CN104277033A - N-(arylalkyl)aryloxy phenoxy carboxylic acid amide compounds, and preparation method and application thereof - Google Patents
N-(arylalkyl)aryloxy phenoxy carboxylic acid amide compounds, and preparation method and application thereof Download PDFInfo
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- CN104277033A CN104277033A CN201310273568.6A CN201310273568A CN104277033A CN 104277033 A CN104277033 A CN 104277033A CN 201310273568 A CN201310273568 A CN 201310273568A CN 104277033 A CN104277033 A CN 104277033A
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- 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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- 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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- 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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- C07D213/00—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
- 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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- 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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- C07D413/00—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
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Abstract
The invention discloses N-(arylalkyl)aryloxy phenoxy carboxylic acid amide compounds show as a formula (I), and a preparation method and application thereof. In the formula (I), Ar1, Ar2, R1, R2, R3 and n are defined in the specification. The formula (I) compounds have biological activity for weeding and/or sterilizing, killing insects and killing mites, some compounds have extremely high weeding activity, and 15-75 g/hectare of the effective composition can help to obtain extremely good effect.
Description
Technical field
The present invention relates to have weeding, sterilization, insecticidal bioactivity N-(arylalkyl) fragrant phenoxy carboxylic acid amide compounds and preparation method thereof and control injurious weed, harmful levels of pathogens, the purposes of insect and method with these compounds.
Background technology
Virtue phenoxy carboxylic acid compound has the activity of preventing and kill off gramineous weeds, and have such active compound multiple to be successfully developed as weedicide, the using dosage being the exploitation of Xian Zhengda Crop protection company limited of Switzerland such as formula the clodinafop-propargyl (clodinafop-propargyl US4505743) shown in (P-1) is 40 ~ 60 grams of effective constituent/hectares, for the aryloxyphenoxypropanoates class weedicide of some kind wheat paddock keeping from ill gramineous weeds; And the cyhalofop-butyl (cyhalofop-butyl EP0302203) shown in formula (P-2) be by The Dow Agrosciences, LLC. in the using dosage of Development and Production in 1987 be the special phenoxy phenoxy propionic acid ester weedicide of the rice terrace of 50 ~ 100 grams of effective constituent/hectares; metamifop shown in formula (P-3) (Metamifop WO200005956A1) is then the using dosage developed by Chemical Engineering Technology research institute of Korea S is another special aryloxyphenoxypropanoates class weedicides of rice terrace of 90 ~ 120 grams of effective constituent/hectares, and other fragrant phenoxy carboxylic-acid weedicide can not be directly used in gramineous crop field controlling weeds substantially when not adding safener.
Virtue phenoxy carboxylic-acid weedicide has activity to gramineous weeds, and what have also has very excellent activity, and unfortunately these weedicides are scarcely safe to gramineous crop (as wheat, paddy rice etc.).As (P-1) although shown in clodinafop-propargyl very high to gramineous weeds activity, it is only to part wheat breed safety, all dangerous to paddy rice; Cyhalofop-butyl shown in formula (P-2) and formula (P-3) although shown in metamifop to rice safety, it to the activity of gramineous weeds again far below the clodinafop-propargyl shown in (P-1), and also dangerous to wheat.
For obtaining gramineous crop particularly paddy rice, the high reactivity virtue phenoxy carboxylic acid compound of wheat safety, unsaturated for O-chain type azanol is introduced in fragrant phenoxy carboxylic acid structure by contriver, design and synthesize N-unsaturated chain oxygen base virtue phenoxy carboxylic acid amide compounds (CN201010221128.2), and therefrom find that comparatively metamifop shown in the cyhalofop-butyl shown in the clodinafop-propargyl shown in (P-1) He (P-2) and (P-3) has wider activity profile and more highly active compound as (P-4) etc., and compared with the clodinafop-propargyl shown in (P-1), we (P-4) of invention is safer to wheat, unfortunately (P-1) and (P-4) is all dangerous to paddy rice, thus the control of paddy field weed can not be used for.
For improving the weeding activity of (P-4) and/or the security to crop particularly paddy rice further, arylalkyl is introduced again in fragrant phenoxy carboxylic acid amide class formation by we, design and synthesize a series of compound with broad spectrum of activity, and obtain the compound of a collection of weeding activity higher than (P-2) and (P-3), and some compounds are to rice safety, thus solve the deficiency that (P-1) and (P-4) can not be used for rice terrace.The compound simultaneously had also demonstrates obvious sterilization or insecticidal activity.
