CN109438333A - A kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application - Google Patents
A kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application Download PDFInfo
- Publication number
- CN109438333A CN109438333A CN201811610231.9A CN201811610231A CN109438333A CN 109438333 A CN109438333 A CN 109438333A CN 201811610231 A CN201811610231 A CN 201811610231A CN 109438333 A CN109438333 A CN 109438333A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- represent
- halogen
- alkoxy
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to technical field of pesticide, and in particular to a kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application.The pyridine oxygroup carboxylic ester derivative as shown in formula I,Wherein, A, B separately represent halogen, contain or not contain the alkyl or cycloalkyl of halogen；C represents hydrogen, halogen, alkyl, halogenated alkyl；Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, without or with alkyl, the alkenyl etc. of halogen；M representative-alkyl-R ,-halogenated alkyl-R,X represents nitro or NR1R2.The activity of weeding of the compound is excellent, and has higher crop safety, establishes good selectivity especially for critical harvests such as rice, soybean.
Description
Technical field
The invention belongs to technical field of pesticide, and in particular to a kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof,
Herbicidal combinations and application.
Background technique
The prevention and treatment of weeds is to realize a vital link during high-efficiency agriculture, although herbicide kind in the market
A series of class multiplicity, for example, DE2335349A1, GB1418979A, US3755339, US4110104 etc. disclose such as general formulasCompound represented and its application as herbicide.But due to market it is continuous expand, the resistance of weeds,
The problems such as service life of drug and the economy of drug and people press down the pay attention to day by day of environment especially with ALS
Penoxsuam, bispyribac-sodium, the pyribenzoxim of mechanism processed, the cyhalofop-butyl of ACCe class inhibiting mechanism, the cities such as metamifop
The serious generation of field mainstream rice field gramineous weed weedicide resistance, paddy field prevent and kill off barnyard grass, herba digitariae, herba setariae viridis, semen euphorbiae etc.
Gramineous grass encounters severe challenge, lacks the medicament for effectively preventing and kill off resistant weed, this just needs scientists constantly to study in turn
Develop new efficient, safety, economy and the herbicide kind with different role mode.
Summary of the invention
The present invention provides a kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application, institutes
The activity of weeding for stating compound is excellent, and has higher crop safety, especially for critical harvests such as rice, soybean
Establish good selectivity.
The technical solution adopted by the invention is as follows:
One kind pyridine oxygroup carboxylic ester derivative as shown in formula I,
Wherein, A, B separately represent halogen, contain or not contain the alkyl or cycloalkyl of halogen；
C represents hydrogen, halogen, alkyl, halogenated alkyl；
Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, without or with the alkane of halogen
Base, alkenyl, alkynyl, naphthenic base, alkoxy, alkylthio group, alkyl-carbonyl, alkoxy carbonyl, alkylaminoalkyl group or alkoxy alkane
Base, unsubstituted or substituted aryl, heteroaryl, aryl alkyl, heteroaryl alkyl；
M representative-alkyl-R ,-halogenated alkyl-R,
R is represented
R3Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl and unsubstituted or substituted
Heterocycle, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；
R4、R5、R6Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, alkoxy, alcoxyl
Base carbonyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted alkyl, alkenyl or alkynyl ,-
COR12, nitro, OR13, SO2R14, NR15R16, N=CR17R18, alkyl-carbamoyl, dialkyl carbamoyl, trialkyl first
Silylation or dialkylphosphono；R2H is represented, it optionally can be by 1-2 R11Substituted alkyl or-COR12；Or NR1R2It represents
N=CR21NR22R23, N=CR24OR25, unsubstituted or halogen, alkyl, alkoxy, halogenated alkoxy, alkane are independently selected from by 1-2
Sulfenyl, amino, alkyl amino, dialkyl amido, does not contain or contains replaced the group in alkoxy carbonyl halogenated alkylthio
There are 5- the or 6- member saturation or unsaturated ring of oxygen atom, sulphur atom or other nitrogen-atoms；
Wherein R11Independently represent halogen, hydroxyl, alkoxy, halogenated alkoxy, alkylthio group, halogenated alkylthio, amino, alkane
Base amino, dialkyl amido, alkoxy carbonyl, unsubstituted or substituted aryl, heteroaryl；
R12Represent H, alkyl, halogenated alkyl, alkoxy, phenyl, phenoxy group or benzyloxy；
R13Represent H, alkyl, halogenated alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, alkyl or alkoxy；
R32Represent H, alkyl or benzyl；
R14Represent alkyl, halogenated alkyl；
R15Represent H, alkyl, formoxyl, alkyl acyl, halogenated alkyl acyl group, alkoxy carbonyl, phenylcarbonyl group, phenoxy group
Carbonyl or benzyloxycarbonyl；R16Represent H, alkyl；
R17Represent H, alkyl, the unsubstituted or phenyl replaced 1-3 group in halogen, alkyl, alkoxy；R18
Represent H, alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or alkyl；
R22、R23Separately represent H or alkyl；Or NR22R23Representative do not contain or containing oxygen atom, sulphur atom or
5- the or 6- member of other nitrogen-atoms is saturated or unsaturated ring；
R25Represent alkyl.
Preferably, A, B separately represent halogen, contain or not contain the C1-C8 alkyl or C3-C8 cycloalkanes of halogen
Base；
C represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl；
Q represents halogen, cyano, cyano C1-C8 alkyl, hydroxyl C1-C8 alkyl, amino, nitro, and formoxyl is free of or contains
There are C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C1-C8 alkoxyl, the C1-C8 alkylthio group, C1- of halogen
C8 alkyl-carbonyl, C1-C8 alkoxyl carbonyl, C1-C8 alkyl amino C1-C8 alkyl or C1-C8 alkoxyl C1-C8 alkyl, do not take
Generation or the aryl replaced, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；
M representative-(C1-C8) alkyl-R ,-halogenated (C1-C8) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 ring
Alkyl C1-C8 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C8 alkyl, aryl C1-C8 alkane
Base, heteroaryl C1-C8 alkyl；
R4、R5、R6Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-
It is C8 naphthenic base C1-C8 alkyl, C1-C8 alkoxyl, C1-C8 alkoxyl carbonyl and unsubstituted or substituted heterocycle, aryl, miscellaneous
Aryl, heterocycle C1-C8 alkyl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted C1-C8 alkyl, C2-C8 alkene
Base or C2-C8 alkynyl ,-COR12, nitro, OR13, SO2R14, NR15R16, N=CR17R18, C1-C8 alkyl-carbamoyl, two C1-
C8 alkyl-carbamoyl, three C1-C8 aIkylsilyl groups or two C1-C8 alkyl phosphonos；R2H is represented, it optionally can be by 1-2
A R11Substituted C1-C8 alkyl or-COR12；Or NR1R2Represent N=CR21NR22R23, N=CR24OR25, unsubstituted or by 1-2
It is a to be independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1-C8 alkane
Sulfenyl, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, replaced the group in C1-C8 alkoxyl carbonyl
Wherein R11Independently represent halogen, hydroxyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogen
For C1-C8 alkylthio group, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, C1-C8 alkoxyl carbonyl is unsubstituted or by halogen
Element, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, naphthalene replaced 1-3 group in nitro,
R12Represent H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, phenoxy group or benzyloxy；
R13Represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, C1-C8
Alkyl or C1-C8 alkoxyl；R32Represent H, C1-C8 alkyl or benzyl；
R14Represent C1-C8 alkyl, halogenated C1-C8 alkyl；
R15Represent H, C1-C8 alkyl, formoxyl, C1-C8 alkyl acyl, halogenated C1-C8 alkyl acyl, C1-C8 alkoxyl
Carbonyl, phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R16Represent H, C1-C8 alkyl；
R17Represent H, C1-C8 alkyl, unsubstituted or by 1-3 group institute in halogen, C1-C8 alkyl, C1-C8 alkoxyl
Substituted phenyl；R18Represent H, C1-C8 alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or C1-C8 alkyl；
R22、R23Separately represent H or C1-C8 alkyl；Or NR22R23It represents
R25Represent C1-C8 alkyl；
" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous
The aromatic cyclic group that aryl " refers to containing 3 to 6 annular atoms and can also be condensed by benzo ring, in the annular atom 1 to
4 hetero atoms are selected from oxygen, nitrogen and sulphur, for example, Wherein, it is selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl is unsubstituted
Or phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in halogen, alkyl, alkoxy, contain
Or alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, OR ", SR " ,-alkyl-OR without containing halogen " ,-alkyl-SR ",
COR”、COOR”、COSR”、SOR”、SO2R ", OCOR ", SCOR ", and it is selected from hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, ring
Alkyl-alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO2Replaced one or two of R ", OR " group
Amino or amino carbonyl at least one group replaced；
R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain alkyl, alkenyl, alkynyl, the ring of halogen
Alkyl, cycloalkenyl, cycloalkyl-alkyl, alkoxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, alkoxyalkyl, alkoxy
Carbonyl, alkylthiocarbonyl, alkyl sulphonyl, Alkylsulfonylalkyl, alkyl-carbonyl, Alkylcarbonylalkyl, alkyl acyloxy, alkane
Base amino, alkyl amino-carbonyl, alkoxy amino carbonyl, alkoxy carbonyl alkyl, alkyl amino-carbonyl alkyl, trialkylsilyl
Base, dialkylphosphono；
R " separately represents hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl.
