CN104277033B - N (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss and preparation method and application - Google Patents
N (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss and preparation method and application Download PDFInfo
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- 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
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- 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
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
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- C07—ORGANIC CHEMISTRY
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—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
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- 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
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- 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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Abstract
The invention discloses formula（I）Shown N (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss and preparation method and application.Ar in formula1And Ar2、R1、R2、R3, n there is given in description definition.Formula（I）Compound has weeding and/or sterilization, parasite killing, mite killing biological activity, and some compounds have very high activity of weeding, are obtained with good effect under 15～75 grams of effective ingredient/hectare consumption.
Description
Technical field
The present invention relates to having N- (aryl alkyl) the virtue phenoxy carboxylic acyloxy amine of weeding, sterilization, insecticidal bioactivity
Compound and preparation method thereof and control injurious weed, harmful levels of pathogens, the purposes of insect and method with these compounds.
Background technology
Fragrant phenoxy carboxylic acid compound has the activity preventing and kill off grassy weed, and has such reactive compound quilt multiple
Successfully develop as herbicide, as formula（P-1）Shown clodinafop-propargyl（clodinafop-propargyl US4505743）It is Switzerland
The using dosage of Xian Zhengda crop protection company limited exploitation is 40～60 grams of effective ingredient/hectares, for some kind Semen Tritici aestivis
The aryloxyphenoxypropanoates class herbicide of field keeping from ill grassy weed；And formula（P-2）Shown cyhalofop-butyl
(cyhalofop-butyl EP0302203) be by The Dow Agrosciences, LLC. in Development and Production in 1987 using dosage be 50
The special phenoxy phenoxy propionic acid ester herbicide of the rice terrace of～100 grams of effective ingredient/hectares；Formula（P-3）Shown azoles acyl
Careless amine (Metamifop WO200005956A1) is then the using dosage by Korea S Chemical Engineering Technology academy exploitation is 90～120
Another special aryloxyphenoxypropanoates class herbicide of rice terrace of gram effective ingredient/hectare, other virtue phenoxy carboxylic acidss remove
Careless agent substantially cannot be directly used to gramineous crop field controlling weeds in the case of without safener.
Fragrant phenoxy carboxylic acidss herbicide is active to grassy weed, and have also has very excellent activity, no
Foot is these herbicides to gramineous crop（As Semen Tritici aestivi, Oryza sativa L. etc.）Mostly dangerous.As（P-1）Although shown clodinafop-propargyl
Very high to grassy weed activity, but it is only to part wheat breed safety, all dangerous to Oryza sativa L.；Formula（P-2）Shown cyanogen
Fluorine grass ester and formula（P-3）Although shown azole amide is to rice safety, it is far below to the activity of grassy weed again
（P-1）Shown clodinafop-propargyl, and also dangerous to Semen Tritici aestivi.
For obtaining the high activity virtue phenoxy carboxylic acid compound to gramineous crop particularly Oryza sativa L., Semen Tritici aestivi safety, send out
O- chain type unsaturation azanol is introduced in fragrant phenoxy carboxylic acid structure a person of good sense, designs and synthesizes N- unsaturated chain epoxide virtue phenoxy
Carboxylic acyloxy aminated compoundss（CN201010221128.2）, and therefrom find relatively（P-1）Shown clodinafop-propargyl and（P-2）Shown
Cyhalofop-butyl and（P-3）Shown azole amide has wider array of activity profile and higher active compound such as（P-4）Deng,
And with（P-1）Shown clodinafop-propargyl is compared, and we invent（P-4）Safer to Semen Tritici aestivi, unfortunately（P-1）With（P-4）Right
Oryza sativa L. is all dangerous, thus cannot be used for the preventing and treating of paddy field weed.
For improving further（P-4）Activity of weeding and/or the safety to crop particularly Oryza sativa L., we are again by aryl
Alkyl is introduced in fragrant phenoxy carboxylic acid amide class formation, designs and synthesizes a series of compounds with broad spectrum of activity, and obtains
A collection of activity of weeding is higher than（P-2）With（P-3）Compound, and the compound having is to rice safety, thus solving（P-1）With
（P-4）Cannot be used for the deficiency of rice terrace.The compound simultaneously having also shows obvious sterilization or insecticidal activity.
Content of the invention
The invention provides formula（I）The shown N- (aryl alkyl) with biological activitys such as weeds, harmful levels of pathogens, insects
Fragrant phenoxy carboxylic acyloxy aminated compoundss and its isomer：
Wherein：
I.Ar1And Ar2It is same or different, and represent C6-C12Aryl or the heteroaryl of band up to 10 carbon atoms,
And
a）C6-C12Hydrogen moiety in aryl or the band up to heteroaryl of 10 carbon atoms or be all selected from following in
Identical or different substituent group replaces：Halogen, nitro, cyano group, amido, hydroxyl, sulfydryl, carboxyl, aldehyde radical, diazanyl, hydrazone group, C1-C6
Alkyl, C1-C6Alkyl oxy, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-
C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6
Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Ring
Alkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amido, two C3-C8Cycloalkyl amido, C6-C12Aryl or band up to 10
The heteroaryl of individual carbon atom, C6-C12The heteroaryl epoxide of aryloxy or band up to 10 carbon atoms, C6-C12Artyl sulfo or
The band up to Heteroarylthio of 10 carbon atoms, C6-C12Arylamine group or the heteroaryl amido of band up to 10 carbon atoms；
II.R1And R2, R3It is same or different, and represent hydrogen, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl group,
C3-C8Cycloalkyl, C6-C12Aryl or the heteroaryl of band up to 10 carbon atoms；
III.n represents 1 or 2,3；And
1) I.a) and II. described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, heteroaryl be unsubstituted or
I.a hydrogen moiety or be all selected from) and in alkyl described in II., cycloalkyl, alkenyl, alkynyl group, aryl, heteroaryl
Identical or different substituent group in following replaces：Halogen, C1-C6Alkyl, C1-C6Alkyl oxy, C1-C6Alkyl sulfenyl, C1-C6Alkane
Base amido, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl
Amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amine
Base, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amine
