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CN108929319B - Isoxazoline derivative and its application in agricultural - Google Patents

Isoxazoline derivative and its application in agricultural Download PDF

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Publication number
CN108929319B
CN108929319B CN201710947363.XA CN201710947363A CN108929319B CN 108929319 B CN108929319 B CN 108929319B CN 201710947363 A CN201710947363 A CN 201710947363A CN 108929319 B CN108929319 B CN 108929319B
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chemical formula
alkyl
formula
base
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CN108929319A (en
Inventor
李义涛
池伟林
张虎
曾水明
刘新烁
林健
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Ningxia Jianpai Agrochemical Technology Co.,Ltd.
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Dongguan Dongyang Guangke Research and Development Co Ltd
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    • 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
    • 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
    • A01N43/82—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 three ring hetero atoms
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides isoxazoline derivative and its application in agricultural；Specifically, the present invention provides a kind of new isoxazoline derivative and preparation method thereof；Composition containing these compounds and its application in agricultural are used to prevent and treat the purposes of undesired plant especially as herbicide active active ingredients.

Description

Isoxazoline derivative and its application in agricultural
Technical field
The present invention provides a kind of new isoxazoline derivative and preparation method thereof；Composition containing these compounds and Its application in agricultural.
Background technique
Isoxazoles compound is a kind of compound with excellent bioactivity, and activity of weeding is reported in such as WO 2002062770, it is described in 2006024820 patent of WO 2003000686 and WO.However, this hair being described in more detail below Bright compound did not describe in those references.
Summary of the invention
The present invention provides a kind of new isoxazoles compound with activity of weeding, living to the weeding of broad-leaved section weeds Property also shows preferable activity of weeding to gramineae weed obviously due to Pyroxasulfone.
On the one hand, the present invention provides formula (I) compound represented, the N- oxide and its salt of compound shown in formula (I):
Wherein:
R1And R2It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, naphthenic base Or cycloalkyl-alkyl；Or R1、R2It is formed together with the carbon atom being connected with them by 3-8 former molecular ring；
R3And R4It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, naphthenic base Or cycloalkyl-alkyl；Or R3、R4It is formed together with the carbon atom being connected with them by 3-8 former molecular ring；
N is 0,1 or 2；
R5And R6It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl or alkyl；
Ay is aryl, heteroaryl, naphthenic base, cycloalkenyl or heterocycle；Wherein Ay is optionally by 1,2,3,4,5,6,7,8,9 Or 10 be selected from RySubstituent group replaced；
Each RyIndependently be hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, alkyl, halogenated alkyl, alkoxy, Halogenated alkoxy, alkylamino, halogenated alkylamino, alkylthio group, halogenated alkylthio ,-NRaRb,-C (=O)-alkyl or-S (=O)2- Alkyl；
Each RaAnd RbIt independently is hydrogen, alkyl, halogenated alkyl, naphthenic base, heterocycle, aryl, heteroaryl ,-C (=O)- Rc,-C (=O)-ORd,-S (=O)2-ReOr-S (=O)2-ORf；
Each RcAnd ReIt independently is hydrogen, fluorine, chlorine, bromine, iodine, alkyl, halogenated alkyl, naphthenic base, heterocycle, aryl or heteroaryl Base；
Each RdAnd RfHydrogen, alkyl, halogenated alkyl, the alkyl of amino substitution, the alkyl of cyano substitution or hydroxyl independently is to take The alkyl in generation；
Wherein R1、R2、R3、R4、R5、R6、Ay、Ry、Ra、Rb、Rc、Re、RdAnd RfOptionally by one or more selected from fluorine, Chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C1-6Alkyl, C2-6Alkenyl, C2-6Alkynyl, halogenated C1-6Alkyl, halogenated C2-6 Alkenyl, halogenated C2-6The C that alkynyl, hydroxyl replace1-6The C that alkyl, amino replace1-6The C that alkyl, cyano replace1-6Alkyl, C1-6Alkane Oxygroup, halogenated C1-6The C that alkoxy, hydroxyl replace1-6The C that alkoxy, amino replace1-6The C that alkoxy, cyano replace1-6Alcoxyl Base, C1-6Alkylamino, C3-8Naphthenic base, C6-10Aryl or C1-9Replaced the substituent group of heteroaryl.
In some of embodiments, R1And R2It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C1-6Alkyl, C3-6Naphthenic base or C3-6Naphthenic base C1-6Alkyl；Or R1、R2Together with the carbon atom being connected with them It is formed by 3-8 former molecular ring.
In some of embodiments, R3And R4It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, C1-6Alkyl, C3-6Naphthenic base or C3-6Naphthenic base C1-6Alkyl；Or R3、R4Together with the carbon atom being connected with them It is formed by 3-8 former molecular ring.
In some of embodiments, R5And R6It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl or C1-6Alkyl.
In some of embodiments, Ay C6-10Aryl, C1-9Heteroaryl, C3-8Naphthenic base, C3-8Cycloalkenyl or C2-12It is miscellaneous Ring group；Wherein Ay is optionally selected from R by 1,2,3,4,5,6,7,8,9 or 10ySubstituent group replaced；
Wherein each RyWith meaning as described in the present invention.
In some of embodiments, each RyIt independently is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, C1-6 Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C1-6Alkylamino, halogenated C1-6Alkylamino, C1-6Alkylthio group, halogen For C1-6Alkylthio group ,-NRaRb,-C (=O)-C1-6Alkyl or-S (=O)2-C1-6Alkyl；
Wherein each RaAnd RbWith meaning as described in the present invention.
In some of embodiments, each RaAnd RbIt independently is hydrogen, C1-6Alkyl, halogenated C1-6Alkyl, C3-8Naphthenic base, C2-12Heterocycle, C6-10Aryl, C1-9Heteroaryl ,-C (=O)-Rc,-C (=O)-ORd,-S (=O)2-ReOr-S (=O)2-ORf；
Wherein each Rc、Re、RdAnd RfWith meaning as described in the present invention.
In some of embodiments, each RcAnd ReIt independently is hydrogen, fluorine, chlorine, bromine, iodine, C1-8Alkyl, halogenated C1-6Alkyl, C3-8Naphthenic base, C2-12Heterocycle, C6-10Aryl or C1-9Heteroaryl.
In some of embodiments, each RdAnd RfIt independently is hydrogen, C1-8Alkyl, halogenated C1-8Alkyl, amino replace C1-8The C that alkyl, cyano replace1-8The C that alkyl or hydroxyl replace1-8Alkyl.
In some of embodiments, R1、R2、R3、R4、R5、R6、Ay、Ry、Ra、Rb、Rc、Re、RdAnd RfOptionally by one Or it is multiple selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C1-4Alkyl, C2-4Alkenyl, C2-4It is alkynyl, halogenated C1-4Alkyl, halogenated C2-4Alkenyl, halogenated C2-4The C that alkynyl, hydroxyl replace1-4The C that alkyl, amino replace1-4Alkyl, cyano replace C1-4Alkyl, C1-4Alkoxy, halogenated C1-4The C that alkoxy, hydroxyl replace1-4The C that alkoxy, amino replace1-4Alkoxy, cyanogen The C that base replaces1-4Alkoxy, C1-4Alkylamino, C3-6Naphthenic base, C6-10Aryl or C1-5Replaced the substituent group of heteroaryl.
In some of embodiments, R1And R2It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, Cvclopropvlmethvl, cyclobutyl Methyl, cyclopentyl-methyl, cyclohexyl methyl, cyclopropylethyl or cyclohexyl-ethyl.
In some of embodiments, R3And R4It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, Cvclopropvlmethvl, cyclobutyl Methyl, cyclopentyl-methyl, cyclohexyl methyl, cyclopropylethyl or cyclohexyl-ethyl.
In some of embodiments, R5And R6It is each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl Base, carboxyl, methyl, ethyl, n-propyl or isopropyl.
In some of embodiments, Ay C6-10Aryl, C1-9Heteroaryl, C3-6Naphthenic base, C3-6Cycloalkenyl or C3-8It is miscellaneous Ring group；Wherein Ay is optionally selected from R by 1,2,3,4,5,6,7,8,9 or 10ySubstituent group replaced；
Wherein each RyWith meaning as described in the present invention.
In some of embodiments, Ay is following subformula:
Wherein Ay is optionally selected from R by 1,2,3,4,5,6,7,8,9 or 10ySubstitution Replaced base；
Wherein each RyWith meaning as described in the present invention.
In some of embodiments, the present invention provides a kind of formula (II) compound represented, compound shown in formula (II) N- oxide and its salt:
Wherein:
X is N or CH；
M is 0,1,2,3,4 or 5；
Each RyWith meaning as described in the present invention.
In some of embodiments, the present invention provides a kind of formula (III) compound represented, chemical combination shown in formula (III) The N- oxide and its salt of object:
Wherein: RyWith meaning as described in the present invention.
In some of embodiments, the present invention provides a kind of formula (IV) compound represented, compound shown in formula (IV) N- oxide and its salt:
Wherein: RyWith meaning as described in the present invention.
In some of embodiments, each RyIt independently is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, C1-4 Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, halogenated C1-4Alkoxy, C1-4Alkylamino, halogenated C1-4Alkylamino, C1-4Alkylthio group, halogen For C1-4Alkylthio group ,-NRaRb,-C (=O)-C1-4Alkyl or-S (=O)2-C1-4Alkyl；
Wherein each RaAnd RbWith meaning as described in the present invention.
In some of embodiments, each RaAnd RbIt independently is hydrogen, C1-4Alkyl, halogenated C1-4Alkyl, C3-6Naphthenic base, C3-8Heterocycle, C6-10Aryl, C1-5Heteroaryl ,-C (=O)-Rc,-C (=O)-ORd,-S (=O)2-ReOr-S (=O)2-ORf；
Wherein each Rc、Re、RdAnd RfWith meaning as described in the present invention.
In some of embodiments, each RcAnd ReIt independently is hydrogen, fluorine, chlorine, bromine, iodine, C1-6Alkyl, halogenated C1-4Alkyl, C3-6Naphthenic base, C3-8Heterocycle, C6-10Aryl or C1-5Heteroaryl.
In some of embodiments, each RdAnd RfIt independently is hydrogen, C1-6Alkyl, halogenated C1-6Alkyl, amino replace C1-6The C that alkyl, cyano replace1-6The C that alkyl or hydroxyl replace1-6Alkyl.
In some of embodiments, each RyIt independently is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxyl, carboxyl, first Base, ethyl, n-propyl, isopropyl, halogenated C1-3Alkyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, halogenated C1-3Alcoxyl Base, methylamino, ethylamino, methyl mercapto, ethylmercapto group, amino ,-NH-C (=O)-Br ,-NH-C (=O)-Cl ,-NH-C (=O)- CH2Br ,-NH-C (=O)-CH2Cl ,-NH-C (=O)-C1-4Alkyl ,-N (C (=O)-C1-4Alkyl)2,-NH-C (=O)-benzene Base ,-NH-C (=O)-OC1-4Alkyl or-N (C (=O)-OC1-4Alkyl)2；
Each RyHydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, first are optionally selected from by one or more Base, ethyl, methoxyl group, ethyoxyl, methylamino or methyl mercapto substituent group replaced.
In some of embodiments, the present invention provides a kind of compound, is the compound with one of following structure Or stereoisomer, nitrogen oxides and salt with one of following structural compounds:
On the other hand, the present invention provides a kind of composition, comprising compound of the present invention as active constituent.
In some of embodiments, the present invention provides a kind of composition, includes compound of the present invention, further Include surfactant acceptable in Pesticide Science and carrier.
In some of embodiments, composition of the present invention includes other at least one pesticidal active substances, institute It states pesticidal active substance and is selected from insecticide, acaricide, herbicide, fungicide, safener and growth regulator.
On the other hand, the present invention provides application of the composition comprising compound of the present invention in agricultural.
On the other hand, the present invention provides composition the answering in control of plant disease comprising compound of the present invention With.
In some of embodiments, the present invention provides the composition comprising compound of the present invention as herbicide Purposes.
