oxide And/or propylene oxide is used for alkoxylate, preferably ethylene oxide.The example for the fatty acid amide that N- replaces is fatty acid glucose acyl Amine or Marlamid.The example of esters is aliphatic ester, glyceride or monoglyceride.The reality of glycosyl surfactant active Example is anhydro sorbitol, ethoxylated sorbitan, sucrose and glucose ester or alkyl polyglucoside.Polymer surfactants The example of agent is the homopolymer or copolymer of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.
Suitable cationic surfactant is season type surfactant, such as the quaternary ammonium with 1 or 2 hydrophobic group The salt of compound or long chain primary amines.Suitable amphoteric surfactant is alkyl betaine and imidazolines.Suitable block is poly- It closes A-B the or A-B-A type block polymer that object is the block comprising polyoxyethylene and polyoxypropylene, or includes alkanol, poly- The A-B-C type block polymer of ethylene oxide and polyoxypropylene.Suitable polyelectrolyte is polyacids or polybases.The example of polyacids is The alkali metal salt or polyacids comb-shaped polymer of polyacrylic acid.The example of polybases is polyvinylamine or polyvinylamine.
Suitable adjuvant is that itself have insignificant pesticide activity or in itself even without pesticide activity and improvement Compound of the compound I to the biology performance of object.Example is surfactant, mineral oil or vegetable oil and other are helped Agent.
Suitable thickener is that polysaccharide (such as xanthan gum, carboxymethyl cellulose), inorganic clay are (organically-modified or unmodified ), polycarboxylate and silicate.
Suitable antifreezing agent is ethylene glycol, propylene glycol, urea and glycerol.
Suitable defoaming agent be polysiloxanes, silicone cream, long-chain alcohol, fatty acid and its salt and organic fluorocompound and its Mixture.
Suitable colorant (such as red coloration, blue or green) is low aqueous solubility pigment and water-soluble dye.Example is Inorganic colourant (such as iron oxide, titanium oxide, Hexacyanoferrate iron) and toner (such as alizarin colouring agent, azo Toner and phthalocyanine colorant).
Suitable tackifier or adhesive are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid Ester, biowax or synthetic wax and cellulose ether.
If appropriate, other additional components, such as protective colloid, adhesive (binder), sticker also may be present (adhesive), thixotroping substance, bleeding agent, stabilizer, chelating agent (sequestrant), complexing agent.In general, it is described activity at Dividing can combine with any solid or liquid additive for being usually used in preparation purpose.
Agrochemicals fungicide of the present invention, insecticide can be applied with its dosage form or use form prepared therefrom With the use form such as aerosol, capsule suspension, harl concentrating agents (cold-fogging concentrate), heat Mist concentrating agents, encapsulated granule, fine grained agent, the mobility concentrating agents (flowable for seed treatment Concentrate), instant solution, can the pulvis of dusting, emulsifiable concentrating agents, oil in water emulsion, water-in-oil emulsion, big Granule, fine granule, oil-dispersing property powder agent, oily compatibility flowing concentrating agents, oily forming ionisable polymer, gas agent are (in pressure Under), produce gas product, foaming agent, paste, suspension concentrating agents, outstanding newborn concentrating agents, soluble concentrating agents, suspension, wettable powder Agent, soluble powder, powders and granules, the granule or tablet of water solubility and water dispersible, for the water-soluble of seed treatment Property or water-dispersible powder, wettable powder, the natural products through active material dipping and synthetic and polymer and kind Microcapsules and ULV (ultra low volume) harl and hot mist preparation in sub- coating material.
The preparation can optionally include the combination containing other agricultural chemical compounds.
The application compound can combine to form Fungicidal mixture and their Synergistic mixtures with other fungicides.This The Fungicidal compounds of application are usually administered in combination with one or more other fungicides, to prevent and treat the not phase of wider range Hope disease.
In addition, compound described herein can be in conjunction with other insecticides, including insecticide, nematicide, mite killing Agent, arthropodicides (arthropodicide), fungicide or their combination, other insecticides are with regard to selected by application Medium in it is compatible with the application compound and not antagonism the application compound activity to form insecticide mixtures and they Synergistic mixtures.
In addition, compound described herein can form biocidal mixtures in conjunction with herbicide and cooperateing with for they is mixed Close object.The Fungicidal compounds of the application are usually administered in combination with one or more herbicides, to prevent and treat wider range not It is expected that plant.
In addition, the agricultural chemical compound can also be bactericide, attractant, growth regulator, fertilizer, safener, Fungicide (sterilant) or their combination, wherein the agricultural chemical compound just application selected medium in this Shen It please compound be compatible and activity of not antagonism the application compound.Therefore, in said embodiment, by other pesticides Compound is used as supplement toxic agent, for identical or different purposes.
Using the compounds of this invention composition to plant and plant parts carry out processing of the invention can directly carry out or It acts on its ambient enviroment, habitat or memory space by conventional treatment method to carry out, the conventional treatment method is, such as leads to Dipping is crossed, sprinkling, spraying, irrigation, evaporation, dusting, atomizing, broadcasts sowing, foam, smearing, being coated with, watering (pouring), instiling, for Plant propagation material can also pass through dry seed treatment, wet seed treatment, slurries processing, crust, coating especially for seed One or more layers coating etc..It can also be injected by ultra-low volume method or by the compounds of this invention preparation or the compounds of this invention itself Active material is efficiently used into soil.
The purposes of the compounds of this invention
Active constituent or composition of the invention, which has, potentially kills microbial activity, in crop protection and material protection It can be used for preventing and treating unwanted microorganism, such as fungi and bacterium.
The disease as caused by powdery mildew pathogen, for example, dlumeria graminis (Blumeria) belongs to, such as grass family Bu Shi white Powder bacterium (Blumeria graminis)；Cross hair list softgel shell (Podosphaera) belongs to, such as white cross hair list softgel shell (Podosphaera leucotricha)；Single softgel shell (Sphaerotheca) belongs to, such as balsamine list softgel shell (Sphaerotheca fuliginea)；Snag shell (Uncinula) belongs to, such as grape snag shell (Uncinulanecator)；
The disease as caused by rust pathogen, for example, glue rest fungus (Gymnosporangium) belongs to, such as brown size rest fungus (Gymnosporangium sabinae)；Hunchbacked spore rust (Hemileia) belongs to, such as coffee rust (Hemileiavastatrix)；Layer rest fungus (Phakopsora) belongs to, such as Phakopsora pachyrhizi (Phakopsora Pachyrhizi) and mountain horseleech layer rest fungus (Phakopsora meibomiae)；Handle rest fungus (Puccinia) belongs to, such as concealment handle Rest fungus (Puccinia recondite), puccinia triticinia (P.triticina), red rust (Puccinia ) or wheat stripe rust (Puccinia striiformis) graminis；Uromyce (Uromyces) belongs to, such as wart top unit cell Rest fungus (Uromyces appendiculatus)；
The disease as caused by Oomycete (Oomycete) pathogen, for example, white rust (Albugo) belongs to, such as white rust (Albugo candida)；Disk downy mildew (Bremia) belongs to, such as lettuce disk downy mildew (Bremia lactucae)；Downy mildew (Peronospora) belong to, such as pea downy mildew (Peronospora pisi) or Cruciferae downy mildew (Peronospora brassicae)；Phytophthora (Phytophthora) belongs to, such as phytophthora infestans (Phytophthora infestans)；Axis downy mildew (Plasmopara) belong to, such as grape is raw axis downy mildew (Plasmopara viticola)；False downy mildew (Pseudoperonospora) belong to, such as the false downy mildew (Pseudoperonospora humuli) of grass or Pseudoperonospora cubensis (Pseudoperonospora cubensis)；Rotten mould (Pythium) belongs to, such as Pythium ultimum (Pythium ultimum)；