Base, two C3-C8Cycloalkyl amido, C6-C12Aryl or the band up to heteroaryl of 10 carbon atoms, C6-C12Aryloxy or band are up to
The heteroaryl epoxide of 10 carbon atoms, C6-C12Artyl sulfo or the band up to Heteroarylthio of 10 carbon atoms, C6-C12Aryl
The heteroaryl amido of amido or band up to 10 carbon atoms, two C6-C12Arylamine group or two heteroaryls of band up to 10 carbon atoms
Base amido, C6-C12Aryl or the band up to Heteroarylaryl of 10 carbon atoms, C6-C12Aryl heteroaryl or band up to 10
The heteroarylheteroaryl of individual carbon atom；And 1）Described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, hydrogen is former in heteroaryl
Subdivision or be all selected from following in identical or different substituent group replace：Hydrogen, halogen, C1-C6Alkyl, C1-C6Alkyl oxygen
Base, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-
C6Alkenyl thio, C2-C6Alkenyl amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6
Alkynyl group sulfenyl, C2-C6Alkynyl group amido, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Ring
Alkyl sulfenyl, C3-C8Cycloalkyl amido, two C3-C8Cycloalkyl amido, C6-C12Aryl or the heteroaryl of band up to 10 carbon atoms
Base, C6-C12The heteroaryl epoxide of aryloxy or band up to 10 carbon atoms, C6-C12Artyl sulfo or up to 10 carbon of band are former
The Heteroarylthio of son, C6-C12The heteroaryl amido of arylamine group or band up to 10 carbon atoms, two C6-C12Arylamine group or
The di (hetero) arylamine group of band up to 10 carbon atoms, C6-C12Aryl or band up to the Heteroarylaryl of 10 carbon atoms,
C6-C12Aryl heteroaryl or the heteroarylheteroaryl of band up to 10 carbon atoms；
Compound given above（I）Definition in, no matter term used is used alone also being used in compound word, represent
Following substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or undersaturated cycloalkyl；
Alkenyl；Refer to straight or branched and double bond can be there are on any position；
Alkynyl group；Refer to straight or branched and three keys can be there are on any position；
Haloalkyl：Refer to straight or branched alkyl, the hydrogen moiety on these alkyl or all replaced by halogen atom；
Halogenated cycloalkyl：Refer to saturation or undersaturated cycloalkyl, and hydrogen moiety therein or all taken by halogen atom
Generation；
Halogenated alkenyl：Refer to straight or branched and double bond can be there are on any position, and hydrogen moiety therein
Or all replaced by halogen atom；
Halo alkynyl：Refer to straight or branched and simultaneously can there are three keys on any position, and hydrogen moiety therein or
All replaced by halogen atom；
C6-C12Aryl means phenyl and by its derivative cyclophane base or polyaromatic, such as naphthyl, xenyl etc.；
The heteroaryl of band up to 10 carbon atoms refers to a ring heteroaryl or polyheteroaromatic, in formula at least 1 N and/or
O, S, P, such as pyridine radicals, thiazolyl, quinoxalinyl, benzoxazolyl group, pyrazolyl, thiadiazolyl group, thienyl, benzothienyl,
Furyl, benzofuranyl, pyrrole radicals, benzopyrrole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, phonetic
Piperidinyl, pyridazinyl, benzopyranyl, benzo pyrimidine radicals, oxazolyl, isoxazolyl, benzo isoxazolyl, benzothiazolyl, different
Thiazolyl, benzisothia oxazolyl, pyrimido triazolyl etc.；
C6-C12The heteroaryl of aryl and band up to 10 carbon atoms can partly or entirely hydrogenate, wherein 1 or 2 CH2
Replaced by CO, such as cyclohexenyl, cyclohexanedione base etc..
Currently preferred compound is：Formula（I）In：
I.Ar1And Ar2It is identical or different, and represent phenyl, pyridine radicals, thiazolyl, quinoxalinyl, benzoxazolyl group,
And the hydrogen moiety in phenyl, pyridine radicals, thiazolyl, quinoxalinyl, benzoxazolyl group or be all selected from following in identical
Or different substituent groups replaces：Halogen, cyano group, C1-C6Alkyl, C1-C6Alkyl oxy, C1-C6Alkyl sulfenyl, C1-C6Alkylamine
Base, C1-C6Haloalkyl, C1-C6Halogenated alkoxy；
II.R1And R2, R3It is same or different, and represent hydrogen, C1-C6Alkyl, C1-C6Haloalkyl；
III.n represents 1.
The further preferred compound of the present invention is：Formula（I）In：
I.Ar1And Ar2It is identical or different, and represent pyridine radicals, thiazolyl, quinoxalinyl, benzoxazolyl group, and pyrrole
Hydrogen moiety in piperidinyl, thiazolyl, quinoxalinyl, benzoxazolyl group or be all selected from following in identical or different taking
Replace for base：Halogen, C1-C3Alkyl, C1-C3Alkoxyl, C1-C3Haloalkyl, C1-C3Halogenated alkoxy；
II.R1And R2, R3It is same or different, and represent hydrogen, C1-C3Alkyl；
III.n represents 1.
Formula specifically preferred according to the invention（I）Compound is following compound R type isomers and any ratio of S type isomer
Mixture：
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) third
Amide；
N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) third
Amide；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) third
Amide；
N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene
Epoxide) propionic acid amide.；
N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene
Epoxide) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) third
Amide；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide..
The present invention particularly preferred formula further（I）Compound is following compound R type isomer：
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
(R)-N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) benzene oxygen
Base) propionic acid amide.；
(R)-N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) benzene oxygen
Base) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene oxygen
Base) propionic acid amide.；
(R)-N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) oxygen)
Phenoxy group) propionic acid amide.；
(R)-N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) oxygen)
Phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene oxygen
Base) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide..
The compound of the present invention can be presented in one or more isomer.Isomer includes enantiomer, non-
Enantiomer, geometric isomer.Formula as the present invention（I）Shown compound, because carbon-carbon double bond therein connects not
With substituent group and geometric isomer (respectively different configurations being represented with Z and E) can be formed, the present invention includes Z-type isomery
Body and the mixture of E-isomer and their any ratios.The formula of the present invention（I）Shown compound, due to wherein same
Connect four different substituent groups on carbon atom and form stereoisomer（Respectively different configurations is represented with R and S), this
Bright inclusion R type isomer and the mixture of S type isomer and their any ratios.
The invention still further relates to a kind of preventing and treating injurious weed, harmful levels of pathogens, the formula containing biologic effective dose of insect（I）Chemical combination
Thing and at least one other compositionss selected from surfactant, solid diluent and liquid diluent.