In some of embodiments, the present invention provides the composition comprising compound of the present invention as fungicide Purposes.
In some of embodiments, the present invention provides the composition comprising compound of the present invention as insecticide Purposes.
In some of embodiments, the present invention provides the composition comprising compound of the present invention and is not desired to for preventing and treating The purposes for the plant wanted.
On the other hand, the present invention provides the method for preventing and treating undesired plant, it is characterised in that by a effective amount of present invention The compound be applied to plant, vegetable seeds, growing plant in which or on which soil or cultural area.
Formula (I) compound represented may be deposited with different stereoisomer or optical isomer or tautomeric form ?.The present invention includes the mixture and isotope form example of all such isomers and tautomer and its various ratios Such as deuterated compound.
The structure that the general formula that there is the compound of isotope enrichment the present invention to provide is described, in addition to one or more atom quilts It is replaced with selected atomic weight or the atom of mass number.The Exemplary isotopes that can be introduced into the compounds of this invention include hydrogen, Carbon, nitrogen, oxygen, phosphorus, sulphur, fluorine and chlorine isotope, such as2H,3H,11C,13C,14C,15N,17O,18O,18F,31P,32P,35S,36Cl With125I。
Any asymmetric atom (for example, carbon etc.) of disclosed compound of present invention can be enriched with racemic or enantiomer Form exist, such as (R)-, (S)-or (R, S)-configuration exist.
Content noted earlier only outlines certain aspects of the invention, but be not limited to these aspect and it is otherwise in Appearance will make more specific complete description below.
Detailed description of the invention
Definition and general terms
It will now be described in more detail certain embodiments of the present invention, the example is by the structural formula and chemical formula explanation that are appended.This Invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in the present invention defined such as claim In range.Those skilled in the art will appreciate that many can be used in similar or equivalent method and material of the present invention The practice present invention.The present invention is not limited to method of the present invention and material.In document, patent and the similar material combined One or more or contradict in the case where (including but not limited to defined in term, term application, institutes different from the application Technology of description, etc.), it is subject to the application.
It will further be appreciated that certain features of the invention, be it is clearly visible, carry out in a number of independent embodiments Description, but can also provide in combination in a single embodiment.Conversely, various features of the invention, for brevity, It is described in a single embodiment, but can also be individually or with the offer of any suitable sub-portfolio.
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference It is bright.
Unless otherwise stated, following definition used in the present invention should be applied.For purposes of the present invention, chemical element With the periodic table of elements CAS editions, and " Handbook of Chemistry and Physics ", the 75th edition, 1994 is consistent.In addition, organic chemistry General Principle can With reference to " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito: 1999, and " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry Description in March, John Wiley&Sons, New York:2007, entire contents are incorporated by reference into the present invention.
There is apparent conflict unless otherwise indicated or in context, the article " one " used herein, " one (kind) " " described " is intended to include "at least one" or " one or more ".Therefore, these articles used herein refer to one or The article of more than one (i.e. at least one) object.For example, " component " refers to one or more components, it is possible to have more than one Component be taken into account in the embodiment of the embodiment and use or use.
Term "comprising" is open language, that is, includes content specified by the present invention, but be not precluded otherwise Content.
" stereoisomer " refers to identical chemical constitution, but the spatially different change of arrangement mode of atom or group Close object.Stereoisomer includes enantiomter, diastereoisomer, conformer (rotational isomer), geometric isomer (cis/trans) isomers, atropisomer, etc..
" enantiomter " refers to two isomers that cannot be overlapped but be mutually mirror of a compound.
" diastereoisomer " refer to there are two or multiple chiral centres and its molecule not alloisomerism of mirror image each other Body.Diastereoisomer has different physical properties, such as fusing point, boiling point, spectral property and reactivity.Diastereoisomer is mixed Such as electrophoresis and chromatography, such as HPLC can be operated by high resolution analysis to separate by closing object.
Stereochemical definitions used in the present invention and rule generally follow S.P.Parker, Ed., McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York；and Eliel,E.and Wilen,S.,“Stereochemistry of Organic Compounds”,John Wiley&Sons, Inc.,New York,1994。
Many organic compounds exist with optical active forms, i.e., they, which have, rotates the plane of linearly polarized light Ability.When describing optically active compound, indicate molecule about one or more hand using prefix D and L or R and S The absolute configuration at property center.Prefix d and l or (+) and (-) are the symbols for the rotation of linearly polarized light caused by appointed compound, Wherein (-) or l indicate that compound is left-handed.Prefix is (+) or the compound of d is dextrorotation.A kind of specific alloisomerism Body is enantiomter, and the mixture of this isomers is referred to as enantiomeric mixture.The 50:50 mixture of enantiomter Referred to as racemic mixture or racemic modification, when chemical reaction or in the process without stereoselectivity or stereospecificity when, It may occur in which such case.
As described in the invention, the compound of the present invention can be optionally replaced one or more substituent groups, such as General formula compound above, or as example special inside embodiment, subclass, and a kind of compound that the present invention is included. It should be appreciated that this term can be used interchangeably " optionally replacing " this term with " substituted or non-substituted ".In general, art " substituted " the one or more hydrogen atoms indicated in given structure of language are replaced specific substituent group.Unless other aspect tables Bright, an optional substituent group can be replaced at various substitutable position of that group.When in given structural formula not Only a position can be replaced one or more substituent groups selected from specific group, then substituent group can identical or differently Replace at various locations.Wherein the substituent group can be, but be not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitre Base, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkyloxy-alkoxy, alkoxy alkylamino, aryloxy group, heteroaryl oxygen Base, heterocycle oxygroup, alkoxy aryl, heteroarylalkoxy, heterocyclylalkoxy, cycloalkyl alkoxy, alkylamino, alkylamino Alkyl, alkylamino alkylamino, cycloalkyl amino, amino-n-cycloalkyl, alkylthio group, halogenated alkyl, halogenated alkoxy, hydroxyl replace Alkyl, hydroxyl replace alkylamino, cyano replace alkyl, cyano replace alkoxy, cyano replace alkylamino, amino Substituted alkyl, alkyl acyl, miscellaneous alkyl, naphthenic base, cycloalkenyl, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, heterocycle Acyl group, aryl, aryl alkyl, fragrant amino, heteroaryl, heteroaryl alkyl, heteroaryl amino, amide groups, sulfonyl, aminosulfonyl Base etc..
In addition, it is necessary to explanation, unless otherwise explicitly point out, in the present invention used by describing mode " each ... independently be " and " ... be each independently " and " ... independently be " can be interchanged, and shall be understood in a broad sense, both may be used To refer among the different groups, does not influence mutually, can also indicate in phase between expressed specific option between the same symbol In same group, do not influenced mutually between expressed specific option between the same symbol.
It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It is special It does not point out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term “C1-C6Alkyl " or " C1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C3Alkyl, C4Alkyl, C5Alkyl and C6Alkyl.
Terminology used in the present invention " alkyl " or " alkyl group ", indicate contain 1 to 20 carbon atom, the straight chain of saturation or Branch univalent hydrocarbyl group；Replaced the substituent group that wherein alkyl group is optionally described by one or more present invention. Unless otherwise detailed instructions, alkyl group contains 1-20 carbon atom.In one embodiment, alkyl group contains 1-12 carbon Atom；In one embodiment, alkyl group contains 1-8 carbon atom；In another embodiment, alkyl group contains 1-6 A carbon atom；In yet another embodiment, alkyl group contains 1-4 carbon atom；Also in one embodiment, alkyl group contains There is 1-3 carbon atom.
The example of alkyl group includes, but is not limited to, methyl (Me ,-CH3), ethyl (Et ,-CH2CH3), n-propyl (n- Pr、-CH2CH2CH3), isopropyl (i-Pr ,-CH (CH3)2), normal-butyl (n-Bu ,-CH2CH2CH2CH3), isobutyl group (i-Bu ,- CH2CH(CH3)2), sec-butyl (s-Bu ,-CH (CH3)CH2CH3), tert-butyl (t-Bu ,-C (CH3)3), n-pentyl (- CH2CH2CH2CH2CH3), 2- amyl (- CH (CH3)CH2CH2CH3), 3- amyl (- CH (CH2CH3)2), 2- methyl -2- butyl (- C (CH3)2CH2CH3), 3- methyl -2- butyl (- CH (CH3)CH(CH3)2), 3- methyl-1-butyl (- CH2CH2CH(CH3)2), 2- first Base -1- butyl (- CH2CH(CH3)CH2CH3), etc..
Term " alkenyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one insatiable hunger And site, that is, there is a carbon-to-carbon sp2Double bond, wherein the alkenyl group can be retouched optionally by one or more present invention Replaced the substituent group stated comprising the positioning of " cis " and " tans ", or the positioning of " E " and " Z ".In one embodiment, Alkenyl group includes 2-8 carbon atom；In another embodiment, alkenyl group includes 2-6 carbon atom；In another embodiment party In case, alkenyl group includes 2-4 carbon atom.The example of alkenyl group includes, but is not limited to, vinyl (- CH=CH2), Allyl (- CH2CH=CH2), acrylic (CH3- CH=CH-), the cyclobutenyl (CH of oxo3- C (=O)-CH=CH-) etc..
Term " alkynyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one carbon- Tri- key of carbon sp.
Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, and wherein alkyl group has Meaning as described in the present invention.The example of alkoxy base includes, but is not limited to, methoxyl group (MeO ,-OCH3), ethyoxyl (EtO、-OCH2CH3), 1- propoxyl group (n-PrO, n- propoxyl group ,-OCH2CH2CH3), 2- propoxyl group (i-PrO, i- propoxyl group ,- OCH(CH3)2) etc..
Term " alkylthio group " refers to that the alkyl of linear chain or branched chain is connected on the sulphur atom of divalent, and wherein alkyl group has such as Meaning of the present invention.The example of alkylthio radicals includes, but is not limited to ,-SCH3、-SCH2CH3、-SCH2CH2CH3Deng Deng.
Term " halogen " refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
Term " halogenated alkyl " indicates alkyl group replaced one or more halogen atoms.
Term " halogenated alkoxy " indicates alkoxy base replaced one or more halogen atoms.
Term " halogenated alkylamino " indicates alkylamino radicals replaced one or more halogen atoms.
Term " halogenated alkylthio " indicates alkylthio radicals replaced one or more halogen atoms.
Term " naphthenic base " indicates containing 3-12 carbon atom, monovalent or multivalence saturation monocyclic, bicyclic or tricyclic body System.In one embodiment, naphthenic base includes 3-10 carbon atom；In another embodiment, naphthenic base includes that 3-8 carbon is former Son；In yet another embodiment, naphthenic base includes 3-6 carbon atom.The group of naphthene base is optionally by one or more sheets It invents replaced described substituent group.Such example includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, hexamethylene Base, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, etc..
Term " cycloalkyl-alkyl " indicates that alkyl group is replaced by group of naphthene base, wherein alkyl group and group of naphthene base With meaning as described in the present invention.
Term " cycloalkenyl " indicates containing 3-12 carbon atom, monovalent or multivalence monocyclic, bicyclic or tricyclic system, until It less include a carbon-carbon double bond, the ring system is nonaromatic.In one embodiment, cycloalkenyl includes that 3-10 carbon is former Son；In another embodiment, cycloalkenyl includes 3-8 carbon atom；In yet another embodiment, cycloalkenyl includes 3-6 carbon Atom.The cycloalkenyl groups are optionally replaced one or more substituent groups described in the invention.Such example packet It includes, but is not limited to, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclohexadienyl etc..
