CN106632007A - Pyridyl-3-yl-aryloxyphenoxynoic acid ester compounds and application thereof - Google Patents

Pyridyl-3-yl-aryloxyphenoxynoic acid ester compounds and application thereof Download PDF

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CN106632007A
CN106632007A CN201611160733.7A CN201611160733A CN106632007A CN 106632007 A CN106632007 A CN 106632007A CN 201611160733 A CN201611160733 A CN 201611160733A CN 106632007 A CN106632007 A CN 106632007A
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acid ester
ester compounds
pyridin
aryloxyphenoxy
alkyl
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CN106632007B (en
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刘祈星
周海峰
朱瑞
陈蕾
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Yichang Xinnada Biotechnology Co.,Ltd.
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China Three Gorges University CTGU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses pyridyl-3-yl-aryloxyphenoxynoic acid ester compounds and herbicidal activities thereof. The chemical structural formula is disclosed as Formula I or II, wherein X is nitrogen or carbon; Y is -N=CH- or oxygen; X1, X2 and X3 are respectively hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano or nitro; X4, X5 and X6 are respectively hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano or nitro or C1-C2 alkyl or C1-C2 alkoxy; and R1 is hydrogen or C1-C3 alkyl or C1-C3 halogenated alkyl. The invention also discloses a composition containing the compounds and application of the pyridyl-3-yl-aryloxyphenoxynoic acid ester compounds in the aspect of agricultural herbicides. Partial compounds have very high herbicidal activities, and can obtain favorable control effects under the amount of 5g/mou.

Description

Pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds and its application
Technical field
The present invention relates to a kind of compound, and in particular to a kind of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds and Its application.
Background technology
Fragrant phenoxy propionic acid (APP) analog derivative as grassy weed class herbicide, because with efficiently, low toxicity, Gao Xuan Selecting property and it is environmentally friendly the features such as, since listing, its research receives much concern.In the inhibited grassy weed of such herbicide Acetyl-CoA carboxylase (ACCase), blocks the synthesis of ester fat acid in plant body, and so as to effective as selective grass family is prevented and kill off Weeds, so as on broad leaf crop without impact.
Generally, the R configuration bodies of such compound are the active component of herbicide.In 1991, Novartis Co., Ltd developed One APP class herbicides --- clodinafop-propargyl for being used for wheat paddock, hereafter, Dow Chemical and Chemical Engineering Technology research institute of Korea develop successively Gone out two kinds for rice terrace APP class herbicides --- (P1) are He metamifop (P2) for cyhalofop-butyl.Research discovery, works as benzene After epoxide is by pyridine epoxide replacement, selective and activity will be greatly improved.In such APP classes herbicide, the spirit of fluorine pyrrole second standing grain (P3) it is representative herbicide.
The compound higher to obtain activity, inventor is introduced into 3- pyridones in fragrant phenoxy alkanoic acid structure, design And synthesize a series of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds for having no document report, it is found that it has significantly Activity of weeding.
The content of the invention
The invention provides a kind of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds and its isomers, its feature exists In its chemical structural formula is as shown in Formulas I or II：
In formula, X is nitrogen or carbon；Y is-N=CH- or oxygen；X1、X2、X3For hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or Any one in cyano group or nitro；X4、X5、X6For hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano group or nitro or C1 ～C2Alkyl or C1～C2Any one in alkoxyl；R1For hydrogen or C1～C3Alkyl or C1～C3It is any one in haloalkyl Kind.
In the definition of compound (I, II) given above, no matter term used is used alone also being used in compound word, Represent following substituent:
Alkyl：Refer to straight or branched alkyl；
Haloalkyl：Refer to straight or branched alkyl, hydrogen moiety on these alkyl or all replaced by halogen atom；
The compound of the present invention can be in the form of one or more isomers.Isomers includes enantiomter, non- Enantiomter, geometric isomer.Compound as shown in the formula (I, II) of the present invention, due to connecting four on a carbon atom Different substituent and form stereoisomer (representing different configurations with R and S respectively), the present invention includes R type isomers With S types isomers and the mixture of their any ratios.
In preferred scheme, the concrete structure formula of described pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds is：
The invention further relates to the activity of weeding of described pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds, 5 grams/ There is significant activity of weeding under mu consumption.
