CN106699649B - The hexa-atomic aryloxyphenoxy of 2-() acid derivative and its application - Google Patents
The hexa-atomic aryloxyphenoxy of 2-() acid derivative and its application Download PDFInfo
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- CN106699649B CN106699649B CN201611162261.9A CN201611162261A CN106699649B CN 106699649 B CN106699649 B CN 106699649B CN 201611162261 A CN201611162261 A CN 201611162261A CN 106699649 B CN106699649 B CN 106699649B
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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
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
Abstract
The invention discloses 2- (hexa-atomic aryloxyphenoxy) acid derivative and as the application on herbicide, chemical structural formula is shown in formula I:In formula, R1、R2、R3、R4、R5、R6For hydrogen or C1~C3Alkyl or C1~C3Any one in halogenated alkyl；X is nitrogen or carbon；Y is nitrogen or oxygen；X1、X2For any one in hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano or nitro.The application in terms of agricultural herbicide the invention further relates to the composition containing above compound and 2- (hexa-atomic aryloxyphenoxy) acid derivative, some compounds have very high activity of weeding, and good control efficiency can be obtained under 5 grams/acre of dosages.
Description
Technical field
The present invention relates to a kind of compounds, and in particular to a kind of 2- (hexa-atomic aryloxyphenoxy) acid derivative and its answers
With.
Background technique
Fragrant phenoxy propionic acid (APP) analog derivative is as gramineae weed class herbicide, because having efficient, low toxicity, Gao Xuan
Selecting property and it is environmentally friendly the features such as, since listing, research be concerned.In such inhibited gramineae weed of herbicide
Acetyl-CoA carboxylase (ACCase), block plant body in ester fat acid synthesis, thus effective as selective prevent and kill off grass family
Weeds, thus on broad leaf crop without influence.
In general, the R configuration body of such compound is the active constituent of herbicide.In 1991, Novartis Co., Ltd developed
One is used for APP class herbicide --- the clodinafop-propargyl of wheat paddock, and hereafter, Dow Chemical and South Korea's chemical technology research institute are developed successively
Two kinds of APP class herbicide --- cyhalofop-butyl (P1) and metamifops (P2) for paddy field are gone out.The study found that working as benzene
After oxygroup is substituted by pyridine oxygroup, selectivity and activity will be greatly improved.In such APP class herbicide, the standing grain spirit of fluorine pyrrole second
It (P3) is representative herbicide.
To obtain the higher compound of activity, inventor, which designs and synthesizes, a series of has no 2- reported in the literature (hexa-atomic virtue
Oxygroup phenoxy group) acid derivative, find it with significant activity of weeding.
Summary of the invention
The present invention provides a kind of 2- (hexa-atomic aryloxyphenoxy) acid derivative and its isomers, which is characterized in that
Its chemical structural formula is shown in formula I:
In formula, R1、R2、R3、R4、R5、R6For hydrogen or C1~C3Alkyl or C1~C3Any one in halogenated alkyl；X is nitrogen
Or carbon；Y is nitrogen or oxygen；X1、X2For any one in hydrogen or fluorine or chlorine or bromine or iodine or trifluoromethyl or cyano or nitro；
In the definition of compound (I) given above, no matter term used exclusive use is also used in compound word, represent
Following substituent group:
Alkyl: refer to linear or branched alkyl group；
Halogenated alkyl: referring to linear or branched alkyl group, hydrogen moiety on these alkyl or is all replaced by halogen atom；
The compound of the present invention can exist in the form of one or more isomers.Isomers includes enantiomter, non-
Enantiomter, geometric isomer.Such as formula (I) compound represented of the invention, due to connecting four on a carbon atom not
With substituent group and form stereoisomer (respectively with R and S to indicate different configurations), the present invention includes R type isomers and S
The mixture of type isomers and their any ratios.
In preferred scheme, the concrete structure formula of the 2- (hexa-atomic aryloxyphenoxy) acid derivative are as follows:
The invention further relates to the activity of weeding of the 2- (hexa-atomic aryloxyphenoxy) acid derivative, 5 grams/acre with
Amount is lower to have significant weeding bioactivity.
Formula (I) compound provided by the invention has good control of weeds effect, can obtain under very low dosage
Obtain good effect.