Term " heterocycle " and " heterocycle " are used interchangeably here, all refer to the saturation comprising 3-15 annular atom or portion Divide unsaturated monocyclic, bicyclic or tricyclic, does not include aromatic rings, and at least one annular atom in monocyclic, bicyclic or tricyclic wherein Selected from nitrogen, sulphur and oxygen atom.Unless otherwise stated, heterocycle can be carbon-based or nitrogen base, and-CH2Group can be optionally It is substituted by-C (=O)-.The sulphur atom of ring can optionally be oxidized to S- oxide.The nitrogen-atoms of ring can be optionally by oxygen It is melted into N- oxygen compound.The example of heterocycle includes, but are not limited to Oxyranyle, azelidinyl, oxetanylmethoxy, sulphur Heterocycle butyl, pyrrolidinyl (such as 2- pyrrolidinyl), 2- pyrrolinyl, 3- pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazoles Alkyl, tetrahydrofuran base, dihydrofuryl, tetrahydro-thienyl, dihydrothiophene, 1,3- dioxy cyclopenta, two sulphur cyclopenta, four Hydrogen pyranose, dihydro pyranyl, 2H- pyranose, 4H- pyranose, tetrahydro thiapyran base, piperidyl (2- piperidyl, 3- piperidyl, 4- piperidyl), morpholinyl, thio-morpholinyl, (1- oxo)-thio-morpholinyl, (1,1- dioxo)-thio-morpholinyl, piperazine Base, dioxanes base, dithianyl, thiophene oxane base, high piperazine base, homopiperidinyl, oxepane alkyl, thia cycloheptyl alkyl, 2- Oxa- -5- azabicyclo [2.2.1] hept- 5- base, tetrahydro pyridyl.- CH in heterocycle2The reality that group is replaced by-C (=O)- Example includes, but are not limited to 2- oxo-pyrrolidine base, oxo -1,3-thiazoles alkyl, 2- piperidone base, 3,5- dioxy piperazine piperidinyls. The example that sulphur atom is oxidized in heterocycle includes, but are not limited to sulfolane base, 1,1- dioxothiomorpholinyl.It is described miscellaneous Cyclic groups are optionally replaced one or more substituent groups described in the invention.
Term " x former molecular ", wherein x is integer, the number of ring member nitrogen atoms in molecule is typically described, described The number of ring member nitrogen atoms is x in molecule.For example, piperidyl is 6 molecular heterocycles of original.
Contain one or more degrees of unsaturation in " unsaturated " the expression group of term as used in the present invention.
Term " hetero atom " refers to O, S, N, P and Si, the form including any oxidation state of N, S and P；Primary, secondary, tertiary amine and season The form of ammonium salt；Or the substituted form of hydrogen in heterocycle on nitrogen-atoms, for example, N is (as in 3,4- dihydro-2 h-pyrrole base N), NH (as the NH in pyrrolidinyl) or NR (NR in pyrrolidinyl replaced as N-).
Term " aryl " indicates the monocycle containing 6-14 annular atom or 6-12 annular atom or 6-10 annular atom, double The carbocyclic ring system of ring and tricyclic, wherein at least one ring system be it is aromatic, wherein each ring system include 3-7 original Molecular ring, and there are one or more attachment points to be connected with the rest part of molecule.Term " aryl " can be with term " fragrance Ring " is used interchangeably.The example of aryl group may include phenyl, indenyl, naphthalene and anthryl.The aryl group is optionally by one Replaced a or multiple substituent groups described in the invention.
Monocycle of term " heteroaryl " expression containing 5-12 annular atom or 5-10 annular atom or 5-6 annular atom, Bicyclic and three-ring system, wherein at least one ring system are aromatic, and at least one ring system includes one or more miscellaneous Atom, wherein each ring system includes 5-7 former molecular ring, and has one or more attachment points and molecule rest part It is connected.Term " heteroaryl " can be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl groups are appointed Selection of land is replaced one or more substituent groups described in the invention.In one embodiment, 5-10 original is molecular miscellaneous Aryl includes 1,2,3 or 4 hetero atom for being independently selected from O, S and N.
The example of heteroaryl groups includes, but is not limited to, 2- furyl, 3- furyl, TMSIM N imidazole base, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazole Base, N- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- Pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, tetrazole radical (such as 5- tetrazole radical), triazole Base (such as 2- triazolyl and 5- triazolyl), 2- thienyl, 3- thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazoles base, 1, 2,5- oxadiazoles bases, 1,2,4- oxadiazoles base, 1,2,3-triazoles base, 1,2,3- thio biphosphole base, 1,3,4- thio biphosphole base, 1, 2,5- thio biphosphole bases, pyrazinyl, 1,3,5-triazines base, pyrimidine ketone group, pyriconyl；It also include below bicyclic, but never It is bicyclic to be limited to these: benzimidazolyl, benzofuranyl, benzo tetrahydrofuran base, benzothienyl, indyl (such as 2- indoles Base), etc..
In one embodiment, heteroaryl groups are following subformula:
Etc..
As described herein, attachment point can be connected any attachable position on ring with molecule rest part；Such as formula a In have an attachment point that can be connected with molecule rest part, as shown in formula b, formula c and formula d.It is attached when ring is bicyclic or polycyclic Point can be connected with molecule rest part any attachable position on each ring；As there is an attachment point can be in formula e Molecule rest part is connected, as shown in formula f, formula g, formula h, formula i and formula j.
When the compound of the present invention includes an acid moieties, the salt of compound of the present invention, including derived from alkali gold Belong to or those of alkaline-earth metal and is derived from those of ammonia and amine.Preferred cation includes sodium, potassium, magnesium and has chemistry Formula N+(R19R20R21R22) ammonium cation, wherein R19、R20、R21And R22Independently selected from hydrogen, C1-C6Alkyl and C1-C6Hydroxyl alkane Base.The salt of compound with chemical formula (I) can by with metal hydroxides (such as sodium hydroxide) or amine (such as ammonia, Trimethylamine, diethanol amine, 2- methyl mercapto propylamine, diallyl amine, 2- butoxyethylamine, morpholine, ring lauryl amine or benzylamine) to tool There is the compound of chemical formula (I) to be handled to prepare.
When the compound of the present invention includes an alkali part, acceptable salt can be formed by organic acid and inorganic acid, Such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, neighbour Phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalene sulfonic acids, benzene sulfonic acid, toluenesulfonic acid, camphorsulfonic acid with And similarly known acceptable acid.
The composition and preparation of the compounds of this invention
The compound of the present invention is made generally useful as the herbicide active active ingredients in composition, that is, preparation, the composition Agent has at least one annexing ingredient as carrier, and the annexing ingredient is selected from surfactant, solid diluent and liquid Diluent.The preparation or composition components are selected, with the physical characteristic, method of application and environmental factor with the active constituent (such as soil types, humidity and temperature) is consistent.
Useful preparation includes liquid composition and solid composite.Liquid composition includes solution (including missible oil), hangs Supernatant liquid, lotion (including microemulsion and/or suspended emulsion) etc., they can optionally be crowded into gel.Aqueous liquid composition General type be solubility concentrate, suspension-concentrates, capsule suspension liquid, concentrated emulsion, microemulsion and suspended emulsion.It is non-aqueous Property liquid composition general type be missible oil, microemulsifiable concentrate, dispersibles concentrate and oil dispersion.
The general type of solid composite is pulvis, powder, particle, pellet, spherolite, pastille, tablet, filling film (packet Include seed pelleting) etc., they can be the (" wettable ") or water-soluble of water dispersible.By film forming solution or flowable The film and coating that suspension is formed are used especially for seed treatment.Active constituent can be by (micro-) capsule encapsulating, and further shape At suspension or solid pharmaceutical preparation；Or it can be by entire active agent preparation capsule encapsulating (or " cladding ").Capsule encapsulating can be controlled The release of system or delay active constituent.The advantages of emulsifiable particle combines both cream preparation and dry granular preparation.It is highly concentrated Degree composition is mainly used as the intermediate of other preparations.
Sprayable preparation is usually dispersed in suitable medium before the spraying.By such liquid preparation and solid pharmaceutical preparation It is configured to be easy to the diluted preparation in spraying medium (usually water).Sprayed volume can rise to several kilolitres in per hectare about one In the range of, but more typically in the range of per hectare about ten rises to several hundred liters.Sprayable preparation can in the sink with water Or another suitable medium mixing, leaf is handled for applying by air or ground, or be administered to the growth of plant In medium.Liquid and dry preparation can be added in drip irrigation system with direct quantitative, or furrow is quantitatively adding during plantation In.
The preparation usually will include a effective amount of active constituent, diluent and surfactant, and summation is by weight 100%.
Solid diluent include for example clay such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, Titanium dioxide, zinc oxide, starch, dextrin, sugar (such as lactose, sucrose), silica, talcum, mica, diatomite, urea, carbonic acid Calcium, sodium carbonate and sodium bicarbonate and sodium sulphate.Typical solid diluent is described in the Handbook of of Watkins et al. Insecticide Dust Diluents and Carriers, second edition, Dorland Books, Caldwell, New In Jersey.
Liquid diluent includes such as water, N, N- dimethyl alkane amide (such as N,N-dimethylformamide), limonene, two Methyl sulfoxide, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, gathers N- alkyl pyrrolidone (such as N-Methyl pyrrolidone) Propylene glycol, propylene carbonate, butylene carbonate, paraffin (such as white mineral oil, normal paraffin hydrocarbons, isoparaffin), alkylbenzene, alkyl Naphthalene, glycerol, glyceryl triacetate, sorbierite, aromatic hydrocarbons, dearomaticized aliphatic compound, alkylbenzene, alkylnaphthalene, ketone (such as hexamethylene Ketone, 2-HEPTANONE, isophorone and 4- hydroxy-4-methyl-2-pentanone), acetic acid esters (such as isoamyl acetate, hexyl acetate, acetic acid heptan Ester, octyl acetate, nonyl acetate, acetic acid tridecane base ester and isobornyl acetate), other esters (as alkylation lactate, binary Ester and gamma-butyrolacton) and can be straight chain, branch, saturated or unsaturated alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, Isopropanol, n-butanol, isobutanol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-octyl alcohol, decyl alcohol, isodecanol, i-octadecanol, cetanol, the moon Cinnamic alcohol, tridecanol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzylalcohol).Liquid diluent further include saturation and not The glyceride of the fatty acid (usually C6-C22) of saturation, such as oil (such as olive oil, castor oil, the Asia of vegetable seeds and fruit Flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grape seed oil, safflower oil, cottonseed oil, soya-bean oil, rapeseed oil, coconut palm Seed oil and palm-kernel oil), animal sources fatty (such as tallow, lard, lard, cod-liver oil, fish oil) and their mixing Object.Liquid diluent further includes the fatty acid of alkylation (such as methylation, ethylization, butylation), and wherein fatty acid can lead to It crosses the glycerol ester hydrolysis from plant and animal to obtain, and can be purified by distillation.Typical liquid diluent is retouched It is set forth in the Solvents Guide of Marsden, second edition, Interscience, New York, in 1950.
Solid composite and liquid composition of the invention generally comprises one or more surfactants.When adding liquid When middle, surfactant (also referred to as " reagent with surface-active ") usually changes, and most commonly reduces the surface tension of liquid. According to the property of hydrophilic radical and lipophilic group in surfactant molecule, surfactant can be used as wetting agent, dispersing agent, Emulsifier or defoaming agent.
Surfactant can be divided into nonionic surfactant, anionic surfactant or cationic surfactant. The nonionic surfactant that can be used as composition of the invention includes but is not limited to: alcohol alkoxylates, is such as based on natural alcohol With synthol (it is branch or straight chain) and by pure and mild ethylene oxide, propylene oxide, epoxy butane or their mixing The alcohol alkoxylates of object preparation；Amine ethoxylation, alkanolamide and ethoxylation alkanolamide；It is alkoxylated sweet Oily three esters, such as the soybean, castor-oil plant and rapeseed oil of ethoxylation；Alkyl phenol alkoxylates, as octyl phenol ethoxylation, Nonyl phenol ethoxy, dinonyl phenol ethoxylate and dodecyl phenol ethoxylate are (by phenol and epoxy second Alkane, propylene oxide, epoxy butane or their mixture preparation)；By ethylene oxide or propylene oxide and reversed block polymer The block polymer of preparation, wherein the end-blocks are prepared by propylene oxide；The fatty acid of ethoxylation；The rouge of ethoxylation Fat race ester and oil；The methyl ester of ethoxylation；Ethoxylation triphenyl vinyl phenol (including by ethylene oxide, propylene oxide, Those of epoxy butane or their mixture preparation)；Aliphatic ester, glyceride, the derivative of wool aliphatic radical, more ethoxylations Ester, such as Span and more ethyoxyls of the sorbitan fatty acid esters of more ethoxylations, more ethoxylations Change fatty acid glyceride；Other dehydrated sorbitol derivatives, such as sorbitan ester；Polymeric surfactant is such as random total Polymers, block copolymer, alkyd PEG (polyethylene glycol) resin, grafting or dressing polymer and star-type polymer；Polyethylene glycol (PEG)；Cithrol；The surfactant of silicone base；And sugar derivatives, such as sucrose ester, alkyl polydextrose Glycosides and alkyl polysaccharide.