The invention still further relates to a kind of preventing and treating injurious weed, harmful levels of pathogens, the method for insect, including by the formula of biologic effective dose
（I）Compound contact injurious weed, harmful levels of pathogens, insect or its environment.Also relate to such a injurious weed, have and fall ill
Bacterium, insect pest control method, injurious weed, the formula of harmful levels of pathogens, insect or its environment biologic effective dose（I）Compound is connect
Touch to prevent and treat injurious weed, harmful levels of pathogens, insect.
The formula of the present invention（I）Compound has broad spectrum of activity：Some compounds can be used for preventing and treating injurious weed, it may also be used for
Preventing and treating harmful levels of pathogens or insect.And some compounds has very high biological activity to some injurious weeds so that very low
Dosage under be obtained with good effect.
Currently preferred compositionss are the compositionss containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent
The method selecting compound.
Segment boundses with listing in table 1～table 2 below（I）Compound is further illustrating the present invention, but does not limit this
Invention.Given in the present invention, fusing point is not all calibrated；Formula synthesized by the present invention（I）When compound is viscous solid, some glue
Property solid refrigerator place after can be cured as non-tacky solids；In table 1, all compounds are at LC-MS (APCI, Pos)
Its molecular ion peak all can be observed in (Agilent1100Series LC/MSD)；Compound in table 11H NMR(Varian
INOVA-300spectrometer) internal standard, deuterochloroform are made with tetramethylsilane (TMS)（CDCl3）Or deuterated two
Methyl sulfoxide（DMSO）Make solvent.
Table 1
*R represents a R type isomer；#R/S represents R type isomer and the mixture of any ratio of S type isomer.
Table 2
Formula（I）Shown compound can be obtained by reaction equation 1 shown below；In reaction equation 1（II）
Can be obtained by reaction equation 2 shown below；In reaction equation 1（III）Can be by reaction equation 3 shown below or reaction
Formula 4 obtains, and the Z in reaction equation 1 to reaction equation 4 is leaving group, such as chlorine, bromine, sulphonic acid ester etc., and other substituent groups are unless specified otherwise
Outer all limit as front.
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
Reaction equation 4：
Formula（I）Compound can so prepare（Reaction equation 1）：In suitable solvent such as dichloromethane or two chloroethenes
In alkane, toluene, in -10～110 DEG C, in the presence of suitable alkali such as triethylamine or pyridine, use formula（II）Shown compound and
Formula（III）Shown compound reaction, obtains formula（I）Shown compound, adds suitable catalyst such as 4- dimethylamino pyridine
（DMAP）Sodium iodide can accelerate react or improve reaction yield.
Formula（II）Compound can so prepare（Reaction equation 2）：In suitable solvent such as N,N-dimethylformamide
（DMF）Or in toluene, oxolane, ethanol, in suitable alkali such as potassium carbonate or potassium hydroxide, sodium carbonate, sodium hydroxide, hydrogenation
In the presence of sodium, under the conditions of 25～150 DEG C, use formula（IV）Shown compound and formula（V）Shown compound reacts to obtain formula
（VI）Shown compound, formula（VI）Shown compound and acyl halide reagent such as thionyl chloride or oxalyl chloride, Phosphorous chloride. etc.
Reaction obtains final product formula（II）Shown compound.
Formula（III）Compound can so prepare（Reaction equation 3 or reaction equation 4）：In suitable solvent such as N, N- bis-
Methylformamide（DMF）Or in oxolane, ethanol, dichloromethane, in suitable alkali such as sodium hydroxide, potassium hydroxide, carbonic acid
In the presence of sodium, potassium carbonate, sodium hydride, triethylamine, pyridine, under the conditions of 25～120 DEG C, use formula（VII）Shown compound and
Formula（VIII）Shown compound reacts to obtain formula（IX）Shown compound, formula（IX）Shown compound is in suitable solvent such as
In ethanol or methanol, obtain final product formula with the such as hydrazine hydrate hydrolysis of suitable reagent（III R2=H）Shown compound；Formula（IIIR2=H）
Shown compound and R2Z alkylated reaction obtains formula（III）Shown compound（Reaction equation 3）；Or in suitable solvent such as three
In chloromethanes and water or oxolane, ethanol, in suitable alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, hydrogenation
In the presence of sodium etc., under the conditions of 0～100 DEG C, use formula（X）Shown compound and formula（VIII）Shown compound reacts to obtain formula
（III）Shown compound（Reaction equation 4）, add suitable phase transfer catalyst such as benzyltriethylammoinium chloride（TEBA）Or four
Butylammonium bromide, tetrabutylammonium chloride etc. can be accelerated to react or improve reaction yield.
Concrete synthetic method has more detailed elaboration in the following embodiments.
The formula that the present invention provides（I）Compound has broad-spectrum biological under 15～2250 grams of effective ingredient/hectare consumption and lives
Property, can be not only used for preventing and treating injurious weed, it may also be used for preventing and treating harmful levels of pathogens or insect, some compounds have harmful miscellaneous well
Careless preventive and therapeutic effect, is obtained with good effect under very low dosage.
The formula that the present invention provides（I）Compound, the compound having biological activity and having has good biological activity. and special
It is not to show activity at the aspect of preventing and treating of agricultural, gardening, flowers and health injurious weed, harmful levels of pathogens, insect.Described here
Harmful organism include but not limited to this：
Grassy weed：Herba Digitariae, barnyard grass, Herba Setariae Viridis, hard grass, grass, Herba bromi japonici, amur foxtail, Triticum tauschii, alkali thatch, Flos Eragrostinis cilianensiss,
Wild oat, rye grass；
Broad leaved weed：Herba Abutili, Herba stellariae mediae, Herba Solani Nigri, Herba chenopodii, concave head amaranth, Amaranthus retroflexus, Amaranthusspinosus L. etc..