The leaf spot blight as caused by following pathogen (Leaf blotch) and sick (leaf wilt) disease of leaf withering: example Such as, rod method (Alternaria) belongs to, such as early blight rod method (Alternaria solani)；Tail spore (Cercospora) Belong to, Li such as Chard dish is raw tail spore (Cercospora beticola)；Branch spore (Cladiosporium) belongs to, such as yellow melon fruit fly (Cladiosporium cucumerinum)；Cochliobolus (Cochliobolus) belongs to, such as standing grain cochliobolus (Cochliobolus sativus) (conidial form: Drechslera (Drechslera), Syn: long compacted spore bacterium (Helminthosporium)), rotation spore in palace portion is mould (Cochliobolus miyabeanus)；Anthrax-bacilus (Colletotrichum) belong to, such as Kidney bean anthrax-bacilus (Colletotrichum lindemuthanium)；Rust staining germ (Cycloconium) belong to, such as hole ephelides (Cycloconium oleaginum)；Between seat shell (Diaporthe) belong to, such as Seat shell (Diaporthe citri) between citrus；Elsinochrome (Elsinoe) belongs to, such as citrus Elsinochrome (Elsinoe fawcettii)；The long spore of disk (Gloeosporium) belongs to, such as happy the long spore of colour disk (Gloeosporium laeticolor)；It is small Clump shell (Glomerella) belongs to, such as GLOMERFLLA CINGULATA (Glomerella cingulata)；Guignardia (Guignardia) belongs to, example Such as grape Guignardia (Guignardia bidwelli)；Ball cavity bacteria (Leptosphaeria) belongs to, such as blotchy ball cavity bacteria (Leptosphaeria maculans), the withered ball cavity bacteria (Leptosphaeria nodorum) of grain husk；Shell is ruined greatly (Magnaporthe) belong to, such as grey ruins greatly shell (Magnaporthe grisea)；Micro- spore category (Microdochium), example Such as avenge mould micro- spore (Microdochium nivale)；Spherical cavity bacterium (Mycosphaerella) belongs to, such as standing grain green-ball chamber bacterium (Mycosphaerella graminicola), peanut spherical cavity bacterium (M.arachidicola) and Fijian spherical cavity bacterium (M.fijiensis)；Septoria musiva (Phaeosphaeria) belongs to, such as phaeosphaeria nodorum (Phaeosphaeria nodorum)； Nuclear cavity bacteria (Pyrenophora) belongs to, such as round nuclear cavity bacteria (Pyrenophora teres), couchgrass nuclear cavity bacteria (Pyrenophora triticirepentis)；Column belongs to every spore (Ramularia), such as pungent strutting is every spore (Ramulariacollo-cygni), white spores (Ramularia areola)；Beak spore (Rhynchosporium) belongs to, example Such as rye beak spore (Rhynchosporium secalis)；Needle spore (Septoria) belongs to, such as Septoria apii (Septoria Apii), tomato septoria musiva (Septoria lycopersii)；Core coral bacterium (Typhula) belongs to, such as meat spore core coral bacterium (Typhulaincarnata)；Black star bacterium (Venturia) belongs to, such as apple black star bacteria (Venturia inaequalis)；
The disease of the root as caused by following pathogen and stem: for example, photovoltaicing leather bacteria (Corticium) belongs to, such as standing grain photovoltaicing leather bacteria (Corticium graminearum)；Fusarium (Fusarium) belongs to, such as sharp fusarium (Fusariumoxysporum)；Top capsule shell (Gaeumannomyces) belong to, such as gaeumannomyce (Gaeumannomyces graminis)；Rhizoctonia (Rhizoctonia) Belong to, such as Rhizoctonia solani Kuhn (Rhizoctonia solani)；Such as drawn by rice broom branch bar spore (Sarocladium oryzae) The broom branch bar spore (Sarocladium) risen belongs to disease；The pyrenomycetes as caused by rice corruption pyrenomycetes (Sclerotium oryzae) (Sclerotium) belong to disease；Tapesia belongs to, such as Tapesia acuformis；Thielaviopsis sp (Thielaviopsis) belongs to, Such as thielaviopsis sp (Thielaviopsis basicola)；
The spadix as caused by following pathogen or panicled spike disease (including corncob): for example, rod method (Alternaria) belong to, such as Alternaria (Alternaria spp.)；Aspergillus (Aspergillus) belongs to, such as aspergillus flavus (Aspergillus flavus)；Branch spore (Cladosporium) belongs to, such as the dendritic branch spore (Cladosporium of bud cladosporioides)；Ergot (Claviceps) belongs to, such as ergot (Claviceps purpurea)；Fusarium (Fusarium) belong to, such as yellow fusarium (Fusarium culmorum)；Red mould (Gibberella) belongs to, such as maize is red Mould (Gibberella zeae)；Small setting-out shell (Monographella) belongs to, such as the rotten small setting-out shell of snow (Monographellanivalis)；The more spores of shell (Stagonospora) belong to, such as many spores of clever withered shell (Stagonospora nodorum)；
The disease as caused by smut, for example, axis smut (Sphacelotheca) belongs to, such as silk spore heap smut (Sphacelotheca reiliana)；Tilletia foetida (Tilletia) belongs to, such as Tilletia caries (Tilletiacaries), T contraversa (T.controversa)；Smut (Urocystis) belongs to, such as hidden item Smut (Urocystis occulta)；Smut (Ustilago) belongs to, such as naked smut (Ustilago nuda), wheat Loose smut (U.nuda tritici)；
The fruit rot as caused by following pathogen: for example, aspergillus (Aspergillus) belongs to, such as aspergillus flavus (Aspergillus flavus)；Grape spore (Botrytis) belongs to, such as Botrytis cinerea (Botrytis cinerea)；Mould (Penicillium) belong to, such as penicillium expansum (Penicillium expansum) and penicillium purpurogenum (P.purpurogenum)； Sclerotinite (Sclerotinia) belongs to, such as sclerotinite (Sclerotinia sclerotiorum)；Take turns branch spore (Verticilium) belong to, such as verticilliumalbo-atrum (Verticilium alboatrum)；
It is the seed decay as caused by following pathogen and that soil passes it is rotten, mouldy, wilt, addle and damping-off: for example, Rod method (Alternaria) belongs to, such as rape rod method (Alternaria brassicicola)；Silk capsule is mould (Aphanomyces) belong to, such as root-rot silk capsule is mould (Aphanomyces euteiches)；Two spore of shell (Ascochyta) belongs to, example Such as two spore of Lens culinaris shell (Ascochyta lentis)；Aspergillus (Aspergillus) belongs to, such as aspergillus flavus (Aspergillusflavus)；Branch spore (Cladosporium) belongs to, such as draft branch spore (Cladosporium herbarum)； Cochliobolus (Cochliobolus) belongs to, such as standing grain cochliobolus (Cochliobolus sativus) (conidial form: interior Navel Helminthosporium, bipolaris (Bipolaris) Syn: long compacted spore bacterium)；Anthrax-bacilus (Colletotrichum) belongs to, such as hair core charcoal Subcutaneous ulcer bacterium (Colletotrichum coccodes)；Fusarium (Fusarium) belongs to, such as yellow fusarium (Fusarium culmorum)；Red mould (Gibberella) belongs to, such as Gibberella zeae (Gibberella zeae)；Shell ball spore (Macrophomina) belong to, such as Kidney bean shell ball spore (Macrophomina phaseolina)；Small setting-out shell (Monographella) belong to, such as the rotten small setting-out shell (Monographella nivalis) of snow；Mould (Penicillium) Belong to, such as penicillium expansum (Penicilliumexpansum)；Phoma sp (Phoma) belongs to, such as balck shank (Phoma lingam)；Phomopsis (Phomopsis species) belongs to, such as soybean Phomopsis (Phomopsis sojae)；Phytophthora (Phytophthora) belong to, such as Phytophthora cactorum (Phytophthora cactorum)；Nuclear cavity bacteria (Pyrenophora) belongs to, such as Wheat nuclear cavity bacteria (Pyrenophora graminea)；Pears spore (Pyricularia) belongs to, such as Magnaporthe grisea (Pyricularia oryzae)；Rotten mould (Pythium) belongs to, such as Pythium ultimum (Pythium ultimum)；Rhizoctonia (Rhizoctonia) belongs to, Such as Rhizoctonia solani Kuhn (Rhizoctonia solani)；Rhizopus (Rhizopus) belongs to, such as rhizopus oryzae (Rhizopus oryzae)；Pyrenomycetes (Sclerotium) belong to, such as Sclerotium rolfsii (Sclerotium rolfsii)；Septoria musiva (Septoria) belong to, such as phaeosphaeria nodorum (Septoria nodorum)；Core coral bacterium (Typhula) belongs to, such as meat spore core coral Bacterium (Typhula incarnata)；Verticillium sp (Verticillium) belongs to, such as Verticilliumdahliae (Verticillium dahliae)；
The carcinous disease as caused by following pathogen, mycoceicidum and witches' broom (witches ' broom): for example, the red shell of clump (Nectria) belong to, such as a kind of fruit, such as apple, pear, etc. does the red shell bacterium of cancer clump (Nectria galligena)；
The atrophy disease as caused by following pathogen: for example, chain sclerotinia sclerotiorum (Monilinia) belongs to, such as drupe chain nuclear disk Bacterium (Monilinia laxa)；
The leaf gas blister as caused by following pathogen or leaf roll are bent: for example, outer cross-arming bacteria (Exobasidium) belongs to, such as corrupted Outer cross-arming bacteria (Exobasidium vexans)；Exoascus (Taphrina), such as lopsided external capsule bacterium (Taphrina deformans)；
The xylophyta degeneration disease as caused by following pathogen: for example, for example by head mold lattice spore bacterium (Phaeomoniella chlamydospora), Phaeoacremonium aleophilum and Mediterranean spore pore fungi It is sick (Esca) according to section caused by (Fomitiporia mediterranea)；Such as by grapevine apical dieback bacterium (Eutypa lata) Caused eutypa dieback (Eutypa dyeback)；Such as caused by long and narrow spore ganoderma lucidum (Ganoderma boninense) Ganoderma lucidum (Ganoderma) belongs to disease；Such as the Rigidoporus durus as caused by Rigidoporus lignosus (Rigidoporus lignosus) (Rigidoporus) belong to disease；
Colored and seed the disease as caused by following pathogen: for example, grape spore (Botrytis) belongs to, such as Botrytis cinerea (Botrytis cinerea)；
The disease of the plant tuber as caused by following pathogen: it for example, rhizoctonia (Rhizoctonia) belongs to, such as stands withered Rhizoctonia (Rhizoctonia solani)；Long compacted spore bacterium (Helminthosporium) belongs to, such as Helminthosporium solani (Helminthosporium solani)；
The knee disease as caused by following pathogen: for example, knee Pseudomonas (Plasmodiophora), such as cloud a kind of sedge knee Bacterium (Plamodiophora brassicae)；
The disease as caused by following bacterial pathogens: for example, Xanthomonas campestris (Xanthomonas) belongs to, such as rice is yellow single Born of the same parents' bacterium bacterial leaf spot mutation (Xanthomonas campestris pv.oryzae)；Pseudomonad (Pseudomonas) belongs to, such as Pseudomonas syringae cucumber pvs oryzae and oryzicola (Pseudomonas syringae pv.lachrymans)；Erwinia (Erwinia) belong to, such as bite Erzvinia amylovora (Erwinia amylovora).