There is formula (the I, II) compound that the present invention is provided good control of weeds to act on, just can be with very low dosage Obtain good effect.
Formula (the I, II) compound that the present invention is provided, with biologically active and the compound that has have it is biological living well Property.Particularly show activity in terms of the preventing and treating of agricultural, gardening, flowers and health weeds.Weeds described here include, but It is not limited only to this：
Grassy weed：Lady's-grass, barnyard grass, green bristlegrass, hard grass, Wang grass, bromegrass, amur foxtail, Triticum tauschii, alkali thatch, stinkgrass flower, Wild oat, rye grass；
Broad leaved weed：Piemarker, chickweed, black nightshade, lamb's-quarters, concave head amaranth, Amaranthus retroflexus etc..
It is effective to controlling weeds when formula (the I, II) compound of the present invention is used alone, they can also be with other Biochemical is used together, and these biochemicals include other herbicides.
The invention further relates to answering in described pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds agricultural herbicide With.
The synthesis material of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds according to the present invention is easy to get, preparation method Simply, it is easy to industrialized production.
Specific embodiment
With reference to being embodied as, the present invention is further elucidated.These embodiments are interpreted as being merely to illustrate the present invention Rather than for limiting the scope of the invention.After the content for having read record of the present invention, those skilled in the art can To make various changes or modifications to the present invention, these equivalence changes and modification equally fall into what claims of the present invention was limited Scope.
Embodiment 1:The system of pyridin-3-yl-(R) -2- [4- (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionic ester (1) It is standby
DMF (40mL), (R)-(+) -2- (4- hydroxy benzenes oxygen) propionic acid (0.02mol, 3.64g), carbonic acid Potassium (0.02mol, 2.76g), stirs after 0.5h at 75 DEG C, adds the potassium carbonate of equivalent, continues to stir 0.5h.It is slowly added dropwise 2, 3- difluoro-5-chloropyridines (0.02mol, 3.00g), after completion of dropping, reaction temperature maintains 75 DEG C, overnight.Stop heating, cooling To room temperature, reactant liquor is poured into 200mL frozen water, watery hydrochloric acid adjusts pH 4-5, filtered, wash three times with a small amount of frozen water, vacuum It is dried, obtains (R) -2- [4- (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionic acid white solid 3.86g, yield 62.0%.
Toluene 40mL, (R) -2- [4- (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionic acid (3.3mmol, 1.04g), plus Enter in the single-necked flask of 100mL, after stirring and dissolving, add thionyl chloride (20mmol, 2.24g), back flow reaction 4h, decompression to steam Evaporate, obtain (R) -2- [4- (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionyl chloride yellow oily liquid, without the need for isolating and purifying, It is directly used in next step reaction.
Add in (R)-(+) -2- [4- (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionyl chloride obtained one step up Dichloromethane (40mL), 3- pyridones (0.31g, 3.3mmol), DMAP (DMAP, 0.02g, 0.17mmol), 15min is stirred under ice bath, triethylamine (1.37mL, 10mmol) is added dropwise over, after completion of dropping, continues to stir 10min, remove ice Bath, warms naturally to room temperature, stirs 4h, stops reaction, and reactant liquor is poured into 150mL frozen water, dichloromethane extraction (40mL* 3), organic phase is successively washed with 50mL saturated sodium bicarbonate solutions and 100mL, and anhydrous sodium sulfate drying is filtered, and removes two under reduced pressure Chloromethanes, silica gel column chromatography separating purification product, eluant, eluent (VPetroleum ether：VEthyl acetate=3:1) pyridin-3-yl-(R) -2- [4-, are obtained (the fluoro- 5- chloropyridines -2- epoxides of 3-) phenoxy group] propionic ester (1) yellow oily liquid 0.23g, yield 18.0%；1H NMR (CDCl3,400MHz)δ:1.81 (d, J=6.8Hz, 3H, CHCH 3 ), 5.00 (q, J=6.8Hz, 1H, CHCH3), 7.02 (d, J= 9.2Hz, 2H, PhH), 7.11 (d, J=9.2Hz, 2H, PhH), 7.35 (dd, J=8.4Hz, 4.4Hz, 1H, Py-H), 7.44～ 7.47 (m, 1H, Py-H), 7.50 (dd, J=9.2Hz, 2.0Hz, 1H, Py-H), 7.88 (d, J=2.0Hz, 1H, Py-H), 8.39 (d, J=2.8Hz, 1H, Py-H), 8.50 (dd, J=4.4Hz, 1.6Hz, 1H, Py-H)；13C NMR(CDCl3,100MHz)δ: 18.57,73.19,116.28,122.47,124.02,124.90,125.08,129.06,140.17,142.94,145.63, 147.00,147.24,147.40,148.28,154.67,170.22.