Harmful pathogen：Phytophthora species, white lead belongs to species, Gibberella species, Venturia species, Sclerotinia kind
Class, Rhizoctonia species, Botrytis species, Pyricularia Sacc. species, Fusarium species, such as rice blast（Pyricularia
oryzae）；Stripe rust of wheat（Puccinia striiformis）, leaf rust（Puccinia recondita）With other rust
Disease；Big wheat yellow rust（Puccinia striiformis）, leaf rust（Puccinia recondita）With other rust；Fructus Hordei Vulgaris
And wheat powdery mildew（Erysiphe graminis）, powdery mildew of cucumber（Sphaerotheca fuligenea）, apple mildew
(Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar)；Wheat sharp eyespot and
Glume blight（Septoria nodorum）.The compacted spore of length on corn, mouth spore are mould, Septoria is sick, caryosphere shell Pseudomonas sick,
Pseudocercosporella herpotrichoides and take-all（Gaeumannomyces graminis）.Semen arachidis hypogaeae
Brown spot（Cercospora arachidicola）And the cercospora black spot of peanut（Cercosporidium personata）；Fructus Mali pumilae wheel
Stricture of vagina harmful levels of pathogens（Botryosphaeria berengriana f.sp piricola）, apple decay harmful levels of pathogens
（Cytospora sp.）；Its Cercospora disease on Radix Betae, Semen sojae atricolor and Oryza glutinosa.Fructus Lycopersici esculenti, Fructus Cucumidis sativi, grape grey mould（Botrytis
cinerea）.Vegetable（As Fructus Cucumidis sativi）On hinge spore belong to disease.Anthrax on Fructus Cucumidis sativi, scab of apple, cucumber downy mildew, Fructus Vitis viniferae
Downy mildew, the epidemic disease on Rhizoma Solani tuber osi and Fructus Lycopersici esculenti, the list bacterium Thanatephorus cucumeris on Oryza glutinosa and other hosts
As the other rhizoctonias on Semen Tritici aestivi and Fructus Hordei Vulgaris, vegetable；Sclerotinia rot of colza（Sclerotonia sclerotiorum）；Gibberella saubinetii
Disease（Gibberella zeae）；Phytophthora capsici disease (Phytophythora capsici) etc..
Insect：Orthoptera such as cockroach, Thysanoptera such as cotton thrips, rice thripses, melon thrips, Homoptera such as leafhopper, plant hopper, aphid
Worm, Lepidoptera such as oriental armyworm, Prodenia litura, diamondback moth, beet armyworm, cabbage looper, Pieris rapae, Hymenoptera such as sawfly children
Worm, Diptera such as yellow-fever mosquito, culex, fly, Acarina such as Jie-Li enzyme-SQ, cotton spider mites.
It is used alone the formula of the present invention（I）During compound, it is effective to controlling injurious weed, harmful levels of pathogens, insect, it
Can also be used together with other materials.
With formula（I）Compound, as the Agrotechnical formulation of active ingredient, can make desired any agent
Type.
The invention will be further described with reference to embodiments, and the yield in embodiment is not all optimized.
Specific embodiment
Embodiment 1
This example demonstrates that in table 1 compound 01 preparation method.
(R) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propanoic acid is being furnished with magnetic stirring apparatuss, thermometer
With addition DMF (DMF) (40mL), (R) 2- (4- hydroxyphenoxy) third in the 100mL there-necked flask of condensing tube
Sour (0.02mol), after stirring and dissolving, is dividedly in some parts potassium carbonate (0.04mol), is warming up to 60～80 DEG C of stirring 0.5～1.0hr.
It is added dropwise over 2,3- difluoro-5-chloropyridine (0.02mol), continue stirring reaction 6～8hr.Reactant is cooled to room temperature, pours into
In frozen water (250mL), then it is slowly added to dilute hydrochloric acid in mixture, adjust to pH=4～5, filter, washing, white admittedly dry
The title compound 5.92g of body.
DMF (40mL) is added, phthalyl is sub- in 2- diuril azoles -5- base methylamine 100mL there-necked flask
Amine (0.05mol) and potassium hydroxide (0.05mol), after dissolving is stirred at room temperature, Deca 2- chloro-5-chloromethyl thiazole (0.05mol),
It is stirred overnight at room temperature.Reactant is poured in frozen water (250mL), filters, wash to obtain white solid.Solid is added to 250mL
In there-necked flask, add ethanol (150ml).After heating for dissolving, Deca hydrazine hydrate (18g, 80%), under the conditions of being stirred at reflux reaction 3～
4hr, cooling, filter, take filtrate, precipitation obtains the grease of yellow, pour in saturated nacl aqueous solution, ethyl acetate extracts,
It is dried, precipitation obtains title compound 2.90g.
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionyl
Toluene (40mL), (R) -2- (4- ((3- fluoro- 5- chloropyridine -2- base) oxygen is added in amine (compound 01 in table 1) 100mL single port bottle
Base) phenoxy group) propanoic acid (3.3mmol) and thionyl chloride (10mmol).Slough toluene after reactant backflow 3～5hr and obtain (R) -2-
(4- ((3- fluoro- 5- chloropyridine -2- base) epoxide) phenoxy group) propionyl chloride.Addition dichloromethane (40mL) in acyl chlorides, 2- diuril azoles-
The 4-dimethylaminopyridine (DMAP) of 5- base methylamine (3.3mmol) and catalytic amount, under ice bath cooling condition stirring 10～
15min, dropwise instills triethylamine (10mmol).Reactant continues stirring 2～3hr, pours in 100～200mL frozen water, uses dichloro
Methane extracts.Organic faciess wash (100mL*2), anhydrous sodium sulfate drying, precipitation.Gained crude product is through column chromatography（Thin layer chromatography
Silica gel VPetroleum ether/VEthyl acetate=5/1）Obtain the title compound 0.36g of faint yellow solid, yield 25%, 100.1-100.9 DEG C of fusing point.
Embodiment 2
This example demonstrates that in table 1 compound 03 preparation method.
2- chloro-5-chloromethyl thiazole is added in N- methyl-(2- diuril azoles -5- base) methylamine 200mL single port bottle
(0.05mol), CHCl3(50mL) Deca methylamine water solution (25g, 25-30%) and sodium hydrate aqueous solution after, stirring
(25ml, 10%), and add a small amount of phase transfer catalyst tetrabutyl ammonium bromide, 25～30 DEG C of stirring reactions are overnight.Dilute hydrochloric acid adjusts pH
To alkalescence, point liquid, anhydrous sodium sulfate drying after organic faciess washing twice, precipitation obtains the titled of the forsythia liquid of 6.67g
Compound.
(R)-N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) benzene oxygen
Base) add toluene (40mL) in propionic acid amide. (compound 03 in table 1) 100mL single port bottle, (R) -2- (4- ((3- fluoro- 5- chloropyridine -
2- yl) epoxide) phenoxy group) propanoic acid (3.3mmol) and thionyl chloride (10mmol).Slough toluene after reactant backflow 3～5hr to obtain
Its acyl chlorides.Dichloromethane (40mL), N- methyl-(2- diuril azoles -5- base) methylamine (3.3mmol) and catalytic amount is added in acyl chlorides
4-dimethylaminopyridine (DMAP), stirs 5～10min under ice bath cooling condition, dropwise instill triethylamine (10mmol).Reaction
Thing is poured in 100～200mL frozen water after continuing stirring 2～3hr, and dichloromethane extracts.Organic phases washed with water (100mL*2), no
Aqueous sodium persulfate is dried, precipitation.Gained crude product is through column chromatography（Thin layer chromatography silica gel VPetroleum ether/VEthyl acetate=5/1）Obtain faint yellow viscosity
The title compound 0.73g of liquid, yield 48%.
