CN108264484A - A kind of substituted phenyl ketone compounds, preparation method and application with ether structure - Google Patents

A kind of substituted phenyl ketone compounds, preparation method and application with ether structure Download PDF

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Publication number
CN108264484A
CN108264484A CN201611258990.4A CN201611258990A CN108264484A CN 108264484 A CN108264484 A CN 108264484A CN 201611258990 A CN201611258990 A CN 201611258990A CN 108264484 A CN108264484 A CN 108264484A
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alkyl
halogenated
hydrogen
halogen
alkoxy
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Inventor
许天明
彭伟立
徐小燕
钟良坤
董德臻
徐永华
姚燕飞
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Corp
Sinochem Lantian Co Ltd
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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

Abstract

The invention discloses a kind of substituted phenyl ketone compounds with ether structure with structural formula (I 1) or (I 2), and structural formula and each substituent group are seen appendix.Substituted phenyl ketone compounds provided by the invention with ether structure are suitable for weeding.

Description

A kind of substituted phenyl ketone compounds, preparation method and application with ether structure
Technical field
The invention belongs to herbicide fields, are related to a kind of substituted phenyl ketone compounds with ether structure.
Background technology
The long-time service of existing pesticide results in disease to which create resistance, so that Pesticide use amount significantly increases Add, serious destruction is caused to environment.Therefore it is required that constantly find the novel pesticide with the new mechanism of action, such as to killing Worm, sterilization or mite killing have higher active novel pesticide.
For herbicide, the prior art carries out structure of modification in terms of two to having herbicide.On the one hand it is based on triketone Structure carries out structure of modification, such as patent to the herbicide such as mesotrione and sulphur humulone using HPPD enzymes as target DE10130709、WO0218331、WO0248121、WO03106448、WO0202536、JP2002114776、WO0218352、 WO03066607、WO2003017766、WO2001007422、DE19846792、DE10301110、EP135191、 WO2001074802, JP01110674, DE10256353, US20110053779, US20120021902 and The structural formula of US20120021904, the mesotrione and sulphur humulone is as follows：
On the other hand using Pyrasulfotole as the transformation based on pyrrazole structure of representative, structural formula is as follows：
Representative patents have US20120021903, US20110045980, US20080254990, WO20080043456, US20080305956 and EP2172104.
Herein described compound is not disclosed in the prior art, also undisclosed work of the herein described compound in weeding Property.
Invention content
The present invention provides a kind of substituted phenyl ketone compounds with ether structure, containing following structural formula (I-1) and/or (I-2) compound represented：
Wherein：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20Halogen For alkoxy, C1- C20Alkylthio group, carboxylic acid, carboxylic acid C1- C20Arrcostab；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from hydrogen, halogen, C1- C20Alkyl or C1- C20Halogenated alkyl；
R6, R7 are independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl,
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, halogen, C1- C20Alkyl or C1- C20Halogenated alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C20Alkyl,
R13 is selected from C1- C20Alkyl, C1- C20Halogenated alkyl, C1- C20Alkoxy, C1- C20Halogenated alkoxy, by selected from Phenyl, furyl or the thienyl of R15, R16 or R17 substitution,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkene Base, C2- C20Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1 C20Halogenated alkoxy, C1- C20Alkylthio group；
R9, R10, R11 are independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl；
B is selected from-CH2Or-CH2CH2O-。
Substituted phenyl ketone compounds provided by the invention with ether structure can be shown in more than structural formula (I-1) Compound or more than structural formula (I-2) compound represented, can also be containing more than structural formula (I-1) Suo Shi Compound and more than structural formula (I-2) compound represented mixture.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 1, R2, R3 are independently selected from hydrogen, halogen Element, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20Alkynyl, C1- C20Halogenated alkyl, C2- C20 Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20Halogenated alkoxy, C1- C20Alkylthio group, carboxylic acid, carboxylic acid C1- C20Arrcostab.
Preferably, the substituent R 1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1 C10Alkyl, C2- C10Alkenyl, C2- C10Alkynyl, C1- C10Halogenated alkyl, C2- C10Halogenated alkenyl, C2- C10Halo alkynyl, C1- C10Alkoxy, C1- C10Halogenated alkoxy, C1- C10Alkylthio group, carboxylic acid, carboxylic acid C1- C10Arrcostab.