In addition, they are suitable for struggling with the fungi of infection timber or plant root.
Fungicide can be used in crop protection, for preventing and treating pseudomonas (Pseudomonadaceae), rhizobium (Rhizobiaceae), enterobacteria (Enterobacteriaceae), bar bacterium (Corynebacteriaceae) and strepto- Bacterium (Streptomycetaceae).
Non-limiting example the present invention relates to the pest for the infringement for controlling or preventing useful plant to be subject to includes:
Semiptera (Hemiptera): plant hopper (Delphacidae (Delphacidae)) such as small small brown rice planthopper (Laodelphax striatellus)；Leafhopper (Deltocephalidae (Deltocephalidae)) such as green rice leafhopper (rice green leafhopper (Nephotettix cincticeps))；Aphid (Aphidiadae (Aphididae)) such as cotten aphid (Aphis gossypii)；Pentatomiddae (Pentatomidae) is such as Nezaraantennata (Nezara antennata)；Aleyrodid (Aleyrodidae) such as greenhouse whitefly (Trialeurodes vaporariorum)；A red-spotted lizard (Coccidae) such as California red scale (Calformia red scale) (Aonidiella aurantii)；Tingidae (Tingidae)；Wood louse (Homoptera, Psyllidea)；
Lepidoptera (Lepidoptera): snout moth (Pyralidae) such as striped rice borer (Chilo suppressalis)；Noctuid (Noctuidae) such as Spodoptera litura (Spodoptera litura), mythimna separata (Pseudaletia separata), real noctuid Belong to (Heliothis spp.) and Helicoverpa (Helicoverpa spp.)；White butterfly (Pieridae) such as cabbage butterfly (Pieris rapae)；Roll up moth (Tortricidae) such as Adoxophyessp (Adoxophyes)；Thin moth (Gracillariidae) such as Caloptiliatheivora (Caloptilia theivora) and the thin moth of apple (Phyllonorycter ringoneella)；Eat into fruit moth (Carposinidae) such as peach fruit moth (Carposina niponensis)；Lyonetid (Lyonetiidae) such as Lyonetiaspp (Lyonetia spp.)；Poison moth (Lymantriidae) such as Euproctis (Lymantria spp.) and Euproctis (Euproctis spp.)；Ermine moth (Yponomeutidae) such as diamondback moth (Plutella xylostella)；Gelechiid (Gelechiidae) such as Pectinophora gossypiella (Pectinophora gossypiella) and potato tuberworm (Phthorimaea operculella)；Moths attracted by lamplight (Arctiidae) such as fall webworms (Hyphantria cunea)；And rain moth (Tineidae) is such as Casemaking clothes moth (Tineatranslucens) and Tineolabisselliella (Tineola bisselliella)；
Thysanoptera (Thysanoptera): Frankliniella occidentalis (Frankliniella occidentalis), palm thrips (Thrips palmi), Scirtothripsdorsalis (Scirtothrips dorsalis), onion thrips (Thrips tabaci), beautiful colored Ji Horse (Frankliniella intonsa) and Frankliniellafusca (Frankliniella fusca)；
Diptera (Diptera): housefly (Musca domestica), Culex pipiens pallens (Culex popiens Pallens), Tabanustrigonus (Tabanus trigonus), onion fly (Hylemya anitqua), delia platura (Hylemya Platura), Anopheles sinensis (Anopheles sinensis), Japanese rice maggot (Agromyza oryzae), rice leafminer (Hydrellia griseola), ricestem-fly (Chlorops oryzae), melon widow's hair on the neck trypetid (Dacus cucurbitae), Middle sea fruit fly (Ceratitis capitata) and Liriomyza trifolii (Liriomyza trifolii)；
Coleoptera (Coleoptera): ladybug of eggplant 28 stars (Epilachna vigintioctopunctata), Huang Qu Dish flea beetle (Phyllotreta striolata), Oulema oryzae (Oulema oryzae), Echinocnemussquameus (Echinocnemus Squameus), Lissorhoptrusoryzophilus (Lissorhoptrus oryzophilus), Anthonomusgrandis (Anthonomus grandis), Callosobruchus chinensis (Callosobruchus chinensis), Sphenophorusvenatus (Sphenophorus venatus), Japan popillia flavosellata fairmaire (Popillia japonica), Anomalacuprea (Anomala cuprea), Diabroticaspp (Diabrotica spp.), Colorado potato beetles (Leptinotarsa decemlineata), click beetle category (Agriotes spp.), tobacco death watch beetle (Lasioderma serricorne), Anthrenus verbasci (Anthrenus verbasci), red flour beetle (Tribolium Castaneum), Lyctus brunneus Stephens (Lyctus brunneus), Anoplophoramalasiaca (Anoplophora malasiaca) and vertical hole are cut Tip bark beetle (Tomicus piniperda)；
Orthoptera (Orthoptera): Asiatic migrotory locust (Locusta migratoria), African mole cricket (Gryllotalpa Afficana), Oxyayezoensis (Oxya yezoensis) and O. japonica (Oxya japanica)；
Hymenoptera (Hymenoptera): Athaliarosae (Athalia rosae), Myrmecina (Acromyrmex ) and Solenopsis (Solenopsis spp.) spp.；
Nematode (Nematodes): aphelenchoides besseyi (Aphelenchoides besseyi), Nothotylenchusacris (Nothotylenchus acris), soy bean cyst roundworm (Heterodera glycines), Meloidogyne incognita (Meloidogyne incognita), Pratylenchus (Pratylenchus penetrans) and Nacobbusaberrans (Nacobbus aberrans)；
Blattaria (Blattariae): Groton bug (Blattella germanica), Peroplaneta fluligginosa (Periplaneta Fuliginosa), American cockroach (Periplaneta Americana), Periplanetabrunnea (Periplaneta brunnea) and east Square blattaria (Blatta orientalis)；
Acarina (Acarina): Tetranychidae (Tetranychidae) is (for example, Tetranychus urticae (Tetranychusurticae), panonychus citri (Panonychus citri) and Oligonychus (Oligonychus spp.))；Eriophyidae (Eriophyidae) (for example, Aculopspelekassi (Aculops pelekassi))；Tarsonemidae (Tarsonemidae)；Tenuipalpidae (Tenuipalpidae)；Tuckerellidae (Tuckerellidae)；Tyroglyphidae (Tuckerellidae Acaridae)；Pyroglyphidae (Pyroglyphidae) is (for example, dust mite (Dermatophagoides Farinae) and dermatophagoides pteronyssinus (Dermatophagoides ptrenyssnus))；Cheyletidae (Cheyletidae), Malacca Cheyletid mite (Cheyletus malaccensis) and Cheyletusmoorei (Cheyletus moorei)；And Dermanyssidae (Dermanyssidae)。
Within the scope of the invention, useful plant includes following floristics: cereal (wheat, barley, rye, oat, Rice, corn, sorghum and relative species)；Beet (preserved carrot and fodder beet)；The operatic circle, drupe and soft water fruit (apple, Pears, plum, peach, almond, cherry, strawberry, raspberry and blackberry, blueberry)；Leguminous plant (hyacinth bean, guest's beans, pea, soybean)；Oil plant is made Object (rape, leaf mustard, olive, sunflower, coconut, castor oil plant, cocoa bean, peanut or soybean)；Mellon plant (pumpkin, Cucumber, muskmelon)；Fibre plant (cotton, flax, hemp, jute)；Citrus fruit (orange, lemon, grape fruit, citrus)；Vegetable Dish (spinach, lettuce, asparagus, wild cabbage, carrot, onion, tomato, potato, hot red pepper)；Laurel class plant (avocado, Cinnamomum, camphor tree Brain) or plant, such as tobacco, nut, coffee, eggplant, sugarcane, tea, pepper, grapevine, hops, banana and natural rubber Plant, together with turf, ornamental and forest plants, such as flowers, shrub, broad leaf tree or evergreen tree, such as coniferous tree and plant Propagation material.
Term " plant propagation material " should be understood as indicating the reproductive part of the plant, such as seed, these parts It can be used for the breeding and nutritive material of the plant, such as cutting or stem tuber (such as potato).
Fungicide and insecticide composition of the invention passes through a effective amount of active material treatability or protectiveness/pre- Anti- property prevention and treatment plant pathogenic fungi and pest.Therefore, the invention further relates to for preventing and treating plant pathogenic fungi and pest is controlled The property treated and protectiveness method, the method is by being applied to seed, plant or plant for active constituent or composition of the invention The soil at position, fruit or plant growth carries out.Application can be in seed, plant or plant parts, fruit or plant growth Soil is carried out before and after pathogenic epiphyte and pestinfestation.