Embodiment 3 this example demonstrates that in table 1 compound 42 preparation method.
(R) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propanoic acid be furnished with magnetic stirring apparatuss,
DMF (DMF) (40mL), (R) -2- (4- hydroxy benzeness are added in the 100mL there-necked flask of thermometer and condensing tube
Oxygen) propanoic acid（[α]589 20℃=+59.5°（Acetone））(0.02mol), after stirring and dissolving, it is dividedly in some parts potassium carbonate (0.04mol), rise
Temperature stirs 1.0～1.5hr to 60～80 DEG C.It is added dropwise over 2,3- bis- chloro-5-trifluoromethylpyridine (0.02mol), continue stirring
Reaction 8～10hr.Reactant is cooled to room temperature, pours in frozen water (250mL), then be slowly added to dilute hydrochloric acid in mixture,
Adjust to pH=4～5, filter, washing, the title compound 6.56g of dry white solid, [α]589 20℃=+37.9°（Acetone）.
DMF (DMF) (40mL), adjacent benzene is added in 2- chloropyridine -5- base methylamine 100mL there-necked flask
Dicarboximide (0.05mol) and potassium hydroxide (0.05mol), are stirred at room temperature dissolving, Deca 2-vhloro-5-chloromethylpyridine
(0.05mol), it is stirred overnight at room temperature.Reactant is poured in frozen water (250mL), filters, wash to obtain white solid.By solid plus
Enter in 250mL there-necked flask, add ethanol (150ml).After heating for dissolving, Deca hydrazine hydrate (18g, 80%), stirring condition is next time
Stream reaction 4-6hr, cooling, filter, take filtrate, precipitation obtains the grease of yellow, pour in saturated nacl aqueous solution, acetic acid second
Ester extracts, and is dried, and precipitation obtains faint yellow title compound 2.96g.
(R) add in -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propionyl chloride 100mL single port bottle
Enter toluene (40mL), (R) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propanoic acid (3.3mmol) and
Thionyl chloride (10mmol).Slough solvent after reactant backflow 4～6hr and excessive thionyl chloride obtains title thing.
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene oxygen
Base) add dichloromethane (40mL), (R) -2- (4- ((chloro- 5- of 3- tri- in propionic acid amide. (compound 42 in table 1) 100mL single port bottle
Fluoromethylpyridin -2- base) epoxide) phenoxy group) propionyl chloride (3.3mmol), 2- chloropyridine -5- base methylamine (3.3mmol) and catalysis
The 4-dimethylaminopyridine (DMAP) of amount, after the lower stirring 10～15min of ice bath cooling, dropwise instills triethylamine (10mmol).
After reactant continues stirring 2～3hr, pour in 200mL frozen water, extracted with dichloromethane.Organic faciess are washed, and anhydrous sodium sulfate is done
Dry, precipitation.Gained crude product is through column chromatography（Thin layer chromatography silica gel VPetroleum ether/VEthyl acetate=3/1）Obtain the title compound of off-white powder
Thing 0.42g, [α]589 20℃=+19.4°（Acetone）, ee%=99.0%, 109.6-112.0 DEG C of fusing point.
Embodiment 4 this example demonstrates that in table 1 compound 43 preparation method.
(R/S) -2- (4- hydroxyphenoxy) propanoic acid, under the conditions of 15～25 DEG C, 2 bromopropionic acid is slowly added into 50%
NaOH（0.1mol）In solution, after stirring and dissolving, add 30ml water, continue stirring 5～10min, standby.In 15～25 DEG C of conditions
Under, add hydroquinone in reaction bulb（0.4mol）With water 50ml, stirring is lower to add 50%NaOH（0.8mol）, add above-mentioned
The NaOH solution of 2 bromopropionic acid, 50～60 DEG C of reaction 4～6hr, cooling, dilute hydrochloric acid adjusts PH to 4.0～4.5, is extracted with ethyl acetate
Take, dilute hydrochloric acid adjusts pH to 1.0～1.5, isopropyl acetate extracts, organic faciess add water and are azeotroped off isopropyl acetate, aqueous solution is used
50%NaOH solution adjusts PH to 2.0～2.5, cooling, is extracted with ethyl acetate, anhydrous sodium sulfate drying, precipitation obtains (R, S) -2-
(4- hydroxyphenoxy) propanoic acid 16.5g, [α]589 20℃=-0.1～+0.1 °（Acetone）.
(R/S) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propanoic acid is being furnished with magnetic agitation
DMF (DMF) (40mL), (R/S) -2- (4- hydroxyl is added in the 100mL there-necked flask of device, thermometer and condensing tube
Phenoxyl) propanoic acid (0.02mol), after stirring and dissolving, it is dividedly in some parts potassium carbonate (0.04mol), be warming up to 60～80 DEG C of stirrings
After 1.0～1.5hr, it is added dropwise over 2,3- bis- chloro-5-trifluoromethylpyridine (0.02mol), continue stirring reaction 8～10hr.Will
Reactant is cooled to room temperature, pours in frozen water (250mL), then is slowly added to dilute hydrochloric acid in mixture, adjusts to pH=4～5,
Filter, washing, the title compound 7.02g of dry white solid, [α]589 20℃=-0.2～+0.2 °（Acetone）.
(R/S) in -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propionyl chloride 100mL single port bottle
Add toluene (40mL), (R/S) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propanoic acid（[α]589 20℃
=-0.2～+0.2 °（Acetone））(3.3mmol) with thionyl chloride (10mmol).Solvent and mistake is sloughed after reactant backflow 4～6hr
The thionyl chloride of amount obtains title compound.
(R/S)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) benzene oxygen
Base) add dichloromethane (40mL), (R/S) -2- (4- (chloro- 5- of 3- tri- in propionic acid amide. (compound 43 in table 1) 100mL single port bottle
Fluoromethylpyridin -2- base epoxide) phenoxy group) propionyl chloride (3.3mmol), 2- chloropyridine -5- base methylamine (3.3mmol) and catalytic amount
4-dimethylaminopyridine (DMAP), after the lower stirring 10～15min of ice bath cooling, dropwise instill triethylamine (10mmol).Instead
After answering thing to continue stirring 2～3hr, pour in 200ml frozen water, extracted with dichloromethane.Organic faciess wash (100mL*2), anhydrous
Sodium sulfate is dried, precipitation.Products obtained therefrom is through column chromatography（Thin layer chromatography silica gel VPetroleum ether/VEthyl acetate=3/1）Obtain the mark of off-white powder
Topic compound 0.37g, yield 22.6%, [α]589 20℃=-0.3°（Acetone）, ee%=0.15%, 109.0-110.5 DEG C of fusing point.