It may further be preferable that the substituent R 1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, mercapto Base, C1- C6Alkyl, C2- C6Alkenyl, C2- C6Alkynyl, C1- C6Halogenated alkyl, C2- C6Halogenated alkenyl, C2- C6Halo alkynyl, C1- C6Alkoxy, C1- C6Halogenated alkoxy, C1- C6Alkylthio group, carboxylic acid, carboxylic acid C1- C6Arrcostab.
It is even furthermore preferable that the substituent R 1, R2, R3 independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, Sulfydryl, C1- C4Alkyl, C2- C4Alkenyl, C2- C4Alkynyl, C1- C4Halogenated alkyl, C2- C4Halogenated alkenyl, C2- C4Acetylenic halide Base, C1- C4Alkoxy, C1- C4Halogenated alkoxy, C1- C4Alkylthio group, carboxylic acid, carboxylic acid C1- C4Arrcostab.
Again it is even furthermore preferable that the substituent R 1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, C1 C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy.
Most preferably, the substituent R 1, R2, R3 are independently selected from hydrogen, halogen, methyl, ethyl, tertiary butyl, methoxy Base, trifluoromethyl, trifluoromethoxy.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 4 is selected from halogen, nitro, methylsulfonyl.
Preferably, the substituent R 4 is selected from nitro, methylsulfonyl.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 5 is selected from hydrogen, halogen, C1- C20Alkyl Or C1- C20Halogenated alkyl.
Preferably, the substituent R 5 is selected from hydrogen, halogen, C1- C10Alkyl or C1- C20Halogenated alkyl.
It may further be preferable that the substituent R 5 is selected from hydrogen, halogen, C1- C6Alkyl or C1- C6Halogenated alkyl.
It is even furthermore preferable that the substituent R 5 is selected from hydrogen, halogen, C1- C4Alkyl or C1- C4Halogenated alkyl.
Again it is even furthermore preferable that the substituent R 5 is selected from halogen, C1- C4Alkyl.
Most preferably, the substituent R 5 is selected from chlorine, methyl.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 6, R7 are independently selected from hydrogen, C1- C20 Alkyl, C1- C20Halogenated alkyl.
Preferably, the substituent R 6, R7 are independently selected from hydrogen, C1- C10Alkyl, C1- C10Halogenated alkyl.
It may further be preferable that the substituent R 6, R7 are independently selected from hydrogen, C1- C6Alkyl, C1- C6Halogenated alkyl.
It is even furthermore preferable that the substituent R 6, R7 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Alkyl halide Base.
Again it is even furthermore preferable that the substituent R 6, R7 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Alkyl halide Base.
Most preferably, the substituent R 6, R7 are independently selected from hydrogen, methyl, ethyl, trifluoromethyl, difluoromethyl.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 8 is selected from H ,-SO2CH3、-SO2C6H4– (R12) or-X-CO-R13.
Wherein substituent R 12, selected from hydrogen, halogen, C1- C20Alkyl or C1- C20Halogenated alkyl.
Preferably, the substituent R 12 is selected from hydrogen, halogen, C1- C10Alkyl or C1- C10Halogenated alkyl.
It may further be preferable that the substituent R 12 is selected from hydrogen, halogen, C1- C6Alkyl or C1- C6Halogenated alkyl.
It is even furthermore preferable that the substituent R 12 is selected from hydrogen, halogen, C1- C4Alkyl or C1- C4Halogenated alkyl.
Most preferably, the substituent R 12 is selected from hydrogen, C1- C4Alkyl.
Wherein substituent X, selected from-CH (R14)-or direct key.
Wherein substituent R 14, selected from H or C1- C20Alkyl.
Preferably, the substituent R 14 is selected from H or C1- C10Alkyl.
It may further be preferable that the substituent R 14 is selected from H or C1- C6Alkyl.
It is even furthermore preferable that the substituent R 14 is selected from H or C1- C4Alkyl.
Most preferably, the substituent R 14 is selected from H or methyl.
Wherein substituent R 13, selected from C1- C20Alkyl, C1- C20Halogenated alkyl, C1- C20Alkoxy, C1- C20Alkyl halide Oxygroup, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17.