Formula (I) compound provided by the invention, with bioactivity and the compound that has has good bioactivity special
It is not to show activity in terms of agricultural, gardening, flowers and the prevention and treatment of hygienic weeds.Weeds described here include, but not only
It is limited to this:
Gramineae weed: herba digitariae, barnyard grass, herba setariae viridis, hard grass, Wang grass, herba bromi japonici, amur foxtail, Triticum tauschii, alkali thatch, stinkgrass flower,
Wild avena sativa, rye grass；
Broadleaf weeds: piemarker, herba stellariae mediae, black nightshade, Chenopodiaceae, concave head amaranth, Amaranthus retroflexus etc..
It is effectively that they can also be with other biological to control weeds when formula of the invention (I) compound is used alone
Chemical substance is used together, these biochemicals include other herbicides.
The invention further relates to the applications in the 2- (hexa-atomic aryloxyphenoxy) acid derivative agricultural herbicide.
The synthesis material of 2- (hexa-atomic aryloxyphenoxy) acid derivative of the present invention is easy to get, preparation method letter
It is single, it is easy to industrialized production.
Specific embodiment
Below with reference to specific implementation, the present invention is furture elucidated.These embodiments are interpreted as being merely to illustrate the present invention
Rather than for limiting the scope of the invention.After having read the content of the invention recorded, those skilled in the art can
To make various changes or modifications to the present invention, these equivalence changes and modification are equally fallen into defined by claims of the present invention
Range.
Embodiment 1:(R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionic acid phenethyl ester (1) preparation
N,N-Dimethylformamide (40mL), (R)-(+) -2- (4- hydroxy benzenes oxygen) propionic acid (0.02mol, 3.64g), carbonic acid
Potassium (0.02mol, 2.76g) adds the potassium carbonate of equivalent after stirring 0.5h at 75 DEG C, continues to stir 0.5h.It is slowly added dropwise 2,
3- difluoro-5-chloropyridine (0.02mol, 3.00g), after being added dropwise, reaction temperature maintains 75 DEG C, overnight.Stop heating, it is cooling
To room temperature, reaction solution is poured into 200mL ice water, dilute hydrochloric acid adjusts pH 4-5, and filtering is washed three times, vacuum with a small amount of ice water
It is dry, obtain (R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionic acid white solid 3.86g, yield 62.0%.
Toluene 40mL, (R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionic acid (3.3mmol, 1.04g), adds
Enter into the single-necked flask of 100mL, after stirring and dissolving, is added thionyl chloride (20mmol, 2.24g), back flow reaction 4h, decompression is steamed
It evaporates, obtains (R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionyl chloride yellow oily liquid, without isolating and purifying,
It is directly used in and reacts in next step.
Dichloro is first added into (R)-(+) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionyl chloride reaction flask
Then benzyl carbinol (0.40g, 3.3mmol) is added in methane (40mL), 4-dimethylaminopyridine (DMAP, 0.02g), stirs under ice bath
It mixes 15 minutes.Triethylamine (1.37mL, 10mmol) is added dropwise, after being added dropwise, continues stirring 10 minutes, then removes ice
Bath, allows it to return naturally and is warmed to room temperature, and stirs 4 hours, the monitoring reaction of period TLC.Stop reaction, reaction solution is poured into separatory funnel
In, then 150mL ice water is poured into wherein, methylene chloride extracts in three times, each 40mL, merges the extraction of lower layer's methylene chloride
Liquid.Organic phase is first washed twice with 50mL saturated sodium bicarbonate solution, finally three times with 100mL washing.Organic phase after water washed
It pours into conical flask, suitable anhydrous sodium sulfate is added, overnight.Filtering, removes methylene chloride under reduced pressure, and silica gel column chromatography separation is pure
Change product, eluant, eluent (VPetroleum ether: VEthyl acetate=4:1), obtain (R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionic acid benzene
Ethyl ester colourless oil liquid 0.35g, yield 25.5%；1H NMR(CDCl3, 400MHz) δ: 1.56 (d, J=6.8Hz, 3H,
CHCH3 ), 2.95 (t, J=6.8Hz, 2H, OCH2CH 2), 4.40 (t, J=6.8Hz, 2H, OCH 2CH2), 4.68 (q, J=6.8Hz,
1H,CHCH3), 6.84 (d, J=9.2Hz, 2H, PhH), 7.03 (d, J=9.2Hz, 2H, PhH), 7.17~7.31 (m, 5H,
), PhH 7.49 (dd, J=9.2Hz, 2.4Hz, 1H, Py-H), 7.85 (d, J=2.4Hz, 1H, Py-H)；13C NMR(CDCl3,
100MHz)δ:18.58,34.94,65.56,73.06,116.01,122.25,124.82,125.00,126.65,128.52,
128.87,137.30,140.09,145.64,146.95,148.28,154.91,172.02.