It is highly preferred that A, B separately represent halogen, the C1-C6 alkyl or C3-C6 cycloalkanes of halogen are contained or not contain
Base；
C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；
Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxyl C1-C6 alkyl, amino, nitro, and formoxyl is free of or contains
There are C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C1-C6 alkoxy, the C1-C6 alkylthio group, C1- of halogen
C6 alkyl-carbonyl, C1-C6 alkoxy carbonyl, C1-C6 alkyl amino C1-C6 alkyl or C1-C6 alkoxy C 1-C6 alkyl, do not take
Generation or the aryl replaced, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；
M representative-(C1-C6) alkyl-R ,-halogenated (C1-C6) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring
Alkyl C1-C6 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C6 alkyl, aryl C1-C6 alkane
Base, heteroaryl C1-C6 alkyl；
R4、R5、R6Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-
It is C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxy carbonyl and unsubstituted or substituted heterocycle, aryl, miscellaneous
Aryl, heterocycle C1-C6 alkyl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted C1-C6 alkyl, C2-C6 alkene
Base or C2-C6 alkynyl ,-COR12, nitro, OR13, SO2R14, NR15R16, N=CR17R18, C1-C6 alkyl-carbamoyl, two C1-
C6 alkyl-carbamoyl, three C1-C6 aIkylsilyl groups or two C1-C6 alkyl phosphonos；R2H is represented, it optionally can be by 1-2
A R11Substituted C1-C6 alkyl or-COR12；Or NR1R2Represent N=CR21NR22R23, N=CR24OR25, unsubstituted or by 1-2
It is a to be independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1-C6 alkane
Sulfenyl, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, replaced the group in C1-C6 alkoxy carbonyl
Wherein R11Independently represent halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogen
For C1-C6 alkylthio group, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, C1-C6 alkoxy carbonyl is unsubstituted or by halogen
Element, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, naphthalene replaced 1-3 group in nitro,
R12Represent H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy group or benzyloxy；
R13Represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, C1-C6
Alkyl or C1-C6 alkoxy；R32Represent H, C1-C6 alkyl or benzyl；
R14Represent C1-C6 alkyl, halogenated C1-C6 alkyl；
R15Represent H, C1-C6 alkyl, formoxyl, C1-C6 alkyl acyl, halogenated C1-C6 alkyl acyl, C1-C6 alkoxy
Carbonyl, phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R16Represent H, C1-C6 alkyl；
R17Represent H, C1-C6 alkyl, unsubstituted or by 1-3 group institute in halogen, C1-C6 alkyl, C1-C6 alkoxy
Substituted phenyl；R18Represent H, C1-C6 alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or C1-C6 alkyl；
R22、R23Separately represent H or C1-C6 alkyl；Or NR22R23It represents
R25Represent C1-C6 alkyl；
" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous
Aryl " refers to
Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by selected from halogen,
Phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in C1-C6 alkyl, C1-C6 alkoxy, contain or not
C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl, OR " containing halogen,
SR " ,-(C1-C6) alkyl-OR " ,-(C1-C6) alkyl-SR ", COR ", COOR ", COSR ", SOR ", SO2R”、OCOR”、
SCOR ", and it is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6
Alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO2Ammonia replaced one or two of R ", OR " group
Replaced 0,1,2 or 3 group in base or amino carbonyl；
R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain C1-C6 alkyl, the C2- of fluorine, chlorine, bromine
C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 cycloalkenyl, C3-C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C2-
C6 alkenyl oxygroup, C2-C6 alkynyl oxygroup, C3-C6 cycloalkyl oxy, C1-C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl
Base, C1-C6 alkylthiocarbonyl, C1-C6 alkyl sulphonyl, C1-C6 alkyl sulphonyl C1-C6 alkyl, C1-C6 alkyl-carbonyl, C1-
C6 alkyl-carbonyl C1-C6 alkyl, C1-C6 alkyl acyloxy, C1-C6 alkyl amino, C1-C6 alkyl amino-carbonyl, C1-C6 alcoxyl
Base amino carbonyl, C1-C6 alkoxy carbonyl C1-C6 alkyl, C1-C6 alkyl amino-carbonyl C1-C6 alkyl, three C1-C6 alkyl first silicon
Alkyl, two C1-C6 alkyl phosphonos；
R " separately represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring
Alkyl C1-C6 alkyl.
It is further preferred that A, B separately represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkanes
Base；
C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；
Q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyanogen
Base, amino, nitro, formoxyl, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkoxy carbonyl group, hydroxyl C1-C6 alkyl, C1-C6
Alkoxy C 1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthalene, furyl, thienyl, thiophene
Oxazolyl, pyridyl group, pyrimidine radicals and unsubstituted or alkyl-substituted by C1-C6It is unsubstituted or by C1-C6 alkyl, halogen
For phenyl replaced at least one group in C1-C6 alkyl, halogen and C1-C6 alkoxy；
M representative-(C1-C6) alkyl-R ,-halogenated (C1-C6) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring
Alkyl C1-C6 alkyl and unsubstituted or by C1-C6 alkyl, C1-C6 alkoxy, halogen and halogenated C1-C6 alkyl
Phenyl replaced at least one group, naphthalene, benzyl,
R4、R5、R6Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-
C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxy carbonyl and it is unsubstituted or by be selected from C1-C6 alkyl, C1-
Phenyl replaced at least one group in C6 alkoxy, halogen and halogenated C1-C6 alkyl, naphthalene, benzyl,
R ' represents C1-C6 alkyl, halogenated C1-C6 alkyl；
X represents amino, C1-C6 alkyl amino, C1-C6 alkyl-carbonyl-amino, benzylcarbonylamino, benzylamino, does not take
Generation or the alkyl-substituted furanylmethylenyl amino of halogenated C1-C6.
It is further preferred that A, B separately represent fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, three
Methyl fluoride, cyclopropyl；
C represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl；
Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, acetenyl, fluorine, chlorine, bromine, cyano, amino, nitre
Base, formoxyl, methoxyl group, methyl mercapto, methoxycarbonyl group, chloromethyl, a methyl fluoride, difluoromethyl, trifluoromethyl, 2- chloroethene
Base, 2,2,2- trifluoroethyl, hydroxymethyl,Benzyl, naphthalene, furan
It mutters base, thienyl, thiazolyl, pyridyl group, pyrimidine radicals and unsubstituted or methyl substitutedIt is unsubstituted or by first
Phenyl replaced at least one group in base, trifluoromethyl, chlorine and methoxyl group；
R ' represents methyl, ethyl, difluoromethyl；
M is represented
X represents NH2、
In the definition of the compound shown in above-mentioned general formula I and following all structural formulas, no matter technical term used individually makes
With or use in compound word, represent following substituent group: can be straight chain or branch with the alkyl group of more than two carbon atom
Chain.Such as compound word "-alkyl-OR " " in alkyl can be-CH2-、-CH2CH2-、-CH(CH3)-、-C(CH3)2Etc..Alkyl group
For for example, methyl；Ethyl；N-propyl or isopropyl；Normal-butyl, isobutyl group, tert-butyl or 2- butyl；Amyl；Hexyl, such as
N-hexyl, isohesyl and 1,3- dimethylbutyl.Halogen is fluorine, chlorine, bromine or iodine.
If a group, replaced group, this is understood to mean that the group by one or more identical or different
The group selected from those of mentioned group replace.In addition, what is contained in identical or different substituent group identical or different takes
It is selected independently, may be the same or different for character.
According to the property of substituent group and its connected mode, compounds of formula I can be used as stereoisomer presence.Example
Such as, if there is one or more asymmetric carbon atoms, then enantiomter and diastereoisomer be may occur in which.Stereoisomer
It is obtained in the mixture that can be obtained from preparation by conventional separation methods, for example by chromatography.Can equally it pass through
Stereoisomer is selectively prepared using Stereoselective reaction and using optically active starting material and/or auxiliary agent.
The invention further relates to comprising in general formula I but all stereoisomers and its mixture that are not specifically defined.
The preparation method of the pyridine oxygroup carboxylic ester derivative, comprising the following steps:
General formula III compound represented is carried out to react chemical combination shown in obtained general formula I with II compound represented of general formula
Object；Its reaction equation is as follows:
Wherein, W represents alkali metal, preferably K, Na；Hal represents halogen, preferably Br, Cl；The reaction is in catalyst and molten
It is carried out in the presence of agent, it is preferable that the catalyst is TBAB, and the solvent is one of DCM, DCE, ACN, THF, DMF
Or multiple combinations.