Available anionic surfactant includes but is not limited to: the salt of alkyl aryl sulphonic acid and they；The alcohol of carboxylation or Alkyl phenol ethoxylate；Diphenyl sulfonate derivatives；Lignin and lignin derivative, such as lignosulfonates；Horse Come sour or succinic acid or their acid anhydrides；Alkene sulfonic acid ester；Phosphate, phosphate, the alkyl phenol alkane of such as alcohol alkoxylates The phosphate of oxygroup compound and the phosphate of styrylphenol ethoxylates；The surfactant of protein base；Sarcosine Derivative；Styrylphenol ether sulfate；The sulfate and sulfonate of oil & fat acid；The sulfate of ethoxylated alkylphenol And sulfonate；The sulfate of alcohol；The sulfate of ethoxylated alcohol；The sulfonate of amine and amide, such as N, N- alkyltaurate； The sulfonate of benzene, isopropyl benzene,toluene,xylene and detergent alkylate and tridane；The sulfonate of polycondensation naphthalene；Naphthalene and The sulfonate of alkylnaphthalene；The sulfonate of petroleum distillate；Sulphosuccinamate；And the derivative of sulfosuccinate and they Object, such as dialkyl sulfosuccinates.
Available cationic surfactant includes but is not limited to: amide and amide ethoxylates；Amine, such as N- alkyl the third two Amine, three propylidene triamines and dipropylene tetramine and ethoxylated amine, ethoxylation diamines and propoxylation amine (by amine and Ethylene oxide, propylene oxide, epoxy butane or their mixture preparation)；Amine salt, such as amine acetate and diamine salts；Quaternary ammonium salt, Such as quaternary salt, ethoxylation quaternary salt and two quaternary salts；And amine oxide, such as alkyl dimethyl amine oxide and two-(2- hydroxyl second Base)-alkyl amine oxide.
Can also be used in composition of the invention is the mixture of nonionic surfactant and anionic surfactant, Or the mixture of nonionic surfactant and cationic surfactant.Nonionic, anion and cationic surfactant And their recommended purposes are disclosed in multiple bibliography announced, including by McCutcheon ' s Division, McCutcheon ' s Emulsifiers published by The Manufacturing Confectioner Publishing Co. And Detergents, North America and international yearbook version；The Encyclopedia of Surface Active of Sisely and Wood Agents, Chemical Publ.Co., Inc., New York, 1964；And A.S.Davidson and B.Milwidsky Synthetic Detergents, the 7th edition, John Wiley and Sons, New York, 1987.
Composition of the invention also may include the formulation auxiliary agents and additive known to those skilled in the art for auxiliary agent (some of them are also considered as playing solid diluent, liquid diluent or Action of Surfactant).Such preparation helps Agent and additive are controllable: blistering (defoaming agent such as polysiloxane), active constituent in pH (buffer), process Sedimentation (suspending agent), viscosity (thixotropic thickening agent), the microorganism growth (antimicrobial) in container, product freezing are (antifreeze Agent), color (dyes/pigments dispersion), elution (film forming agent or adhesive), evaporation (anti-evaporant) and other preparation categories Property.Film forming agent includes that such as polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate are total Polymers, polyvinyl alcohol, polyvinyl alcohol copolymer and wax.The example of formulation auxiliary agents and additive includes by McCutcheon ' s McCutcheon ' s published by Division, The Manufacturing Confectioner Publishing Co. Volume 2:Functional Materials, North America and international yearbook version；And listed in PCT Publication WO03/024222 Those.
Usually by by active constituent be dissolved in solvent or by liquid diluent or dry diluent grind activity at Divide and the compound of the present invention and any other active constituent are incorporated into composition of the invention.It can be by simply mixing The ingredient prepares solution, including missible oil.If be used as missible oil liquid composition solvent be it is unmixing with water, lead to Being commonly incorporated into emulsifier emulsifies the solvent containing active constituent when being diluted with water.Medium mill can be used to carry out wet lapping partial size At most 2,000 μm of active component slurry, to obtain the particle that average diameter is lower than 3 μm.It is water-soluble serous to be prepared as into Product suspension-concentrates (see, for example, U.S.3,060,084) are further processed to form water dispersible by spray drying Particle.Dry preparation usually requires dry milling procedures, generates the average grain diameter in 2 μm to 10 μ ms.Pulvis and powder can To be prepared by mixing, and usually by grinding (such as with hammer-mill or fluid energy mill).It can be by the way that active material be sprayed Particle and pellet are prepared on pre-formed granules carrier or through agglomeration technique.Referring to Browning's " Agglomeration " (Chemical Engineering, 4 days, the 147-48 pages December in 1967；The Chemical of Perry Engineer ' s Handbook, the 4th edition, McGraw-Hill, New York, 1963, the 8-57 pages and page and WO91/ thereafter 13546.Pellet can be prepared as described in U.S.4,172,714.Water dispersible and water-soluble particle can be as It is prepared proposed in U.S.4,144,050, U.S.3,920,442 and DE.3,246,493.Tablet can such as U.S.5, 180,587, it is prepared proposed in U.S.5,232,701 and U.S.5,208,030.Film can such as GB2,095,558 and It is prepared proposed in U.S.3,299,566.
Other information relevant to formulation art, referring to " The Formulator ' the s Toolbox- of T.S.Woods Product Forms for Modern Agriculture ", Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T.Brooks and T.R.Roberts are edited, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, the 120-133 pages.Referring also to U.S.3,235,361 the 6th columns, the 16th row to the 7th column, the 19th row and Embodiment 10-41；U.S3,309,192 the 5th columns, the 43rd row to the 7th column, the 62nd row and embodiment 8,12,15,39,41,52, 53,58,132,138-140,162-164,166,167 and 169-182；U.S.2,891,855 the 3rd columns, the 66th row to the 5th column, 17th row and embodiment 1-4；Weed Control as a Science, John the Wiley and Sons of Klingman, Inc., New York, 1961, the 81-96 pages；The Weed Control Handbook of Hance et al., the 8th edition, Blackwell Scientific Publications, Oxford, 1989；And Developments in formulation Technology, PJB Publications, Richmond, UK, 2000.
The application of the compounds of this invention
Herbicide of the present invention can by plant spray, be applied in soil, be applied on water surface and to use.Suitably Determine the dosage of active component to meet application purpose.The content of active component is suitably determined according to the purpose.
The dosage of the compounds of this invention is according to the type of compound used therefor, target weeds, the trend of weeds appearance, environment item Part and the type of herbicide etc..When herbicide of the present invention itself form for example in the form of powder or particle in use, its use Amount is suitably chosen for 1g-50kg, preferably 10g-10kg/1 hectares of active component.When herbicide of the invention in liquid form Such as in use, its dosage is suitably chosen in the form of emulsifiable concentrate, wettable powder or flowable formulation 0.1-50,000ppm, preferably 10-10,000ppm.
The method for the weeds in crop that the present invention provides a kind of for controlling useful plant, this method include to described Weeds apply chemical combination of the invention to the place of the weeds or to the useful plant or to the place of the useful plant Object or composition.
The present invention also provides the method for grass and/or weeds in a kind of crop of selectivity control useful plant, the party Method includes to useful plant or its place or to the compound with chemical formula (I) of cultural area application herbicidally effective amount.
Term " herbicide " means a kind of compound controlled or change plant growth.Term " herbicidally effective amount " means energy The amount of the composition of enough such a compounds for generating control or changing plant growth effect or such compound.Control or The effect of change includes the deviation of all organic growths, for example, murdering, postponing, leaf is burnt, albinism, dwarfing etc..Term " plant " refers to all tangible parts of plant, including seed, seedling, shoot, root, stem tuber, stem, stalk, leaf and fruit.Term " location " is intended to include soil, seed and seedling, together with the plant (established vegetation) having built up And the region that may have not only been grown including weeds, but also the region not yet occurred including weeds, and further include closing In the region of the plantation of useful plant crop." region of plantation " includes the soil that crop plants have been grown on it, and It is intended to plant the soil of such crop plants.Term " weeds " as used herein means any undesirable plant, and And therefore not only including important agronomy weeds as described below, but also including volunteer crops plant.
The useful plant crop that may have been used composition according to the present invention includes but is not limited to perennial crop, such as Citrus fruit, vine, nut, oil palm, olive, pomaceous fruits fruit, drupe and rubber and it is annual can farming object, Such as cereal (such as barley and wheat), cotton, rape, corn, rice, soybean, beet, sugarcane, sunflower, ornamental plant, willow Branch millet, turf and vegetables, especially cereal, corn and soybean.
Herbicide of the present invention is to the tables such as crops, especially rice, wheat, barley, corn, sorghum, soybean, cotton, beet Reveal tight security.
The grass to be controlled and weeds are either monocotyledonous species, such as Agrostis, amur foxtail category, Avena, arm Shape grass category, Brome, Cenchrus, Cyperus, knotgrass, Echinochloa, wild Panicum, Lolium, Monochoria, Panicum, precocity Standing grain category, Rottboellia exaltata L. F category, Sagittaria, Scirpus, setaria, chrysanthemum harvest spp and sorghum, are also possible to dicots species, example Such as hemp category, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, galium, Ipomoea, Kochia, Nasturtium, arsesmart, chrysanthemum Harvest category, sinapsis alba category, Solanum, Stellaria, Veronica, Viola and Xanthium.
The compounds of this invention can show the tolerance to important crops, and the crops include but is not limited to clover, big Wheat, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oat, peanut, vegetables, tomato, Ma Ling Potato, perennial long-term cropping include coffee, cocoa, oil palm, rubber, sugarcane, citrus, grape, fruit tree, nutwood, banana, Chinese herbaceous peony Such as by tree and coniferous tree (such as torch pine) and turf species, (such as meadow is precocious for grass, pineapple, hops, tea and forest Standing grain, saint augustine grass (St.Augustine grass), Kentucky fescue and bermudagrass grass).
If necessary, the compound with chemical formula (I) according to the present invention can also be with other active components, example Such as other herbicides and/or insecticide and/or acaricide and/or nematicide and/or invertebrate poison and/or antifungal Agent and/or plant growth regulator are applied in combination.These mixtures and these mixtures to control weeds and/or not The purposes of the growth of desired plant forms other aspects of the invention again.To avoid query, the mixture of invention is also wrapped Include the mixture of two or more different compounds with chemical formula (I).Specifically, the invention further relates to a kind of hairs Bright composition, the composition include at least one other herbicide in addition to the compound of chemical formula (I).