The system of embodiment 2:N- phenethyl-(R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionamide (2)
It is standby
(R)-(+) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionyl chloride preparation method such as embodiment 1, to
Methylene chloride (40mL) wherein is added, 2- phenyl ethylamine (0.33g, 2.7mmol), 4-dimethylaminopyridine (DMAP, 0.02g), ice
Bath lower stirring 15 minutes.Triethylamine (1.1mL, 8.2mmol) is added dropwise, after being added dropwise, continues stirring 10 minutes, then removes
Ice bath is removed, allows it to return naturally and is warmed to room temperature, is stirred 4 hours, the monitoring reaction of period TLC.Stop reaction, reaction solution is poured into liquid separation
In funnel, then 150mL ice water is poured into wherein, methylene chloride extracts in three times, each 40mL, merges lower layer's methylene chloride extraction
Take liquid.Organic phase is first washed twice with 50mL saturated sodium bicarbonate solution, and finally three times with 100mL washing, anhydrous sodium sulfate is dry,
Filtering, removes methylene chloride, silica gel column chromatography separating purification product, eluant, eluent (V under reduced pressurePetroleum ether: VEthyl acetate=3:1), obtain N- benzene second
Base-(R) -2- [4- (the fluoro- 5- chloropyridine -2- oxygroup of 3-) phenoxy group] propionamide white solid 0.25g, yield 22.3%, fusing point
108.0 DEG C~109.1 DEG C；1H NMR(CDCl3, 400MHz) and δ: 1.54 (d, J=6.8Hz, 3H, CHCH 3), 2.71~2.85 (m,
2H,NHCH2CH 2), 3.47~3.66 (m, 2H, NHCH 2CH2), 4.61 (q, J=6.8Hz, 1H, CHCH3),6.45(br,s,1H,
), NH 6.86 (d, J=8.8Hz, 2H, PhH), 7.08~7.10 (m, 4H, PhH), 7.18~7.29 (m, 3H, PhH), 7.51
(dd, J=8.8Hz, 2.4Hz, 1H, Py-H), 7.85 (d, J=2.4Hz, 1H, Py-H)；13C NMR(CDCl3,100MHz)δ:
18.93,35.67,40.06,75.57,116.24,122.55,124.90,125.09,126.53,128.64,128.76,
138.46,140.09,140.15,147.23,150.14,154.26,171.92.
Embodiment 3:(R) -2- [4- (3- chloro-5-trifluoromethylpyridine -2- oxygroup) phenoxy group] propionic acid phenethyl ester (3)
Preparation
(R) -2- (4- hydroxyphenoxy) propionic acid (3g), DMF (35ml) are slowly added to K2CO3(4.55g), it is warming up to 70~
80 DEG C, 1h is stirred, 2,3-, bis- chloro-5-trifluoromethylpyridine (3.56g) is added dropwise, keeps 70~80 DEG C of stirring 8h, is stopped anti-
It answers, cooled to room temperature, pours the mixture into ice water (200mL), adjust pH 4~5 using dilute hydrochloric acid, use ethyl acetate
Extraction, organic phase washing is dry, and precipitation obtains (R) -2- [4- (5- trifluoromethyl -3- chloropyridine -2- oxygroup) phenoxy group] propionic acid palm fibre
Color liquid 5.03g, yield 84.4%.
(R) -2- [4- (5- trifluoromethyl -3- chloropyridine -2- oxygroup) 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- fluoroform
Base -3- chloropyridine -2- oxygroup) phenoxy group] propionyl chloride be directly used in next step.