Preferably, R13 is selected from C1- C10Alkyl, C1- C10Halogenated alkyl, C1- C10Alkoxy, C1- C10Haloalkoxy Base, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17
It may further be preferable that the substituent R 13 is selected from C1- C6Alkyl, C1- C6Halogenated alkyl, C1- C6Alkoxy, C1- C6Halogenated alkoxy, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17.
It is even furthermore preferable that the substituent R 13 is selected from C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alcoxyl Base, C1- C4Halogenated alkoxy, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17.
Again it is even furthermore preferable that the substituent R 13 is selected from C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkane Oxygroup, C1- C4Halogenated alkoxy, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17.
Most preferably, the substituent R 13 be selected from methyl, ethyl, trifluoromethyl, methoxyl group, ethyoxyl, butoxy, 2- chloroethoxies, the phenyl, furyl or thienyl replaced selected from R15, R16 or R17.
Wherein substituent group from R15, R16 and R17, described R15, R16, R17 independently selected from hydrogen, halogen, nitro, itrile group, Hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2 C20Halo alkynyl, C1- C20Alkoxy, C1- C20Halogenated alkoxy, C1- C20Alkylthio group.
Preferably, the substituent R 15, R16, R17 independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C10Alkyl, C2- C10Alkenyl, C2- C10Alkynyl, C1- C10Halogenated alkyl, C2- C10Halogenated alkenyl, C2- C10Acetylenic halide Base, C1- C10Alkoxy, C1- C10Halogenated alkoxy, C1- C10Alkylthio group.
It may further be preferable that the substituent R 15, R16, R17 independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, Sulfydryl, C1- C6Alkyl, C2- C6Alkenyl, C2- C6Alkynyl, C1- C6Halogenated alkyl, C2- C6Halogenated alkenyl, C2- C6Acetylenic halide Base, C1- C6Alkoxy, C1- C6Halogenated alkoxy, C1- C6Alkylthio group.
It is even furthermore preferable that the substituent R 15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl Base, sulfydryl, C1- C4Alkyl, C2- C4Alkenyl, C2- C4Alkynyl, C1- C4Halogenated alkyl, C2- C4Halogenated alkenyl, C2- C4It is halogenated Alkynyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy, C1- C4Alkylthio group.
Again it is even furthermore preferable that the substituent R 15, R16, R17 independently selected from hydrogen, halogen, nitro, itrile group, C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy.
Most preferably, the substituent R 15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, methyl, second Base, tertiary butyl, trifluoromethyl, methoxyl group, ethyoxyl, trifluoromethoxy.
Phenyl ketone compounds provided by the invention, in structural formula, substituent R 9, R10, R11 independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl.
Preferably, the substituent R 9, R10, R11 are independently selected from hydrogen, C1- C10Alkyl, C1- C10Halogenated alkyl.
It may further be preferable that the substituent R 9, R10, R11 are independently selected from hydrogen, C1- C6Alkyl, C1- C6It is halogenated Alkyl.
It is even furthermore preferable that the substituent R 9, R10, R11 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Halogen Substituted alkyl.
Again it is even furthermore preferable that the substituent R 9, R10, R11 are independently selected from hydrogen, C1- C4Alkyl.
Most preferably, the substituent R 9, R10, R11 are independently selected from hydrogen, methyl.
Phenyl ketone compounds provided by the invention, in structural formula, substituent B is selected from-CH2Or-CH2CH2O-。
Phenyl ketone compounds provided by the invention, as most preferred mode, the structural formula (I-1) or (I-2) institute The phenyl ketone compounds shown are selected from least one of following compound：
When R7 is methyl, the substituted phenyl ketone compounds tool with ether structure shown in structural formula (I-1) of the present invention There is following structural formula [E-a],
Table 1 lists the part typical compound shown in structural formula [E-a].
Table 1
When R7 is ethyl, the substituted phenyl ketone compounds tool with ether structure shown in structural formula (I-1) of the present invention There is following structural formula [F-a],
Table 2 lists the part typical compound shown in structural formula [F-a].