When a kind of compound with chemical formula (I) and at least one other combinations of herbicides, there is chemical formula (I) The following mixture of compound be preferred.Compound+Acetochlor with chemical formula (I), the chemical combination with chemical formula (I) Object+acifluorfen, compound+acifluorfen-sodium with chemical formula (I), the compound with chemical formula (I)+benzene grass Ether, compound+methacrylaldehyde with chemical formula (I), the compound with chemical formula (I)+drawing grass, the change with chemical formula (I) Object+alloxydimsodium is closed, compound+allyl alcohol with chemical formula (I), compound+ametryn with chemical formula (I), has and changes Compound+amicarbazone of formula (I), compound+amidosulfuron with chemical formula (I), the compound with chemical formula (I) + cyclopropyl pyrimidine acid, the compound with chemical formula (I)+chlorine Fampridine acid, compound+Amrol, tool with chemical formula (I) There are compound+Amcide Ammate, the compound+anilofos with chemical formula (I), the change with chemical formula (I) of chemical formula (I) Close the careless spirit of object+sulphur, compound+atrazine with chemical formula (I), chemistry formula (I)+Ai Wei hormone (aviglycine), chemistry Formula (I)+azafenidin, compound+azimsulfuron with chemical formula (I), the compound+BCPC with chemical formula (I), tool There are compound+beflubutamid, compound+benazolin with chemical formula (I), chemical formula (I)+benzoic acid grass of chemical formula (I) Ketone (bencarbazone), compound+benfluralin with chemical formula (I), compound+benfuresate, tool with chemical formula (I) There is compound+bensulfuron-methyl of chemical formula (I), compound+bensulfuron-methyl-methyl with chemical formula (I), there is chemical formula (I) compound+bensulide, compound+bentazone with chemical formula (I), the compound with chemical formula (I)+bis- benzene are phonetic Humulone, compound+benzofenap with chemical formula (I), has chemical formula at compound+benzobicylon with chemical formula (I) (I)+two ring pyranone (bicyclopyrone) of compound, compound+bifenox with chemical formula (I) have and change Compound+bialaphos of formula (I), compound+bispyribac-sodium with chemical formula (I), the compound with chemical formula (I)+ Bispyribac-sodium-sodium, compound+bromacil with chemical formula (I), has chemical formula at compound+borax with chemical formula (I) (I) compound+bromobutide, chemical formula (I)+bromofenoxim (bromophenoxim), the compound with chemical formula (I)+ Brominal, compound+butafenacil with chemical formula (I), has chemistry at compound+butachlor with chemical formula (I) Compound+butamifos of formula (I), compound+butralin with chemical formula (I), compound+butylbenzene with chemical formula (I) Humulone, compound+cacodylic acid with chemical formula (I), has chemical formula at compound+butylate with chemical formula (I) Compound+calcium chlorate (I), compound+cafenstrole with chemical formula (I), the compound with chemical formula (I)+card grass amine, Compound+azoles humulone (carfentrazone) with chemical formula (I), compound+carfentrazoneethyl-second with chemical formula (I) Base, the compound+CDEA with chemical formula (I), the compound+CEPC with chemical formula (I), the chemical combination with chemical formula (I) Object+chlorflurenol, compound+chloridazon with chemical formula (I), has compound+chlorflurenol-methyl with chemical formula (I) Compound+chlorimuronethyl (chlorimuron) of chemical formula (I), compound+chlorimuronethyl-ethyl with chemical formula (I), Compound+chloroacetic acid with chemical formula (I), compound+chlortoluron with chemical formula (I), the chemical combination with chemical formula (I) Object+chlorpropham, compound+chlorsulfuron with chemical formula (I), compound+chlorthal with chemical formula (I) (chlorthal), compound+chlorthal-dimethyl with chemical formula (I), compound+indolone with chemical formula (I) Careless ester (cinidon-ethyl), compound+cinmethylin with chemical formula (I), the compound with chemical formula (I)+ether sulphur Compound+cisanilide grand, with chemical formula (I), compound+clethodim with chemical formula (I), with chemical formula (I) Compound+clodinafop-propargyl (clodinafop), compound+clodinafop-propargyl-propargyl with chemical formula (I) (clodinafoppropargyl), compound+clomazone with chemical formula (I), compound+chloromethane with chemical formula (I) The vertical special, compound+cloransulammethyl with chemical formula (I) of acyl grass amine, the compound with chemical formula (I)+gram grass (cloransulam), the compound with chemical formula (I)+cloransulammethyl-methyl (cloransulam-methyl), have Compound+the CMA of chemical formula (I), the compound+4-CPB with chemical formula (I), the compound+CPMF with chemical formula (I), Compound+4-CPP with chemical formula (I), the compound+CPPC with chemical formula (I), the compound with chemical formula (I)+ Cresols, compound+cumyluron with chemical formula (I), compound+cyanamide (cyanamide) with chemical formula (I), tool There is compound+cyanazine (cyanazine) of chemical formula (I), compound+cycloate with chemical formula (I), there is chemical formula (I) compound+cypromisulfuron (cyclosulfamuron), the compound with chemical formula (I)+grass thiapyran have chemistry Compound+cyhalofop-butyl (cyhalofop) of formula (I), compound+cyhalofop-butyl-butyl with chemical formula (I) (cyhalofop-butyl), the compound+2,4-D with chemical formula (I), the compound+3,4-DA with chemical formula (I), tool There are compound+daimuron, the compound+Dalapon with chemical formula (I), the compound with chemical formula (I) of chemical formula (I) + dazomet (dazomet), the compound+3,4-DB with chemical formula (I), has the compound+2,4-DB with chemical formula (I) Compound+the 2,4-DEB of chemical formula (I), compound+desmedipham with chemical formula (I), chemical formula (I)+desmetryn, have Compound+dicamba of chemical formula (I), compound+dichlobenil with chemical formula (I), the compound with chemical formula (I)+ O-dichlorohenzene, the compound with chemical formula (I)+drop propionic acid, has chemistry at compound+paracide with chemical formula (I) The compound of formula (I)+drop propionic acid-P, compound+diclofop-methyl with chemical formula (I), compound+standing grain with chemical formula (I) Careless spirit-methyl, the compound with chemical formula (I)+bis- chlorine sulphur grass peace, have compound+difenzoquat with chemical formula (I) The compound of chemical formula (I)+difenzoquat metilsulfate, compound+Diflufenican with chemical formula (I) have chemical formula (I) Compound+diflufenzopyr, compound+dimefuron with chemical formula (I), compound+dimepiperate with chemical formula (I), Compound+dimethachlor with chemical formula (I), compound+dimethametryn with chemical formula (I), with chemical formula (I) Compound+dimethenamid, the compound with chemical formula (I)+dimethenamid-P, compound+thiophene with chemical formula (I) Section because, the compound with chemical formula (I)+dimethyl arsinic acid, compound+dinitramine with chemical formula (I), have it is chemical Compound+dinoterb of formula (I), compound+enide with chemical formula (I), chemical formula (I)+dipropetryn (dipropetryn), compound+diquat dibromide with chemical formula (I), the compound with chemical formula (I)+diquat dibromide dibrominated Object, compound+diuron with chemical formula (I), has chemical formula (I) at compound+dithiopyr with chemical formula (I) Compound+DNOC, the compound+3,4-DP with chemical formula (I), the compound+DSMA with chemical formula (I), have change Compound+the EBEP of formula (I), compound+endothal with chemical formula (I), the compound+EPTC with chemical formula (I), Compound+esprocarb with chemical formula (I), compound+ethalfluralin with chemical formula (I), with chemical formula (I) Compound+ethametsulfuron, chemical formula (I)+ethephon (CEPHA),2-(chloroethyl) phosphonic acid, has chemistry at compound+ethametsulfuron-methyl with chemical formula (I) Compound+ethofumesate of formula (I), compound+ethoxyfenethyl with chemical formula (I), the compound with chemical formula (I) + ethoxysulfuron, compound+ethobenzanid with chemical formula (I), compound+fenoxaprop-P with chemical formula (I) (fenoxaprop), compound+fenoxapropPethyl (fenoxaprop-P) with chemical formula (I), with chemical formula (I) Compound+fenoxaprop-P-ethyl (fenoxaprop-ethyl), compound+fenoxapropPethyl-with chemical formula (I) Ethyl (fenoxaprop-Pethyl), compound+fentrazamide with chemical formula (I), the chemical combination with chemical formula (I) Object+ferrous sulfate, the compound with chemical formula (I)+wheat straw volt-M, compound+flazasulfuron, tool with chemical formula (I) There are compound+florasulam of chemical formula (I), compound+fluazifop (fluazifop) with chemical formula (I), tool There is compound+fluazifop-butyl of chemical formula (I), the compound with chemical formula (I)+fluazifop-P, have and change Compound+efficient fluazifop (fluazifop-p-butyl) of formula (I), chemical formula (I)+fluazolate (fluazolate), compound+flucarbazonesodium with chemical formula (I), compound+flucarbazonesodium-with chemical formula (I) Sodium, compound+fluchloralin with chemical formula (I), has chemical formula (I) at compound+flucetosulfuron with chemical formula (I) Compound+flufenacet, the compound with chemical formula (I)+fluorine pyridazine (flufenpyr), the chemical combination with chemical formula (I) Object+fluorine pyridazine-ethyl, chemical formula (I)+flumetralim (flumetralin), compound+flumetsulam with chemical formula (I) Amine, compound+Flumiclorac pentyl (flumiclorac) with chemical formula (I), the compound with chemical formula (I)+fluorine alkene grass Acid-amyl, the compound with chemical formula (I)+the alkynes benfluralin that goes out, has and changes chemical formula (I)+alkynes grass amine (flumipropin) Compound+fluometuron of formula (I), has compound+fluoroglycofen-ethyl (fluoroglycofen) with chemical formula (I) The compound of chemical formula (I)+fluoroglycofen-ethyl-ethyl (fluoroglycofen-ethyl), chemical formula (I)+fluorine are general (fluoxaprop), chemical formula (I)+flupoxam (flupoxam), the phonetic careless ester (flupropacil) of chemical formula (I)+the third, tool There are compound+fluorine propionic acid (flupropanate), compound+flupyrsulfuron-methyl-sodium, the tool with chemical formula (I) of chemical formula (I) There is compound+flupyrsulfuron-methyl-sodium-methyl-sodium of chemical formula (I), compound+Florencol with chemical formula (I), there is chemistry Compound+fluridone (fluridone) of formula (I), has chemical formula at compound+fluorochloridone with chemical formula (I) (I) compound+fluroxypramide, compound+flurtamone with chemical formula (I), compound+KIH 9201 with chemical formula (I), Compound+KIH 9201-methyl with chemical formula (I), has chemical formula at compound+fomesafen with chemical formula (I) (I) compound+foramsulfuron, the compound with chemical formula (I)+adjusting phosphine, compound+grass with chemical formula (I) Fourth phosphine, compound+glyphosate with chemical formula (I), has chemical formula (I) at compound+glufosinate-ammonium with chemical formula (I) Compound+Ha Laokexifen, compound+Ha Laokexifen methyl esters, the chemical combination with chemical formula (I) with chemical formula (I) Object+halosulfuronmethyl, compound+halosulfuronmethyl-methyl with chemical formula (I), compound+pyrrole with chemical formula (I) The spirit of fluorine chlorine standing grain, the compound+HC-252 with chemical formula (I), has the compound with chemical formula (I)+haloxyfop-P Compound+hexazinone of chemical formula (I), the compound with chemical formula (I)+miaow oxalic acid, the compound with chemical formula (I)+ Miaow oxalic acid-methyl, compound+imazamox with chemical formula (I), the compound with chemical formula (I)+methyl miaow grass Cigarette, compound+Arsenal with chemical formula (I), compound+Scepter with chemical formula (I), with chemical formula (I) Compound+Imazethapyr, compound+imazosulfuron with chemical formula (I), compound+indanofan with chemical formula (I), Compound and indaziflam grass amine (indaziflam), compound+iodomethane, tool with chemical formula (I) with chemical formula (I) There is compound+iodine metsulfuron-methyl of chemical formula (I), the compound with chemical formula (I)+iodine metsulfuron-methyl-methyl-sodium, there is chemistry Compound+ioxynil, the compound with chemical formula (I) and the Chinese mugwort of formula (I) divide carbazones (ipfencarbazone), have and change Compound+isoproturon of formula (I), compound+isouron with chemical formula (I), the compound with chemical formula (I)+different Dislike careless amine, compound+isoxachlorotole with chemical formula (I), compound+isoxaflutole, chemistry with chemical formula (I) Formula (I)+isoxapyrifop (isoxapyrifop), compound+karbutilate with chemical formula (I), the chemical combination with chemical formula (I) Object+lactofen, compound+linuron with chemical formula (I), has compound+lenacil with chemical formula (I) Compound+the MAA of chemical formula (I), the compound+MAMA with chemical formula (I), the compound+MCPA with chemical formula (I), Compound+MCPA- thio-ethyl with chemical formula (I), the compound+MCPB with chemical formula (I), there is chemical formula (I) Compound+chlorine phenoxy propionic acid (mecoprop), the compound with chemical formula (I)+chlorine phenoxy propionic acid-P, have chemical formula (I) compound+mefenacet, compound+mefluidide with chemical formula (I), the compound with chemical formula (I)+ Two sulphurs grand (mesosulfuron) ,+two sulphur of compound with chemical formula (I) is grand-and the methyl, compound with chemical formula (I)+ Mesotrione, compound+metamifop with chemical formula (I), has chemistry at compound+metham-sodium with chemical formula (I) Compound+metamitron of formula (I), compound+metazachlor with chemical formula (I), the compound with chemical formula (I) and Bis ether halosulfuronmethyl (metazosulfuron), the compound with chemical formula (I)+first benzthiazuron, chemical formula (I)+weed eradication Azoles (methazole), the compound with chemical formula (I) and first match quinoline (methiozolin), the chemical combination with chemical formula (I) Object+methanearsonic acid, compound+methyldymron with chemical formula (I), the compound with chemical formula (I)+isothiocyanic acid first Ester, chemical formula (I)+metobromuron (metobromuron), has chemical formula at compound+metobenzuron with chemical formula (I) (I) compound+isopropyl methoxalamine, compound+S-metolachlor with chemical formula (I), the chemical combination with chemical formula (I) Object+metosulam, compound+metribuzin with chemical formula (I), has and changes compound+metoxuron with chemical formula (I) Compound+metsulfuron-methyl (metsulfuron) of formula (I), compound+metsulfuron-methyl-methyl with chemical formula (I) (metsulfuron-methyl), the compound+MK-616 with chemical formula (I), compound+dogstail with chemical formula (I) Spy, compound+afesin with chemical formula (I), compound and monosulfmeturon with chemical formula (I) (monosulfuron), compound and monosulfmeturon ester (monosulfuron-ester) with chemical formula (I) have chemistry Compound+the MSMA of formula (I), compound+naproanilide with chemical formula (I), compound+napropamide with chemical formula (I), Compound+quinclorac, chemical formula (I)+NDA-402989 with chemical formula (I), compound+grass with chemical formula (I) are not Compound+nicosulfuron grand, with chemical formula (I), chemical formula (I)+nipyralofen (nipyraclofen), chemical formula (I)+ N- methyl glyphosate, compound+norflurazon with chemical formula (I), has chemistry at compound+n-nonanoic acid with chemical formula (I) Compound+oleic acid (fatty acid), the compound+orbencarb with chemical formula (I), the chemical combination with chemical formula (I) of formula (I) Object+orthosulfamuron, compound+oryzalin with chemical formula (I), the compound with chemical formula (I)+propine dislike grass Ketone, compound+oxasulfuron with chemical formula (I), has chemical formula at compound+oxadiazon with chemical formula (I) (I) compound+chlorine oxazines grass, compound+Oxyfluorfen with chemical formula (I), the compound with chemical formula (I)+ Paraquat, compound+pebulate with chemical formula (I), has the compound with chemical formula (I)+paraquat dihydrochloride Compound+Pendimethalin of chemical formula (I), compound+penoxsuam with chemical formula (I), with chemical formula (I) Compound+pentachlorophenol, compound+pentanochlor with chemical formula (I), compound+ring penta with chemical formula (I) are disliked Humulone, the compound with chemical formula (I)+petroleum oil class, has chemical formula at compound+pethoxamid with chemical formula (I) (I) compound+phenmedipham, compound+phenmedipham-ethyl with chemical formula (I), compound+poison with chemical formula (I) Green bristlegrass is fixed, the compound with chemical formula (I)+fluorine pyrrole acyl grass amine, compound+pinoxaden with chemical formula (I), has chemistry Compound+piperophos of formula (I), compound+potassium arsenite with chemical formula (I), the compound with chemical formula (I)+folded Potassium nitride, compound+primisulfuronmethyl with chemical formula (I), has chemical formula at compound+pretilachlor with chemical formula (I) (I) compound+primisulfuronmethyl-methyl, compound+prodiamine with chemical formula (I), the chemical combination with chemical formula (I) Object+profluazol, compound+clefoxidim with chemical formula (I), chemical formula (I)+Prohexadione calcium (prohexa diketone- Calcium), compound+prometon with chemical formula (I), compound+prometryn with chemical formula (I), have chemical formula (I) compound+propachlor, compound+propanil with chemical formula (I), compound+propaquizafop, tool with chemical formula (I) There are compound+propazine, the compound+Chem hoe with chemical formula (I), the compound with chemical formula (I) of chemical formula (I) + propisochlor, compound+procarbazone with chemical formula (I), compound+procarbazone-sodium, tool with chemical formula (I) There are compound+propyzamide, the compound+prosulfocarb with chemical formula (I), the change with chemical formula (I) of chemical formula (I) It closes object+prosulfuron, compound+pyraclonil with chemical formula (I), compound+pyraflufen-ethyl with chemical formula (I), have Compound+pyraflufen-ethyl-ethyl of chemical formula (I), has chemical formula at chemical formula (I)+sulphonyl grass pyrazoles (pyrasulfotole) (I) compound+pyrazolate, compound+pyrazosulfuron with chemical formula (I), compound+pyrrole with chemical formula (I) are phonetic Sulphur is grand-ethyl, compound+pyrazoxyfen with chemical formula (I), compound+pyribenzoxim with chemical formula (I), has Compound+pyributicarb of chemical formula (I), has chemical formula at compound+chlorobenzene cluck alcohol (pyridafol) with chemical formula (I) (I) compound+pyridate, compound+pyriftalid with chemical formula (I), the compound with chemical formula (I)+phonetic grass Ether, compound+KIH 6127-methyl with chemical formula (I), compound+Nylar with chemical formula (I) (pyrimisulfan), compound+pyrithiobac-sodium with chemical formula (I), compound+pyrithiobacsodium-with chemical formula (I) Sodium, chemical formula (I)+phonetic metazachlor (pyroxulam), has chemical formula at chemical formula (I)+sulfonyl pyrrole grand (pyroxasulfone) (I) compound+dichloro quinolinic acid, compound+quinmerac with chemical formula (I), the compound with chemical formula (I) + quinoclamine, compound+quizalofop-ethyl (quizalofop) with chemical formula (I), the compound with chemical formula (I)+essence quinoline standing grain Spirit, the compound with chemical formula (I)+quizalofop-ethyl-ethyl (quizalofop-ethyl), the compound with chemical formula (I)+ Quizalotop-ethyl-ethyl (quizalofop-P-ethyl), has chemical formula at compound+rimsulfuron 25 with chemical formula (I) (I) compound+benzene flumetsulam, compound+sethoxydim with chemical formula (I), compound+ring with chemical formula (I) Grass compound+Simanex grand, with chemical formula (I), has chemical formula (I) at compound+symetryne with chemical formula (I) Compound+SMA, compound+sodium arsenite with chemical formula (I), compound+sodium azide, tool with chemical formula (I) There are compound+sodium chloride, the compound with chemical formula (I)+sulphur humulone, the compound with chemical formula (I) of chemical formula (I) + sulfentrazone, compound+Sulfometuron Methyl-methyl with chemical formula (I), has compound+Sulfometuron Methyl with chemical formula (I) Compound+sulphosate of chemical formula (I), compound+Sulfosulfuron with chemical formula (I), the compound with chemical formula (I) + sulfuric acid, the compound+2,3,6-TBA with chemical formula (I), has chemical formula at the compound with chemical formula (I)+tar class (I) compound+TCA, the compound+TCA- sodium with chemical formula (I), chemical formula (I)+tebutam (tebutam), have and change Compound+tebuthiuron of formula (I), chemical formula (I)+benzobicylon, compound+tembotrions with chemical formula 1 (Tembotrione), compound with chemical formula (I)+herbicide, compound+terbacil with chemical formula (I), have Compound+the Te Dingtong of chemical formula (I), compound+Garagard with chemical formula (I), the compound with chemical formula (I)+ Terbutryn, compound+thenylchlor with chemical formula (I), compound+thiazfluron with chemical formula (I) (thiazafluron), compound+thiazopyr with chemical formula (I), compound+thifensulfuronmethyl, tool with chemical formula (I) There are+two thiophene ketone sulphur grand (thiencarbazone) of compound, the compound with chemical formula (I)+thiophene sulphur of chemical formula (I) Grand-methyl, compound+tiocarbazil with chemical formula (I), has chemical formula at compound+benthiocarb with chemical formula (I) (I) compound+benzene pyrazoles humulone, compound+tralkoxydim with chemical formula (I), the compound with chemical formula (I) With fluorine ketone sulphur grass amine (triafamone), compound+tri-allate with chemical formula (I), the compound with chemical formula (I)+ Triasulfuron, compound+triaziflam with chemical formula (I), compound+tribenuron-methyl with chemical formula (I) (tribenuron), compound+tribenuron-methyl-methyl with chemical formula (I), compound+tricamba with chemical formula (I), Compound+Triclopyr with chemical formula (I), compound+trietazine with chemical formula (I), the chemical combination with chemical formula (I) Object+trifloxysulfuron, compound+trifloxysulfuron-sodium with chemical formula (I), the compound with chemical formula (I)+fluorine are happy Spirit, compound+triflusulfuronmethyl-methyl with chemical formula (I), has and changes compound+triflusulfuronmethyl with chemical formula (I) The compound of formula (I)+trifluoromethoxy phenoxy propionic acid (trifop), the compound with chemical formula (I)+trifluoromethoxy phenoxy propionic acid-methyl (trifop-methyl), the compound with chemical formula (I)+trihydroxy triazine, compound+TrinexAN_SNacethyl with chemical formula (I) (trinexapac-ethyl), compound+tritosulfuron with chemical formula (I), the compound with chemical formula (I)+[3- [the fluoro- 5- of the chloro- 4- of 2- (1- methyl -6- trifluoromethyl -2,4- dioxo -1,2,3,4- tetrahydropyrimidine -3- base) phenoxy group] -2- pyrrole Piperidinyl oxygroup] ethyl acetate (CAS RN 353292-31-6), compound+2- [[the chloro- 3,4- bis- of 8- with chemical formula (I) Hydrogen -4- (4- methoxyphenyl) -3- oxo -2- quinoxalinyl] carbonyl]-hydroresorcinol and the change with chemical formula (I) Close object+VX-573.