Term " effective quantity " used indicates to be enough on cultivated plant or prevent and treat in material protection harmful fungoid and pest And do not cause the present composition or compound I for the amount significantly damaged to plant processed.The amount can become in a wide range Change and depend on various factors fungi and pest species such as to be prevented and treated, processed cultivated plant or material, weather conditions with And particular compound I used.
The composition application method of the compounds of this invention is simple, and the composition of the compounds of this invention is imposed on to the disease On bacterium, pest or its somatomedin.When the administration dosage of the composition of the compounds of this invention is according to weather condition, dosage form, application The variation such as machine, method of administration, administration area, target disease, target crop.
General synthesis process
In the present specification, if there are any difference between chemical name and chemical structure, structure is dominant.Generally Ground, the compound of the present invention described method can be prepared through the invention, unless there are further instruction, wherein taking The definition of Dai Ji is such as shown in (I).Following synthetic schemes and embodiment 1-44 is for being further illustrated the contents of the present invention.
Those skilled in the art will realize that: chemical reaction described in the invention can be used to suitably prepare perhaps Other compounds mostly of the invention, and other methods for the preparation of the compounds of the present invention are considered as in model of the invention Within enclosing.For example, the synthesis of the compound of those non-illustrations can be successfully by those skilled in the art according to the present invention It is completed by method of modifying, such as protection interference group appropriate, by utilizing other known reagent (in addition to described in the invention ), or reaction condition is made into some conventional modifications.In addition, reaction disclosed in this invention or known reaction condition are also public It is suitable for the preparation of other compounds of the invention with recognizing.
Chromatographic column is using silicagel column.Silica gel (300-400 mesh) is purchased from Haiyang Chemical Plant, Qingdao.Spectroscopic data of the nuclear magnetic resonance It is measured by Bruker Avance400 nuclear magnetic resonance spectrometer or 600 nuclear magnetic resonance spectrometer of Bruker Avance III HD, It is solvent (report is as unit of ppm) with CDC13, DMSO-d6, CD3OD or acetone-d6, with TMS (0ppm) or chloroform (7.25ppm) is used as reference standard.When there is multiplet, following abbreviation: s (singlet, unimodal), d will be used (doublet, bimodal), t (triplet, triplet), m (multiplet, multiplet), br (broadened, broad peak), dd (doublet of doublets, quartet), dt (doublet of triplets, double triplets), ddd (doublet of Doublet of doublets, in pairs doublet), and ddt (doublet of doublet of triplets, it is triple in pairs Peak), dddd (doublet of doublet of doublet of doublets, in pairs double doublet).Coupling constant is used Hertz (Hz) indicates.
The condition of low resolution mass spectrometry (MS) data determination is: 6120 Quadrupole HPLC-MS (pillar of Agilent Model: Zorbax SB-C18,2.1x30mm, 3.5 μm, 6min, flow velocity 0.6mL/min, mobile phase: 5%-95% (contains The CH3CN of 0.1% formic acid) ratio in (H2O containing 0.1% formic acid))), it is detected in 210/254nm with UV, uses electron spray Ionization mode (ESI).
The use of logogram word below is through the present invention:
CDC13 deuterated chloroform
G grams
Mg milligrams
Mol moles
Mmol mMs
ML milliliters
Following reaction scheme describes the step of preparation disclosed compound of present invention.Wherein, R1、R2、R3、R4a、R4b、R4c、 R5、R6、R8、Rm、RnAnd L2With meaning described in the invention.
Synthetic schemes
Synthetic schemes 1
Formula (I-1) compound represented can be synthesized by method disclosed in synthetic schemes 1.Compound 1a is in alkaline item It is reacted under part with compound 1b, obtains compound 1c.Compound 1c obtains compound 1d by reduction reaction.Compound 1d and change Close object 1e in acid condition, heating, the intermediate reacted heats reaction in diphenyl ether, obtains compound 1f.Chemical combination Object 1f reacts to obtain compound I-1 with compound 1g heating.
Synthetic schemes 2
Formula (I-2) compound represented can be synthesized by method disclosed in synthetic schemes 2.Compound 1h and compound In acid condition, heating, the intermediate reacted heats reaction in diphenyl ether, obtains compound 1i 1e.Compound 1i It reacts to obtain compound 1j with compound 1g heating.Compound 1j obtains compound 1k by reduction reaction.Compound 1k is in alkali It is reacted under the conditions of property with compound 1b, obtains compound I-2.
Synthetic schemes 3
Formula (I-3) compound represented can be synthesized by method disclosed in synthetic schemes 3.Compound 1k and compound 1m reaction, obtains compound I-3.
Synthetic schemes 4
Formula (I-4) compound represented can be synthesized by method disclosed in synthetic schemes 4.Compound 1i and compound 1o reacts under alkaline condition, obtains compound 1p.Compound 1p obtains compound 1q by reduction reaction.Compound 1q and change Object 1m reaction is closed, compound I-4 is obtained.
Synthetic schemes 5
Formula (I-5) compound represented can be synthesized by method disclosed in synthetic schemes 5.Compound 1s is in alkaline item It is reacted under part with compound 1t, obtains compound 1u.Compound 1u obtains compound 1v by reduction reaction.Compound 1v and change Close object 1e in acid condition, heating, the intermediate reacted heats reaction in diphenyl ether, obtains compound 1w.Chemical combination Object 1w reacts to obtain compound I-5 with compound 1g heating.
Synthetic schemes 6
Formula (I-5) compound represented can also be synthesized by method disclosed in synthetic schemes 6.Compound 1w and chemical combination Object 1y reacts under alkaline condition, obtains compound I-5.
Synthetic schemes 7
Formula (I-6) compound represented can be synthesized by method disclosed in synthetic schemes 7.Compound 1s is in alkaline item It is reacted under part with compound 1z, obtains compound 11a.Compound 11a obtains compound 11b by reduction reaction.Compound 11b In acid condition with compound 1e, it heats, the intermediate reacted heats reaction in diphenyl ether, obtains compound 11c. Compound 11c reacts under alkaline condition with compound 1y, obtains compound I-6.
Synthetic schemes 8
Formula (I-7) compound represented can be synthesized by method disclosed in synthetic schemes 8.Compound 11c and chemical combination Object 11e reacts under alkaline condition, obtains compound I-7.
Synthetic schemes 9
Formula (I-8) compound represented can be synthesized by method disclosed in synthetic schemes 9.Compound 11c and chemical combination Object 11g reacts under alkaline condition, obtains compound I-8.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment
In the examples below, the compounds of this invention is described in detail by taking part of compounds of the invention as an example in inventor Preparation process.
Embodiment 1:2- ethyl -3,7- dimethyl -6- (N- is to Methyl benzenesulfonyl yl acetamide base) quinolyl-4 acetic acid esters Synthesis
Step 1: the synthesis of 4- methyl-N- (2- methyl -4- nitrobenzophenone) benzsulfamide
At 0 DEG C, 2- methyl-4-nitrophenylamine (2.28g, 15.0mmol) and pyridine (2.37g, 30.0mmol) are successively added Enter into the 100mL single port bottle equipped with methylene chloride (40mL), then paratoluensulfonyl chloride (3.42g, 18.0mmol) is slowly added Into reaction system, room temperature is raised to after adding, and the reaction was continued 12 hours.After completion of the reaction plus water quenching is gone out (50mL), water phase dichloro Methane extracts (30mLx3), merges organic phase, and organic phase is dried, filtered with anhydrous sodium sulfate, and filtrate, residue warp is concentrated under reduced pressure Silica gel column chromatography separates [petrol ether/ethyl acetate (v/v)=3/1], obtains 3.50g yellow solid, yield: 76.3%.
Step 2: the synthesis of N- (4- amino-2-methyl phenyl) -4- methyl benzenesulfonamide
By 4- methyl-N- (2- methyl -4- nitrobenzophenone) benzsulfamide (3.00g, 9.8mmol), iron powder (2.74g, 49.0mmol), ethyl alcohol (40mL), water (5mL) and hydrochloric acid (0.2g, 35% aqueous solution) are added in 100mL single port bottle, and nitrogen is protected Under shield, it is heated to 90 DEG C and stirs 12 hours.After completion of the reaction, it filters, filtrate is concentrated under reduced pressure, ethyl acetate dilution is added (50mL), with saturated common salt water washing (30mLx3), organic phase anhydrous sodium sulfate is dried, filtered, and filtrate, residue is concentrated under reduced pressure [petrol ether/ethyl acetate (v/v)=3/1] is separated through silica gel column chromatography, obtains 2.35g yellow solid, yield: 87.0%.
Step 3: N- (2- ethyl -3,7- dimethyl -4- oxo -1,4- dihydroquinoline -6- base) -4- methyl benzenesulfonamide Synthesis
Under nitrogen protection, by N- (4- amino-2-methyl phenyl) -4- methyl benzenesulfonamide (2.30g, 8.3mmol), 2- first Base -3- oxopentanoic acid methyl ester (2.62g, 16.6mmol), glacial acetic acid (0.2g) and toluene (30mL) are added to water segregator In 100mL single port bottle, 120 DEG C are heated to, reflux water-dividing 18 hours, is concentrated under reduced pressure and removes toluene, obtain brown oil.It is added Diphenyl ether (15mL) is heated to 255 DEG C, stirs 30 minutes, the reaction is cooled to room temperatures, are slowly added into petroleum ether (30mL), have Solid is precipitated, and filtering, filter cake washs (v/v=10/1,10mLx3) with petrol ether/ethyl acetate solution, obtains 1.6g taupe Solid, yield: 51.6%.