Or when X represents NR1R2(R1、R2Simultaneously it is not hydrogen) when, by general formula I-1 compound represented
React with corresponding halides and be made；
Wherein, the preferred chloro thing of halides or bromo-derivative；The reaction carries out in the presence of alkali and solvent, the alkali choosing
From one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate；Solvent is selected from
In THF, 1,4- dioxane, toluene, 1,2- dichloroethanes, ethyl acetate, acetonitrile, DMF, acetone, methylene chloride and chloroform
One or more combinations；Catalyst, preferably DMAP can also be added in the reaction process.
A kind of Herbicidal combinations, including (i) at least one of pyridine oxygroup carboxylic ester derivative shown in formula I；It is excellent
Selection of land further includes (ii) one or more other herbicides and/or safener；It is highly preferred that further including (iii) agriculture chemistry
Upper acceptable formulation auxiliary agents.
A method of control weeds, including in the pyridine oxygroup carboxylic ester derivative by herbicidally effective amount extremely
Few a kind of or herbicidal composition use is on plant or weed regions, it is preferable that the plant is rice (such as round-grained rice
Rice, long-grained nonglutinous rice), soybean, the weeds be grass family (such as barnyard grass, herba digitariae), broadleaf weeds (such as Monochoria vaginalis, piemarker, clearvers) and
Sedge weed (such as cyperus iria).
At least one of described pyridine oxygroup carboxylic ester derivative or the herbicidal composition are in control weeds
On purposes, it is preferable that the pyridine oxygroup carboxylic ester derivative is used to prevent and kill off the weeds in useful crop, it is described useful
Crop is genetically modified crops or the processed crop of genome editing technique, it is highly preferred that the crop is rice (such as round-grained rice
Rice, long-grained nonglutinous rice), soybean, the weeds be grass family (such as barnyard grass, herba digitariae), broadleaf weeds (such as Monochoria vaginalis, piemarker, clearvers) and
Sedge weed (such as cyperus iria).
For many economically important unifacial leaves and dicotyledonous harmful plants, compound of formula I of the invention, which has, to be protruded
Activity of herbicide.Active material of the invention is effective also for perennial weeds, these weeds are from rhizome, rhizomes or other
Perennial organ on grow out, be difficult to control.In this regard, if prior to seeding, sprout before or sprout after using should
Substance is generally inessential.The representative example of unifacial leaf and broadleaf weed group that specifically mentioned the compounds of this invention can control,
The species for the determination being not limited to.The example of the weed species of active material useful effect includes monocotyledon: annual
In Avena, rye, careless category, amur foxtail category, farad this, barnyard grass, knotgrass, setaria and Cyperus and perennial wheatgrass
Category, Cynodon, cogon and sorghum and perennial Cyperus.
About dicotyldenous weed species, act on for example annual Bedstraw of species that can extend to, Viola,
Veronica, lamium, Stellaria, Amaranthus, sinapsis alba category, Ipomoea, chrysanthemum harvest spp, Matricaria and abutilon and perennial
Weeds japanese bearbind genus, Cirsium, Rumex and artemisia.Effectively control has active material of the present invention under the conditions of rice growing is this undetermined
Evil plant, such as barnyard grass, Sagittaria, Waterplantain, Eleocharis, sugarcane grass and Cyperus.If the compounds of this invention applied before rudiment
For soil surface, the rice shoot of weeds can be prevented completely before weeds grow, or just stopped growing when weeds grow cotyledon,
It is finally completely dead after three to four weeks.The compounds of this invention especially resists the good activity of following plants, and A Pila is careless, small
White dead nettle, volume stem smartweed, herba stellariae mediae, Changchun cane leaves Veronica, Veronica persica, heartsease and amaranth, Bedstraw and summer cypress.
Although the compounds of this invention has excellent activity of herbicide for unifacial leaf and dicots weeds, for important
Economy class crop plants, such as wheat, barley, rye, rice, corn, beet, cotton and soybean do not damage but at all,
Either damage is inappreciable.It is especially compatible very well with cereal crops, such as wheat, barley and corn, especially
Wheat.Therefore, the compounds of this invention is very suitable for the useless plant being selectively controlled in agricultural crop or ornamental plant.
Due to their deweeding property, in the plant cultivation of genetic engineering that is known or will occurring, these active matters
Matter can be used for controlling noxious plant.Genetically modified plants usually have superior character, such as especially special to specific insecticide
The resistance for determining herbicide, to the resistance of the pathogenic microorganisms of plant disease or plant disease, such as specific insect or true
The microorganism of bacterium, bacterium or virus.Other especially characters are related with following conditions of product, for example, quantity, quality, storage
Stability, component and special ingredient.So, it is known that the transgenic plant product of acquisition have increased content of starch or
Improved starch quality or different Fatty acid components.
Compound of formula I of the invention is preferred for, the crop and ornamental plant of economically important transgenosis, such as paddy
Class, for example, wheat, barley, rye, oat, grain, rice, cassava and corn or be used for beet, cotton, soybean, rapeseed, horse
The cultivation of bell potato, tomato, pea and other vegetable plants.Compound of formula I is preferred for the herbicide of useful plant cultivation, this
A little plants have drug resistance to the toxic action of herbicide with drug resistance or by genetic engineering.
Traditional breeding includes with the method than known plants with improvement shape plant, such as traditional mating method
It is bred with mutant strain.It in other words, can be by means of the method for genetic engineering (see, e.g. EP-0221044A, EP-
0131624A) come obtain with improve character new plant.Such as, it has been described that several methods:
In order to improve the Starch synthesis in plant, change crop plants (such as WO 92/11376, WO using genetic engineering
92/14827, WO 91/19806)；
The transgenic crop plant resistant to specific herbicide, to glufosinate herbicide (such as EP-0242236
A, EP-0242246 A) or to glyphosate-class herbicides (WO 92/00377), or to sulfonylurea herbicide (EP-0257993
A, US-5013659 A)；
Such as the transgenic crop plant of cotton, it can generate bacillus thuringiensis toxin (Bt toxin), and this toxin can
To defend the infringement (EP-0142924 A, EP-0193259 A) of specific pests on plants；
Transgenic crop plant (WO91/13972) with improved Fatty acid component.
Known many can prepare have improve character genetically modified plants molecular biotechnology (see, e.g.
Sambrook etc., 1989, molecule amplification, the laboratory manual second edition, Cold Spring Harbor Laboratory publication, Cold SpringHarbor, New York；Or
Winnacker " Gene und Klone " [gene and clone], VCH Weinheim, the second edition 1996 or Christou, " plant
1 (1996) 423-431 of the trend of science ")).In order to realize the operation of genetic engineering, nucleic acid molecules may be introduced plasmid, led to
The recombination of DNA sequence dna is crossed, mutates or sequence changes.Using above-mentioned standard method, such as substrate, removing unit can be exchanged
Sub-sequence increases the sequence naturally or synthesized.In order to which DNA fragmentation is interconnected, it is possible to be accompanied with combination in segment
Body or connector.
The plant cell for reducing active gene prod can be prepared with following methods, such as at least one suitable by expression
When antisense-RNA, justice-RNA achieve the effect that co-suppression, or ribozyme by expressing at least one appropriate structuring, it
The transcription product of specific cleavage said gene product.
For this purpose, it is possible to use the DNA molecular comprising gene product whole coded sequence, includes that may be present
Any flanking sequence, and use the DNA molecular comprising only only a part coded sequence, these parts must long enough to reach
The effect of antisense in cell.Also can be used with gene product coded sequence has high homology but not exactly the same sequence
Column.
When expressing nucleic acid molecules in plant, the protein of synthesis can be determined in any desired plant cell room
Position.However in order to be positioned in specific room, it is possible to for example code area is connected with DNA sequence dna, it is fixed in specific position to ensure
Position.These sequences be known to those skilled in the art (see, e.g. Braun etc., EMBO J.11 (1992) 3219-
3227；Wolter etc., Proc.Natl.Acad.Sci.USA 85 (1988), 846-850；The Plant such as Sonnewald are J.1
(1991), 95-106).
Transgenic plant cells can be recombinated onto entire plant using known technology.Genetically modified plants can be to appoint
What desired plant variety, i.e. unifacial leaf and dicotyledon.In such a way, by overexpressing, forbidding or inhibit homologous
(=naturally) gene or gene order, or pass through (=external) gene or the expression of gene order of xenogenesis, it is possible to
Obtain the genetically modified plants for improving character.