Embodiment 2:Pyridin-3-yl-(R) -2- [4- (3- chloro-5-trifluoromethylpyridine -2- epoxides) phenoxy group] propionic ester (2) preparation
(R) -2- (4- hydroxyphenoxies) propionic acid (3g), DMF (35ml), are slowly added to K2CO3(4.55g), it is warming up to 70～ 80 DEG C, 1h is stirred, be added dropwise over the chloro-5-trifluoromethylpyridines of 2,3- bis- (3.56g), keep 70～80 DEG C of stirring 8h, stopped anti- Should, room temperature is naturally cooled to, in pouring the mixture into frozen water (200mL), pH 4～5 is adjusted using watery hydrochloric acid, use ethyl acetate Extraction, organic phase washing, is dried, and precipitation obtains (R) -2- [4- (5- trifluoromethyl -3- chloropyridine -2- epoxides) phenoxy group] propionic acid palm fibre Color liquid 5.03g, yield 84.4%.
(R) -2- [4- (5- trifluoromethyl -3- chloropyridine -2- epoxides) phenoxy group] propionic acid (3.3mmol, 1.08g), is dissolved in In toluene (35mL), SOCl is added dropwise2(20mmol, 2.24g), is heated to reflux, and reacts 4h, and precipitation obtains (R) -2- [4- (5- fluoroforms Base -3- chloropyridine -2- epoxides) phenoxy group] propionyl chloride is directly used in next step.
Gained acyl chlorides is dissolved in dichloromethane (35mL), adds intermediate 3- pyridones (0.26g) and catalytic amount DMAP, is slowly dropped into stirring triethylamine (0.85g), stirring reaction 5h.Reaction is completed, by mixture to pouring frozen water into (100mL) in, extracted with dichloromethane (80mL*2), organic phase washing is dried, precipitation.Jing column chromatographies purify to obtain pyridine -3- Base-(R) -2- [4- (3- chloro-5-trifluoromethylpyridine -2- epoxides) phenoxy group] propionic ester (2) light yellow transparent liquid 0.06g, Yield 5.20%.1H NMR:δ 1.83 (d, J=6.8Hz, 3H, CHCH 3 ), 5.02 (q, J=6.8Hz, 1H, CHCH3),7.05(d, J=8.8Hz, 2H, Ph-H), 7.12 (d, J=8.8Hz, 2H, Ph-H), 7.35 (dd, J=8.4Hz, 4.8Hz, 1H, Py-H), 7.44-7.48 (m, 1H, Py-H), 7.97 (d, J=2.4Hz, 1H, Py-H), 8.27-8.28 (m, 1H, Py-H), 8.39 (d, J= 2.4Hz, 1H, Py-H), 8.50 (d, J=4.0Hz, 1H, Py-H)；13C NMR:δ18.56,73.20,116.10,116.30, 119.18,122.61,122.86,124.00,129.03,136.30,142.61,142.95,147.19,147.27,155.03, 161.29,170.18,172.27.
Embodiment 3:The preparation of pyridin-3-yl-(R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] propionic ester (3)
In DMF (DMF, 40mL), addition (R) -2- (4- hydroxy benzenes oxygen) propionic acid (3.03g, 0.02mol), potassium carbonate (5.52g, 0.04mol) is dividedly in some parts, is warmed up at 70 DEG C～80 DEG C, persistently stir 1h, added by amount (2.38g, the 0.02mol) of 3,4- difluorobenzonilyiles, continues 6～7h of stirring reaction.Room temperature is cooled to, in pouring frozen water (250mL) into, Be slowly added to watery hydrochloric acid, adjust to pH 4～5, suction filtration, washing, vacuum dried case it is dry (R) -2- [4- (4- cyano group -2- Fluorophenoxy) phenoxy group] propionic acid gray solid (R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] propionic acid 3.26g, produce Rate 65.7%.