Step 4: 2- ethyl -3,7- dimethyl -6- (N- is to Methyl benzenesulfonyl yl acetamide base) quinolyl-4 acetic acid esters Synthesis
By N- (2- ethyl -3,7- dimethyl -4- oxo -1,4- dihydroquinoline -6- base) -4- methyl benzenesulfonamide (0.20g, 0.54mmol) is dissolved in acetic anhydride (10mL), under nitrogen protection, is heated to 120 DEG C and is reacted 12 hours.It depressurizes dense Contracting removes acetic anhydride, is added ethyl acetate (20mL), and with saturated common salt water washing (10mLx3), organic phase is dry with anhydrous sodium sulfate Dry, filtrate is concentrated under reduced pressure in filtering, and residue separates [petrol ether/ethyl acetate (v/v)=4/1] through silica gel column chromatography, obtains 143mg white solid, yield: 58.4%.
MS(ES-API,pos.ion)m/z:455.2[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.01-7.96 (m, 3H), 7.39 (d, J=8.0Hz, 2H), 7.28 (s, 1H), 3.06 (q, J=7.6Hz, 2H), 2.78 (s, 3H), 2.49 (s, 6H), 2.30 (s, 3H), 2.29 (s, 3H), 1.41 (t, J =7.6Hz, 3H)
The mesh in table 1 is obtained using the phenylsulfonylchloride accordingly replaced as raw material by the similar synthetic method of embodiment 1 Mark compound.
Table 1
Embodiment 12:2- (difluoromethyl) -7- methyl -6- (1- methyl-1 H- pyrazoles -4- sulfoamido) quinolyl-4 second The synthesis of acid esters
Step 1: the synthesis of -4 (1H) -one of 2- (difluoromethyl) -7- methyl -6- nitroquinoline
Under nitrogen protection, by 3- methyl-4-nitrophenylamine (4.56g, 30.0mmol), 4,4- bis- fluoro- 3- ketobutyric acid second Ester (9.96g, 60.0mmol), glacial acetic acid (0.2g) and toluene (40mL) are added in the 100mL single port bottle with water segregator, are added Heat is concentrated under reduced pressure to 120 DEG C, reflux water-dividing 18 hours and removes toluene, obtain brown oil.It is added diphenyl ether (15mL), adds Heat stirs 30 minutes to 255 DEG C, and the reaction is cooled to room temperatures, are slowly added into petroleum ether (30mL), there is solid precipitation, filters, filter Cake washs (v/v=10/1,10mLx3) with petrol ether/ethyl acetate solution, obtains 5.60g beige solid, yield: 73.4%.
Step 2: the synthesis of 2- (difluoromethyl) -7- methyl -6- nitroquinoline -4- yl acetate
- 4 (1H) -one (5.50g, 21.7mmol) of 2- (difluoromethyl) -7- methyl -6- nitroquinoline is dissolved in acetic anhydride In (30mL), under nitrogen protection, be heated to 120 DEG C and react 12 hours.It is concentrated under reduced pressure and removes acetic anhydride, ethyl acetate is added (20mL), with saturated common salt water washing (15mLx3), organic phase is dried, filtered with anhydrous sodium sulfate, and filtrate, residual is concentrated under reduced pressure Object separates [petrol ether/ethyl acetate (v/v)=4/1] through silica gel column chromatography, obtains 4.40g yellow solid, yield: 68.5%.
Step 3: the synthesis of 6- amino -2- (difluoromethyl) -7- methylquinoline -4- yl acetate
By 2- (difluoromethyl) -7- methyl -6- nitroquinoline -4- yl acetate (4.00g, 13.5mmol), iron powder (3.78g, 67.5mmol), ethyl alcohol (45mL), water (5mL) and hydrochloric acid (0.2g, 35% aqueous solution) are added to 100mL single port bottle In, under nitrogen protection, it is heated to 90 DEG C and stirs 12 hours.After completion of the reaction, it filters, filtrate is concentrated under reduced pressure, ethyl acetate is added It dilutes (50mL), with saturated common salt water washing (30mLx3), organic phase anhydrous sodium sulfate is dried, filtered, and filtrate is concentrated under reduced pressure, residual It stays object to separate [petrol ether/ethyl acetate (v/v)=3/1] through silica gel column chromatography, obtains 3.38g yellow solid, yield: 94.2%.
Step 4: 2- (difluoromethyl) -7- methyl -6- (1- methyl-1 H- pyrazoles -4- sulfoamido) quinolyl-4 acetic acid The synthesis of ester
At 0 DEG C, by 6- amino -2- (difluoromethyl) -7- methylquinoline -4- yl acetate (0.21g, 0.8mmol) and pyrrole Pyridine (10mL) is added sequentially in 50mL single port bottle, then 1- methylpyrazole -4- sulfonic acid chloride (0.22g, 1.2mmol) is added slowly to In reaction system, room temperature is raised to after adding, and the reaction was continued 12 hours.Ethyl acetate (30mL) is added after completion of the reaction, is washed with water (20mLx3), organic phase is dried, filtered with anhydrous sodium sulfate, and filtrate is concentrated under reduced pressure, and residue separates [petroleum through silica gel column chromatography Ether/ethyl acetate (v/v)=3/1], 162mg yellow solid is obtained, yield: 49.4%.
MS(ES-API,pos.ion)m/z:411.0[M+1]+；
1H NMR(400MHz,CDCl3)δ(ppm):9.92(s,1H),8.66(s,1H),8.01-7.95(m,2H),7.45 (s, 1H), 7.13 (t, J=54.6Hz, 1H), 3.88 (s, 3H), 2.61 (s, 3H), 2.21 (s, 3H).
Intermediate 6- amino -2- (difluoromethyl) -7- methylquinoline -4- yl acetate that 12 third step of embodiment obtains with Compound B reaction, obtains the target compound in table 2.
Table 2
Embodiment 19:(E) -2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methyl-N- (4- (trifluoromethyl) benzene Methylene) quinoline -6- amino synthesis
Step 1: the synthesis of 2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methyl -6- nitroquinoline
By 2- (difluoromethyl) -7- methyl -6- nitroquinoline -4 (1H) -one (5.00g, 19.7mmol, embodiment 12 first The intermediate of step reaction synthesis), potassium carbonate (5.44g, 39.4mmol) and n,N-Dimethylformamide (40mL) are added to 100mL In single port bottle, it is slowly dropped in reaction system by 4- fluorine bromobenzyl (4.46g, 23.6mmol), reacts 12 at room temperature Hour.It is added water (50mL), (30mLx3) is extracted with ethyl acetate, organic phase is dried, filtered with anhydrous sodium sulfate, is concentrated under reduced pressure Filtrate, residue separate [petrol ether/ethyl acetate (v/v)=4/1] through silica gel column chromatography, obtain 4.10g yellow solid, receive Rate: 62.7%.
Step 2: the synthesis of 2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methylquinoline -6- amino
By 2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methyl -6- nitroquinoline (4.00g, 11.0mmol), Iron powder (3.08g, 55.0mmol), ethyl alcohol (45mL), water (5mL) and hydrochloric acid (0.2g, 35% aqueous solution) are added to 100mL single port In bottle, under nitrogen protection, it is heated to 90 DEG C and stirs 12 hours.After completion of the reaction, it filters, filtrate is concentrated under reduced pressure, acetic acid second is added Ester dilutes (50mL), and with saturated common salt water washing (30mLx3), organic phase anhydrous sodium sulfate is dried, filtered, and filtrate is concentrated under reduced pressure, Residue separates [petrol ether/ethyl acetate (v/v)=3/1] through silica gel column chromatography, obtains 3.20g yellow solid, yield: 87.7%.
Step 3: (4- (trifluoromethyl) benzene is sub- by (E) -2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methyl-N- Methyl) quinoline -6- amino synthesis
By 2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methylquinoline -6- amino (0.23g, 0.7mmol), 4- Trifluoromethylated benzaldehyde (0.19g, 1.1mmol) and ethyl alcohol (10mL) are added sequentially to 50mL single port bottle, at room temperature instead It answers 12 hours.After completion of the reaction, it is concentrated under reduced pressure and removes ethyl alcohol, residue separates [petrol ether/ethyl acetate through silica gel column chromatography (v/v)=10/1 0.23g white solid], is obtained, yield: 67.6%.MS(ES-API,pos.ion)m/z:489.2[M+1]+；
1H NMR(400MHz,CDCl3): δ (ppm) 8.48 (s, 1H), 8.07 (d, J=8.0Hz, 2H), 7.92 (s, 1H), 7.75 (d, J=8.0Hz, 2H), 7.61 (s, 1H), 7.51-7.47 (m, 2H), 7.15-7.10 (m, 3H), 6.72 (t, J= 55.5Hz,1H),5.30(s,2H),2.53(s,3H)。
Embodiment 20:(E)-N- benzylidene -2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methylquinoline -6- The synthesis of amino
By 2- (difluoromethyl) -4- ((4- luorobenzyl) oxygroup) -7- methylquinoline -6- amino, (0.23g, 0.7mom are implemented The intermediate of 19 second step of example reaction synthesis), it is mono- that benzaldehyde (0.12g, 1.1mom) and ethyl alcohol (10mL) are added sequentially to 50mL Mouth bottle, reacts 12 hours at room temperature.After completion of the reaction, it is concentrated under reduced pressure and removes ethyl alcohol, residue is through silica gel column chromatography point From [petrol ether/ethyl acetate (v/v)=10/1], 0.17g white solid is obtained, yield: 58.6%.