When a kind of compound with chemical formula (I) and at least one other antimicrobial combination, there is chemical formula (I) The following mixture of compound be preferred.Compound+benomyl with chemical formula (I), the chemical combination with chemical formula (I) Object+carbendazim, compound+procymidone with chemical formula (I), has compound+thiophanate-methyl with chemical formula (I) Compound+iprodione of chemical formula (I), compound+vinclozolin with chemical formula (I), the chemical combination with chemical formula (I) Object+epoxiconazole, compound+Triadimenol with chemical formula (I), has chemistry at compound+Fluquinconazole with chemical formula (I) Compound+simeconazoles of formula (I), compound+kind bacterium azoles with chemical formula (I), the compound with chemical formula (I)+piperazine ammonia Spirit, compound+cyproconazole with chemical formula (I), compound+Difenoconazole with chemical formula (I), with chemical formula (I) Compound+Flusilazole, compound+metconazole with chemical formula (I), has compound+Flutriafol with chemical formula (I) Compound+nitrile bacterium azoles of chemical formula (I), compound+prochloraz with chemical formula (I), the compound with chemical formula (I)+ Propiconazole, compound+Tebuconazole with chemical formula (I), has chemical formula at compound+prothioconazoles with chemical formula (I) (I) compound+fluorine ether azoles, compound+Metalaxyl-M with chemical formula (I), the compound with chemical formula (I)+first frost Spirit, has chemical formula at compound+mefenoxam with chemical formula (I), compound+M 9834 with chemical formula (I) (I) compound+benalaxyl-M, compound+furalaxyl with chemical formula (I), compound+furan with chemical formula (I) Amide, compound+cartap with chemical formula (I), has chemical formula (I) at compound+Wakil with chemical formula (I) Compound+dodemorph, compound+butadiene morpholine with chemical formula (I), the compound+ten three with chemical formula (I) Morpholine, compound+fenpropidin with chemical formula (I), has chemical formula at compound+Trimorfamid Fademorf with chemical formula (I) (I) compound+pipron, compound+volution bacterium amine with chemical formula (I), the compound with chemical formula (I)+enemy's pest Phosphorus, compound+Boscalid with chemical formula (I), has chemical formula (I) at compound+Isoprothiolane with chemical formula (I) Compound+pyrrole metsulfovax, the compound+bixafen with chemical formula (I), compound+carboxin with chemical formula (I), Compound+oxycarboxin with chemical formula (I), compound+ethirimol with chemical formula (I), with chemical formula (I) Compound+cyprodinil, compound+diethofencarb with chemical formula (I), compound+Fluoxastrobin, tool with chemical formula (I) Have that compound+pyraclostrobin, the compound with the chemical formula (I)+gram receipts of chemical formula (I) are glad, chemical combination with chemical formula (I) Object+trifloxystrobin, compound+ZEN 90160 with chemical formula (I), the compound+pyribencarb with chemical formula (I), tool There are compound+Famoxate, the compound+Fenamidone with chemical formula (I), the change with chemical formula (I) of chemical formula (I) Close object+discostrobin, the compound+enestrobin with chemical formula (I), the compound with chemical formula (I)+ether bacterium Amine, compound+orysastrobin with chemical formula (I), has chemical formula at compound+SSF 126 with chemical formula (I) (I) compound+fluoxastrobin, the compound+fenpiclonil, the compound with chemical formula (I)+with chemical formula (I) cough up bacterium Nitrile, the compound with chemical formula (I)+fast promise sweet smell, compound+chloroneb with chemical formula (I), with chemical formula (I) Compound+pyroquilon, compound+tricyclazole with chemical formula (I), compound+ring propionyl bacterium amine with chemical formula (I), Compound+fenhexamid with chemical formula (I), compound+pyributicarb with chemical formula (I), the change with chemical formula (I) Object+polyoxin, compound+Pencycuron with chemical formula (I), the compound with chemical formula (I)+match seat is closed to go out, have Compound+amisulbrom of chemical formula (I), compound+oxamides with chemical formula (I), the chemical combination with chemical formula (I) Object+blasticidin S-S, compound+kasugarnycin with chemical formula (I), compound+streptomysin with chemical formula (I), Compound+jinggangmeisu with chemical formula (I), compound+cymoxanil with chemical formula (I), the change with chemical formula (I) Close object+Propamocarb, compound+prothiocarb with chemical formula (I), the compound with chemical formula (I)+iodo propinyl butyl Carbamate, compound+binapacryl with chemical formula (I), has chemical formula at compound+fluazinam with chemical formula (I) (I) compound+ferimzone, compound+dinocap with chemical formula (I), compound+dinocap with chemical formula (I), Compound+fentin acetate with chemical formula (I), compound+oxolinic acid with chemical formula (I) have chemical formula (I) Compound+hymexazol, compound+phosphorous acid with chemical formula (I) and its various salt, the compound with chemical formula (I)+ Phosethyl-Al, compound+tecloftalam with chemical formula (I), the compound with chemical formula (I)+azoles bacterium piperazine have chemistry Compound+flusulfamide of formula (I), compound+diclomezine with chemical formula (I), the compound with chemical formula (I)+silicon thiophene Bacterium amine, compound+dimethomorph with chemical formula (I), has chemical formula at the compound with chemical formula (I)+difluoro woods (I) compound+benzene metsulfovax, compound+benzene metsulfovax-isopropyl with chemical formula (I), the change with chemical formula (I) Close object+Propineb, compound+downy mildew with chemical formula (I) goes out, compound+mandipropamid, tool with chemical formula (I) There are compound+flumorph, the compound+oxytetracycline with chemical formula (I), the chemical combination with chemical formula (I) of chemical formula (I) Object+methasulfocarb, compound+fluopicolide with chemical formula (I), with compound+fluopyram of chemical formula (I), tool There is the compound of chemical formula (I)+my acid benzene-S-methyl, compound+Cupravit with chemical formula (I), there is chemical formula (I) compound+copper sulphate, compound+Kocide SD with chemical formula (I), compound+bohr with chemical formula (I) More liquid compositions (ternary copper sulphate), compound+elementary sulfur with chemical formula (I), compound+generation with chemical formula (I) Gloomy MnZn, compound+Propineb with chemical formula (I), has chemical formula at compound+Carbatene with chemical formula (I) (I) compound+fervam, compound+maneb with chemical formula (I) ,+two sulphur four of compound with chemical formula (I) First thiuram, compound+ziram with chemical formula (I), has chemical formula at compound+zineb with chemical formula (I) (I) compound+folpet, compound+captan with chemical formula (I), compound+difoltan with chemical formula (I), Compound+Bravo with chemical formula (I), compound+Guardian with chemical formula (I), the change with chemical formula (I) Close object+cyflufenamid, compound+the third oxygen quinoline with chemical formula (I), compound+metrafenone, tool with chemical formula (I) There is the chloro- 6- of compound+5- (2,4,6- trifluorophenyl) -7- (4- methyl piperidine -1- base) [1,2,4] triazol of chemical formula (I) [1,5-a] pyrimidine, the iodo- 3- propyl -4H-1- benzopyran-4-one of compound+2- butoxy -6- with chemical formula (I), tool There is compound+3- [5- (4- chlorphenyl) -2,3- dimethyl -3- isoxazolidinyl] pyridine of chemical formula (I), there is chemical formula (I) compound+N- [1- [[[1- (4- cyano-phenyl) ethyl] sulfonyl] methyl] propyl] carbamic acid 4- fluorobenzene ester has Compound+the N- [[(cyclo propyl methoxy) amino] [6- (difluoro-methoxy) -2,3- difluorophenyl] methylene] of chemical formula (I) Phenyl acetamide, compound+N '-[4- [4- chloro- 3- (trifluoromethyl) phenoxy group] -2,5- dimethyl benzene with chemical formula (I) Base]-N- ethyl-N-methyl carboximidamide, the compound+2- [[2- fluoro- 5- (trifluoromethyl) phenyl] with chemical formula (I) Sulfenyl] -2- [3- (2- methoxyphenyl) Asia -2- thiazolidinyl] acetonitrile and compound+N- (the chloro- 2- of 4- with chemical formula (I) Nitrobenzophenone)-N- ethyl -4- methyl benzenesulfonamide.
These compounds with chemical formula (I) according to the present invention can also make with one or more safener combinations With.Similarly, the compound with chemical formula (I) according to the present invention and one or more other active constituents are (especially With one or more other herbicides) mixture can also be used with one or more safener combinations.As used herein Term " safener " mean a kind of chemicals, the chemicals with combinations of herbicides using when reduce herbicide to non-targeted The undesirable effect of organism, for example, a kind of damage of safener cover crop from antiweed, but will not prevent from removing Weeds are killed in careless agent.When a kind of compound with chemical formula (I) and a kind of safener combination, there is the change of chemical formula (I) It is particularly preferred for closing the following combination of object and safener.Compound+AD 67 (MON4660) with chemical formula (I), has Compound+benoxacor of chemical formula (I) has compound+methyl cloquintocetmexyl of chemical formula (I), has the chemical combination of chemical formula (I) Object+cyometrinil and compound+corresponding cyometrinil (Z) isomer with chemical formula (I) have chemistry Compound+cyclopropyl-sulfonylamide (cyprosulfamide) (CAS RN221667-31-8) of formula (I) has the change of chemical formula (I) Object+allyl dichloride amine is closed, there is the compound and two cyclic ketones (dicyclonon) of chemical formula (I), there is the chemical combination of chemical formula (I) Object and diethyl alcoholates (dietholate) have compound+ethyl fenchlorazole of chemical formula (I), have the change of chemical formula (I) Object+fenclorim is closed, there is compound+flurazole of chemical formula (I), there is compound+fluxofenim of chemical formula (I), have and change Compound+furilazole of formula (I) and a kind of compound with chemical formula (I)+corresponding R isomer or INF furilazone has compound+ethyl isoxadifen of chemical formula (I), and there is compound+pyrroles of chemical formula (I) to solve grass Ester has the compound and cresylate (mephenate) of chemical formula (I), has compound+oxabetrinil of chemical formula (I), has Compound+naphthalic anhydride (CAS RN 81-84-5) of chemical formula (I) has the compound and TI-35 of chemical formula (I), tool There is compound+N- isopropyl -4- (2- methoxv-benzoyl sulfonamides)-benzamide (CAS RN of chemical formula (I) 221668-34-4) and the compound+N- with chemical formula (I) (2- anisoyl base) -4- [(amino-carbonyl) amino] Benzsulfamide.Compound and benoxacor, the compound with chemical formula (I) and first particularly preferably with chemical formula (I) Base cloquintocetmexyl, compound+cyclopropyl-sulfonylamide with chemical formula (I) and the compound with chemical formula (I) and N- (2- methoxy Base benzoyl) -4- [(methylaminocarbonyl) amino] benzsulfamide mixture.
General synthesis process
In the present specification, if there are any difference between chemical name and chemical structure, structure is dominant.Generally Ground, the compound of the present invention described method can be prepared through the invention, unless there are further instruction.Following Synthetic schemes and embodiment are for being further illustrated the contents of the present invention.
Synthetic schemes one
Formula (c) compound and formula (d) compound can be prepared by synthetic schemes one, and wherein Ay has such as the present invention The meaning.Formula (a ') compound reacts to obtain formula (b ') compound in HBr with thiocarbamide；Formula (a) compound passes through bromination Reaction obtains formula (b) compound；Formula (b) compound is reacted with formula (b ') compound, obtains formula (c) compound；Formula (c) compound Further occurrence aoxidizes to obtain formula (d) compound.
Embodiment
Embodiment 1: compound 4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) is thio) methyl) -1,3, 4- oxadiazoles -2- base)-N, the synthesis of the bis- Boc aniline of N-
Step 1: the synthesis of compound 2- methyl -5- (4- nitrobenzophenone) -1,3,4- oxadiazoles
By p-nitrobenzoylhydrazide (9.05g, 50mmol), ammonium chloride (1.28g, 25mmol), triethly orthoacetate (9.73g, 60mmol) is dissolved in dehydrated alcohol (125mL), stops reaction after 80 DEG C of reaction 12h of oil bath.Stone is added into reaction solution Oily ether (50mL) filters after solid is precipitated, and filter cake is washed with ethyl acetate (50mL), dries to obtain 9.43g yellow solid, yield: 92%.
Step 2: the synthesis of compound 4- (5- Methyl-1,3,4-oxadiazole-2-2- base) aniline
By compound 2- methyl -5- (4- nitrobenzophenone) -1,3,4- oxadiazoles (9.7g, 47mmol), iron powder (10.6g, It 189mmol) is dissolved in the mixed liquor (v/v=90/10mL) of second alcohol and water, 5 drop concentrated hydrochloric acids are instilled at 90 DEG C of oil bath, are reacted 30 minutes Stop reaction afterwards.It filters to take off after removing solid and does to obtain 7.6g yellow solid, yield: 92%.