Table 2
The part typical compound of the substituted phenyl ketone compounds with ether structure shown in structural formula (I-2) of the present invention It has following structure formula [E-b], is listed in table 3,
Table 3
Table 4 lists the core of the part typical compound of the substituted phenyl ketone compounds of the present invention with ether structure Magnetic and mass spectrometric data.
Table 4
The present invention also provides the substituted phenyl ketone chemical combination with ether structure shown in the structural formula (I-1) or (I-2) The preparation method of object.
When the phenyl ketone compounds are the phenyl ketone compounds shown in structural formula (I-1), preparation method packet It includes：
As an example, the preparation method of the phenyl ketone compounds shown in structure above (I-1) can be：
(1) equimolar compound (I) and compound (II), (such as triethylamine, carbonic acid in the presence of 1.0-1.5 mol alkalis Potassium), 0.5-24 hours (reaction temperature is 0 degree Celsius-solvent boiling point), cooled and filtered, desolventizing are reacted in organic solvent Compound (III)；
(2) compound (III) and 1.0-1.5 mole of triethylamine are dissolved in solvent, add in catalytic amount (0.001-0.1 moles) Catalyst (acetone cyanohydrin), reaction 0.5-24 hour (reaction temperature be 0 degree Celsius-solvent boiling point) adds in water after precipitation, dilute Hydrochloric acid is acidified to PH=1-2, is extracted with organic solvent immiscible with water, obtains compound (IV)；
(3) midbody compound (IV) exists with 1.0-1.5 moles of R8-X (X=chlorine, bromine), in 1.0-1.5 mol alkalis Under (such as triethylamine, potassium carbonate), react in organic solvent 0.5-24 hour (reaction temperature be 0 degree Celsius-solvent boiling point), it is cold But it filters afterwards, precipitation, with silica gel column chromatography up to target chemical combination [E-a].
The organic solvent wherein used can be tetrahydrofuran, ether, ethyl acetate, dichloromethane, dichloroethanes, chlorine Imitative, carbon tetrachloride, toluene or acetonitrile.
When the phenyl ketone compounds are the phenyl ketone compounds shown in structural formula (I-2), preparation method includes：
As an example, the preparation method of the phenyl ketone compounds shown in structure above (I-2) can be：
(1) equimolar compound (I) and compound (V), (such as triethylamine, carbonic acid in the presence of 1.0-1.5 mol alkalis Potassium), 0.5-24 hours (reaction temperature is 0 degree Celsius-solvent boiling point), cooled and filtered, desolventizing are reacted in organic solvent Compound (VI)；
(2) compound (VI) and 1.0-1.5 mole of triethylamine are dissolved in solvent, add in catalytic amount (0.001-0.1 moles) Catalyst (acetone cyanohydrin), reaction 0.5-24 hour (reaction temperature be 0 degree Celsius-solvent boiling point) adds in water after precipitation, dilute Hydrochloric acid is acidified to PH=1-2, is extracted with organic solvent immiscible with water, obtains compound (VII)；
(3) midbody compound (VII) exists with 1.0-1.5 moles of R8-X (X=chlorine, bromine), in 1.0-1.5 mol alkalis Under (such as triethylamine, potassium carbonate), react in organic solvent 0.5-24 hour (reaction temperature be 0 degree Celsius-solvent boiling point), it is cold But it filters afterwards, precipitation, with silica gel column chromatography up to target chemical combination [E-b].
The organic solvent wherein used can be tetrahydrofuran, ether, ethyl acetate, dichloromethane, dichloroethanes, chlorine Imitative, carbon tetrachloride, toluene or acetonitrile.
Structural formula (I-1) provided by the invention or the substituted phenyl ketone compounds with ether structure shown in (I-2), are fitted It shares in weeding.It is suitable for the control of weeds of the crops such as rice, soybean, wheat, cotton, corn and rape.
Structural formula (I-1) provided by the invention or the substituted phenyl ketone compounds with ether structure shown in (I-2), energy Enough effectively preventions sensitive grass family, broad leaved weed and nutgrass flatsedge, including：Barnyard grass (Echinochloa crusgalli), lady's-grass (Digitaria sanguinalis), eleusine indica (Eleusine indica), green bristlegrass (Setaria viridis), precocity Standing grain (Poa annua), wild oat (Avena fatua), amur foxtail (Alopecurus aequalis), Sorghum halepense (Sorghum Halepense), Amaranthus retroflexus (Amaranthus retroflexus), lamb's-quarters (Chenopodium album), leaf mustard (Brassica Juncea), purslane (Portulaca oleracea), chickweed (Stallaria media), piemarker (Abutilon Theophrasti), Veronica (Veronica didyma) and difformed galingale herb (Cyperus difformis) etc..