MS(ES-API,pos.ion)m/z:421.2[M+1]+；
1H NMR(400MHz,CDCl3):δ(ppm)8.45(s,1H),7.99-7.97(m,2H),7.93(s,1H),7.61 (s, 1H), 7.54-7.47 (m, 5H), 7.17-7.13 (m, 2H), 7.11 (s, 1H), 6.74 (t, J=55.6Hz, 1H), 5.32 (s,2H),2.55(s,3H)。
Embodiment 21:2- ethyl -3,7- dimethyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinolyl-4 acetic acid esters Synthesis
Step 1: the synthesis of 2- methyl -4- nitro -1- ((4- (trifluoromethyl) benzyl) oxygroup) benzene
By 2- methyl -4- nitrophenol (7.66g, 50mom), potassium carbonate (13.8g, 100mom), dry N, N- diformazan Base formamide (70mL) is added in 250mL single port bottle, after being stirred at room temperature 30 minutes, dropwise addition 4- trifluoromethyl benzyl bromine (14.34g, N,N-Dimethylformamide solution (30mL) 60mom) is warming up to 60 DEG C and reacts 10 hours after being added dropwise.After completion of the reaction Reaction mixture is cooled to room temperature and is poured into ice water (300mL) and is vigorously stirred 30 minutes, there is solid precipitation, is filtered, filter cake It is washed with water (100mLx3), it is dry, 14.94g yellow solid is obtained, yield: 96%.
Step 2: the synthesis of 3- methyl -4- ((4- (trifluoromethyl) benzyl) oxygroup) aniline
By 2- methyl -4- nitro -1- ((4- (trifluoromethyl) benzyl) oxygroup) benzene (3.11g, 10mom), ammonium chloride (642mg, 12mom), ethyl alcohol (45mL) and water (5mL) are added in 100mL single port bottle, are heated to flowing back, are slowly added to iron powder (2.24g, 40mom) continues back flow reaction 5 hours.After completion of the reaction, iron filings are filtered to remove, filtrate is concentrated under reduced pressure, acetic acid is added Ethyl ester dilutes (100mL), and with saturated common salt water washing (30mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, is concentrated under reduced pressure Filtrate, residue separate [petrol ether/ethyl acetate (v/v)=5/1] through silica gel column chromatography, obtain 2.05g yellow solid, receive Rate: 73%.
Step 3: the conjunction of 2- ethyl -3,7- dimethyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinoline -4 (1H) -one At
By 3- methyl -4- ((4- (trifluoromethyl) benzyl) oxygroup) aniline (1.4g, 5mom), 2- methyl -3- oxopentanoic acid Ethyl ester (949mg, 6mom), glacial acetic acid (0.5mL) and dry toluene (20mL) are added to the 100mL single port bottle with water segregator In, 120 DEG C are heated to, reflux water-dividing 18 hours, is concentrated under reduced pressure and removes toluene, obtain brown oil.Diphenyl ether is added (5mL) is heated to 260 DEG C, stirs 30 minutes, the reaction is cooled to room temperatures, are slowly added into petroleum ether (30mL), there is solid analysis Out, it filtering, filter cake washs (v/v=10/1,10mLx3) with petrol ether/ethyl acetate solution, obtains 1.02g light yellow solid, Yield: 54.3%.
Step 4: 2- ethyl -3,7- dimethyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinolyl-4 acetic acid esters Synthesis
By 2- ethyl -3,7- dimethyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinoline -4 (1H) -one (230mg, It 0.61mom) is dissolved in acetic anhydride (10mL), under nitrogen protection, is heated to 130 DEG C and reacts 12 hours.It is concentrated under reduced pressure and removes second Acid anhydrides is added ethyl acetate (20mL), and saturated common salt water washing (10mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, is subtracted Pressure concentration filtrate, residue separate [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, it is solid to obtain 160mg white Body, yield: 63%.
MS(ES-API,pos.ion)m/z:418.10[M+1]+；
1H NMR(400MHz,DMSO-d6)δ(ppm):7.77(m,5H),7.06(s,1H),5.40(s,2H),2.92(q,J =7.2Hz, 2H), 2.51 (s, 3H), 2.41 (s, 3H), 2.19 (s, 3H), 1.28 (t, J=7.2Hz, 3H)；
13C NMR(100MHz,DMSO-d6)δ(ppm):169.70,160.28,158.29,152.41,143.98, 142.27,132.04,131.70,129.08,128.31,126.09,125.55,123.06,120.40,100.75,71.56, 27.27,20.91,15.37,10.53,10.34。
The target compound of table 3 is obtained using corresponding raw material by the similar synthetic method of embodiment 21.
Table 3
Embodiment 33:2- (difluoromethyl) -7- methyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinolyl-4 acetic acid The synthesis of ester
Step 1: 2- (difluoromethyl) -7- methyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinoline -4 (1H) -one Synthesis
By 3- methyl -4- ((4- (trifluoromethyl) benzyl) oxygroup) aniline (1.4g, 5mmol, the reaction of 21 second step of embodiment Obtained intermediate), 4,4- difluoro ethyl acetoacetate (997mg, 6mmol), glacial acetic acid (0.5mL) and dry toluene (20mL) It is added in the 100mL single port bottle with water segregator, is heated to 120 DEG C, reflux water-dividing 18 hours, is concentrated under reduced pressure and removes toluene, Obtain brown oil.Be added diphenyl ether (5mL), be heated to 260 DEG C, stir 30 minutes, the reaction is cooled to room temperatures, slowly plus Enter petroleum ether (30mL), there is solid precipitation, filter, filter cake washed with petrol ether/ethyl acetate solution (v/v=10/1, 10mLx3), 800mg sepia solid, yield: 41.7% are obtained.
Step 2: 2- (difluoromethyl) -7- methyl -6- (4- (trifluoromethyl) benzyl) oxygroup) quinolyl-4 acetic acid esters Synthesis
By 2- (difluoromethyl) -7- methyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinoline -4 (1H) -one (420mg, It 1.1mmol) is dissolved in acetic anhydride (10mL), under nitrogen protection, is heated to 130 DEG C and reacts 12 hours.Vacuum distillation removes second Acid anhydrides is added ethyl acetate (20mL), and saturated common salt water washing (10mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, is subtracted Pressure concentration filtrate, residue separate [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, it is solid to obtain 170mg white Body, yield: 36.5%.
MS(ES-API,pos.ion)m/z:426.10[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 7.95 (s, 1H), 7.70 (d, J=8.4Hz, 2H), 7.62 (d, J= 8.4Hz, 2H), 7.54 (s, 1H), 7.12 (s, 1H), 6.74 (t, J=55.2Hz, 1H), 5.28 (s, 2H), 2.50 (s, 3H), 2.47(s,3H)；
13C NMR(100MHz,CDCl3)δ(ppm):169.70,160.28,158.29,152.41,143.98,142.27, 132.04,131.70,129.08,128.31,126.09,125.55,123.06,120.40,100.75,71.56,27.27, 20.91,15.37,10.53,10.34。
By the similar synthetic method of embodiment 33, using the benzyl bromine accordingly replaced as raw material, the target chemical combination of table 4 is obtained Object.
Table 4
Embodiment 37:2- (difluoromethyl) -7- methyl -6- ((4- trifluoromethyl) benzyl) oxygroup) quinolyl-4 benzoic acid The synthesis of ester
By 2- (difluoromethyl) -7- methyl -6- ((4- (trifluoromethyl) benzyl) oxygroup) quinoline -4 (1H) -one (190mg, 0.5mmol, the intermediate that 33 first step of embodiment is reacted) it is dissolved in anhydrous methylene chloride (20mL), it is added under ice bath Triethylamine (101mg, 1mmol) and catalytic amount 4-dimethylaminopyridine stir after ten minutes, dropwise addition chlorobenzoyl chloride (85mg, Dichloromethane solution (20mL) 0.6mmol) reacts 10 hours after dripping off in lower 25 DEG C of nitrogen protection.(20mL) is quenched with water, Water (20mLx1) and saturated common salt water washing (10mLx3) are successively used, organic phase is dried, filtered with anhydrous magnesium sulfate, is concentrated under reduced pressure Filtrate, residue separate [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, obtain 110mg white solid, receive Rate: 45.3%.