Raw survey embodiment
Synthesized compound is carried out with weeding, sterilization and insecticidal activity test, part of test results is as follows.
Embodiment 5 activity of weeding evaluation
Method is as follows：（1）In sectional area 64cm2Plastic tub alms bowl in quantitative dress soil pressure put down, be placed in Stainless steel basin, choose
Full seed, seed of the same size, point monocotyledon weed【Herba Digitariae（Digitaria sanguinalis）, barnyard grass
（Echinochloa crus-galli）, Herba Setariae Viridis（Setaria viridis）】And broadleaf weed【Herba Abutili（Abutilon
theophrasti）, Amaranthusspinosus L.（Amaranthus spinosus）, Herba chenopodii（Chenopodium album）】Divide alms bowl sowing, respectively account for alms bowl
The 1/3 of area, covers 1cm thickness fine earth, adds water to upper layer of soil infiltration from plastic tub alms bowl bottom, be placed in hot-house culture, material to be tried is long
Carry out test process to required leaf age；（2）Weigh the formula that the appropriate present invention provides（I）Compound, with DMF
Dissolving, adds a small amount of Tween 80 emulsifying agent, stirs, and adds quantitative clear water, is configured to desired concn, if coordinative solvent and
Clear water is comparison；（3）Processing mode：Examination material sowing next day carries out before seedling soil treatment, unifacial leaf examination material length to 1 leaf 1 heart stage, double
Cotyledon examination material length carries out after seedling cauline leaf process to 2 leaf periods；（4）By setting dosage quantitatively pipette medicinal liquid carry out stem and leaf spraying and
Soil spraying treatment, respectively with spraying solvent and clear water for comparison；（5）Process examination material and be placed in hot-house culture；（6）Process 15-25
Visually upper grown situation after it, according to survey result, calculates the preventive effect to weeds for each compound as follows：Preventive effect
（%）=100×（Comparison plant height-process plant height）/ comparison plant height.Result shows that the compounds of this invention has remarkable activity to weeds.
Partial results such as table 3～table 4.In view of the result of table 3 and table 4, test the safety to Oryza sativa L. and Semen Tritici aestivi for the part of compounds（Knot
Fruit is shown in Table 5）, compare part of compounds with similar commercial References medicament azole amide and cyhalofop-butyl to rice terrace weight simultaneously
Want the activity of weeding of weed moleplant seed and barnyard grass, the results are shown in Table 6.Result shows that compound 42 has safety to Oryza sativa L., and right
Rice terrace the worst weeds Semen Euphorbiae and barnyard grass have excellent activity, and compound 42 also has excellent work to other grassy weeds
Property.
Activity of weeding under 2250 grams/ha of dosage for table 3 part of compounds
Cauline leaf process activity of weeding under 15-60 gram/ha of dosage for table 4 part of compounds
*/ represent and do not test,#Represent that dosage (g a.i/ha) is 18.75,37.50,75.00.
The cauline leaf process safety testing result to Oryza sativa L. Hunan morning Xian 24 for table 5 part of compounds
| Dosage (g a.i/ha) | 120 | 60 | 30 | 15 |
| 13 | 40% suppression, dead seedling | 50% suppression | 30% suppression | 10% suppression |
| 35 | 60% suppression | 40% suppression | 20% suppression | 10% suppression |
| 42 | Normally | Normally | Normally | Normally |
| 56 | 70% suppression, dead seedling | 30% suppression, dead seedling | 20% suppression | 10% suppression |
| 62 | 60% suppression, dead seedling | 30% suppression, dead seedling | 20% suppression | 10% suppression |
| Clodinafop-propargyl | 100% suppression, dead seedling | 100% suppression, dead seedling | 80% suppression, dead seedling | 70% suppression, dead seedling |
The cauline leaf process activity of weeding to rice terrace the worst weeds Semen Euphorbiae and barnyard grass for table 6 compound 42
*/ represent and do not test.
Embodiment 6 is to Sclerotinia sclerotiorum（Sclerotonia sclerotiorum）Bactericidal activity
Method is as follows：Testing compound is dissolved in suitable solvent such as N,N-dimethylformamide（DMF）In, then with containing 0.1%
The sterilized water of Tween80 emulsifying agent is diluted to desired concn；With pipet take 3mL medicinal liquid add be cooled to 45 DEG C 27mL horse
Bell potato agar culture medium（PDA）In and pour culture dish into after fully shaking up；Inoculating needle is used from the culture Brassica campestris L sclerotium of 7 days after cooling
Pathogenic bacteria colony edge takes 6mm diameter mycelia block, moves to culture dish central authorities, mycelia faces down, and sets without testing compound simultaneously
Blank is comparison, often processes 4 repetitions；After being disposed, culture dish is placed in 28 DEG C of constant temperature biochemical cultivation case and cultivates, 4 days
Measure mycelial growth diameter afterwards, be analyzed using EXCEL statistical software and calculate mycelial growth inhibition rate（%）.Activity is relatively
In blank in percentage, it is divided into A, B, C, D level Four, 100% suppression ratio 90% is A level, 90% ＞ suppression ratio 70%
For B level, 70% ＞ suppression ratio 50% is C level, and 50% ＞ suppression ratio 0% is D level.Result shows the compound of the present invention to Brassica campestris L
Hyphal cluster germ is active, such as compound 32 and 48,67 grade under 25mg/L concentration, Sclerotinia sclerotiorum is respectively provided with C level with
On activity.
Embodiment 7 is to botrytis cinerea pers（Botrytis cinerea）Bactericidal activity
Using the assay method of the bactericidal activity to Sclerotinia sclerotiorum for the embodiment 6, determine formula（I）Compound
Activity to botrytis cinerea pers, result shows that the compound of the present invention is active to botrytis cinerea pers, such as compound 03
With 05,20,22 grades are respectively provided with the activity of more than C level under 25mg/L concentration to botrytis cinerea pers.