Gained acyl chlorides is dissolved in methylene chloride (35mL), and intermediate 2- phenylethanol (0.34g) and catalytic amount is added
DMAP is slowly dropped into triethylamine (0.85g) with stirring, is stirred to react 5h.Reaction is completed, by mixture to pouring into ice water
It in (100mL), is extracted with methylene chloride (80mL*2), organic phase washing, dry, precipitation.(R) -2- [4- is obtained through column chromatographic purifying
(3- chloro-5-trifluoromethylpyridine -2- oxygroup) phenoxy group] propionic acid phenethyl ester (3) clear viscous shape liquid 0.27g, yield
21.27%.1H NMR: δ 1.57 (d, J=6.8Hz, 3H, CHCH 3), 2.95 (t, J=6.8Hz, 2H, CH2CH 2),4.41(t,J
=6.8Hz, 2H, CH2CH 2), O 4.698 (q, J=6.8Hz, 1H, CHCH3), 6.87 (d, J=9.2Hz, 2H, Ph-H), 7.03
(d, J=9.2Hz, 2H, Ph-H), 7.17-7.31 (m, 5H, Ph-H), 7.96 (d, J=2.4Hz, 1H, Py-H), 8.24 (s, 1H,
Py-H)；13C NMR:δ18.57,34.93,65.58,73.03,116.00,119.13,121.48,122.07,122.58,
126.65,128.52,128.86,136.22,137.28,142.56,146.70,155.22,161.35,171.95.
Embodiment 4:N- phenethyl-(R) -2- [4- (3- chloro-5-trifluoromethylpyridine -2- oxygroup) phenoxy group] propionamide
(4) preparation
(R)-(+) -2- [4- (3- chloro-5-trifluoromethylpyridine -2- oxygroup) phenoxy group] propionyl chloride preparation method is as implemented
Example 3, gained acyl chlorides are dissolved in methylene chloride (35mL), the DMAP of 2- phenylethylamine (0.33g) and catalytic amount are added, with stirring
It is slowly dropped into triethylamine (0.85g), is stirred to react 5h.Reaction is completed, by mixture to pouring into ice water (100mL), with two
Chloromethanes (80mL*2) extraction, organic phase washing is dry, filters, precipitation.N- phenethyl-(R) -2- [4- is obtained through column chromatographic purifying
(3- chloro-5-trifluoromethylpyridine -2- oxygroup) phenoxy group] propionamide (4) white solid 0.65g, m.p.146~148 DEG C, yield
50.79%.1H NMR: δ 1.59 (d, J=6.8Hz, 3H, CHCH3 ),2.74-2.91(m,2H,CH2CH2 ),3.48-3.57(m,
1H,CH2CH2 N),3.64-3.73(m,1H,CH2CH2 ), N 4.66 (q, J=6.8Hz, 1H, CHCH3),6.50(br,1H,NH),
6.93 (d, J=9.2Hz, 2H, Ph-H), 7.12-7.15 (m, 3H, Ph-H), 7.24-7.33 (m, 4H, Ph-H), 8.02 (s, 1H,
Py-H),8.29(s,1H,Py-H)；13C NMR:δ18.93,35.68,40.06,75.59,116.25,119.12,122.87,
126.53,128.64,128.75,136.28,138.40,142.51,146.96,154.59,171,85.
Embodiment 5:(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid phenethyl ester (5) preparation
In n,N-Dimethylformamide (DMF, 40mL), addition (R) -2- (4- hydroxy benzenes oxygen) propionic acid (3.03g,
0.02mol), potassium carbonate (5.52g, 0.04mol) is added portionwise, is warming up at 70 DEG C~80 DEG C, persistently stirs 1h, is added by amount
(2.38g, the 0.02mol) of 3,4- difluorobenzonilyiles, continues to be stirred to react 6~7h.It is cooled to room temperature, pours into ice water (250mL),
Be slowly added to dilute hydrochloric acid, be adjusted to pH 4~5, filter, washing, vacuum dried case it is dry (R) -2- [4- (4- cyano -2-
Fluorophenoxy) phenoxy group] propionic acid gray solid title compound 3.26g, yield 65.7%.
(R) -2- [4- (4- cyano -2- fluorophenoxy) 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 after sloughing solvent with Rotary Evaporators, obtain (R) -2- [4-
(4- cyano -2- fluorophenoxy) phenoxy group] propionyl chloride, directly progress next step reaction.