MS(ES-API,pos.ion)m/z:488.10[M+1]+；
1H NMR(400MHz,DMSO-d6) δ (ppm): 8.23 (d, J=7.2Hz, 2H), 8.04 (s, 1H), 7.86 (t, J= 7.2Hz, 1H), 7.80 (s, 1H), 7.71 (t, J=8.0Hz, 2H), 7.65 (s, 4H), 7.32 (s, 1H), 7.10 (t, J= 55.2Hz,1H),5.44(s,2H),2.49(s,3H)；
13C NMR(100MHz,CDCl3)δ(ppm):169.70,160.28,158.29,152.41,143.98,142.27, 132.04,131.70,129.08,128.31,126.09,125.55,123.06,120.40,100.75,71.56,27.27, 20.91,15.37,10.53,10.34。
Target compound embodiment 38 is obtained using corresponding raw material by the similar synthetic method of embodiment 37:
Embodiment 38:2- (difluoromethyl) -7- methyl -6- (naphthalene -2- ylmethoxy) quinolyl-4 benzoic ether
MS(ES-API,pos.ion)m/z:471.10[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.25 (d, J=7.2Hz, 2H), 7.98 (s, 1H), 7.83 (t, J= 8.4Hz, 3H), 7.75 (dd, J=14.4,7.2Hz, 2H), 7.63-7.55 (m, 3H), 7.49 (dd, J=8.4,4.8Hz, 3H), 7.25 (s, 1H), 6.77 (t, J=55.6Hz, 2H), 5.33 (s, 2H), 2.53 (s, 3H)；
13C NMR(100MHz,CDCl3)δ(ppm):170.13,158.07,157.34,155.37,147.75,139.39, 134.46,133.66,133.02,131.42,129.50,128.87,127.77,127.57,126.71,126.17,124.65, 112.00,106.33,101.64,71.69,20.91,15.37。
Embodiment 39:4- acetoxyl group -2- ethyl -3,7- dimethyl quinoline -6- base 4- fluorobenzoate
Step 1: 2- methyl -4- nitrobenzophenone 4- fluorobenzoate
2- methyl -4- nitrophenol (1.53g, 10mmol) is dissolved in anhydrous methylene chloride (50mL), is added three at 0 DEG C Ethamine (2.02g, 20mmol) and catalytic amount 4-dimethylaminopyridine stir after twenty minutes, dropwise addition 4- fluorobenzoyl chloride (1.9g, 12mmol), after being added dropwise, reaction 12 hours is stirred at room temperature.After the reaction was completed, reaction (20mL) is quenched with water, uses according to this Water (20mLx1) and saturated common salt water washing (30mLx2), organic phase is dried, filtered with anhydrous magnesium sulfate, and filtrate is concentrated under reduced pressure, 2.55g yellow solid is obtained, yield: 92.7%.
Step 2: 4- amino-2-methyl phenyl 4- fluorobenzoate
By 2- methyl -4- nitrobenzophenone 4- fluorobenzoate (2.7g, 10mmol), ammonium chloride (648mg, 12mmol), second Alcohol (45mL) and water (5mL) are added in 100mL single port bottle, are heated to flowing back, and are slowly added to iron powder (2.24g, 40mmol), after Continuous back flow reaction 5 hours.After completion of the reaction, it is filtered to remove iron filings, filtrate is concentrated under reduced pressure, be added ethyl acetate (100mL), with full With brine It (30mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, filtrate is concentrated under reduced pressure, residue is through silicagel column Chromatography [petrol ether/ethyl acetate (v/v)=5/1], obtains 2.03g light yellow solid, yield: 84.6%.
Step 3: the synthesis of 2- ethyl -3,7- dimethyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate
By 4- amino-2-methyl phenyl 4- fluorobenzoate (1.03g, 4.2mmol), 2- methyl -3- oxopentanoic acid methyl ester (864mg, 5.46mmol), glacial acetic acid (0.5mL) and dry toluene (20mL) are added to the 100mL single port bottle with water segregator In, it is heated to 120 DEG C, reflux water-dividing 18 hours.It is concentrated under reduced pressure and removes toluene, obtain brown oil.Diphenyl ether is added (5mL) is heated to 260 DEG C, stirs 30 minutes, the reaction is cooled to room temperatures, are slowly added into petroleum ether (30mL), there is solid analysis Out, it filters, filter cake washs (v/v=10/1,10mLx3) with petrol ether/ethyl acetate solution, obtains 750mg gray solid, receives Rate: 52.8%.
Step 4: the synthesis of 4- acetoxyl group -2- ethyl -3,7- dimethyl quinoline -6- base 4- fluorobenzoate
By 2- ethyl -3,7- dimethyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate (200mg, It 0.59mmol) is dissolved in anhydrous methylene chloride (20mL), triethylamine (119mg, 1.18mmol) and catalytic amount is added under ice bath After ten minutes, the dichloromethane solution (10mL) of chloroacetic chloride (56mg, 0.71mmol), drop is added dropwise in 4-dimethylaminopyridine, stirring It is reacted 10 hours after complete in lower 25 DEG C of nitrogen protection.Reaction (10mL) is quenched with water, successively uses water (20mLx1) and saturated common salt Water washing (10mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, filtrate is concentrated under reduced pressure, residue is through silica gel column chromatography point From [petrol ether/ethyl acetate (v/v)=10/1], 90mg white solid is obtained, yield: 40%.MS(ES-API,pos.ion) m/z:383.10[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.28 (dd, J=7.6,5.6Hz, 2H), 7.98-7.94 (m, 1H), 7.48-7.37 (m, 1H), 7.24-7.18 (m, 2H), 3.02 (q, J=7.6Hz, 2H), 2.58 (s, 3H), 2.42 (s, 3H), 2.25 (s, 3H), 1.38 (t, J=7.6Hz, 3H)；
13C NMR(100MHz,CDCl3)δ(ppm):169.70,162.65,160.28,159.28,158.29,146.39, 143.98,137.24,133.05,126.14,125.55,125.12,122.49,116.53,109.41,27.27,20.91, 15.37,10.53,10.34。
Embodiment 40:2- ethyl -4- ((methoxycarbonyl) oxygroup) -3,7- dimethyl quinoline -6- base 4- fluorobenzoate
By 2- ethyl -3,7- dimethyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate (115mg, 0.34mmol, the intermediate that 39 third step of embodiment is reacted) it is dissolved in anhydrous tetrahydro furan (20mL), it is added under ice bath After ten minutes, the dichloromethane of methylchloroformate (39mg, 0.41mmol) is added dropwise in 60% sodium hydride (20mg, 0.51mmol), stirring Alkane solution (20mL) reacts 10 hours after dripping off in lower 25 DEG C of nitrogen protection.Reaction (20mL) is quenched with water, is extracted with ethyl acetate (20mL) is taken, successively uses water (20mLx1) and saturated common salt water washing (10mLx3), organic phase is dry with anhydrous magnesium sulfate, mistake Filter, is concentrated under reduced pressure filtrate, and residue separates [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, it is white to obtain 55mg Color solid, yield: 40.7%.
MS(ES-API,pos.ion)m/z:399.10[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.28 (dd, J=8.8,5.6Hz, 2H), 7.96 (d, J=9.2Hz, 1H), 7.41 (d, J=9.2Hz, 1H), 7.22 (t, J=8.4Hz, 2H), 3.95 (s, 3H), 3.02 (q, J=7.6Hz, 2H), 2.57 (s, 3H), 2.32 (s, 3H), 1.38 (t, J=7.6Hz, 3H).
The synthesis of embodiment 41:4- acetoxyl group -2- (difluoromethyl) -7- methylquinoline -6- base 4- fluorobenzoate
Step 1: the synthesis of 2- (difluoromethyl) -7- methyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate
By 4- amino-2-methyl phenyl 4- fluorobenzoate, (1g, 4.08mmol, 39 second step of embodiment react Intermediate), 4,4- difluoro ethyl acetoacetate (813mg, 4.90mmol), glacial acetic acid (0.5mL) and dry toluene (20mL) plus Enter into the 100mL single port bottle with water segregator, is heated to 120 DEG C, reflux water-dividing 18 hours.It is concentrated under reduced pressure and removes toluene, obtain To brown oil.It is added diphenyl ether (5mL), is heated to 260 DEG C, stir 30 minutes, the reaction is cooled to room temperatures, are slowly added into Petroleum ether (30mL) has solid precipitation, and filtering, filter cake washs (v/v=10/1,10mLx3) with petrol ether/ethyl acetate solution, 680mg brown solid is obtained, yield: 48.2%.