(R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] propionic acid (1g, 3.3mmol) is dissolved in toluene (40ml) In, it is slowly added to SOCl2(1.18g, 10mmol), back flow reaction 5h is sloughed after solvent with Rotary Evaporators, obtains (R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] propionyl chloride, directly carry out next step reaction.
Gained acyl chlorides is dissolved in dichloromethane (40ml), 3- pyridones (0.31g, 3.3mmol) and catalytic amount is added 4-dimethylaminopyridine (DMAP), 10min is stirred under ice bath, dropwise be added dropwise triethylamine (1g, 10mmol).Continue to stir 10h.After the completion of reaction, in pouring 100ml frozen water into, organic phase is collected in dichloromethane extraction, and is washed with water (100ml × 2), institute Crude product anhydrous sodium sulfate drying, after precipitation Jing silica gel chromatographic columns purify yellow mucus shape pyridin-3-yl-(R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] propionic ester (3) 0.15g, yield 11.6%.1H NMR:δ 1.85 (d, J= 6.4Hz,3H,CHCH 3), 5.03 (q, J=6.4Hz, 1H, CHCH3), 6.91～7.09 (m, 4H, PhH), 7.30～7.51 (m, 5H,PhH,Py-H),8.43(s,1H,Py-H),8.55(s,1H,Py-H)；13C NMR:δ18.56,73.13,116.52, 116.65,116.83,118.81,120.57,120.78,121.12,124.13,129.11,129.40,135.26,142.82, 147.03,147.25,149.11,154.69,170.07.
Embodiment 4:The preparation of pyridin-3-yl-(R) -2- [4- (6- chloro-quinoxaline -2- epoxides) phenoxy group] propionic ester (4)
DMF (DMF) is added in 100mL reaction bulbs (40mL), by (R) -2- (4- hydroxy benzenes oxygen) third During sour (3.00g, 0.02mol) is added to reaction bulb, stirring and dissolving.At room temperature, be slowly added in batches potassium carbonate (4.46g, 0.03mol), continue stir 15～30min, be warming up to 75 DEG C stirring 2h, be slowly added to 2,6- dichloro-quinoxalines (3.28g, 0.02mol), 145 DEG C of reaction 6h are warming up to.After reaction terminates, room temperature is cooled to, reactant liquor is poured into frozen water (250mL), dripped Plus watery hydrochloric acid is to pH=4～5, filter, washing is dried to obtain solid (R) -2- (4- ((6- chloro-quinoxaline -2- bases) oxygen) of yellow Benzene oxygen) propionic acid 5.55g, yield 97%.
Toluene (40mL), (R) -2- (4- ((6- chloro-quinoxaline -2- bases) oxygen) benzene oxygen) propionic acid are added in 100mL reaction bulbs (1.0g, 3.3mmol), stirring is lower to add thionyl chloride (1.19g, 10mmol), is warming up to 125 DEG C, and back flow reaction 4h, cooling is de- It is molten to obtain (R) -2- (4- ((6- chloro-quinoxaline -2- bases) oxygen) benzene oxygen) propionic acid acyl chlorides, it is directly used in next step.
Equipped with acyl chlorides reaction bulb in add dichloromethane (40mL), 3- pyridones (0.32g, 3.3mmol) and DMAP (catalytic amount), ice bath stirring is lower to instill triethylamine (1.0g, 10mmol).Reactant mixture is stirred and pour 200mL into after 8h In frozen water, extracted with dichloromethane.Organic phase is washed, anhydrous sodium sulfate drying is added, solvent is sloughed and is obtained crude product.Post layer Analysis (V petroleum ethers/ethyl acetate=4:1) 0.30g faint yellow solid product pyridine -3- bases-(R) -2- [4- (6- chloroquines are obtained Quinoline -2- epoxides) phenoxy group] propionic ester (4), yield 21.89%, m.p.81-82 DEG C,1HNMR:δ 1.85 (d, J=6.8Hz, 3H, CHCH 3), 5.05 (d, J=6.8Hz, 1H, CHCH3), 7.07 (d, J=9.2Hz, 2H, PhH), 7.23 (d, J=9.2Hz, 2H, PhH), 7.35 (dd, J=8.4Hz, 4.8Hz, 1H, Py-H), 7.47-7.50 (m, 1H, Py-H), 7.62 (dd, J=8.8Hz, 2.4Hz, 1H, quinoxaline-H), 7.70 (d, J=8.8Hz, 1H, quinoxaline-H), 8.05 (d, J=2.4Hz, 1H, ), quinoxaline-H 8.41 (d, J=2.8Hz, 1H, Py-H), 8.52 (dd, J=4.8Hz, 1.2Hz, 1H, Py-H), 8.69 (s,1H,quinoxaline-H)；13C NMR:δ18.59,73.14,116.21,122.68,123.99,127.93,128.82, 129.01,131.18,132.91,138.48,139.78,140.10,142.96,146.93,146.99,147.30,154.82, 157.15,170.23.