Gained acyl chlorides is dissolved in methylene chloride (40ml), the 4- of benzyl carbinol (0.40g, 3.3mmol) and catalytic amount is added
Dimethyl aminopyridine (DMAP) stirs 10min under ice bath, and triethylamine (1g, 10mmol) is added dropwise dropwise.Continue stirring 3h to arrive
10h.After the reaction was completed, it pours into 100ml~200ml ice water, is extracted with dichloromethane, collect organic phase, and be washed with water
(100ml × 2), gained crude product is dry with anhydrous sodium sulfate, purifies to obtain transparent oily liquid through silica gel chromatographic column after precipitation
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid phenethyl ester (5) 0.71g, yield 52.8%.1H NMR:δ
1.57 (d, J=6.8Hz, 3H, CHCH 3), 2.95 (t, J=6.8Hz, 2H, CH 2), 4.41 (t, J=6.8Hz, 2H, CH 2),4.67
(q, J=6.8Hz, 1H, CHCH3), 6.81-6.87 (m, 3H, Ph-H), 6.94 (d, J=9.2Hz, 2H, Ph-H), 7.17-7.34
(m, 6H, Ph-H), 7.44 (dd, J=10.0Hz, 2.0Hz, 1H, Ph-H)；13C NMR:δ18.52,34.93,65.56,72.98,
105.93,116.52,118.47,120.41,120.62,121.00,126.67,128.50,128.82,129.31,137.24,
148.44,151.08,153.58,154.95,171.81.
Embodiment 6:N- phenethyl-(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group) propionamide (6) preparation
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionyl chloride preparation method such as embodiment 5, by gained acyl chlorides
It is dissolved in methylene chloride (40ml), the 4-dimethylaminopyridine of phenyl ethylamine (0.40g, 3.3mmol) and catalytic amount is added
(DMAP), 10min is stirred under ice bath, and triethylamine (1g, 10mmol) is added dropwise dropwise.Continue to stir 3h to 10h.After the reaction was completed,
It pours into 100ml ice water, is extracted with dichloromethane, collect organic phase, and (100ml × 2) are washed with water, gained crude product is with anhydrous
Sodium sulphate is dry, after precipitation through silica gel chromatographic column purify white solid N- phenethyl-(R) -2- [4- (4- cyano -2- fluorobenzene
Oxygroup) phenoxy group) propionamide (6) 0.90g, yield 67.4%, 104 DEG C~105 DEG C of fusing point.1H NMR: δ 1.54 (d, J=
6.8Hz,3H,CHCH 3), 2.71~2.84 (m, 2H, Ph-CH 2), 3.46~3.54 (m, 1H, NH-CH 2), 3.58~3.67 (m,
1H,NH-CH 2), 4.59 (q, J=6.8Hz, 1H, CHCH3), 6.43 (br s, 1H, NH), 6.84~6.90 (m, 3H, PhH),
6.99 (d, J=8.8Hz, 2H, PhH), 7.09 (d, J=6.4Hz, 2H, PhH), 7.19~7.28 (m, 3H, PhH), 7.34 (dt,
J=8.4Hz, 1.6Hz, 1H, PhH), 7.46 (dd, J=10.0Hz, 2.0Hz, 1H, PhH)；13C NMR:δ18.88,35.64,
40.04,75.73,116.86,117.57,118.73,120.55,120.77,121.06,126.57,128.62,128.71,
129.32,129.36,138.44,148.99,153.72,154.26,171.73.