The present invention also provides a kind of herbicide, the herbicide contains the structural formula (I-1) of 1~99% mass percentage Or the phenyl ketone compounds shown in (I-2).
Herbicide of the present invention can be configured to liquor, missible oil, suspending agent, water according to method commonly used in the art Suspension, microemulsion, emulsion, pulvis, granule or capsule.
Structural formula (I-1) provided by the invention or the substituted phenyl ketone compounds with ether structure shown in (I-2), tool There is following advantage：
(1) there is efficient activity of weeding：Before showing preferable bud under 75gai/ha relatively low-doses, after bud weeding imitate Fruit；
(2) herbicide controlling spectrum is wider：Simultaneous it can control grassy weed in farmland, broad leaved weed and nutgrass flatsedge etc.；
(3) there is preferable selectivity, it is good to safeties such as part crop such as corns；
(4) residual life, is short in the soil, has no adverse effects to succession crop growth；
(5) there is rational toxicity, eco-toxicity and Environmental compatibility, belong to less toxic environmentally friendly agricultural chemical.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope All alternatives, improvement project and equivalent scheme.
In following embodiment, " % " refers both to weight percent, and " gai/ha " refers both to every gram of active matter/hectare.
First, prepared by compound
Embodiment 1,2- methyl -4- methylsulfonyls -3- (2- (to toloxyl) ethyoxyl) benzoic acid 1,3- dimethyl -1-H- The synthesis of pyrazoles -5- esters (III-1)
2- methyl -4- methylsulfonyls -3- (2- (to toloxyl) ethyoxyl) 0.20 mole of chlorobenzoyl chloride (I-1) is dissolved in tetrahydrochysene Furans, be added dropwise under ice bath 0.20 mole of 1,3- dimethyl -1-H-5- hydroxypyrazoles (II-1), 0.24 mole of triethylamine and In the mixed solution of tetrahydrofuran, continue stirring 2 hours, filtering, mother liquor concentrations precipitation obtains compound 2- methyl -4- methyl sulfone Base -3- (2- (to toloxyl) ethyoxyl) benzoic acid 1,3- dimethyl -1-H- pyrazoles -5- esters (III-1).
With same method, various intermediates (III) can be synthesized using different raw materials (I) and (II).
With same method, various intermediates (VI) can be synthesized using different raw materials (I) and (V).
Embodiment 2, (5- hydroxyl -1,3- dimethyl -1-H- pyrazoles -4-) ((2- is (to toluene by 2- methyl -4- methylsulfonyls -3- Oxygroup) ethoxyl phenenyl) ketone (IV-1) synthesis
1 0.2 mole of obtained compound (III-1) of example is dissolved in acetonitrile, adds in 0.28 mole of triethylamine and third 0.02 mole of ketone cyanalcohol, room temperature continue stirring 12 hours, and TLC detection translocation reactions are complete, concentrate precipitation, add in water dissolution, 1N Dilute hydrochloric acid be acidified to PH=2, dry precipitation obtains compound (IV-1) after dichloromethane extraction.
With same method, various intermediates (IV) can be synthesized using different raw materials (III).
With same method, various intermediates (VII) can be synthesized using different raw materials (VI).
The preparation of embodiment 3, compound E-166
0.012 mole of 0.010 mole of 2 obtained compound (IV-1) of example and triethylamine are dissolved in tetrahydrofuran, The tetrahydrofuran solution of 0.010 mole of sec-butyl chloroformate is instilled under ice bath, room temperature continues stirring 4 hours, and TLC detection indexings are anti- Should be complete, filtering concentrates the isolated compound E-166 of silica gel column chromatography after precipitation.
With same method, various substituent Xs can be synthesized as direct key using different raw materials (IV) and chloro-formate Compound.
With same method, various substituent Xs can be synthesized as direct key using different raw materials (VII) and chloro-formate Compound.