Step 2: the synthesis of 4- acetoxyl group -2- (difluoromethyl) -7- methylquinoline -6- base 4- fluorobenzoate
By 2- (difluoromethyl) -4- hydroxyl -7- methyl-1,4- dihydroquinoline -6- base 4- fluorobenzoate (208mg, It 0.6mmol) is dissolved in methylene chloride (20mL), triethylamine (121mg, 1.2mmol) and catalytic amount 4- diformazan is added under ice bath Aminopyridine, stirring after ten minutes, be added dropwise chloroacetic chloride (57mg, 0.72mmol) dichloromethane solution (10mL), after dripping off in Lower 25 DEG C of nitrogen protection are reacted 10 hours.Reaction (10mL) is quenched with water, successively uses water (20mLx1) and saturated common salt water washing (10mLx3), organic phase is dried, filtered with anhydrous magnesium sulfate, and filtrate is concentrated under reduced pressure, and residue separates [petroleum through silica gel column chromatography Ether/ethyl acetate (v/v)=10/1], 50mg white solid is obtained, yield: 21.5%.MS(ES-API,pos.ion)m/z: 391.10[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.28 (d, J=5.2Hz, 2H), 8.12-8.05 (m, 2H), 7.62- 7.53(m,1H),7.50(s,1H),7.22(s,1H),6.61-6.90(m,2H),2.66(s,3H),2.45(s,3H)。
The synthesis of embodiment 42:2- (difluoromethyl) -7- methylquinoline -4,6- diyl bis- (4- fluorobenzoates)
By 2- (difluoromethyl) -7- methyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate (174mg, 0.5mmol, the intermediate that 41 first step of embodiment is reacted) it is dissolved in methylene chloride (20mL), three second are added under ice bath Amine (101mg, 1mmol) and catalytic amount 4-dimethylaminopyridine stir after ten minutes, dropwise addition 4- fluorobenzoyl chloride (95mg, Dichloromethane solution (10mL) 0.6mmol) reacts 10 hours after dripping off in lower 25 DEG C of nitrogen protection.Reaction is quenched with water (10mL) successively uses water (20mLx1) and saturated common salt water washing (10mLx3), and organic phase is dried, filtered with anhydrous magnesium sulfate, Filtrate is concentrated under reduced pressure, residue separates [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, obtains 55mg white Solid, yield: 23.4%)
MS(ES-API,pos.ion)m/z:471.10[M+1]+；
1H NMR(400MHz,CDCl3)δ(ppm):8.35-8.20(m,4H),7.80(s,1H),7.73(s,1H),7.56 (s,1H),7.25-7.16(m,4H),6.80(m,2H),2.59(s,3H)。
Embodiment 43:2- (difluoromethyl) -4- ((methoxycarbonyl) oxygroup) -7- methylquinoline -6- base 4- fluobenzoic acid The synthesis of ester
By 2- (difluoromethyl) -7- methyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate (278mg, 0.8mmol, the intermediate that 41 first step of embodiment is reacted) it is dissolved in tetrahydrofuran (20mL), 60% is added under ice bath After ten minutes, the tetrahydrofuran solution of methylchloroformate (98mg, 1.04mmol) is added dropwise in sodium hydride (48mg, 1.2mmol), stirring (10mL) reacts 10 hours after dripping off in lower 25 DEG C of nitrogen protection.Reaction (10mL) is quenched with water, is extracted with ethyl acetate (20mL), organic phase washed with water (20mLx1) and saturated common salt water washing (10mLx3), organic phase is dry with anhydrous magnesium sulfate, Filtering, is concentrated under reduced pressure filtrate, and residue separates [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, obtains 75mg White solid, yield: 18.6%.
MS(ES-API,pos.ion)m/z:406.15[M+1]+；
1H NMR(400MHz,CDCl3)δ(ppm):8.34-8.24(m,2H),8.08(s,1H),7.89(s,1H),7.63 (s, 1H), 7.23 (d, J=8.8Hz, 2H), 6.95-6.56 (m, 1H), 4.00 (s, 3H), 2.66 (s, 3H)；
13C NMR(100MHz,CDCl3)δ(ppm):175.77,166.66,165.26,157.23,155.66,154.67, 150.00,149.36,135.20,132.99,128.15,126.25,116.53,112.00,110.50,101.88,52.97, 15.37。
Embodiment 44:2- (difluoromethyl) -4- ((N, N- dimethylaminosulfonyl) oxygroup) -7- methylquinoline -6- base 4- The synthesis of fluorobenzoate
By 2- (difluoromethyl) -7- methyl -4- oxo -1,4- dihydroquinoline -6- base 4- fluorobenzoate (278mg, 0.8mmol, the intermediate that 41 first step of embodiment is reacted) it is dissolved in methylene chloride (20mL), three second are added under ice bath After ten minutes, dimethylsufamoyl chloride is added dropwise in the 4-dimethylaminopyridine of amine (162mg, 1.6mmol) and catalytic amount, stirring The dichloromethane solution (20mL) of (138mg, 0.96mmol) reacts 10 hours after dripping off in lower 25 DEG C of nitrogen protection.Use water quenching Go out reaction (20mL), organic phase washed with water (20mLx1) and saturated common salt water washing (10mLx3), organic phase anhydrous slufuric acid Magnesium dries, filters, and filtrate is concentrated under reduced pressure, and residue separates [petrol ether/ethyl acetate (v/v)=10/1] through silica gel column chromatography, 90mg white solid is obtained, yield: 24.8%.
MS(ES-API,pos.ion)m/z:455.20[M+1]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.29 (dd, J=8.8,5.6Hz, 2H), 8.08 (s, 1H), 7.96 (s, 1H), 7.76 (s, 1H), 7.24 (d, J=8.8Hz, 2H), 6.76 (t, J=55.2Hz, 1H), 3.11 (s, 6H), 2.48 (s, 3H)。
Active testing
In following tests example, inventor has detected the compounds of this invention to having by taking part of compounds of the invention as an example The effect of evil fungi, pest.
Effect of the test example 1 to harmful fungoid
The method for preparing solution: it is spare that compound with DMF is dissolved into 1%EC.Using living body pot-culture method, evaluates compound and exist To experiment target target bactericidal activity under 200mg/L dosage.
Botrytis cinerea pers (Botrytis cinerea)
Using blade bacterination process.The consistent potting cucumber seedling of two leaf period growing ways is selected to connect bacterium after reagent spray dries Cake is on blade.24~26 DEG C after half-light moisturizing 24 hours, are restored natural lighting moisturizing culture about 3 days.Wait compare abundant morbidity Each vaccination lesion diameter is measured with slide calliper rule afterwards, calculates preventive effect.
Test result: embodiment 1, embodiment 2, embodiment 3, embodiment 9 and embodiment 33 are at 200mg/L to cucumber ash Inhibiting rate >=50% of mildew bacterium；Under same dose, tebufloquin is 5.33% to the inhibiting rate of botrytis cinerea pers, Flometoquin is to botrytis cinerea pers unrestraint activity.
2 insecticidal activity assay of test example
The method for preparing solution: weighing the raw medicine of certain mass with assay balance (0.0001g), with containing 1% Tween-80 cream The DMF dissolution of agent is configured to 1% mother liquor, is then diluted with distilled water spare.
Test method:
Leaf dipping method: being mythimna separata for examination target, i.e., naturally negative after sufficiently infiltrating appropriate maize leaf in the medical fluid prepared It is dry, it is put into the culture dish for being lined with filter paper, connects mythimna separata 3 age mid-term larva, 10/ware, be placed in 24~27 DEG C of observation ward and cultivate, 3 Investigation result after it.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Experimental concentration 500mg/L.
Test result: embodiment 1, embodiment 10, embodiment 11, embodiment 12, embodiment 13, embodiment 17, embodiment 21, embodiment 23, embodiment 26, embodiment 27, embodiment 28, embodiment 30, embodiment 31, embodiment 32,37 and of embodiment Embodiment 39 is suitable with flometoquin to the lethality of mythimna separata at 500mg/L, is 100%；Under same dose, Tebufloquin is 80% to the lethality of mythimna separata.

Claims (6)

1. a kind of compound is the salt of the compound as shown in formula (I) compound represented or formula (I):
Wherein:
R1For-COR6；Wherein, R6For C1-4Alkyl；
R2For hydrogen or C1-4Alkyl；
R3For C1-4Alkyl or halogenated C1-4Alkyl；
R4aFor hydrogen；
R4bFor hydrogen or C1-4Alkyl；
R4cFor hydrogen or C1-4Alkyl；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen；
L1For-NR9-；
L2For-SO2-；
Wherein, R9For hydrogen or C1-4Alkyl-carbonyl；
R5For C6-10Aryl, 5-10 unit's heteroaryl or C3-8Naphthenic base；R5Optionally A is selected from by 1,2 or 34Substituent group replace；
Wherein, A4It is each independently halogen, cyano, nitro, oxo (=O), C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, Halogenated C1-4Alkoxy or C2-6Alkenyl.
2. compound according to claim 1, wherein
R1For following subformula:
R2For hydrogen or-CH3；
R3For-CH3、-CH2CH3Or-CHF2；
R4aFor hydrogen；
R4bFor hydrogen or-CH3；
R4cFor hydrogen or-CH3；
Condition are as follows: R4a、R4bAnd R4cIt is not simultaneously hydrogen.
3. compound according to claim 1, wherein
L1For-NH-；
Or L1For following subformula:
L2For-SO2-；
R5For following subformula:
4. a kind of compound, the compound with one of following structure or the alloisomerism with one of following structural compounds Body, nitrogen oxides and salt:
5. a kind of composition is further included and is subjected in Pesticide Science comprising compound described in claim 1-4 any one Surfactant and carrier.
6. application of the composition in agricultural described in compound described in claim 1-4 any one or claim 5.
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CN1259124A (en) * 1997-06-02 2000-07-05 罗纳-普朗克油化农业株式会社 4-quinolinol derivatives and agrohorticultural bactericides containing the same as active ingredient
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WO2007088978A1 (en) * 2006-02-03 2007-08-09 Meiji Seika Kaisha, Ltd. Novel quinoline derivative and pesticide for agricultural and horticultural applications comprising the derivative as active ingredient
CN103214461A (en) * 2013-04-22 2013-07-24 山东省联合农药工业有限公司 Quinoline derivative and application thereof

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CN1259124A (en) * 1997-06-02 2000-07-05 罗纳-普朗克油化农业株式会社 4-quinolinol derivatives and agrohorticultural bactericides containing the same as active ingredient
WO2002026713A1 (en) * 2000-09-29 2002-04-04 King's College London Antiparasitic compounds
CN1993328A (en) * 2004-08-04 2007-07-04 明治制果株式会社 Quinoline derivative and insecticide containing same as active constituent
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