Summary of the invention
The invention provides, shown in formula (I), there is bioactive N-(arylalkyl) fragrant phenoxy carboxylic acid amide compounds and the isomer thereof such as weeds, harmful levels of pathogens, insect:
Wherein:
I.Ar
1and Ar
2be identical or different, and represent C
6-C
12the heteroaryl of aryl or band as many as 10 carbon atoms, and
A) C
6-C
12hydrogen moiety in the heteroaryl of aryl or band as many as 10 carbon atoms or be all selected from following in identical or different substituting group replace: halogen, nitro, cyano group, amido, hydroxyl, sulfydryl, carboxyl, aldehyde radical, diazanyl, hydrazone group, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12the heteroaryl amido of arylamine group or band as many as 10 carbon atoms;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkynyl group, C
3-C
8cycloalkyl, C
6-C
12the heteroaryl of aryl or band as many as 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) and II. described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, in heteroaryl hydrogen moiety or be all selected from following in identical or different substituting group replace: halogen, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12heteroaryl amido, two C of arylamine group or band as many as 10 carbon atoms
6-C
12two heteroaryl amidos, the C of arylamine group or band as many as 10 carbon atoms
6-C
12heteroarylaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12the heteroarylheteroaryl of aryl heteroaryl or band as many as 10 carbon atoms; And 1) described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, in heteroaryl hydrogen moiety or be all selected from following in identical or different substituting group replace: hydrogen, halogen, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12heteroaryl amido, two C of arylamine group or band as many as 10 carbon atoms
6-C
12two heteroaryl amidos, the C of arylamine group or band as many as 10 carbon atoms
6-C
12heteroarylaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12the heteroarylheteroaryl of aryl heteroaryl or band as many as 10 carbon atoms;
In the definition of the compound (I) provided, no matter term used is used alone or is used in compound word, represent following substituting group above:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to straight or branched alkyl;
Cycloalkyl: refer to saturated or undersaturated cycloalkyl;
Alkenyl; Refer to straight or branched and double bond can be had on any position;
Alkynyl group; Refer to straight or branched and triple bond can be had 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 saturated or undersaturated cycloalkyl, and hydrogen moiety wherein or all replaced by halogen atom;
Halogenated alkenyl: refer to straight or branched double bond can be had on any position, and hydrogen moiety wherein or all replaced by halogen atom;
Halo alkynyl: refer to straight or branched triple bond can be had on any position, and hydrogen moiety wherein or all replaced by halogen atom;
C
6-C
12aryl means phenyl and by its derivative cyclophane base or polyaromatic, as naphthyl, xenyl etc.;
Heteroaryl with as many as 10 carbon atoms refers to a ring heteroaryl or polyheteroaromatic, 1 N and/or O is had at least in formula, S, P, as pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, pyrazolyl, thiadiazolyl group, thienyl, benzothienyl, furyl, benzofuryl, pyrryl, benzopyrrole base, imidazolyl, benzimidazolyl-, quinolyl, pyranyl, pyrazinyl, pyrimidyl, pyridazinyl, benzopyranyl, benzo pyrimidyl, oxazolyl, isoxazolyl, benzoisoxazole base, benzothiazolyl, isothiazolyl, benzisothiazole base, Kui Linpyrimido quinoline triazolyl etc.,
C
6-C
12the heteroaryl of aryl and band as many as 10 carbon atoms can partly or entirely hydrogenation, wherein 1 or 2 CH
2replaced by CO, as cyclohexenyl, cyclohexanedione base etc.
The preferred compound of the present invention is: in formula (I):
I.Ar
1and Ar
2identical or different, and represent phenyl, pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and hydrogen moiety in phenyl, pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl or be all selected from following in identical or different substituting group replace: halogen, cyano group, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
6alkyl, C
1-C
6haloalkyl;
III.n represents 1.
The present invention further preferred compound is: in formula (I):
I.Ar
1and Ar
2be identical or different, and represent pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and hydrogen moiety in pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl or be all selected from following in identical or different substituting group replace: halogen, C
1-C
3alkyl, C
1-C
3alkoxyl group, C
1-C
3haloalkyl, C
1-C
3halogenated alkoxy;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
3alkyl;
III.n represents 1.
The particularly preferred formula of the present invention (I) compound is the mixture of following compound R type isomer and any ratio of S type isomer:
N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide.
The present invention's further particularly preferred formula (I) compound is following compound R type isomer:
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) 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) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide.
Compound of the present invention can one or more isomer form exist.Isomer comprises enantiomer, diastereomer, geometrical isomer.Compound as shown in formula of the present invention (I), geometrical isomer (respectively with Z and E to represent different configurations) can be formed because carbon wherein-carbon double bond connects different substituting groups, the present invention includes the mixture of any ratio of Z-type isomer and E-isomer and they.Compound shown in formula of the present invention (I), form steric isomer (respectively with R and S to represent different configurations) owing to wherein same carbon atom connecting four different substituting groups, the present invention includes the mixture of R type isomer and S type isomer and their any ratios.
The invention still further relates to a kind of prevent and treat injurious weed, harmful levels of pathogens, insect containing formula (I) compound of biologic effective dose and the other composition being selected from tensio-active agent, solid diluent and liquid diluent of at least one.
The invention still further relates to a kind of method of preventing and treating injurious weed, harmful levels of pathogens, insect, comprise the formula of biologic effective dose (I) compound contact injurious weed, harmful levels of pathogens, insect or its environment.Simultaneously also relate to so a kind of injurious weed, harmful levels of pathogens, insect pest control method, formula (I) compound of injurious weed, harmful levels of pathogens, insect or its environment biologic effective dose carries out contact to prevent and treat injurious weed, harmful levels of pathogens, insect.
Formula of the present invention (I) compound has broad spectrum of activity: the compound had can be used for preventing and treating injurious weed, also can be used for control harmful levels of pathogens or insect.And the compound had has very high biological activity to some injurious weed, make just can obtain good effect under very low dosage.
The preferred composition of the present invention is the composition containing above-mentioned preferred compound.Preferred method is the method using above-mentioned preferred compound.
Further illustrate the present invention with the segment bounds listed in table 1 ~ table 2 (I) compound below, but do not limit the present invention.In the present invention give fusing point all not calibrated; When formula (I) compound synthesized by the present invention is viscous solid, some viscous solid refrigerator can be cured as non-tacky solids after placing; In table 1, all compounds all can be observed its molecular ion peak in LC-MS (APCI, Pos) (Agilent1100Series LC/MSD); Compound in table 1
1mark in H NMR (Varian INOVA-300spectrometer) does with tetramethylsilane (TMS), deuterochloroform (CDCl
3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1
*r represents a R type isomer;
#r/S represents the mixture of R type isomer and any ratio of S type isomer.
Table 2
Compound shown in formula (I) can be obtained by reaction formula 1 shown below; (II) in reaction formula 1 can be obtained by reaction formula 2 shown below; (III) in reaction formula 1 can be obtained by the reaction formula 3 shown in below or reaction formula 4, and the Z in reaction formula 1 to reaction formula 4 is leavings group, and as chlorine, bromine, sulphonate etc., other substituting group is outer unless specified otherwise all to be limited as front.