The preparation of embodiment 4, compound E-160
2 0.010 mole of obtained compound (IV-1) of example is dissolved in acetonitrile, add in 0.015 mole of sodium carbonate and 0.011 mole of 1- chloroethyls ethyl carbonate adds catalyst sodium iodide (5% equivalent), is heated to reflux 8 hours, and TLC detections are anti- Should be complete, filtering concentrates the isolated compound E-160 of silica gel column chromatography after precipitation.
With same method, using different raw material (IV) and 1- chloroethyls carbonic ester can synthesize various substituent Xs for- CH (CH3)-compound.
With same method, various substituent Xs can be synthesized using different raw material (VII) and 1- chloroethyls carbonic ester For-CH (CH3)-compound.
2nd, preparation is prepared
Embodiment 5, wettable powder agent prescription
By 15% compound (I) (table 1), 5% lignosulfonates (Mq), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% precipitated calcium carbonate equably mix, and crush to get wettable powder.
Embodiment 6, missible oil
By 10% compound (I) (table 1), 5% agriculture breast No. 500 (calcium salts), 5% agriculture breast 602,5% N- first Base -2-Pyrrolidone and 75% dimethylbenzene heating stirring are uniformly to get missible oil.
Embodiment 7, granule
By 5% compound (I) (table 1), 1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) It equably mixes, crushes with 90% clay, then add in 20 parts of water to this 100 parts of mixtures, mediate, with extruding granulating machine, system It is dry to get granule into the particle of 14-32 mesh.
3rd, biological activity determination
Implement to provide the example for being given below and carrying out biological activity determination using the compound of the present invention below, it should be pointed out that Be that the present invention is not limited in the range of following examples.
Activity of weeding evaluation test is carried out according to following method：
Experiment soil is the sandy loam prepared, and activity of weeding is tested with a diameter of 9.5cm of basin alms bowl, safety testing basin alms bowl A diameter of 12.0cm.
The basin alms bowl of pre-emergence test processing carries out soil surface spraying treatment one day after in sowing, and the liquid of processing is compound It is dissolved with organic solvents such as acetone, DMF, and adds in the laboratory reagent of 0.5% Tween-80, added water and be diluted to need dosage.
The basin alms bowl of post-emergence test processing carries out foliar spray processing, processing after hot-house culture is after planting put into 7~9 days Liquid be the dissolving of the organic solvents such as compound acetone, DMF, and add in the laboratory reagent of 0.5% Tween-80, add water It is diluted to need dosage.
The compound concentration for the treatment of of first time active determination test is 750,150gai/ha or 75gai/ha, and second living Property measure experiment compound concentration for the treatment of for 75,150 and 300gai/ha or 37.5,75,150gai/ha.The basin alms bowl of processing is quiet After putting 1 day, greenhouse is put into, is periodically watered, ocular estimate observes and records the activity of weeding of compound after 14~21 days.
With the activity of weeding of hazard of plant symptom (inhibition, deformity, yellow, albefaction) performance degree range estimation compound, 0 represents There is no herbicidal effect or to crop safety, 100% represents to kill weeds or crop completely.
Activity of weeding and crop safety ocular estimate evaluation criterion such as the following table 5.
Table 5
The weeds of the biological activity determination experiment of selection and crop species such as the following table 6.
Table 6
Biological activity test result such as following table 7- tables 9.
The screening of cauline leaf process indoor pot is active (%) after table 7, compound seedling
The screening of cauline leaf process indoor pot is active (%) after table 8, compound seedling
After table 9, seedling in cauline leaf process room basin to the inhibiting rate (%) of crop
From biological activity test result it is found that phenyl ketone compounds provided by the invention not only there is good weeding to live Property, and with wider herbicide controlling spectrum, grassy weed and broadleaved herb to farmland all have good control effect, to dog tail The activity of grass is higher than mesotrione, to corn safety.