When using active material of the invention on the crop in transgenosis, can be observed on other crops in addition to having
Inhibition noxious plant effect outside, special effect is often had on corresponding genetically modified crops, for example, can improve or
Expand the range of control weeds, improves amount of application when application, the preferably drug resistance of genetically modified crops and the performance of herbicide very
Good combination, and the growth of the crop plants of transgenosis and the influence of yield.Therefore present invention provides the compounds
Purposes, as herbicide control transgenic crop plant in noxious plant.
In addition the compounds of this invention can obviously adjust the growth of crop plants.Plant metabolism is participated in by adjusting, is used
The component and promotion harvest of these compound oriented control plants, such as make plant desiccation and stunted growth.And they are also fitted
Growth in adjusting and inhibiting undesirable plant growth, without destroying crop.Many unifacial leaves that are grown in of plant are inhibited to plant
Play very important effect in object and dicotyledon crop because can reduce in this way or completely pre- lodging-prevention.
General preparation can be used to apply the compound of the present invention, wettable powder can be used, emulsifiable concentrates, can spray
Solution, powder or the particle spilt.Present invention provides the herbicidal compositions including compound of formula I in this way.According to common
The physical parameter of biology and/or chemistry can prepare compound of formula I with various ways.Suitable preparation selects example are as follows: can
Wet powder (WP), water-soluble powder (SP), water-soluble concentrate, emulsifiable concentrates (EC), for example oil in water dispersion and
Emulsion (EW) that water disperses in the oil, sprayable solution, suspending agent concentrate (SC), dispersible oil-suspending agent (OD), with oil or
Water is the suspension of diluent, the solution of miscible oil, powder (DP), capsule suspension liquid (CS), packet core (seeddressing)
Composition, for broadcasting sowing with the particle of soil pesticide, injection particle, coated particle and absorbing particles, dispersible particle in water
(WG), water-soluble particle (SG), ULV (ultra-low volume) formula, micro-capsule and wax work.These single preparation types are known
, it is described in the following references, such as Winnacker-K ü chler, " Chemische Techonologie " [chemical work
Skill], volume 7, C.Hauser Verlag Munich, the 4th edition 1986；Wade van Valkenburg, " Pesticide
Formulations ", Marcel Dekker, N.Y., 1973；K.Martens, " Spray Drying " handbook, the 3rd edition 1979,
G.Goodwin Ltd.London。
Necessary formulation auxiliary agents, such as inert substance, surfactant, solvent and other additives are similarly known,
And it is described in following files, such as " powder diluent insecticide and the carrier handbook " of Watkins, the second edition, Darland book
Caldwell N.J.；H.v.01phen " introduction of Clay Colloids chemistry ", the second edition, J.Wiley and Sons, N.Y.；
" solvent guide " second edition of C.Marsden, Interscience, N.Y.1963；" detergent and the emulsifier of McCutcheon
Annual report ", MC distributing and releasing corporation, Ridgewood N.J.；Sisley and Wood, " surfactant encyclopedia ", chemistry is published public
Department, N.Y.1964；'s[ethylene oxide adduct surface
Activating agent], Wiss.Verlagagesell.Stuttgart 1976；" the Chemische of Winnacker-K ü chler
Technologie " [chemical technology], volume 7, C.Hauser Verlag Munich, the 4th edition 1986.
Wettable powder can equably can be dispersed in water, in addition to active material, further include diluent or inert substance, from
Son and nonionic surface active agent (wetting agent, dispersing agent), such as polyethoxy alkylphenol, polyethoxy fatty alcohol, polyoxy
Ethyl fatty race amine, poly alkyl alcohol ether sulfates, alkylsulfonate, alkyl benzene sulfonate, wooden sodium sulfonate, 2,2 '-
Dinaphthyl methane -6,6 '-sodium disulfonate, nekal or oleoyl N-methyltaurine sodium.It, will in order to prepare wettable powder
The active material fine grinding of herbicide, such as using common instrument, hammer-mill, fan grater and jet-propelled grater are such as used,
Simultaneously or sequentially it is mixed into auxiliary agent.
Active material dissolution is prepared into emulsifiable concentrates, solvent such as butanol, cyclohexanone, dimethyl formyl in organic solvent
The mixture of amine, the aromatic compounds of dimethylbenzene or higher or hydrocarbon or solvent, and add one or more
Ion and/or nonionic surface active agent (emulsifier).The example for the emulsifier that can be used is such as detergent alkylate
The alkyl aryl sulphonic acid calcium or nonionic emulsifier of sulfoacid calcium, for example, fatty acid polyglycol diol ester, alkylaryl polyglycol ether,
The mountain of poly alkyl alcohol glycol ethers, propylene oxide-oxirane condensation product, alkyl, polyether, such as sorbitan fatty acid ester
Pears glycan ester, or the polyoxyethylene sorbitan ester of such as Polyoxyethylene sorbitan fatty ester.
Active material and solid matter fine crushing are ground to obtain powder, solid matter such as talcum, such as kaolin, bentonite
With the natural clay or diatomite of pyrophyllite.It can be prepared by following methods with water or oil for the suspension of substrate, such as benefit
Wet-milling is carried out with commercially general bead mill, is added or is added without the surfactant of another above-mentioned preparation type.
The emulsion for preparing such as oil-water emulsifiers (EW), can be used aqueous organic solvent, uses blender, colloid
Dismembyator and/or static mixer, if it is desired, the surfactant of another preparation type as described above is added.
Granule is prepared with following methods, active material is sprayed on adsorbate, using inert material particle, or will be lived
Property substance be concentrated to for example husky, kaolinite carrier surface, inert material is granulated by adhesive, adhesive such as polyethylene
Alcohol, Sodium Polyacrylate or mineral oil.Suitable active material can be granulated with the method for preparing fertiliser granulates agent, if necessary
Fertilizer can be mixed with.Aqueous suspension granule is prepared using usual way, such as sprinkling-drying, fluidized bed prilling, mill are made
Grain is mixed using high-speed mixer, and squeezed in the case where no solid, inert material.
About the preparation method for using mill, fluidized bed, extruder and sprayed particle agent, referring to following techniques, such as
" Spray Drying handbook " third edition 1979, G.Goodwin Co., Ltd, London；J.E.Browning,
" Agglomeration ", chemistry and engineering 1967,147ff pages；" engineer's handbook of Perry ' s chemistry ", the 5th edition,
McGraw-Hill, New York 1973,8-57 pages.If it is to be understood that the preparation about crop protection products, see, for example,
G.C.Klingman, " Weed Control as a Science ", John Wiley and Sons company, New York, 1961 81-96
Page and J.D.Freyer, S.A.Evans " weed control handbook ", the 5th edition, Blackwell Scientific
Rublications, Oxford University 1968,101-103 pages.
Agrochemical formulation generally comprises the active material Formulas I of by weight 0.1 to 99%, especially 0.1 to 95%.
The concentration of active material is in wettable powder, and by weight for example from about 10 to 99%, common formulation components composition is pressed
Poidometer surplus is to 100%.Concentration by weight of the active material in emulsifiable concentrates can be about 1 to 90%, preferably 5
To 80%.Powder formulation includes by weight 1 to 30% active material, it is usually preferred to by weight 5 to 20% active matter
Matter, however sprayable solution includes by weight about 0.05 to 80%, preferably 2 to 50% active material.It is outstanding about water
The content of active material in floating particles agent, mainly according to active material be liquid or solid-state, and be granulated when use auxiliary agent, fill out
Material etc..The content of active material is for example by weight between 1 to 95% in aqueous suspension granule, preferably by weight 10
To between 80%.
In addition the preparation of the active material may include tackifier, wetting agent, dispersing agent, emulsifier, bleeding agent, prevent
Rotten agent, antifreezing agent, solvent, filler, carrier, colorant, defoaming agent, evaporation suppressor and usually all common in all cases
PH and viscosity modifier.
Based on these preparations, it is also possible to and other biocidal activity substances for example insecticide, acaricide, herbicide and
Fungicide mixing, can also mix, hybrid mode can be to be pre-mixed with safener, fertilizer and/or plant growth regulator
Good or filling mixing.