Reaction formula 1:
Reaction formula 2:
Reaction formula 3:
Reaction formula 4:
The compound of formula (I) can be prepared (reaction formula 1) like this: at suitable solvent as in methylene dichloride or ethylene dichloride, toluene, in-10 ~ 110 DEG C, at suitable alkali as under triethylamine or pyridine existence, with the compound reaction shown in the compound shown in formula (II) and formula (III), obtain the compound shown in formula (I), add suitable catalyzer and can add fast response as 4-dimethylamino pyridine (DMAP) or sodium iodide or improve reaction yield.
The compound of formula (II) can be prepared (reaction formula 2) like this: at suitable solvent as N, in dinethylformamide (DMF) or toluene, tetrahydrofuran (THF), ethanol, at suitable alkali as under salt of wormwood or potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydride exist, under 25 ~ 150 DEG C of conditions, react to obtain the compound shown in formula (VI) with the compound shown in formula (IV) and the compound shown in formula V, the compound shown in formula (VI) and acyl halide reagent react as sulfur oxychloride or oxalyl chloride, phosphorus trichloride etc. and obtain compound shown in formula (II).
The compound of formula (III) can be prepared (reaction formula 3 or reaction formula 4) like this: at suitable solvent as N, dinethylformamide (DMF) or tetrahydrofuran (THF), ethanol, in methylene dichloride, at suitable alkali as sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium hydride, triethylamine, under pyridine exists, under 25 ~ 120 DEG C of conditions, the compound shown in formula (IX) is reacted to obtain with the compound shown in the compound shown in formula (VII) and formula (VIII), compound shown in formula (IX) at suitable solvent as in ethanol or methyl alcohol, to be hydrolyzed as hydrazine hydrate with suitable reagent and to obtain formula (III R
2=H) shown in compound, formula (IIIR
2=H) shown in compound and R
2z alkylated reaction obtains the compound (reaction formula 3) shown in formula (III), or at suitable solvent as in trichloromethane and water or tetrahydrofuran (THF), ethanol, at suitable alkali as under the existence such as sodium hydroxide, potassium hydroxide, salt of wormwood, sodium carbonate, sodium hydride, under 0 ~ 100 DEG C of condition, react to obtain the compound (reaction formula 4) shown in formula (III) with the compound shown in the compound shown in formula (X) and formula (VIII), add suitable phase-transfer catalyst and can add fast response as benzyltriethylammoinium chloride (TEBA) or Tetrabutyl amonium bromide, tetrabutylammonium chloride etc. or improve reaction yield.
Concrete synthetic method has more detailed elaboration in the following embodiments.
Formula provided by the invention (I) compound has broad-spectrum biological activity under 15 ~ 2250 grams of effective constituents/hectare consumption, both can be used for preventing and treating injurious weed, also can be used for control harmful levels of pathogens or insect, some compounds have good injurious weed preventive and therapeutic effect, under very low dosage, just can obtain good effect.
Formula provided by the invention (I) compound, has biological activity and some compounds have good biological activity. particularly in agricultural, gardening, flowers and health injurious weed, harmful levels of pathogens, the preventing and treating of insect, show activity.Harmful organism described here include but not limited to this:
Gramineous weeds: lady's-grass, barnyard grass, Herba Setariae Viridis, hard Cao, Wang grass, bromegrass, amur foxtail, Triticum tauschii, alkali thatch, flower of Stinkgrass, wild avena sativa, rye grass;
Broadleaf weeds: piemarker, chickweed, black nightshade, lamb's-quarters, recessed head amaranth, Amaranthus retroflexus, thorn amaranth etc.
Harmful pathogenic bacteria: phytophthora kind, white powder belongs to kind, Gibberella kind, Venturia kind, species of Monilinia fructicola, Rhizoctonia kind, Staphlosporonites kind, Pyricularia Sacc. kind, fusarium kind, as rice blast (Pyricularia oryzae); Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Large wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Barley and wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew (Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar); Wheat hypochnus and glume blight (Septoria nodorum).The compacted spore of length on cereal, mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas is sick, Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).The cercospora brown spot of peanut (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata); Apple wheel line harmful levels of pathogens (Botryosphaeria berengriana f.sp piricola), apple decay harmful levels of pathogens (Cytospora sp.); The mould genus of its tail spore on beet, soybean and paddy is sick.Tomato, cucumber, grape grey mould (Botrytis cinerea).Hinge spore on vegetables (as cucumber) belongs to sick.Anthrax on cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, the epidemic disease on potato and tomato, the list bacterium Thanatephorus cucumeris on paddy and other hosts are as other rhizoctonia on Wheat and barley, vegetables; Sclerotinia rot of colza (Sclerotonia sclerotiorum); Wheat scab (Gibberella zeae); Phytophthora capsici disease (Phytophythora capsici) etc.
Insect: Orthoptera is as blattaria, Thysanoptera is as cotton thrips, rice thrips, melon thrips, Homoptera is as leafhopper, plant hopper, aphid, lepidopteran is as oriental armyworm, prodenia litura, small cabbage moth, beet armyworm, cabbage looper, cabbage caterpillar, Hymenoptera is as sawfly larva, and Diptera is as yellow-fever mosquito, culex, fly, and acarina is as Jie-Li enzyme-SQ, cotton spider mites.
When being used alone formula of the present invention (I) compound, be effective to control injurious weed, harmful levels of pathogens, insect, they also can use together with other materials.
Using formula (I) compound as the Agrotechnical formulation of effective ingredient, desired any one formulation can be made.
Below in conjunction with embodiment, the invention will be further described, and the yield in embodiment is all without optimization.
Embodiment
Embodiment 1
The preparation method of compound 01 in the present embodiment instruction card 1.
(R)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid adds N in the 100mL there-necked flask being furnished with magnetic stirring apparatus, thermometer and prolong, dinethylformamide (DMF) (40mL), (R) 2-(4-hydroxyphenoxy) propionic acid (0.02mol), after stirring and dissolving, add salt of wormwood (0.04mol) in batches, be warming up to 60 ~ 80 DEG C and stir 0.5 ~ 1.0hr.Dropwise add 2,3-difluoro-5-chloropyridine (0.02mol), continue stirring reaction 6 ~ 8hr.Reactant is cooled to room temperature, pours in frozen water (250mL), more slowly add dilute hydrochloric acid in mixture, be adjusted to pH=4 ~ 5, filter, washing, the dry title compound 5.92g obtaining white solid.