Claims (12)

1. a kind of substituted phenyl ketone compounds with ether structure, containing shown in following structural formula (I-1) and/or (I-2) Compound：
Wherein：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2 C20Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20Alkyl halide Oxygroup, C1- C20Alkylthio group, carboxylic acid, carboxylic acid C1- C20Arrcostab；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from hydrogen, halogen, C1- C20Alkyl or C1- C20Halogenated alkyl；
R6, R7 are independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, halogen, C1- C20Alkyl or C1- C20Halogenated alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C20Alkyl,
R13 is selected from C1- C20Alkyl, C1- C20Halogenated alkyl, C1- C20Alkoxy, C1- C20Halogenated alkoxy, by selected from R15, Phenyl, furyl or the thienyl of R16 or R17 substitutions,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C20Alkyl, C2- C20Alkenyl, C2- C20Alkynyl, C1- C20Halogenated alkyl, C2- C20Halogenated alkenyl, C2- C20Halo alkynyl, C1- C20Alkoxy, C1- C20Halogen For alkoxy, C1- C20Alkylthio group；
R9, R10, R11 are independently selected from hydrogen, C1- C20Alkyl, C1- C20Halogenated alkyl；
B is selected from-CH2Or-CH2CH2O-。
2. the substituted phenyl ketone compounds described in accordance with the claim 1 with ether structure, it is characterised in that：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C10Alkyl, C2- C10Alkenyl, C2 C10Alkynyl, C1- C10Halogenated alkyl, C2- C10Halogenated alkenyl, C2- C10Halo alkynyl, C1- C10Alkoxy, C1- C10Alkyl halide Oxygroup, C1- C10Alkylthio group, carboxylic acid, carboxylic acid C1- C10Arrcostab；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from hydrogen, halogen, C1- C10Alkyl or C1- C20Halogenated alkyl；
R6, R7 are independently selected from hydrogen, C1- C10Alkyl, C1- C10Halogenated alkyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, halogen, C1- C10Alkyl or C1- C10Halogenated alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C10Alkyl,
R13 is selected from C1- C10Alkyl, C1- C10Halogenated alkyl, C1- C10Alkoxy, C1- C10Halogenated alkoxy, by selected from R15, Phenyl, furyl or the thienyl of R16 or R17 substitutions,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C10Alkyl, C2- C10Alkenyl, C2- C10Alkynyl, C1- C10Halogenated alkyl, C2- C10Halogenated alkenyl, C2- C10Halo alkynyl, C1- C10Alkoxy, C1- C10Halogen For alkoxy, C1- C10Alkylthio group；
R9, R10, R11 are independently selected from hydrogen, C1- C10Alkyl, C1- C10Halogenated alkyl.
3. the substituted phenyl ketone compounds described in accordance with the claim 2 with ether structure, it is characterised in that：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C6Alkyl, C2- C6Alkenyl, C2- C6 Alkynyl, C1- C6Halogenated alkyl, C2- C6Halogenated alkenyl, C2- C6Halo alkynyl, C1- C6Alkoxy, C1- C6Halogenated alkoxy, C1- C6Alkylthio group, carboxylic acid, carboxylic acid C1- C6Arrcostab；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from hydrogen, halogen, C1- C6Alkyl or C1- C6Halogenated alkyl；
R6, R7 are independently selected from hydrogen, C1- C6Alkyl, C1- C6Halogenated alkyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, halogen, C1- C6Alkyl or C1- C6Halogenated alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C6Alkyl,
R13 is selected from C1- C6Alkyl, C1- C6Halogenated alkyl, C1- C6Alkoxy, C1- C6Halogenated alkoxy, by selected from R15, R16 Or phenyl, furyl or the thienyl of R17 substitutions,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C6Alkyl, C2- C6Alkenyl, C2 C6Alkynyl, C1- C6Halogenated alkyl, C2- C6Halogenated alkenyl, C2- C6Halo alkynyl, C1- C6Alkoxy, C1- C6Haloalkoxy Base, C1- C6Alkylthio group；
R9, R10, R11 are independently selected from hydrogen, C1- C6Alkyl, C1- C6Halogenated alkyl.