In mixture preparation or bucket mix formulation, can be with the suitable active material of active material of the invention mixing,
Such as " world pesticide new varieties technology complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in
Known substance.Such as herbicidal activity substance mentioned below can be mixed with Formulas I mixture, (remarks: the name of compound
Title is perhaps the common name according to International Organization for standardization (ISO) or is chemical name, there is code name when appropriate):
Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, S-metolachlor, pretilachlor, propachlor, kecaoan, naphthalene
Propionyl grass amine, the left-handed naphthalene propionyl grass amine of R-, propanil, mefenacet, diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, fluorine butyryl
Careless amine, bromobutide, dimethenamid, dimethenamidP, ethobenzanid, flufenacet, thenylchlor, pyrrole grass
Amine, isoxaben, flampropMmethyl, flampropMisopropyl, allidochlor, pethoxamid, chloranocryl, cyclopropyl grass
Amine, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood,
Front three ring grass amine, propyzamide, valeryl benzene grass amine, blocks careless amine, suffer, the careless amine of tricyclic match, butylene grass at clomeprop
Amine, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene
More grams of grass is dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, atrazine, Simanex, prometryn, cyanatryn, symetryne,
Ametryn, dipropetryn, flur, terbutryn, Garagard, triaziflam, cyprazine, proglinazine, trietazine, is flutterred propazine
Going out, logical, Gesadrual, nitrine be net, desmetryn, dimethametryn, cyclopropyl blueness saliva, green bristlegrass of going out saliva, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy
Third net, cyanatryn, ipazine, chlorazine, atraton, weed eradication be logical, Radix Glycyrrhizae saliva, cyanuric acid, Indaziflam, green sulphur are grand, first
Sulphur is grand, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, mesosulfuron, iodosulfuron-methyl-sodium, formyl
Amino Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, ring
Third Sulfometuron Methyl, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium,
Fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, procarbazone, prosulfuron, Sulfosulfuron, trifluoro pyridine
Sulphur is grand, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, Sulfonylurea, orthosulfamuron,
Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fomesafen, lactofen, second carboxylic
Fluofazone, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox, fluoroform grass ether, methoxy weeding
Ether, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass ether, fluorine lactazone grass ether, fluofazone ester,
Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron,
Ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, phenobenzuron, methoxy daimuron, metobromuron, first
Oxygen is grand, afesin, telvar, Tupersan, fenuron, fluorine sulphur are grand, neburea, chloroxifenidium, herban, isonoruron, Alipur-O,
Thiazfluron, tebuthiuron, difenoxuron, to fluon, methylamine methabenz thiazuron, Long Caote, front three isourea, dimefuron, Monisouron,
Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-ethyl ester, desmedipham, the spirit of sulphur grass, special grass
Spirit, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, Carboxazole, Chlorprocarb,
Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate, molinate, tri-allate, dimepiperate, dogstail
Fear, pyributicarb, cycloate, Avadex, bactericide, the careless spy of second sulphur, orbencarb, pebulate, prosulfocarb, tiocarbazil, sulfuric acid,
Dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, 2 first, 4 chlorine sodium, the different monooctyl ester of 2,4- drop, 2 first, 4 chlorine are different pungent
Ester, 2,4- drop sodium salt, 2,4- drop dimethylamine salt, 2 first, 4 chloroethene thioesters, 2 first, 4 chlorine, 2,4- drop propionic acid, high 2,4- drop propionate, 2,
4- Embutox, Vi par, Vi par salt, Thistrol, 2,4,5- tears, 2,4,5- tears propionic acid, 2,4,5- tears fourth
Acid, 2 first, 4 chloramines salt, dicamba, erbon, Fenac, match pine, trichlorobenzoic acid, chloramben, methoxy trichlorobenzoic acid, dogstail
Spirit, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient haloxyfop, quizalofop-ethyl, Quizalotop-ethyl, oxazole dogstail
Spirit, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, diclofop-methyl thiazole, chloroazifoppropynyl, the spirit of hydroxyl penta standing grain,
Trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, ethalfluralin, isopropalin, nitralin, cyclopropyl fluorine
Spirit, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin, chloroethene dipropalin, Methalpropalin,
Third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, amiprophos-methyl, sulphosate, piperazine grass phosphine, bialaphos, bensulide, butamifos,
Creeping weed phosphorus cuts down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, imazethapyr, imazaquin, imazamox, first
Oxygen Imazethapyr ammonium salt, AC 263222, miaow grass ester, fluroxypyr, the different monooctyl ester of fluroxypyr, clopyralid, ammonia
Chloropyridine acid, trichlopyr, dithiopyr, halogen grass be fixed, phenolate trichloropyridine, thiazopyr, fluridone, chlorine Fampridine acid,
Diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, sethoxydim, clethodim, cycloxydim, alloxydimsodium, ring benzene grass
Ketone, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, metribuzin, hexazinone, metamitron, ethiozin,
Ametridione, Amibuzin, Brominal, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenatril, polybenzobisoxazole
Oxalic acid dinitrile, chloroxynil, Iodobonil, Flumetsulam, florasulam, penoxsuam, metosulam, cloransulammethyl,
Diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyribenzoxim, pyriftalid, KIH 6127, pyrithiobacsodium, bicyclic sulphur
It is humulone, mesotrione, sulphur humulone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, different
Oxazole humulone, isoxachlorotole, Fenoxasulfone, Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, wild swallow
Withered, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, fluorine amine grass
Azoles, Amrol, amicarbazone, azafenidin, profluazone, sulfentrazone, Bencarbazone, benzfendizone, fluorine third are phonetic
Careless ester, bromacil, isoprocil, lenacil, terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin,
Alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachlorophenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol,
Medinoterb acetate, Di Lete, oxadiargyl, oxadiazon, pentoxazone, profluazol, fluthiacet, fentrazamide, fluorine
Pyridazine grass ester, pyrazon, brompyrazon, diformazan reach careless volt, Kusakira, grass pyridazone, grass and rattle away pine, norflurazon, Pyridafol, dichloro
Quinolinic acid, quinmerac, Bentazon, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, iso-propyl-ester nitrofen,
Propyl-ester nitorfen, indanofan, sodium chlorate, Dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro propionic acid, herbage is fast, bromine phenol
Oxime, triazole sulphur, kill azoles, flurtamone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde,
Bentranil, tridiphane, Bidisin, thiadiazoles grass amine, phenisopham, hydroxyl humulone, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, three
Chloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-
Methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin,
Cambendichlor, cyclopropyl pyrimidine acid, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, solve careless quinoline, oxabetrinil,
Oxalane, cyometrinil, desorpenic, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine
Chloropyridine ester, DOW chlorine fluorine pyridine ester, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218,
DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、
KIH-6127 and KIH-2023.
In the context of the present specification, if the abbreviated form of the adopted name using reactive compound, at every kind
In the case of include all conventional derivatives, such as ester and salt and isomers, especially optical isomer are especially a kind of
Or a variety of commercial forms.It in each case further include every other conventional derivatisation if adopted name indicates ester or salt
Object, such as other esters and salt, free acid and neutral compound and isomers, especially optical isomer, it is especially a kind of
Or a variety of commercial forms.The chemical name of the compound provided indicates at least one compound covered by adopted name, usually
It is preferred compound.
When in use, if desired, commercially available preparation is diluted in common mode, such as in wettable powder, concentration
When emulsion, suspension and the particle to suspend in water, make to be diluted with water.Granule used in powder, soil pesticide or broadcast sowing and
The solution of sprinkling does not need generally further to be diluted with inert substance before use.With the variation of external condition, it is desirable that formula
The usage amount of Compound I is also different, and external condition is, such as temperature, humidity, the property of herbicide used etc..It can be with
Have a big amplitude of variation, such as 0.001 between 1.0kg/ha, or more active material, but preferably arrived 0.005
Between 750g/ha, especially 0.005 between 500g/ha.
Specific embodiment
Following embodiment should not be regarded it as limiting the invention in any way for illustrating the present invention.The present invention
Claimed interest field is illustrated by claims.
In view of the economy and diversity of compound, we are preferably synthetic some compounds, in many chemical combination of synthesis
In object, selected part is listed in the table below in 1.Specific compound structure and corresponding compound information are as shown in table 1-2.In table 1
Compound be intended merely to better illustrate the present invention, but limit the present invention, for a person skilled in the art, no
The range that this should be interpreted as to the above-mentioned theme of the present invention is only limitted to following compound.
1 compound structure of table
2 compound of table1HNMR data
The several methods detailed annotation for preparing the compounds of this invention is illustrated in following scheme and embodiment.Raw material can be through market
It buys or can be prepared by known in the literature method or as shown in detailed annotation.Those skilled in the art should manage
Solution, also can use other synthetic routes and synthesizes the compound of the present invention.Although hereinafter to the tool in synthetic route
Body raw material and condition are illustrated, however, it is possible to easily be replaced with other similar raw materials and condition, these are right
Modification or the variant of preparation method of the present invention and the various isomeries of compound etc. generated are included in the scope of the invention
It is interior.In addition, preparation method as described below can routinize according to the disclosure of invention, using well known to those skilled in the art
Method is further modified.For example, during the reaction group appropriate protect etc..
For embodiment of the method presented below for promoting further appreciating that preparation method of the invention, what is used is specific
Substance, type and condition are determined as not being the limitation to its zone of reasonableness to further explanation of the invention.In the following table
Reagent used in the synthesis compound shown can perhaps be bought with market or can be light by those of ordinary skill in the art
Easily it is prepared.
The embodiment of representative compound is as follows:
1, the synthesis of compound 2
(1) compound 2-1 (300mg, 3.33mmol), TEA (404mg, 4.00mmol) are dissolved in anhydrous methylene chloride
In (20mL), it is cooled to 0 DEG C, compound a (791mg, 3.66mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued
When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry,
Concentration, obtains compound 2-2 (800mg, crude product), does not have to purifying, is directly used in next step.