Embodiment 5:The system of pyridin-3-yl-(R) -2- [4- (6- Lv benzoxazole -2- epoxides) phenoxy group] propionic ester (5) It is standby
Weigh the NaOH that 2- (4- hydroxy benzenes oxygen) propionic acid 3.64g (0.02mol) is added to the 20mL10% for being placed in ice-water bath In solution, stirring 0.5h is obtained 2- (4- hydroxy benzenes oxygen) sodium propionate.It is added dropwise to the 2,6- dichloro benzoxazoles of 30mL In the toluene solution of (3.67g, 0.02mol), 0.2g TBABs are added, temperature are raised into 50 DEG C, be allowed to react after 3h, It is warming up to 115 DEG C of backflow 1h.After reactant liquor is cooled down, point liquid water intaking layer watery hydrochloric acid adjusts PH makes product analyse completely for 3～4 Go out, then filter and wash with water product, product vacuum drying chamber is drying to obtain into (R) -2- [4- (6- benzoxazole -2- oxygen Base) phenoxy group) propionic acid 2.53g, yield 36.83%.
(R) -2- [4- (6- benzoxazole -2- epoxides) phenoxy group) propionic acid (3.3mmol, 1.13g), toluene 40mL, chlorination Sulfoxide (10mmol, 1.18g), 115 DEG C of back flow reactions 4h, revolving sloughs that toluene is molten to obtain (R) -2- [4- (6- benzoxazole -2- Epoxide) phenoxy group) propionyl chloride, it is directly used in next step.
By (R) -2- [4- (6- benzoxazole -2- epoxides) phenoxy group) propionyl chloride is dissolved in dichloromethane (40mL), adds 3- Pyridone (0.31g, 3.3mmol) and DMAP (DMAP, 0.02g), drip after stirring 10 minutes in ice-water bath Enter triethylamine 1.00g, 3h is stirred in continuation in ice-water bath.Then reactant liquor is poured into 100mL frozen water, dichloromethane extraction, Organic phase is washed twice with the frozen water of 100mL, anhydrous sodium sulfate drying, is filtered, and revolving is sloughed solvent and obtains crude product.By post Chromatography (petroleum ether：Ethyl acetate=4：1) pyridin-3-yl-(R) -2- [4- (6- Lv benzoxazole -2- epoxides) phenoxy group] is obtained Propionic ester (5) yellow-brown solid 0.17g, yield 15.6%, 105.2 DEG C～107.4 DEG C of fusing point；1H NMR:δ 1.82 (d, J= 6.8Hz,3H,CHCH 3 ), 5.02 (q, J=6.8Hz, 1H,CHCH3), 7.05 (d, J=9.2Hz, 2H, PhH), 7.24 (dd, J1= 8.4Hz,J2=2.0Hz, 1H, benzoxazole-H), 7.34 (dd, J1=8.4Hz, J2=4.4Hz, 1H, Py-H), 7.38 (d, J=9.2Hz, 2H, PhH), 7.41 (d, J=8.4Hz, 1H, benzoxazole-H), 7.45 (d, J=2.0Hz, 1H, ), benzoxazole-H 7.46～7.49 (m, 1H, Py-H), 8.41 (d, J=2.8Hz, 1H, Py-H), 8.50 (dd, J1= 4.4Hz,J2=1.6Hz, 1H, Py-H).13C NMR:δ18.54,73.19,110.69,116.48,119.21,121.45, 123.99,124.37,125.09,128.95,140.28,142.98,146.79,146.95,147.39,151.73,153.17, 153.85,169.72.