N is added in 2-diuril azoles-5-base methylamine 100mL there-necked flask, dinethylformamide (40mL), phthalic imidine (0.05mol) and potassium hydroxide (0.05mol), after stirring at room temperature is dissolved, drip 2-chloro-5-chloromethyl thiazole (0.05mol), stirred overnight at room temperature.Reactant is poured in frozen water (250mL), filter, wash to obtain white solid.Solid is joined in 250mL there-necked flask, add ethanol (150ml).After heating for dissolving, drip hydrazine hydrate (18g, 80%), under stirring and refluxing condition, react 3 ~ 4hr, cooling, filters, gets filtrate, and precipitation obtains yellow oily matter, pour in saturated nacl aqueous solution, extraction into ethyl acetate, dry, precipitation obtains title compound 2.90g.
(R) toluene (40mL) is added in-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide (in table 1 compound 01) 100mL single port bottle, (R)-2-(4-((the fluoro-5-chloropyridine of 3--2-base) oxygen base) phenoxy group) propionic acid (3.3mmol) and thionyl chloride (10mmol).Slough toluene after reactant backflow 3 ~ 5hr and obtain (R)-2-(4-((the fluoro-5-chloropyridine of 3--2-base) oxygen base) phenoxy group) propionyl chloride.Methylene dichloride (40mL) is added in acyl chlorides, the 4-dimethylaminopyridine (DMAP) of 2-diuril azoles-5-base methylamine (3.3mmol) and catalytic amount, stir 10 ~ 15min under ice bath cooling conditions, dropwise instill triethylamine (10mmol).Reactant continues stirring 2 ~ 3hr, pours in 100 ~ 200mL frozen water, uses dichloromethane extraction.Organic phase washing (100mL*2), anhydrous sodium sulfate drying, precipitation.The thick product of gained is through column chromatography (thin-layer chromatography silica gel V
sherwood oil/ V
ethyl acetate=5/1) the title compound 0.36g of faint yellow solid is obtained, yield 25%, fusing point 100.1-100.9 DEG C.
Embodiment 2
The preparation method of compound 03 in the present embodiment instruction card 1.
2-chloro-5-chloromethyl thiazole (0.05mol) is added, CHCl in N-methyl-(2-diuril azoles-5-base) methylamine 200mL single port bottle
3(50mL), drip aqueous methylamine solution (25g, 25-30%) and aqueous sodium hydroxide solution (25ml, 10%) after stirring, and add a small amount of phase-transfer catalyst Tetrabutyl amonium bromide, 25 ~ 30 DEG C of stirring reactions spend the night.Dilute hydrochloric acid adjusts pH to weakly alkaline, separatory, and organic phase washing twice rear anhydrous sodium sulfate drying, precipitation obtains the title compound of the forsythia liquid of 6.67g.
(R) toluene (40mL) is added in-N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide (in table 1 compound 03) 100mL single port bottle, (R)-2-(4-((the fluoro-5-chloropyridine of 3--2-base) oxygen base) phenoxy group) propionic acid (3.3mmol) and thionyl chloride (10mmol).Slough toluene after reactant backflow 3 ~ 5hr and obtain its acyl chlorides.Methylene dichloride (40mL) is added in acyl chlorides, the 4-dimethylaminopyridine (DMAP) of N-methyl-(2-diuril azoles-5-base) methylamine (3.3mmol) and catalytic amount, stir 5 ~ 10min under ice bath cooling conditions, dropwise instill triethylamine (10mmol).Reactant is poured in 100 ~ 200mL frozen water after continuing stirring 2 ~ 3hr, dichloromethane extraction.Organic phases washed with water (100mL*2), anhydrous sodium sulfate drying, precipitation.The thick product of gained is through column chromatography (thin-layer chromatography silica gel V
sherwood oil/ V
ethyl acetate=5/1) the title compound 0.73g of faint yellow viscous liquid is obtained, yield 48%.
The preparation method of compound 42 in embodiment 3 the present embodiment instruction card 1.
(R)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid adds N in the 100mL there-necked flask being furnished with magnetic stirring apparatus, thermometer and prolong, dinethylformamide (DMF) (40mL), (R)-2-(4-hydroxybenzene oxygen) propionic acid ([α]
589 20 DEG C=+59.5 ° (acetone)) (0.02mol), after stirring and dissolving, add salt of wormwood (0.04mol) in batches, be warming up to 60 ~ 80 DEG C and stir 1.0 ~ 1.5hr.Dropwise add 2,3-bis-chloro-5-trifluoromethylpyridine (0.02mol), continue stirring reaction 8 ~ 10hr.Reactant is cooled to room temperature, pours in frozen water (250mL), more slowly add dilute hydrochloric acid in mixture, be adjusted to pH=4 ~ 5, filter, washing, the dry title compound 6.56g obtaining white solid, [α]
589 20 DEG C=+37.9 ° (acetone).
N is added in 2-chloropyridine-5-base methylamine 100mL there-necked flask, dinethylformamide (DMF) (40mL), phthalic imidine (0.05mol) and potassium hydroxide (0.05mol), stirring at room temperature is dissolved, drip CCMP (0.05mol), stirred overnight at room temperature.Reactant is poured in frozen water (250mL), filter, wash to obtain white solid.Solid is joined in 250mL there-necked flask, add ethanol (150ml).After heating for dissolving, drip hydrazine hydrate (18g, 80%), back flow reaction 4-6hr under agitation condition, cooling, filters, gets filtrate, and precipitation obtains yellow oily matter, pour in saturated nacl aqueous solution, extraction into ethyl acetate, dry, precipitation obtains faint yellow title compound 2.96g.