Embodiment 7: activity of weeding evaluation
Method is as follows: (1) in sectional area 64cm2Plastic tub alms bowl in quantitatively to fill soil pressure flat, be placed in Stainless steel basin, choose
Full seed, seed of the same size divide monocotyledon weed (herba digitariae Digitaria sanguinalis, barnyard grass
Echinochloa crus-galli, herba setariae viridis Setaria viridis) and broadleaf weed (piemarker Abutilon
It is theophrasti (or herba stellariae mediae Stelleria media or black nightshade Solanum nigrum), Chenopodiaceae Chenopodium album, recessed
Head amaranth Amaranthus ascedense or Amaranthus retroflexus Amaranthus retroflexus) divide alms bowl to sow, respectively account for alms bowl area
1/3,1cm thickness fine earth is covered, upper layer of soil infiltration is added water to from plastic tub alms bowl bottom, is placed in hot-house culture, it is long to required to test material
Leaf age carries out test process；(2) appropriate 2- (hexa-atomic aryloxyphenoxy) acid derivative provided by the invention is weighed, with N, N-
Dimethylformamide dissolution, adds a small amount of Tween 80 emulsifier, stirs evenly, and quantitative clear water is added, is configured to required concentration,
If coordinative solvent and clear water are control；(3) processing mode: test material sows soil treatment before next day progress seedling, and unifacial leaf test material is long
Stem and leaf treatment after seedling is carried out to long to 21 heart stage of 1 leaf, dicotyledonous test material leaf periods；(4) medical fluid is quantitatively pipetted by setting dosage
Progress cauline leaf is sprayed and soil spraying treatment, is respectively control with spraying solvent and clear water；(5) processing test material is placed in greenhouse training
It supports；(6) visually upper grown situation according to investigation result calculates each compound to miscellaneous as follows after handling 15-25 days
The preventive effect of grass: preventive effect (%)=100* (control plant height-processing plant height)/control plant height；(7) activity of weeding point is carried out according to preventive effect
Grade: A grades of preventive effect > 90%, B grades of preventive effects 75~90%, C grades of preventive effects 50~75%, D grades of preventive effects 25~50%, E grades of preventive effect <
25%.The result shows that the compounds of this invention, under 5g/ mus of dosage, all compounds are to the selective weeding of monocotyledon weed
Activity, wherein 1,3,4 pair of monocotyledon weed cauline leaf process of compound and soil treatment all have A grades of activity of weeding, and compound 2 is right
Monocotyledon weed cauline leaf process mostly has A grades of activity of weeding, and there are 5,6 pairs of monocotyledon weed cauline leaf process of compound C grades to be lived
Property, partial results are as follows.
Claims (4)
1. a kind of 2- (hexa-atomic aryloxyphenoxy) acid derivative except gramineae weed, which is characterized in that its chemical structure
Formula includes the following:
2. 2- (hexa-atomic aryloxyphenoxy) acid derivative according to claim 1 further includes that R type isomers and S type are different
The mixture of structure body and their any ratios.
3. 2- (hexa-atomic aryloxyphenoxy) acid derivative according to claim 1 or 2 is preparing answering on herbicide
With the weeds of the herbicide action are selected from herba digitariae, barnyard grass, herba setariae viridis, hard grass , Wang grass, herba bromi japonici, amur foxtail, Triticum tauschii, alkali
Thatch, stinkgrass flower, wild avena sativa, rye grass.
4. application according to claim 3, which is characterized in that the dosage of the herbicide is 5 grams/acre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611162261.9A CN106699649B (en) | 2016-12-15 | 2016-12-15 | The hexa-atomic aryloxyphenoxy of 2-() acid derivative and its application |
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| GB2042503A (en) * | 1977-12-24 | 1980-09-24 | Hoechst Ag | Optically active herbicides |
| US4227009A (en) * | 1976-05-26 | 1980-10-07 | Hoechst Aktiengesellschaft | Phenoxyphenoxy-propionic acid derivatives |
| EP0095117A1 (en) * | 1982-05-26 | 1983-11-30 | Bayer Ag | Phenoxypropionic-acid derivatives, processes for their preparation and their use as herbicides |
| CN101747263A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Pyridyloxy phenoxyalkanoic acids compound and application |
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| US4227009A (en) * | 1976-05-26 | 1980-10-07 | Hoechst Aktiengesellschaft | Phenoxyphenoxy-propionic acid derivatives |
| GB2042503A (en) * | 1977-12-24 | 1980-09-24 | Hoechst Ag | Optically active herbicides |
| EP0095117A1 (en) * | 1982-05-26 | 1983-11-30 | Bayer Ag | Phenoxypropionic-acid derivatives, processes for their preparation and their use as herbicides |
| CN101747263A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Pyridyloxy phenoxyalkanoic acids compound and application |
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| 2-(4-芳氧苯氧基)丙酸类化合物的研究进展;刘祈星,等;《农药》;20150831;第54卷(第8期);第551-558、572页 * |
| N-氮杂环甲氧基-O-(4-芳氧基苯基)乳酸酰胺的合成与除草活性;刘祈星,等;《有机化学》;20141231;第34卷;第118-125页 * |
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