4. the substituted phenyl ketone compounds described in accordance with the claim 3 with ether structure, it is characterised in that：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C4Alkyl, C2- C4Alkenyl, C2- C4 Alkynyl, C1- C4Halogenated alkyl, C2- C4Halogenated alkenyl, C2- C4Halo alkynyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy, C1- C4Alkylthio group, carboxylic acid, carboxylic acid C1- C4Arrcostab；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from hydrogen, halogen, C1- C4Alkyl or C1- C4Halogenated alkyl；
R6, R7 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Halogenated alkyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, halogen, C1- C4Alkyl or C1- C4Halogenated alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C4Alkyl,
R13 is selected from C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy, by selected from R15, R16 Or phenyl, furyl or the thienyl of R17 substitutions,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, sulfydryl, C1- C4Alkyl, C2- C4Alkenyl, C2 C4Alkynyl, C1- C4Halogenated alkyl, C2- C4Halogenated alkenyl, C2- C4Halo alkynyl, C1- C4Alkoxy, C1- C4Haloalkoxy Base, C1- C4Alkylthio group；
R9, R10, R11 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Halogenated alkyl.
5. according to the substituted phenyl ketone compounds with ether structure described in claim 4, it is characterised in that：
R1, R2, R3 are independently selected from hydrogen, halogen, nitro, itrile group, C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy；
R4 is selected from halogen, nitro, methylsulfonyl；
R5 is selected from halogen, C1- C4Alkyl；
R6, R7 are independently selected from hydrogen, C1- C4Alkyl, C1- C4Halogenated alkyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, C1- C4Alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or C1- C4Alkyl,
R13 is selected from C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alkoxy, C1- C4Halogenated alkoxy, by selected from R15, R16 Or phenyl, furyl or the thienyl of R17 substitutions,
R15, R16, R17 are independently selected from hydrogen, halogen, nitro, itrile group, C1- C4Alkyl, C1- C4Halogenated alkyl, C1- C4Alcoxyl Base, C1- C4Halogenated alkoxy；
R9, R10, R11 are independently selected from hydrogen, C1- C4Alkyl.
6. according to the substituted phenyl ketone compounds with ether structure described in claim 5, it is characterised in that：
R1, R2, R3 are independently selected from hydrogen, halogen, methyl, ethyl, tertiary butyl, methoxyl group, trifluoromethyl, trifluoromethoxy；
R4 is selected from nitro, methylsulfonyl；
R5 is selected from chlorine, methyl；
R6, R7 are independently selected from hydrogen, methyl, ethyl, trifluoromethyl, difluoromethyl；
R8 is selected from H ,-SO2CH3、-SO2C6H4(R12) or-X-CO-R13, and：
R12 is selected from hydrogen, C1- C4Alkyl,
X is selected from-CH (R14)-or direct key, and R14 is selected from H or methyl,
R13 is selected from methyl, ethyl, trifluoromethyl, methoxyl group, ethyoxyl, butoxy, 2- chloroethoxies, by selected from R15, R16 or Phenyl, furyl or the thienyl of R17 substitutions,
R15, R16, R17 independently selected from hydrogen, halogen, nitro, itrile group, methyl, ethyl, tertiary butyl, trifluoromethyl, methoxyl group, Ethyoxyl, trifluoromethoxy,
R9, R10, R11 are independently selected from hydrogen, methyl.
7. according to the substituted phenyl ketone compounds with ether structure described in claim 6, it is characterised in that the structural formula (I-1) the phenyl ketone compounds or shown in (I-2) are selected from least one of following compound：
8. the substituted phenyl ketone compounds described in accordance with the claim 1 with ether structure, it is characterised in that the structural formula (I-1) the phenyl ketone compounds shown in, preparation method include：
9. the substituted phenyl ketone compounds described in accordance with the claim 1 with ether structure, it is characterised in that the structural formula (I-2) the phenyl ketone compounds shown in, preparation method include：
10. the substituted phenyl ketone compounds described in accordance with the claim 1 with ether structure, it is characterised in that the structural formula (I-1) the phenyl ketone compounds or shown in (I-2) are used for weeding.
11. a kind of herbicide, it is characterised in that the herbicide contain 1~99% mass percentage structural formula (I-1) or (I-2) the phenyl ketone compounds shown in.
12. according to the herbicide described in claim 11, it is characterised in that the herbicide is formulated into liquor, missible oil, suspension Agent, aqueous suspension, microemulsion, emulsion, pulvis, granule or capsule.
CN201611258990.4A 2016-12-30 2016-12-30 A kind of substituted phenyl ketone compounds, preparation method and application with ether structure Pending CN108264484A (en)

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