(R) toluene (40mL) is added in-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionyl chloride 100mL single port bottle, (R)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid (3.3mmol) and sulfur oxychloride (10mmol).Solvent is sloughed and excessive sulfur oxychloride obtains title thing after reactant backflow 4 ~ 6hr.
(R) methylene dichloride (40mL) is added in-N-(2-chloropyridine-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide (in table 1 compound 42) 100mL single port bottle, (R)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionyl chloride (3.3mmol), the 4-dimethylaminopyridine (DMAP) of 2-chloropyridine-5-base methylamine (3.3mmol) and catalytic amount, after the lower stirring 10 ~ 15min of ice bath cooling, dropwise instill triethylamine (10mmol).Reactant is poured in 200mL frozen water, is used dichloromethane extraction after continuing stirring 2 ~ 3hr.Organic phase is washed, anhydrous sodium sulfate drying, precipitation.The thick product of gained is through column chromatography (thin-layer chromatography silica gel V
sherwood oil/ V
ethyl acetate=3/1) the title compound 0.42g of off-white color solid is obtained, [α]
589 20 DEG C=+19.4 ° (acetone), ee%=99.0%, fusing point 109.6-112.0 DEG C.
The preparation method of compound 43 in embodiment 4 the present embodiment instruction card 1.
(R/S) 2 bromopropionic acid, under 15 ~ 25 DEG C of conditions, is slowly joined 50%NaOH(0.1mol by-2-(4-hydroxyphenoxy) propionic acid) in solution, after stirring and dissolving, add 30ml water, continue stirring 5 ~ 10min, for subsequent use.Under 15 ~ 25 DEG C of conditions, Resorcinol (0.4mol) and water 50ml is added in reaction flask, 50%NaOH(0.8mol is added) under stirring, add the NaOH solution of above-mentioned 2 bromopropionic acid again, 50 ~ 60 DEG C of reaction 4 ~ 6hr, cooling, dilute hydrochloric acid adjusts PH to 4.0 ~ 4.5, be extracted with ethyl acetate, dilute hydrochloric acid adjusts pH to 1.0 ~ 1.5, isopropyl acetate extracts, organic phase add water azeotropic removing isopropyl acetate, aqueous solution 50%NaOH solution adjusts PH to 2.0 ~ 2.5, cooling, be extracted with ethyl acetate, anhydrous sodium sulfate drying, precipitation obtains (R, S)-2-(4-hydroxyphenoxy) propionic acid 16.5g, [α]
589 20 DEG C=-0.1 ~+0.1 ° (acetone).
(R/S)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid adds N in the 100mL there-necked flask being furnished with magnetic stirring apparatus, thermometer and prolong, dinethylformamide (DMF) (40mL), (R/S)-2-(4-hydroxyphenoxy) propionic acid (0.02mol), after stirring and dissolving, add salt of wormwood (0.04mol) in batches, after being warming up to 60 ~ 80 DEG C of stirring 1.0 ~ 1.5hr, dropwise add 2,3-bis-chloro-5-trifluoromethylpyridine (0.02mol), continues stirring reaction 8 ~ 10hr.Reactant is cooled to room temperature, pours in frozen water (250mL), more slowly add dilute hydrochloric acid in mixture, be adjusted to pH=4 ~ 5, filter, washing, the dry title compound 7.02g obtaining white solid, [α]
589 20 DEG C=-0.2 ~+0.2 ° (acetone).
(R/S) toluene (40mL) is added in-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionyl chloride 100mL single port bottle, (R/S)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid ([α]
589 20 DEG C=-0.2 ~+0.2 ° (acetone)) (3.3mmol) and sulfur oxychloride (10mmol).Solvent is sloughed and excessive sulfur oxychloride obtains title compound after reactant backflow 4 ~ 6hr.
(R/S) methylene dichloride (40mL) is added in-N-(2-chloropyridine-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide (in table 1 compound 43) 100mL single port bottle, (R/S)-2-(4-(3-chloro-5-trifluoromethylpyridine-2-base oxygen base) phenoxy group) propionyl chloride (3.3mmol), the 4-dimethylaminopyridine (DMAP) of 2-chloropyridine-5-base methylamine (3.3mmol) and catalytic amount, after the lower stirring 10 ~ 15min of ice bath cooling, dropwise instill triethylamine (10mmol).Reactant is poured in 200ml frozen water, is used dichloromethane extraction after continuing stirring 2 ~ 3hr.Organic phase washing (100mL*2), anhydrous sodium sulfate drying, precipitation.Products obtained therefrom is through column chromatography (thin-layer chromatography silica gel V
sherwood oil/ V
ethyl acetate=3/1) the title compound 0.37g of off-white color solid is obtained, yield 22.6%, [α]
589 20 DEG C=-0.3 ° (acetone), ee%=0.15%, fusing point 109.0-110.5 DEG C.
Raw survey embodiment
Carried out weeding, sterilization and insecticidal activity test to synthesized compound, part of test results is as follows.