1H NMR(400MHz,CDCl3): δ ppm 7.81 (d, J=8.4Hz, 2H), 6.72 (d, J=8.4Hz, 2H), 4.07 (s,2H),2.57(s,3H)。
Step 3: compound 4- (5- Methyl-1,3,4-oxadiazole-2-2- base)-N, the synthesis of the bis- Boc aniline of N-
By compound 4- (5- methyl-1,3,4- oxadiazoles -2- bases) aniline (7.46g, 42.6mmol), DMAP (1.04g, 8.5mmol), triethylamine (12.9g, 127.8mmol) is dissolved in dry tetrahydrofuran (125mL), is slowly added to (Boc) at 0 DEG C2O (27.9g, 127.8mmol) stops reaction after reacting at room temperature 12h.Add water (250mL) into reaction solution, methylene chloride (100mL × 3) extraction, uses anhydrous Na after merging organic phase2SO4It is dry, solvent is removed, concentrate carries out column chromatography for separation (elution Agent: Petroleum ether/EtOAc (v/v)=5/1), 8.0g white solid is obtained, yield: 50%.
Step 4: compound 4- (5- bromomethyl -1,3,4- oxadiazoles -2- base)-N, the synthesis of the bis- Boc aniline of N-
By compound 4- (5- methyl-1,3,4- oxadiazoles -2- bases)-N, the bis- Boc aniline (7.8g, 20mmol) of N-, NBS (9.25g, 50mmol), AIBN (1.37g, 8mmol) are dissolved in dry carbon tetrachloride (160mL), and 90 DEG C of oil bath reactions stop afterwards for 24 hours Only react.Precipitation after removing solid is filtered, concentrate carries out column chromatography for separation (eluant, eluent: Petroleum ether/EtOAc (v/v)=10/1 5.57g light yellow solid), is obtained, yield: 59%.
Step 5: the synthesis of compound 5,5- dimethyl -4,5- dihydro-isoxazole -3- base isothiourea hydrobromide
Thiocarbamide (6g, 79mmol) is dissolved in acetonitrile (65mL) at room temperature, is added dropwise hydrobromic acid (48%, 10mL), is stirred at room temperature 1h.To chloro- 5,5- dimethyl -4, the 5- dihydro-isoxazole (12.6g, 95mmol) of above-mentioned mixed solution and dripping 3-, it is warming up to 40 It DEG C is stirred overnight.Pressurization boils off solvent, and obtained solid obtains 19.2g white crystal, yield: 96.0% with re-crystallizing in ethyl acetate.
Step 6: compound 4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) is thio) methyl) -1,3,4- Oxadiazoles -2- base)-N, the synthesis of the bis- Boc aniline of N-
By compound 4- (5- bromomethyl -1,3,4- oxadiazoles -2- base)-N, the bis- Boc aniline (0.54g, 1.18mmol) of N-, Potassium carbonate (0.49g, 3.56mmol), 5,5- dimethyl -4,5- dihydro-isoxazole -3- base isothiourea hydrobromides (0.36g, It 1.4mmol) is dissolved in dry acetonitrile (10mL), stops reaction after reacting at room temperature 12h.Filter precipitation after removing solid, concentrate It carries out column chromatography for separation (eluant, eluent: Petroleum ether/EtOAc (v/v)=4/1), obtains 0.4g white solid, yield: 66%.
1H NMR(400MHz,CDCl3): δ ppm 8.05 (d, J=8.0Hz, 2H), 7.28 (d, J=8.0Hz, 2H), 4.52 (s,2H),2.87(s,2H),1.44(s,6H),1.42(s,18H)。
Embodiment 2: compound 4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1,3, 4- oxadiazoles -2- base)-N, the synthesis of the bis- Boc aniline of N-
By compound 4-, (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) is thio) methyl) -1,3,4- dislikes two Azoles -2- base)-N, the bis- Boc aniline (2g, 3.96mmol) of N-, metachloroperbenzoic acid (2.28g, 9.9mmol) is dissolved in dry two Chloromethanes (20mL), 35 DEG C of oil bath reactions stop reaction afterwards for 24 hours.Precipitation after removing solid is filtered, concentrate carries out column chromatography point From (eluant, eluent: Petroleum ether/EtOAc (v/v)=3/1), 1.3g white solid is obtained, yield: 61%.
MS-ESI:m/z 537.2[M+H]+；
1H NMR(400MHz,CDCl3): δ ppm 8.08 (d, J=8.0Hz, 2H), 7.31 (d, J=8.0Hz, 2H), 5.00 (s,2H),3.11(s,2H),1.54(s,6H),1.43(s,18H)。
Embodiment 3: compound 4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1,3, 4- oxadiazoles -2- base) aniline synthesis
By compound 4-, (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1,3,4- dislikes two Azoles -2- base)-N, the bis- Boc aniline (1.24g, 2.31mmol) of N-, trifluoroacetic acid (2.62g, 23.1mmol) is dissolved in methylene chloride (80mL), room temperature reaction stop reaction afterwards for 24 hours.After system precipitation, concentrate progress column chromatography for separation (eluant, eluent: Petroleum ether/EtOAc (v/v)=3/1), 0.63g white solid is obtained, yield: 82%.
MS-ESI:m/z 337.1[M+H]+；
1H NMR(400MHz,d6- DMSO): δ ppm 7.63 (d, J=8.6Hz, 2H), 6.68 (d, J=8.6Hz, 2H), 6.02(s,2H),5.54(s,2H),3.25(s,2H),1.45(s,6H)。
Embodiment 4: compound tert-butyl group (4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) is thio) first Base) -1,3,4- oxadiazoles -2- base) phenyl) and carbamate synthesis
By compound 4-, (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) is thio) methyl) -1,3,4- dislikes two Azoles -2- base)-N, the bis- Boc aniline (0.19g, 0.37mmol) of N-, trifluoroacetic acid (0.22g, 1.88mmol) is dissolved in methylene chloride (50mL) stops reaction after reacting at room temperature 1h.After system precipitation, concentrate progress column chromatography for separation (eluant, eluent: Petroleum ether/EtOAc (v/v)=3/1), 0.13g white solid is obtained, yield: 87%.
1H NMR(400MHz,CDCl3): δ ppm 7.97 (d, J=8.8Hz, 2H), 7.51 (d, J=8.8Hz, 2H), 6.71 (s,1H),4.50(s,2H),2.86(s,2H),1.54(s,9H),1.44(s,6H)。
Embodiment 5: compound N-(4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1, 3,4- oxadiazoles -2- base) phenyl) acetamide synthesis
By compound 4-, (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1,3,4- dislikes two Azoles -2- base) aniline (67mg, 0.2mmol) is dissolved in pyridine (2.5mL), chloroacetic chloride (24mg, 0.3mmol) is added dropwise under ice bath, room Stop reaction after temperature reaction 1.5h.After system precipitation, concentrate carries out column chromatography for separation (eluant, eluent: Petroleum Ether/EtOAc (v/v)=2/1), 70mg white solid is obtained, yield: 93%.
1H NMR(400MHz,d6- DMSO): δ ppm 10.33 (s, 1H), 7.92 (d, J=8.8Hz, 2H), 7.82 (d, J= 8.8Hz,2H),5.62(s,2H),3.27(s,2H),2.10(s,3H),1.45(s,6H)。
Embodiment 6: compound N-(4- (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1, 3,4- oxadiazoles -2- base) phenyl) propionamide synthesis
By compound 4-, (5- (((5,5- dimethyl -4,5- dihydro-isoxazole -3- base) sulfuryl) methyl) -1,3,4- dislikes two Azoles -2- base) aniline (85mg, 0.25mmol) is dissolved in pyridine (2.5mL), propionyl chloride (35mg, 0.38mmol) is added dropwise under ice bath, Stop reaction after reacting at room temperature 1h.After system precipitation, concentrate carries out column chromatography for separation (eluant, eluent: Petroleum Ether/EtOAc (v/v)=2/1), 92mg white solid is obtained, yield: 93%.
1H NMR(400MHz,d6- DMSO): δ ppm 10.26 (s, 1H), 7.92 (d, J=8.8Hz, 2H), 7.84 (d, J= 8.8Hz, 2H), 5.62 (s, 2H), 3.27 (s, 2H), 2.38 (q, J=7.6Hz, 2H), 1.45 (s, 6H), 1.10 (t, J= 7.6Hz,3H)。
The target compound of table 1 can be obtained using corresponding raw material by the similar synthetic method of embodiment 1.
Table 1
The target compound of table 2 can be obtained using corresponding raw material by the similar synthetic method of embodiment 2.
Table 2
The target compound of table 3 can be obtained using corresponding raw material by the similar synthetic method of embodiment 3.
Table 3
The target compound of table 4 can be obtained using corresponding raw material by the similar synthetic method of embodiment 4.
Table 4
The target compound of table 5 can be obtained using corresponding raw material by the similar synthetic method of embodiment 5.
Table 5
Biological Examples
Compound is prepared: the raw medicine of certain mass is weighed with assay balance (0.0001g), with containing 1% Tween-80 emulsifier DMF dissolution be configured to 1.0% mother liquor, then with distilled water dilute it is spare.
Test method: pot-culture method is piemarker, Amaranthus retroflexus, Eclipta prostrata and barnyard grass for examination target.Internal diameter 7.5cm flowerpot is taken, dress is multiple Native (vegetable garden soil: seedling medium, 1:2, v/v) is closed at 3/4, above-mentioned six kinds of weeds targets (bud rate >=85%) is directly sowed, covers Native 0.2cm, it is spare to or so the 3 leaf phases to weeds length.Each compound exists according to 300g a.i./ha or 150g a.i./ha dosage After auto spraying tower (model: 3WPSH-700E) application, after weeds blade face, medical fluid moves into hot-house culture after drying, and investigates after 25 days To the activity (%) of weeds.
Test result is shown in Table A-C.
Wherein ND expression is not tested.
The result shows that in 300g ai/ha, activity of weeding of the compounds of this invention to piemarker, Amaranthus retroflexus, Eclipta prostrata and barnyard grass It is superior to Pyroxasulfone or suitable with Pyroxasulfone activity；In 150g ai/ha, the compounds of this invention to piemarker, Amaranthus retroflexus, Eclipta prostrata activity of weeding be superior to Pyroxasulfone.
The compounds of this invention all has good control efficiency to piemarker, Amaranthus retroflexus, Eclipta prostrata and barnyard grass.To crop safety, And it is better than the isoxazoles compound of commercial herbicide and structure proximate to the control efficiency of weeds.

Claims (5)

1. a kind of compound is the salt of the compound as shown in formula (I) compound represented or formula (I):
Wherein:
R1And R2It is each independently methyl；
R3And R4It is each independently hydrogen；
N is 0,1 or 2；
R5And R6It is each independently hydrogen；
Ay isWherein Ay is optionally selected from R by 1ySubstituent group replaced；
RyFor fluorine, chlorine, bromine, iodine or-NRaRb；
Each RaAnd RbIt independently is hydrogen ,-C (=O)-RcOr-C (=O)-ORd；
Each RcIt independently is hydrogen, C1-6Alkyl or halogenated C1-4Alkyl；
Each RdIt independently is C1-6Alkyl.
2. compound according to claim 1, wherein
Each RyIt independently is fluorine, chlorine, bromine, iodine, amino ,-NH-C (=O)-CH2Br ,-NH-C (=O)-CH2Cl ,-NH-C (=O)- C1-4Alkyl ,-N (C (=O)-C1-4Alkyl)2,-NH-C (=O)-OC1-4Alkyl or-N (C (=O)-OC1-4Alkyl)2。
3. a kind of compound is the compound with one of following structure or the salt with one of following structural compounds:
4. a kind of composition is further included and is subjected in Pesticide Science comprising compound described in claim 1-3 any one Surfactant and carrier.
5. the application of compound or composition as claimed in claim 4 in agricultural described in claim 1-3 any one.
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CN101052628A (en) * 2004-09-03 2007-10-10 先正达有限公司 Isoxazolines derivatives and its weedicide application
WO2008074991A1 (en) * 2006-12-21 2008-06-26 Syngenta Limited Novel herbicides

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CN101052628A (en) * 2004-09-03 2007-10-10 先正达有限公司 Isoxazolines derivatives and its weedicide application
WO2008074991A1 (en) * 2006-12-21 2008-06-26 Syngenta Limited Novel herbicides

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