(2) by compound b (400mg, 1.59mmol), the compound 2-2 (800mg, crude product) that upper step obtains, catalytic amount
TBAB (10mg), DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.The reaction of liquid quality detection raw material
It is complete, room temperature, water (50mL) and methyl tertiary butyl ether(MTBE) (50mL) extraction are down in reaction, organic phase is dry, is concentrated, after post separation
It obtains compound 2 (300mg, yield 49%), compound 2 is white solid.
2, the synthesis of compound 54
(1) compound 54-1 (1g, 7.03mmol), compound 54-2 (845mg, 7.03mmol) are dissolved in 20mL methanol
In, it is cooled to 0 DEG C, thionyl chloride (920mg, 7.74mmol) is slowly added dropwise, reaction is slowly increased to room temperature, reaction is stirred at room temperature
12 hours.High performance liquid chromatography detection raw material fundamental reaction is complete, concentration.With ethyl acetate (100mLx 2) and unsaturated carbonate hydrogen
Sodium water solution (50mL) is washed, and organic phase is dry, is concentrated to get compound (1.5g, crude product), does not purify, is directly used in next step.
(2) the compound 54-3 (1.5g, crude product) that obtains aforesaid operations, NBS (1.09g, 6.14mmol), catalytic amount
AIBN (10mg), carbon tetrachloride (100mL) are placed in 100mL single port bottle, and 60 DEG C are stirred 12 hours, high performance liquid chromatography detection
Raw material has reacted, and reaction solution is down to room temperature, filters out solid, and carbon tetrachloride is mutually concentrated, obtain compound 54-4 (1g, slightly
Product), it does not purify, is directly used in next step.
(3) by compound b (400mg, 1.70mmol), compound 54-4 (826mg, 1.91), the TBAB of catalytic amount
(10mg), DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.Liquid quality detection raw material has reacted, will
Room temperature, water (50mL) and methyl tertiary butyl ether(MTBE) (50mL) extraction are down in reaction, and organic phase is dry, is concentrated, and are obtained after post separation
Compound 54 (400mg, yield 57%).
3, the synthesis of compound 78
(1) compound 78-1 (300mg, 1.46mmol), TEA (178mg, 175mmol) are dissolved in anhydrous methylene chloride
In (20mL), it is cooled to 0 DEG C, compound a (347mg, 1.61mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued
When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry,
Concentration, obtains compound 78-2 (460mg, crude product), does not have to purifying, is directly used in next step.
(2) by compound b (400mg, 1.70mmol), the compound 78-2 (826mg, 2.56mmol) that upper step obtains is urged
The TBAB (10mg) of change amount, DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.Liquid quality detection is former
Material has reacted, and room temperature, water (50mL) and methyl tertiary butyl ether(MTBE) (50mL) extraction is down in reaction, organic phase is dry, is concentrated, through column
Compound 78 (300mg, yield 38%) is obtained after separation.
4, the synthesis of compound 79
(1) compound 79-1 (300mg, 4.1mmol) is dissolved in anhydrous methanol (20mL), is cooled to 0 DEG C, in batches plus
Enter solid sodium methylate (244mg, 4.51mmol).10min is stirred at 0 DEG C, and compound 79-2 is slowly added dropwise at such a temperature
(199mg, 4.51mmol).It is slowly raised to room temperature, the reaction was continued 12 hours.High performance liquid chromatography detects raw material fundamental reaction
It is complete, a small amount of acetum is added dropwise to neutrality.Methanol is removed into reaction solution concentration, with water (100mL) and ethyl acetate (100mL x
2) it extracts, organic phase is dry, is concentrated, and obtains compound 79-3 (500mg, crude product), does not have to purifying, is directly used in anti-in next step
It answers.
(2) by compound 79-3 (500mg, crude product), TEA (518mg, 5.12mmol) is dissolved in anhydrous methylene chloride
In (20mL), it is cooled to 0 DEG C, compound a (1.01g, 4.69mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued
When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry,
Concentration, obtains compound 79-4 (1g, crude product), does not have to purifying, is directly used in next step.
(3) by compound b (400mg, 2.13mmol), the compound 79-4 (1g, crude product) that upper step obtains, catalytic amount
TBAB (10mg), DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.The reaction of liquid quality detection raw material
It is complete, room temperature, water (100mL) and methyl tertiary butyl ether(MTBE) (50mL x 2) extraction are down in reaction, organic phase is dry, is concentrated, through column
It is obtained after separation compound 79 (240mg, yield 38%), compound 79 is white solid.
5, the synthesis of compound 74 and 128
(1) compound 74-1 (300mg, 2.08mmol), TEA (253mg, 2.50mmol) are dissolved in anhydrous methylene chloride
In (20mL), it is cooled to 0 DEG C, compound a (494mg, 2.29mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued
When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry,
Concentration, obtains compound 74-2 (500mg, crude product), does not have to purifying, is directly used in next step.
(2) by compound b (400mg, 1.70mmol), the compound 74-2 (533mg, 1.91mmol) that upper step obtains is urged
The TBAB (10mg) of change amount, DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.Liquid quality detection is former
Material has reacted, and room temperature, water (50mL) and methyl tertiary butyl ether(MTBE) (50mL) extraction is down in reaction, organic phase is dry, is concentrated, through column
Compound 74 (300mg, yield 48%) is obtained after separation.
(3) by compound 74 (300mg, 0.76mmol), compound 128-1 (195mg, 1.14mmol), potassium carbonate
(210mg, 1.52mmol), the DMAP (10mg) of catalytic amount, acetonitrile (20mL) are placed in 50mL round-bottomed flask, are heated to 80 DEG C instead
It answers 12 hours.Liquid quality detection raw material has reacted, and room temperature is down in reaction, and concentration obtains compound 128 through column chromatography for separation
(150mg, yield 41%).
6, the synthesis of compound 130
(1) compound 130-1 (300mg, 3.37mmol), TEA (443mg, 4.38mmol) are dissolved in anhydrous dichloromethane
In alkane (20mL), it is cooled to 0 DEG C, compound a (871mg, 4.04mmol) is slowly added dropwise.It is slowly raised to room temperature, the reaction was continued 12
Hour.Reaction solution is poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, organic relevant
Dry, concentration obtains compound 130-2 (800mg, crude product), does not have to purifying, is directly used in next step.
(2) by compound b (400mg, 1.70mmol), the compound 130-2 (800mg, crude product) that upper step obtains, catalytic amount
TBAB (10mg), DMF (10mL) is placed in 50mL round-bottomed flask, is heated to 85 DEG C and reacts 12 hours.Liquid quality detection raw material is anti-
It has been answered that, room temperature, water (50mL) and methyl tertiary butyl ether(MTBE) (50mL) extraction are down in reaction, organic phase is dry, is concentrated, through post separation
After obtain compound 130 (300mg, yield 49%).
Biological evaluation:
The active class criteria that noxious plant destroys (i.e. growth control rate) is as follows:
5 grades: growth control rate is 85% or more；
4 grades: growth control rate is more than or equal to 60% and less than 85%；
3 grades: growth control rate is more than or equal to 40% and less than 60%；
2 grades: growth control rate is more than or equal to 20% and less than 40%；
1 grade: growth control rate is more than or equal to 5% and less than 20%；
0 grade: growth control rate is less than 5%.
The above growth control rate is fresh weight control rate.
Test experiments after seedling: by unifacial leaf and broadleaf weed seed and chief crop seed (wheat, corn, rice,
Soybean, cotton, rape, millet, sorghum) it is placed in the plastic tub equipped with soil, 0.5-2 centimetres of soil is then covered, it is made
It is grown in good greenhouse, handles test plants in the 2-3 leaf phase after sowing 2 weeks, it respectively will be for the chemical combination of the present invention of examination
Object acetone solution, is then added Tween 80, dilute with certain water using the missible oil of 1.5 liter/hectare methyl oleates as synergist
It is interpreted into certain density solution, is sprayed application on plant with spray tower.It is cultivated in the greenhouse after application 3 weeks, the experiment of weeds after 3 weeks
Effect is listed in table 3-4.