The evaluation of embodiment 5 weeding activity
Method is as follows: (1) is at sectional area 64cm
2plastic tub alms bowl in quantitatively dress soil pressure put down, be placed in Stainless steel basin, choose full seed, seed of the same size, divide monocotyledon weed [lady's-grass (Digitaria sanguinalis), barnyard grass (Echinochloa crus-galli), Herba Setariae Viridis (Setaria viridis)] and broadleaf weed [piemarker (Abutilon theophrasti), thorn amaranth (Amaranthus spinosus), lamb's-quarters (Chenopodium album)] point alms bowl sowing, respectively account for 1/3 of alms bowl area, cover the thick fine earth of 1cm, bottom plastic tub alms bowl, add water to upper layer of soil infiltrate, be placed in hot-house culture, treat that examination material grows to required leaf age and carries out test process, (2) take appropriate formula provided by the invention (I) compound, dissolve with DMF, then add a small amount of tween 80 emulsifying agent, stir, add quantitative clear water, be mixed with desired concn, if coordinative solvent and clear water are contrast, (3) processing mode: next day is carried out soil treatment before seedling in the sowing of examination material, unifacial leaf examination material grew to for 1 leaf 1 heart stage, dicotyledonous examination material grows to 2 leaf periods and carries out cauline leaf process after seedling, (4) quantitatively pipette liquid carry out cauline leaf spraying and soil spraying process by arranging dosage, respectively with spray solvent and clear water for contrasting, (5) process examination material is placed in hot-house culture, (6) to process after 15-25 days visually upper grown situation, according to investigation result, calculate the preventive effect of each compound to weeds as follows: preventive effect (%)=100 × (contrast plant height-process plant height)/contrast plant height.Result shows that the compounds of this invention has remarkable activity to weeds.Partial results is as table 3 ~ table 4.In view of the result of table 3 and table 4, test the security (the results are shown in Table 5) of part of compounds to paddy rice and wheat, compare part of compounds and similar commercial References Yao Ji metamifop and the cyhalofop-butyl weeding activity to rice terrace the worst weeds Semen Euphorbiae and barnyard grass simultaneously, the results are shown in Table 6.Result shows that compound 42 pairs of paddy rice have security, and has excellent activity to rice terrace the worst weeds Semen Euphorbiae and barnyard grass, and compound 42 also has excellent activity to other gramineous weeds.
The weeding activity of table 3 part of compounds under 2250 grams/ha of dosage
The cauline leaf process weeding activity of table 4 part of compounds under 15-60 gram/ha of dosage
*/ represent and do not test,
#represent that dosage (g a.i/ha) is 18.75,37.50,75.00.
Table 5 part of compounds is to the cauline leaf process safety testing result of paddy rice-Hunan No. 24, Xian morning
| Dosage (g a.i/ha) | 120 | 60 | 30 | 15 |
| 13 | 40% suppresses, dead seedling | 50% suppresses | 30% suppresses | 10% suppresses |
| 35 | 60% suppresses | 40% suppresses | 20% suppresses | 10% suppresses |
| 42 | Normally | Normally | Normally | Normally |
| 56 | 70% suppresses, dead seedling | 30% suppresses, dead seedling | 20% suppresses | 10% suppresses |
| 62 | 60% suppresses, dead seedling | 30% suppresses, dead seedling | 20% suppresses | 10% suppresses |
| Clodinafop-propargyl | 100% suppresses, dead seedling | 100% suppresses, dead seedling | 80% suppresses, dead seedling | 70% suppresses, dead seedling |
The cauline leaf process weeding activity of table 6 compound 42 pairs of rice terrace the worst weeds Semen Euphorbiaes and barnyard grass
*/ represent and do not test.
The fungicidal activity of embodiment 6 pairs of Sclerotinia sclerotiorums (Sclerotonia sclerotiorum)
Method is as follows: testing compound is dissolved in suitable solvent as in DMF (DMF), then is diluted to desired concn with the sterilized water containing 0.1%Tween80 emulsifying agent; Get 3mL liquid with transfer pipet to add in the potato agar substratum (PDA) of the 27mL being cooled to 45 DEG C and to pour culture dish into after fully shaking up; Cool rear inoculating needle and get 6mm diameter mycelia block from the cultivation Sclerotinia sclerotiorum colony edge of 7 days, move to culture dish central authorities, mycelia faces down, and setting the blank not containing testing compound as contrasting simultaneously, often processing and repeating for 4 times; Constant temperature biochemical cultivation case culture dish being placed in 28 DEG C after being disposed is cultivated, and within 4 days, measures mycelial growth diameter afterwards, adopts EXCEL statistical software carry out analyzing and calculate mycelial growth inhibition rate (%).Active relative to blank with percentages, be divided into A, B, C, D level Four, 100%≤suppression Shuai≤90% is A level, 90% > suppression Shuai≤70% is B level, 70% > suppression Shuai≤50% is C level, and 50% > suppression Shuai≤0% is D level.Result shows that compound of the present invention has activity to Sclerotinia sclerotiorum, and as compound 32 and 48,67 grades all have the activity of more than C level under 25mg/L concentration to Sclerotinia sclerotiorum.
The fungicidal activity of embodiment 7 pairs of botrytis cinerea pers (Botrytis cinerea)
Adopt the measuring method of the fungicidal activity of embodiment 6 pairs of Sclerotinia sclerotiorums, determine formula (I) compound to the activity of botrytis cinerea pers, result shows that compound of the present invention has activity to botrytis cinerea pers, as compound 03 and 05,20,22 grades all have the activity of more than C level under 25mg/L concentration to botrytis cinerea pers.
The fungicidal activity (leaf culture in vitro method) of embodiment 8 pairs of Rhizoctonia solani Kuhns (Rhizoctonia solani)
Method is as follows: testing compound is dissolved in suitable solvent as in DMF (DMF), then is diluted to desired concn with the sterilized water containing 0.1%Tween80 emulsifying agent; Get fresh, children tender Vicia faba seedling plant leaf lie in after certain density chemicals treatment be covered with moisture filter paper culture dish in, blade and filter paper self-made punching brandreth are separated by.Connecting diameter after blade dries is 6mm, cultivates the fresh mycelia block of 2 ~ 3 days.Often process and repeat for 3 times, separately set the blank not containing testing compound as contrasting, moisturizing thermophilic checks lesion area after being cultured to blank morbidity, calculates pharmacy control efficacy.Active relative to blank with percentages.Result shows that compound of the present invention has prevention effect to rice sheath blight disease, as compound 01 reaches more than 50% to the preventive effect of rice sheath blight disease under 500mg/L concentration.