Embodiment 8 is to Rhizoctonia solani Kuhn（Rhizoctonia solani）Bactericidal activity（Leaf culture in vitro method）
Method is as follows：Testing compound is dissolved in suitable solvent such as N,N-dimethylformamide（DMF）In, then with containing 0.1%
The sterilized water of Tween80 emulsifying agent is diluted to desired concn；Take Vicia faba seedling plant leaf fresh, that children is tender through certain density
Lie in the culture dish being covered with aqueous filter paper after chemicals treatment, blade is separated by with filter paper self-made punching brandreth.Blade dries
It is followed by a diameter of 6mm, the culture fresh mycelia block of 2～3 days.Often process 3 repetitions, separately set the blank without testing compound
For comparison, moisturizing thermophilic is cultivated to blank morbidity, checks lesion area, calculating pharmacy control efficacy.Activity is with respect to blank
Comparison is in percentage.Result shows that the compound of the present invention has prevention effect to rice sheath blight disease, and such as compound 01 exists
Under 500mg/L concentration, more than 50% is reached to the preventive effect of rice sheath blight disease.
Embodiment 9 is to wheat powdery mildew（Erisiphe griminis）Bactericidal activity（Pot-culture method）
Method is as follows：Testing compound is dissolved in suitable solvent such as N,N-dimethylformamide（DMF）In, then with containing 0.1%
The sterilized water of Tween80 emulsifying agent is diluted to desired concn；Cut-off stem 15cm about basin alms bowl, every alms bowl sows the full stalwartness of Semen Tritici aestivi
20, seed, be wholeheartedly for experiment afterwards wait growing two leaves；Ready wheat seedling plant is taken to spray through certain density medicament
Mist is processed, and carries out harmful levels of pathogens inoculation after one day.Often process 3 repetitions, separately setting blank without testing compound is comparison, guarantor
Wet thermophilic is cultivated to blank morbidity, checks lesion area, calculates pharmacy control efficacy.Activity is with respect to blank with percentage
Than meter.Result shows that the compound of the present invention has prevention effect to wheat powdery mildew, and such as compound 03 is under 500mg/L concentration
More than 80% is reached to the preventive effect of wheat powdery mildew.
Embodiment 10 is to bean aphid（Aphis fabae）Insecticidal Activity
Method is as follows：Weigh the formula that the appropriate present invention provides（I）Compound, with suitable solvent such as DMF
Dissolving, adds a small amount of Tween 80 emulsifying agent, stirs, and adds quantitative clear water, is configured to desired concn, if clear water is right
According to.Bean aphid is connected on the bean seedlings being just unearthed, every plant connects more than 20, then together with test worm, bean seedlings is dipped in the present invention and carries
For formula（I）In the medicinal liquid of compound, take out after 5 seconds, suck unnecessary medicinal liquid, in the sponge of insertion water suction, covered with glass-tube,
Survival and dead borer population is checked after 24 hours.It is repeated 3 times, results averaged.Activity blank relatively is in percentage.Knot
Fruit shows that the compound of the present invention is active to bean aphid, such as under 500mg/L concentration, compound 13 and 20, and 22 grades are to Semen Viciae fabae
The activity of aphid（Mortality rate）It is all higher than 50%.
Embodiment 11 is to two-spotted spider mite（Tetranychus urticae）Acaricidal activity
Method is as follows：Weigh the formula that the appropriate present invention provides（I）Compound, with suitable solvent such as DMF
Dissolving, adds a small amount of Tween 80 emulsifying agent, stirs, and adds quantitative clear water, is configured to desired concn, if clear water is right
According to.Select the bean seedlings inoculation red spider growing fine, after red spider colonizes, will cut in the medicinal liquid preparing with demodicid mite bean seedlings
Dipping 10 seconds, taking-up filter paper sucks unnecessary medicinal liquid, inserts in and is filled with water in beaker, in observing indoor cultivation, checks after 24 hours
Survival and dead demodicid mite number, every plant of bean seedlings have 100-200 demodicid mite.Experiment is repeated 3 times.Results averaged.Activity is with respect to sky
White comparison in percentage, is divided into A, B, C, D level Four, 100% mortality rate 90% is A level, 90% ＞ mortality rate 70% is B
Level, 70% ＞ mortality rate 50% is C level, and 50% ＞ mortality rate 0% is D level.Result show the compound of the present invention to cotton red spider
Spider is active, such as under 500mg/L concentration, the activity to two-spotted spider mite for compound 48 grade（Mortality rate）More than 50%.
Claims (8)
1.N- (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss are it is characterised in that represented with logical formula (I)：
Wherein：
I.Ar1Represent phenyl, 2- pyridine radicals, 2- quinoxalinyl or 2- benzoxazolyl group；Ar2Represent 2- halogen pyridine -5- base or 2-
Halogen thiazole -5- base；And Ar1Middle hydrogen moiety or all can be selected from following in identical or different substituent group replace：
Halogen, cyano group or C1-C6Haloalkyl；
II.R1Represent C1-C6Alkyl；R2Represent hydrogen or C1-C6Alkyl；R3Represent hydrogen or C1-C6Alkyl；And R1, R2And R3Middle C1-C6
Hydrogen moiety or all can be optionally substituted by halogen in alkyl；
III.n represents 1 or 2,3；
In the definition of compound (I) given above, no matter term used is used alone also being used in compound word, represent as follows
Substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Halo：Refer to the hydrogen moiety in straight or branched alkyl or all can be replaced by halogen atom.
2. N- (aryl alkyl) according to claim 1 virtue phenoxy carboxylic acyloxy aminated compoundss are it is characterised in that formula
(I) in compound shown in：
I.Ar1Represent phenyl, 2- pyridine radicals, 2- quinoxalinyl or 2- benzoxazolyl group；Ar2Represent 2- halogen pyridine -5- base or 2-
Halogen thiazole -5- base；And Ar1In hydrogen moiety or all can be selected from following in identical or different substituent group take
Generation：Halogen, cyano group or C1-C6Haloalkyl；
II.R1Represent C1-C6Alkyl；R2Represent hydrogen or C1-C6Alkyl；R3Represent hydrogen or C1-C6Alkyl；And R1, R2And R3Middle C1-C6
Hydrogen moiety or all can be optionally substituted by halogen in alkyl；
III.n represents 1.