Embodiment 6:Activity of weeding is evaluated
Method is as follows：(1) in sectional area 64cm2Plastic tub alms bowl in quantitative dress soil pressure put down, in being placed in Stainless steel basin, choose Full seed, seed of the same size, point monocotyledon weed (lady's-grass Digitaria sanguinalis, barnyard grass Echinochloa crus-galli, green bristlegrass Setaria viridis) and broadleaf weed (piemarker Abutilon It is theophrasti (or chickweed Stelleria media or black nightshade Solanum nigrum), lamb's-quarters Chenopodium album, recessed Head amaranth Amaranthus ascedense or Amaranthus retroflexus Amaranthus retroflexus) point alms bowl sowing, respectively account for alms bowl area 1/3,1cm thickness fine earths are covered, upper layer of soil infiltration is added water to from plastic tub alms bowl bottom, it is placed in hot-house culture, material length to be tried is to required Leaf age carries out test process；(2) the pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds that the appropriate present invention is provided are weighed, with DMF dissolves, and adds a small amount of Tween 80 emulsifying agent, stirs, and adds quantitative clear water, needed for being configured to Concentration, if coordinative solvent and clear water are control；(3) processing mode：Examination material sowing next day carries out before seedling soil treatment, unifacial leaf examination Material length to the heart stage of 1 leaf 1, dicotyledonous examination material length carry out after seedling cauline leaf process to 2 leaf periods；(4) quantitatively pipette by setting dosage Liquid carries out cauline leaf spraying and soil spraying treatment, respectively with spraying solvent and clear water as control；(5) process examination material and be placed in greenhouse Culture；(6) visually upper grown situation after processing 15-25 days, according to investigation result, calculates as follows each compound pair The preventive effect of weeds：Preventive effect (%)=100* (control plant height-process plant height)/control plant height；(7) activity of weeding is carried out according to preventive effect Classification：A levels preventive effect ＞ 90%, B levels preventive effect 75～90%, C levels preventive effect 50～75%, D levels preventive effect 25～50%, E level preventive effects ＜ 25%.As a result the compounds of this invention is shown under 5g/ mu dosage, compound is lived to the selective weeding of monocotyledon weed Property, wherein 1,2,4 pairs of monocotyledon weed cauline leaf process of compound and soil treatment are respectively provided with A level activity of weeding, 3 pairs of lists of compound Cotyledon weeds cauline leaf process have C level activity of weeding, and partial results are as follows.

Claims (6)

1. a kind of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds, it is characterised in that its chemical structural formula such as Formulas I or II It is shown：
In formula, X is nitrogen or carbon；Y is-N=CH- or oxygen；X1、X2、X3For hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano group Or any one in nitro；X4、X5、X6For hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano group or nitro or C1～C2Alkane Base or C1～C2Any one in alkoxyl；R1For hydrogen or C1～C3Alkyl or C1～C3Any one in haloalkyl；
In the definition of compound I or II given above, no matter term used is used alone also being used in compound word, represent such as Lower substituent：
Alkyl：Refer to straight or branched alkyl；
Haloalkyl：Refer to straight or branched alkyl, hydrogen moiety on these alkyl or all replaced by halogen atom.
2. pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds according to claim 1, it is characterised in that：Described The concrete structure formula of pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds is：
3. the pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds described in claim 1 or 2 also include R types isomers and S types The mixture of isomers and their any ratios.
4. the pyridin-3-yl aryloxyphenoxy alkanoic acid ester compounds described in claim 1 or 2 on herbicide is prepared should With.
5. the application described in claim 4, it is characterised in that the weeds of described herbicide action include grassy weed, tool Body includes lady's-grass, and barnyard grass, green bristlegrass, hard grass ， Wang is careless, bromegrass, amur foxtail, Triticum tauschii, alkali thatch, stinkgrass flower, wild oat, rye Grass.
6. the application described in claim 4, it is characterised in that the consumption of described herbicide is 5 grams/acre.
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CN114671824A (en) * 2022-03-10 2022-06-28 南京康立瑞生物科技有限公司 Improved method for industrial production of metamifop

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