The fungicidal activity (pot-culture method) of embodiment 9 pairs of wheat powdery mildews (Erisiphe griminis)
Method is as follows: testing compound is dissolved in suitable solvent as in DMF (DMF), then is diluted to desired concn with the sterilized water containing 0.1%Tween80 emulsifying agent; The basin alms bowl of cut-off stem about 15cm, 20, the seed of the full stalwartness of every alms bowl sowing wheat, is wholeheartedly for experiment afterwards wait growing two leaves; Get ready wheat seedling plant through certain density reagent spray process, after one day, carry out harmful levels of pathogens inoculation.Often process and repeat for 3 times, separately set the blank not containing testing compound as contrasting, moisturizing thermophilic checks lesion area after being cultured to blank morbidity, calculates pharmacy control efficacy.Active relative to blank with percentages.Result shows that compound of the present invention has prevention effect to wheat powdery mildew, as compound 03 reaches more than 80% to the preventive effect of wheat powdery mildew under 500mg/L concentration.
The Insecticidal Activity of embodiment 10 pairs of bean aphids (Aphis fabae)
Method is as follows: take appropriate formula provided by the invention (I) compound, with suitable solvent as DMF dissolves, then add a small amount of tween 80 emulsifying agent, stir, add quantitative clear water, be mixed with desired concn, if clear water is contrast.Bean aphid is connected on just unearthed bean seedlings, every strain connects more than 20, then bean seedlings are dipped in the liquid of formula provided by the invention (I) compound together with examination worm, take out after 5 seconds, suck unnecessary liquid, insert in the sponge of water suction, cover with glass-tube, after 24 hours, check survival and dead borer population.Repeat 3 times, results averaged.Active blank is relatively with percentages.Result shows that compound of the present invention has activity to bean aphid, and as under 500mg/L concentration, compound 13 and 20, the activity (mortality ratio) of 22 grades to black bean aphid is all greater than 50%.
The acaricidal activity of embodiment 11 pairs of two-spotted spider mites (Tetranychus urticae)
Method is as follows: take appropriate formula provided by the invention (I) compound, with suitable solvent as DMF dissolves, then add a small amount of tween 80 emulsifying agent, stir, add quantitative clear water, be mixed with desired concn, if clear water is contrast.Select the bean seedlings inoculation red spider grown fine, after red spider grows surely, band mite bean seedlings are cut and floods 10 seconds in the liquid prepared, taking-up filter paper sucks unnecessary liquid, insert in and be filled with water in beaker, in observation indoor cultivation, check survival and dead mite number after 24 hours, every strain bean seedlings have 100-200 mite.Experiment repetition 3 times.Results averaged.Active relative to blank with percentages, be divided into A, B, C, D level Four, 100%≤Si Wang Shuais≤and 90% be A level, 90% > Si Wang Shuais≤and 70% be B level, 70% > Si Wang Shuais≤and 50% be C level, 50% > Si Wang Shuais≤and 0% be D level.Result shows that compound of the present invention has activity to two-spotted spider mite, and as under 500mg/L concentration, the activity (mortality ratio) of compound 48 grade to two-spotted spider mite is greater than 50%.
Claims (9)
1.N-(arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that representing with general formula (I):
Wherein:
I.Ar
1and Ar
2be identical or different, and represent C
6-C
12the heteroaryl of aryl or band as many as 10 carbon atoms, and
A) C
6-C
12hydrogen moiety in the heteroaryl of aryl or band as many as 10 carbon atoms or be all selected from following in identical or different substituting group replace: halogen, nitro, cyano group, amido, hydroxyl, sulfydryl, carboxyl, aldehyde radical, diazanyl, hydrazone group, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12the heteroaryl amido of arylamine group or band as many as 10 carbon atoms;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkynyl group, C
3-C
8cycloalkyl, C
6-C
12the heteroaryl of aryl or band as many as 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) and II. described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, in heteroaryl hydrogen moiety or be all selected from following in identical or different substituting group replace: halogen, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12heteroaryl amido, two C of arylamine group or band as many as 10 carbon atoms
6-C
12two heteroaryl amidos, the C of arylamine group or band as many as 10 carbon atoms
6-C
12heteroarylaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12the heteroarylheteroaryl of aryl heteroaryl or band as many as 10 carbon atoms; And 1) described in alkyl, cycloalkyl, alkenyl, alkynyl group, aryl, in heteroaryl hydrogen moiety or be all selected from following in identical or different substituting group replace: hydrogen, halogen, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, two (C
1-C
6) alkyl amine group, C
2-C
6alkenyl, C
2-C
6alkenyl oxy, C
2-C
6alkenyl thio, C
2-C
6alkenyl amido, two C
2-C
6alkenyl amido, C
2-C
6alkynyl group, C
2-C
6alkynyl group oxygen base, C
2-C
6alkynyl group sulfenyl, C
2-C
6alkynyl group amido, two C
2-C
6alkynyl group amido, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl oxy, C
3-C
8cycloalkylsulfanyl, C
3-C
8cycloalkyl amido, two C
3-C
8cycloalkyl amido, C
6-C
12heteroaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12heteroaryl oxygen base, the C of aryloxy or band as many as 10 carbon atoms
6-C
12heteroarylthio, the C of artyl sulfo or band as many as 10 carbon atoms
6-C
12heteroaryl amido, two C of arylamine group or band as many as 10 carbon atoms
6-C
12two heteroaryl amidos, the C of arylamine group or band as many as 10 carbon atoms
6-C
12heteroarylaryl, the C of aryl or band as many as 10 carbon atoms
6-C
12the heteroarylheteroaryl of aryl heteroaryl or band as many as 10 carbon atoms;
In the definition of the compound (I) provided, no matter term used is used alone or is used in compound word, represent following substituting group above:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to straight or branched alkyl;
Cycloalkyl: refer to saturated or undersaturated cycloalkyl;
Alkenyl; Refer to straight or branched and double bond can be had on any position;
Alkynyl group; Refer to straight or branched and triple bond can be had 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 saturated or undersaturated cycloalkyl, and hydrogen moiety wherein or all replaced by halogen atom;
Halogenated alkenyl: refer to straight or branched double bond can be had on any position, and hydrogen moiety wherein or all replaced by halogen atom;
Halo alkynyl: refer to straight or branched triple bond can be had on any position, and hydrogen moiety wherein or all replaced by halogen atom;
C
6-C
12aryl means phenyl and by its derivative cyclophane base or polyaromatic;
Heteroaryl with as many as 10 carbon atoms refers to a ring heteroaryl or polyheteroaromatic, heteroatoms identical or different in following containing 1-5 in ring: N, O, S, P;
C
6-C
12the heteroaryl of aryl and band as many as 10 carbon atoms can partly or entirely hydrogenation, wherein 1 or 2 CH
2replaced by CO, as cyclohexenyl, cyclohexanedione base etc.