3 compound activity test result of table (1000 grams/ha)
Weeds test result after 4 seedling of table
| Compound numbers | Japonica rice | Long-grained nonglutinous rice | Cyperus iria | Barnyard grass |
| 2 | 0 | 0 | 5 | 5 |
| 3 | 0 | 0 | 5 | 5 |
| 4 | 0 | 0 | 5 | 5 |
| 12 | 0 | 0 | 5 | 5 |
| 69 | 0 | 0 | 5 | 5 |
| 88 | 0 | 0 | 5 | 5 |
| 100 | 0 | 0 | 5 | 5 |
| 104 | 0 | 0 | 5 | 5 |
| 121 | 0 | 0 | 5 | 5 |
| 125 | 0 | 0 | 5 | 5 |
| 126 | 0 | 0 | 5 | 5 |
| 131 | 0 | 0 | 5 | 5 |
| Control compound A (600 grams/ha) | 3 | 3 | 5 | 5 |
| Control compound A (300 grams/ha) | 2 | 3 | 4 | 4 |
| Control compounds B (600 grams/ha) | 2 | 2 | 3 | 2 |
| Bispyribac-sodium (100 grams/ha) | 4 | 2 | 2 | 1 |
Note: administration dosage is 600 grams/ha of effective component, and the amount of being watered is 450 kilograms/hectare.The barnyard grass, cyperus iria
Hunan China is picked up from, it is resistant to ALS inhibitor class herbicide.
Control compound A:Control compound B:
Control compound B is commercialized product, has preferable selection to wheat paddock broadleaved herb, low dosage can be used for
Part broadleaved herb is prevented and kill off, (50-100 grams/ha) is only effective to paddy field minority broadleaved herb under acceptable safety, to rice
The key grassy weed effect such as field barnyard grass, herba digitariae, semen euphorbiae, herba setariae viridis is excessively poor, or does not have effect.Control compound A
It is known compound, since safety is poor, selects index low, it is difficult to production application.Making us unexpected is, knot of the invention
Although structure is similar with some are compareed, but on the basis of retention, safety is greatly improved, to the main grass of paddy field
Section weeds and broadleaved herb, nutgrass flatsedge have good selectivity, have good commercial value, especially confrontation ALS inhibitor is miscellaneous
Grass, still superior.
Test experiments before seedling:
By unifacial leaf and broadleaf weed seed and chief crop seed (wheat, corn, rice, soybean, cotton, oil
Dish, millet, sorghum) it is placed in the plastic tub equipped with soil, 0.5-2 centimetres of soil is then covered, it respectively will be for this hair of examination
Bright compound acetone solution, is then added Tween 80, is diluted to certain density solution with certain water, after planting sprays immediately
It applies.It is cultivated in the greenhouse after application 4 weeks, observation experiment after 3 weeks is as a result, find that medicament majority of the invention is counted at 250 grams/ha
Lower superior is measured, especially to weeds such as barnyard grass, herba digitariae, piemarkers, and many compounds are to corn, wheat, rice, soybean, oil
Dish has good selectivity.
By testing we have found that compound of the present invention generally has preferable Weed-control effect, particularly with corn
The main gramineae weed such as weeds barnyard grass, herba digitariae, herba setariae viridis that field, paddy field, wheat paddock occur extensively and piemarker, indian rorippa herb,
The main broadleaf weeds such as beggar-ticks has good effect, has good commercial value.Especially it was noted that for ALS
The broadleaf weeds such as the resistant indian rorippa herb of inhibitor, Descurainia sophia, shepherd's purse, corn gromwell, clearvers, herba stellariae mediae have high activity.
Transplanting rice safety evaluatio and paddy land weed preventive effect are evaluated:
After being packed into paddy field soil in 1/1,000,000 hectare of tank, the seed of Monochoria vaginalis is sowed, is lightly covered on it
Soil is statically placed in greenhouse with 0.5-1 centimetres of state of water storage depth.Thereafter 3-4 centimetres of water storage depth is kept, reaches 0.5 in Monochoria vaginalis
Leaf will modulate the water diluent of wettable powder made of the compounds of this invention or suspending agent according to common formulation method,
Uniformly drip processing with pipette to reach defined active ingredient amount.
In addition, after being packed into paddy field soil in 000,000 hectare of tank, progress is smooth 1/1, make 3-4 centimetres of water storage depth, the
The rice (japonica rice) of 3 leaf phases is transplanted within two days with 3 centimetres of transplanting depth.The present invention is handled as described above within the 5th day after transplanting
Compound.
The fertility status of 14th day Monochoria vaginalis after the chemicals treatment that detects by an unaided eye respectively, the 21st day rice after chemicals treatment
Fertility status, with above-mentioned 0-5 grades of activity criteria's level evaluation herbicidal effect, many compounds show excellent activity and
Selectivity.
5 assay activity of table and security test result (1000 grams/ha)
Note: Monochoria vaginalis seed collection is from Chinese Heilungkiang, after testing to the pyrazosulfuron of routine dose, penoxsuam
There is drug resistance.
The compounds of this invention is to the anti-ALS Inhibitory Mechanism to face severe challenge in production it can be seen from this experiment
Weeds have outstanding activity, be able to solve the resistance problem got worse.
Hormone herbicide is very sensitive to broad leaf crop, and being easy to happen leads to periphery crop damage because elegant.We
The compound of the present invention is tested.Under breeze conditions, the system of the compounds of this invention is sprayed with big boundary multi-rotor unmanned aerial vehicle
Agent (sprays height as 1 meter, 20 kilograms of water of per hectare), and per hectare, with acetone solution, is diluted to and is spat with 600 grams of effective component
In the aqueous solution of temperature 80, soybean kind is implanted in 10 meters of distance of place, and soybean is about 15 centimetres high when spray.Control compound C is used
Same dosage and condition.
6 active testing result of table
Note: compound C is
It can be seen that the compounds of this invention is not only to rice safety, it is also very safe to periphery crop, under the conditions of low wind not
It can be because elegant problem causes sensitive broad leaf crop aggrieved.And although control compound structure is similar with the compounds of this invention,
But it is dangerous to rice, while phytotoxicity is be easy to cause to the sensitive broad leaf crop in periphery.With being widely applied for unmanned plane, need
This herbicide safer to environment of the present invention.
Simultaneously by many test discoveries, compound of the present invention and combinations thereof is much to Korea lawn grass, Bermuda grass, height
The Gramineae lawns such as fescue grass, annual bluegrass, rye grass, seashore paspalum have good selectivity, and it is miscellaneous to prevent and kill off many crucial grass family
Grass and broadleaf weeds.To the wheat under different insecticide-applying way, corn, rice, sugarcane, soybean, cotton, oily certain herbaceous plants with big flowers, potato, fruit
The tests such as tree, vegetables also show that fabulous selectivity and commercial value.
Claims (10)
1. a kind of pyridine oxygroup carboxylic ester derivative as shown in formula I,
Wherein, A, B separately represent halogen, contain or not contain the alkyl or cycloalkyl of halogen；
C represents hydrogen, halogen, alkyl, halogenated alkyl；
Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, alkyl, alkene without or with halogen
Base, alkynyl, naphthenic base, alkoxy, alkylthio group, alkyl-carbonyl, alkoxy carbonyl, alkylaminoalkyl group or alkoxyalkyl, not
Aryl, the heteroaryl, aryl alkyl, heteroaryl alkyl for replacing or replacing；
M representative-alkyl-R ,-halogenated alkyl-R,
R is represented
R3Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl and unsubstituted or substituted heterocycle
Base, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；
R4、R5、R6Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, alkoxy, alkoxy carbonyl
Base and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted alkyl, alkenyl or alkynyl ,-COR12,
Nitro, OR13, SO2R14, NR15R16, N=CR17R18, alkyl-carbamoyl, dialkyl carbamoyl, trialkylsilyl
Base or dialkylphosphono；R2H is represented, it optionally can be by 1-2 R11Substituted alkyl or-COR12；Or NR1R2Represent N=
CR21NR22R23, N=CR24OR25, unsubstituted or halogen, alkyl, alkoxy, halogenated alkoxy, alkane sulphur are independently selected from by 1-2
Base, amino, alkyl amino, dialkyl amido, does not contain or contains replaced the group in alkoxy carbonyl halogenated alkylthio
5- the or 6- member of oxygen atom, sulphur atom or other nitrogen-atoms is saturated or unsaturated ring；
Wherein R11Independently represent halogen, hydroxyl, alkoxy, halogenated alkoxy, alkylthio group, halogenated alkylthio, amino, alkyl ammonia
Base, dialkyl amido, alkoxy carbonyl, unsubstituted or substituted aryl, heteroaryl；
R12Represent H, alkyl, halogenated alkyl, alkoxy, phenyl, phenoxy group or benzyloxy；
R13Represent H, alkyl, halogenated alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, alkyl or alkoxy；R32It represents
H, alkyl or benzyl；
R14Represent alkyl, halogenated alkyl；
R15Represent H, alkyl, formoxyl, alkyl acyl, halogenated alkyl acyl group, alkoxy carbonyl, phenylcarbonyl group, phenyloxycarbonyl
Or benzyloxycarbonyl；R16Represent H, alkyl；
R17Represent H, alkyl, the unsubstituted or phenyl replaced 1-3 group in halogen, alkyl, alkoxy；R18Represent H,
Alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or alkyl；
R22、R23Separately represent H or alkyl；Or NR22R23Representative does not contain or contains oxygen atom, sulphur atom or other
5- the or 6- member of nitrogen-atoms is saturated or unsaturated ring；
R25Represent alkyl.