3. N- (aryl alkyl) according to claim 1 virtue phenoxy carboxylic acyloxy aminated compoundss are it is characterised in that formula
(I) in compound shown in：
I.Ar1Represent phenyl, 2- pyridine radicals, 2- quinoxalinyl or 2- benzoxazolyl group；Ar2Represent 2- halogen pyridine -5- base or 2-
Halogen thiazole -5- base；And Ar1In hydrogen moiety or all can be selected from following in identical or different substituent group take
Generation：Halogen or C1-C3Haloalkyl；
II.R1Represent C1-C3Alkyl；R2Represent hydrogen or C1-C3Alkyl；R3Represent hydrogen or C1-C3Alkyl；
III.n represents 1.
4. N- (aryl alkyl) according to claim 1 virtue phenoxy carboxylic acyloxy aminated compoundss are it is characterised in that formula
(I) compound shown in is following compound：
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionyl
Amine；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group)
Propionic acid amide.；
N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group)
Propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide.；
N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide..
5. N- (aryl alkyl) according to claim 1 virtue phenoxy carboxylic acyloxy aminated compoundss are it is characterised in that formula
(I) shown in, compound is：
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- chloro-3-fluoropyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- methyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) oxygen) benzene oxygen
Base) propionic acid amide.；
(R)-N- ethyl-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) oxygen) benzene oxygen
Base) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((3- chloro-5-trifluoromethylpyridine -2- base) epoxide) phenoxy group) third
Amide；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((5- trifluoromethyl pyridine -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((2- fluoro- 4- cyano-phenyl) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chlorobenzene simultaneously [d] azoles -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- diuril azoles -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide.；
(R)-N- (2- chloropyridine -5- ylmethyl) -2- (4- ((6- chloro-quinoxaline -2- base) epoxide) phenoxy group) propionic acid amide..
6. the preparation method of N- (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss according to claim 1, it is special
Levy and be that the compound shown in formula (I) is prepared by reaction shown below,
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
Reaction equation 4：
In methylene chloride, dichloroethanes or toluene, in -10～110 DEG C, in the presence of alkali triethylamine or pyridine, use formula
(II) compound shown in and the reaction of the compound shown in formula (III), obtain the compound shown in formula (I), add catalyst 4- bis-
Picolilamine or sodium iodide can be accelerated to react or improve reaction yield；
In solvent DMF, toluene, oxolane or ethanol, alkali potassium carbonate, potassium hydroxide, sodium carbonate,
In the presence of sodium hydroxide or sodium hydride, under the conditions of 25～150 DEG C, with the change shown in the compound shown in formula (IV) and formula (V)
Compound reacts to obtain the compound shown in formula (VI), the compound shown in formula (VI) and acyl halide reagent thionyl chloride, oxalyl chloride or
Phosphorous chloride. reaction obtains final product compound shown in formula (II)；
In solvent DMF, oxolane, ethanol or dichloromethane, in alkali sodium hydroxide, potassium hydroxide, carbon
In the presence of sour sodium, potassium carbonate, sodium hydride, triethylamine or pyridine, under the conditions of 25～120 DEG C, with the compound shown in formula (VII)
React to obtain the compound shown in formula (IX) with the compound shown in formula (VIII), the compound shown in formula (IX) in etoh solvent or
In methanol, obtain final product the compound shown in formula (XI), the compound shown in formula (XI) and R with hydrazine hydrate hydrolysis2Z alkylated reaction obtains
Compound shown in formula (III)；Or in solvent chloroform and water, oxolane or ethanol, in alkali sodium hydroxide, hydroxide
In the presence of potassium, potassium carbonate, sodium carbonate or sodium hydride, under the conditions of 0～100 DEG C, with the compound shown in formula (X) and formula (VIII)
Shown compound reacts to obtain the compound shown in formula (III), adds phase transfer catalyst benzyltriethylammoinium chloride, the tetrabutyl
Ammonium bromide or tetrabutylammonium chloride can be accelerated to react or improve reaction yield；
Ar in formula1And Ar2、R1、R2、R3, n there is given in claim 1 definition, Z is leaving group chlorine, bromine or sulphonic acid ester.
7. the purposes of N- (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss according to claim 1, its feature exists
In tool weeding, sterilization, parasite killing and/or mite killing biological activity under 15～2250 grams of effective ingredient/hectare consumption.
8. N- (aryl alkyl) virtue phenoxy carboxylic acyloxy aminated compoundss according to claim 1 have weeding for preparation
Activity, the purposes of the medicine of plant sterilization activity, plant insecticide activity and/or plant acaricidal activity.
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| CN106608873B (en) * | 2015-10-26 | 2019-05-24 | 湖南化工研究院有限公司 | Pyrazol acid amide compounds and the preparation method and application thereof |
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| CN105613515A (en) * | 2016-03-11 | 2016-06-01 | 李为忠 | Weed killer composition capable of being used for paddy field and application thereof |
| CN105580816A (en) * | 2016-03-11 | 2016-05-18 | 李为忠 | Metamifop composition and application thereof |
| CN105746538A (en) * | 2016-03-11 | 2016-07-13 | 李为忠 | Bentazone composition and application thereof |
| CN105669584A (en) * | 2016-03-11 | 2016-06-15 | 李为忠 | High-selectivity herbicide N-substitutive alkyl aryloxy phenoxyl propanamide compound and preparation and application thereof |
| CN105660658A (en) * | 2016-03-11 | 2016-06-15 | 李为忠 | Cyhalofop-butyl composition and application thereof |
| CN105906618B (en) * | 2016-05-24 | 2018-06-19 | 长沙理工大学 | N- (5- benzyls thiazol-2-yl) -2- [4- (quinoxaline -2- oxygroups) phenoxy group] amide derivatives |
| CN105859707B (en) * | 2016-06-08 | 2018-07-20 | 河北大学 | (R)-N- (thiazol-2-yl) -2- [4- (quinoxaline -2- oxygroups) phenoxy group] amide derivatives and its preparation method and application |
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| CN108003142A (en) * | 2017-12-10 | 2018-05-08 | 杨子辉 | A kind of preparation method and application of virtue phenoxy propionyl hydrazine class compound |
| CN108084108B (en) * | 2017-12-28 | 2020-12-29 | 青岛清原化合物有限公司 | 5-chlorobenzoxazole derivative and preparation method, herbicidal composition and application thereof |
| CN108689921A (en) * | 2018-05-22 | 2018-10-23 | 安徽农业大学 | It is a kind of virtue phenoxy base Propionamides compound preparation method with application |
| CN112625035B (en) * | 2019-09-24 | 2024-04-12 | 海利尔药业集团股份有限公司 | 5-chlorobenzoxazole derivative or salt acceptable as pesticide, composition and application thereof |
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