2. N-according to claim 1 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that in compound shown in general formula (I):
C
6-C
12aryl means phenyl and by its derivative naphthyl or xenyl;
Heteroaryl with as many as 10 carbon atoms refers to pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, pyrazolyl, thiadiazolyl group, thienyl, benzothienyl, furyl, benzofuryl, pyrryl, benzopyrrole base, imidazolyl, benzimidazolyl-, quinolyl, pyranyl, pyrazinyl, pyrimidyl, pyridazinyl, benzopyranyl, benzo pyrimidyl, oxazolyl, isoxazolyl, benzoisoxazole base, benzothiazolyl, isothiazolyl, benzisothiazole base, Kui Linpyrimido quinoline triazolyl.
3. N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that in compound shown in general formula (I):
I.Ar
1and Ar
2identical or different, and represent phenyl, pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and hydrogen moiety in phenyl, pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl or be all selected from following in identical or different substituting group replace: halogen, cyano group, C
1-C
6alkyl, C
1-C
6alkyl oxy, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl amine group, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
6alkyl, C
1-C
6haloalkyl;
III.n represents 1.
4. N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that in compound shown in general formula (I):
I.Ar
1and Ar
2be identical or different, and represent pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl, and hydrogen moiety in pyridyl, thiazolyl, quinoxalinyl, benzoxazolyl or be all selected from following in identical or different substituting group replace: halogen, C
1-C
3alkyl, C
1-C
3alkoxyl group, C
1-C
3haloalkyl, C
1-C
3halogenated alkoxy;
II.R
1and R
2, R
3be identical or different, and represent hydrogen, C
1-C
3alkyl;
III.n represents 1.
5. N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that compound shown in general formula (I) is the mixture of following compound R type isomer and any ratio of S type isomer:
N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide.
6. N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that shown in general formula (I), compound is:
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-methyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-ethyl-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-chloro-3-fluoropyridine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((3-chloro-5-trifluoromethylpyridine-2-base) oxygen base) phenoxy group) 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) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((5-5-flumethiazine-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((the fluoro-4-cyano-phenyl of 2-) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chlorobenzene also [d] oxazole-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-diuril azoles-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide;
(R)-N-(2-chloropyridine-5-ylmethyl)-2-(4-((6-chloro-quinoxaline-2-base) oxygen base) phenoxy group) propionic acid amide.
7. the preparation method of N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, is characterized in that the compound shown in formula (I) is prepared by the reaction below,
Reaction formula 1:
Reaction formula 2:
Reaction formula 3:
Reaction formula 4:
In methylene chloride or ethylene dichloride, toluene, in-10 ~ 110 DEG C, under alkali triethylamine or pyridine exist, with the compound reaction shown in the compound shown in formula (II) and formula (III), the compound shown in formula (I), add catalyzer 4-dimethylamino pyridine or sodium iodide and can add fast response or improve reaction yield (reaction formula 1);
At solvent N, in dinethylformamide (DMF) or toluene, tetrahydrofuran (THF), ethanol, under alkali salt of wormwood or potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydride exist, under 25 ~ 150 DEG C of conditions, react to obtain the compound shown in formula (VI) with the compound shown in formula (IV) and the compound shown in formula V, the compound shown in formula (VI) and acyl halide reagent sulfur oxychloride or oxalyl chloride, phosphorus trichloride react and obtain compound (reaction formula 2) shown in formula (II);
At solvent N, in dinethylformamide or tetrahydrofuran (THF), ethanol, methylene dichloride, under alkali sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium hydride, triethylamine, pyridine exist, under 25 ~ 120 DEG C of conditions, the compound shown in formula (IX) is reacted to obtain with the compound shown in the compound shown in formula (VII) and formula (VIII), compound shown in formula (IX), in etoh solvent or methyl alcohol, is hydrolyzed with hydrazine hydrate and obtains formula (III R
2=H) shown in compound, formula (III R
2=H) shown in compound and R
2z alkylated reaction obtains the compound (reaction formula 3) shown in formula (III); Or in solvent trichloromethane and water or tetrahydrofuran (THF), ethanol, under alkali sodium hydroxide or potassium hydroxide, salt of wormwood, sodium carbonate, sodium hydride exist, under 0 ~ 100 DEG C of condition, react to obtain the compound shown in formula (III) with the compound shown in the compound shown in formula (X) and formula (VIII), add phase-transfer catalyst benzyltriethylammoinium chloride or Tetrabutyl amonium bromide, tetrabutylammonium chloride can add fast response or improve reaction yield (reaction formula 4);
Ar in formula
1and Ar
2, R
1, R
2, R
3, n to have in claim 1 to definition, Z is leavings group chlorine or bromine, sulphonate.
8. the purposes of N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof, to is characterized in that under 15 ~ 2250 grams of effective constituents/hectare consumption tool weeding and/or sterilization, desinsection, kills mite biological activity.
9. N-according to claim 1 and 2 (arylalkyl) fragrant phenoxy carboxylic acid amide compounds and isomer thereof are for the preparation of the purposes of medicine with weeding activity and/or fungicidal activity, insecticidal activity, acaricidal activity.
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| WO2015000392A1 (en) | 2015-01-08 |
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