2. pyridine oxygroup carboxylic ester derivative according to claim 1, which is characterized in that
A, B separately represents halogen, contains or not contain the C1-C8 alkyl or C3-C8 naphthenic base of halogen；
C represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl；
Q represents halogen, cyano, cyano C1-C8 alkyl, hydroxyl C1-C8 alkyl, amino, nitro, formoxyl, without or with halogen
C1-C8 alkyl, the C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C1-C8 alkoxyl, C1-C8 alkylthio group, C1-C8 alkane of element
Base carbonyl, C1-C8 alkoxyl carbonyl, C1-C8 alkyl amino C1-C8 alkyl or C1-C8 alkoxyl C1-C8 alkyl, it is unsubstituted or
Substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；
M representative-(C1-C8) alkyl-R ,-halogenated (C1-C8) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 naphthenic base
C1-C8 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C8 alkyl, aryl C1-C8 alkyl,
Heteroaryl C1-C8 alkyl；
R4、R5、R6Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 ring
Alkyl C1-C8 alkyl, C1-C8 alkoxyl, C1-C8 alkoxyl carbonyl and unsubstituted or substituted heterocycle, aryl, heteroaryl
Base, heterocycle C1-C8 alkyl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted C1-C8 alkyl, C2-C8 alkenyl or
C2-C8 alkynyl ,-COR12, nitro, OR13, SO2R14, NR15R16, N=CR17R18, C1-C8 alkyl-carbamoyl, two C1-C8 alkane
Base carbamoyl, three C1-C8 aIkylsilyl groups or two C1-C8 alkyl phosphonos；R2H is represented, it optionally can be by 1-2 R11
Substituted C1-C8 alkyl or-COR12；Or NR1R2Represent N=CR21NR22R23, N=CR24OR25, unsubstituted or only by 1-2
It is vertical selected from halogen, C1-C8 alkyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1-C8 alkylthio group,
Amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, replaced the group in C1-C8 alkoxyl carbonyl
Wherein R11Independently represent halogen, hydroxyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1-
C8 alkylthio group, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, C1-C8 alkoxyl carbonyl, it is unsubstituted or by halogen,
C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, naphthalene replaced 1-3 group in nitro,
R12Represent H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, phenoxy group or benzyloxy；
R13Represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, C1-C8 alkyl
Or C1-C8 alkoxyl；R32Represent H, C1-C8 alkyl or benzyl；
R14Represent C1-C8 alkyl, halogenated C1-C8 alkyl；
R15Represent H, C1-C8 alkyl, formoxyl, C1-C8 alkyl acyl, halogenated C1-C8 alkyl acyl, C1-C8 alkoxyl carbonyl,
Phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R16Represent H, C1-C8 alkyl；
R17Represent H, C1-C8 alkyl, unsubstituted or replaced 1-3 group in halogen, C1-C8 alkyl, C1-C8 alkoxyl
Phenyl；R18Represent H, C1-C8 alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or C1-C8 alkyl；
R22、R23Separately represent H or C1-C8 alkyl；Or NR22R23It represents
R25Represent C1-C8 alkyl；
" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous
Aryl " refers to
Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by be selected from halogen
Element, alkyl, phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in alkoxy, contain or not contain halogen
Element alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, OR ", SR " ,-alkyl-OR " ,-alkyl-SR ", COR ", COOR ",
COSR”、SOR”、SO2R ", OCOR ", SCOR ", and it is selected from hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, benzene
Base, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO2Amino replaced one or two of R ", OR " group or ammonia
Replaced at least one group in base carbonyl；
R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain alkyl, alkenyl, alkynyl, the cycloalkanes of halogen
Base, cycloalkenyl, cycloalkyl-alkyl, alkoxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, alkoxyalkyl, alkoxy carbonyl
Base, alkylthiocarbonyl, alkyl sulphonyl, Alkylsulfonylalkyl, alkyl-carbonyl, Alkylcarbonylalkyl, alkyl acyloxy, alkyl
Amino, alkyl amino-carbonyl, alkoxy amino carbonyl, alkoxy carbonyl alkyl, alkyl amino-carbonyl alkyl, trialkylsilyl
Base, dialkylphosphono；
R " separately represents hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl.
3. pyridine oxygroup carboxylic ester derivative according to claim 2, which is characterized in that
A, B separately represents halogen, contains or not contain the C1-C6 alkyl or C3-C6 naphthenic base of halogen；
C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；
Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxyl C1-C6 alkyl, amino, nitro, formoxyl, without or with halogen
C1-C6 alkyl, the C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkane of element
Base carbonyl, C1-C6 alkoxy carbonyl, C1-C6 alkyl amino C1-C6 alkyl or C1-C6 alkoxy C 1-C6 alkyl, it is unsubstituted or
Substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；
M representative-(C1-C6) alkyl-R ,-halogenated (C1-C6) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base
C1-C6 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C6 alkyl, aryl C1-C6 alkyl,
Heteroaryl C1-C6 alkyl；
R4、R5、R6Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring
Alkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxy carbonyl and unsubstituted or substituted heterocycle, aryl, heteroaryl
Base, heterocycle C1-C6 alkyl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；
X represents nitro or NR1R2, wherein R1H is represented, it optionally can be by 1-2 R11Substituted C1-C6 alkyl, C2-C6 alkenyl or
C2-C6 alkynyl ,-COR12, nitro, OR13, SO2R14, NR15R16, N=CR17R18, C1-C6 alkyl-carbamoyl, two C1-C6 alkane
Base carbamoyl, three C1-C6 aIkylsilyl groups or two C1-C6 alkyl phosphonos；R2H is represented, it optionally can be by 1-2 R11
Substituted C1-C6 alkyl or-COR12；Or NR1R2Represent N=CR21NR22R23, N=CR24OR25, unsubstituted or only by 1-2
It is vertical selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1-C6 alkylthio group,
Amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, replaced the group in C1-C6 alkoxy carbonyl
Wherein R11Independently represent halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1-
C6 alkylthio group, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, C1-C6 alkoxy carbonyl, it is unsubstituted or by halogen,
C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, naphthalene replaced 1-3 group in nitro,
R12Represent H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy group or benzyloxy；
R13Represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR31C(O)OR32；R31Represent H, C1-C6 alkyl
Or C1-C6 alkoxy；R32Represent H, C1-C6 alkyl or benzyl；
R14Represent C1-C6 alkyl, halogenated C1-C6 alkyl；
R15Represent H, C1-C6 alkyl, formoxyl, C1-C6 alkyl acyl, halogenated C1-C6 alkyl acyl, C1-C6 alkoxy carbonyl,
Phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R16Represent H, C1-C6 alkyl；
R17Represent H, C1-C6 alkyl, unsubstituted or replaced 1-3 group in halogen, C1-C6 alkyl, C1-C6 alkoxy
Phenyl；R18Represent H, C1-C6 alkyl；Or N=CR17R18It represents
R21、R24Separately represent H or C1-C6 alkyl；
R22、R23Separately represent H or C1-C6 alkyl；Or NR22R23It represents
R25Represent C1-C6 alkyl；
" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous
Aryl " refers to
Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by be selected from halogen
Phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in element, C1-C6 alkyl, C1-C6 alkoxy, contain
Or C1-C6 alkyl without containing halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl,
OR ", SR " ,-(C1-C6) alkyl-OR " ,-(C1-C6) alkyl-SR ", COR ", COOR ", COSR ", SOR ", SO2R”、OCOR”、
SCOR ", and it is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6
Alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO2Ammonia replaced one or two of R ", OR " group
Replaced 0,1,2 or 3 group in base or amino carbonyl；
R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain fluorine, chlorine, the C1-C6 alkyl of bromine, C2-C6 alkene
Base, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 cycloalkenyl, C3-C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkene
Base oxygroup, C2-C6 alkynyl oxygroup, C3-C6 cycloalkyl oxy, C1-C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl, C1-
C6 alkylthiocarbonyl, C1-C6 alkyl sulphonyl, C1-C6 alkyl sulphonyl C1-C6 alkyl, C1-C6 alkyl-carbonyl, C1-C6 alkyl
Carbonyl C1-C6 alkyl, C1-C6 alkyl acyloxy, C1-C6 alkyl amino, C1-C6 alkyl amino-carbonyl, C1-C6 alkoxy amino
Carbonyl, C1-C6 alkoxy carbonyl C1-C6 alkyl, C1-C6 alkyl amino-carbonyl C1-C6 alkyl, three C1-C6 aIkylsilyl groups, two
C1-C6 alkyl phosphono；
R " separately represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base
C1-C6 alkyl.
4. pyridine oxygroup carboxylic ester derivative according to claim 3, which is characterized in that
A, B separately represents halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base；
C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；
Q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, ammonia
Base, nitro, formoxyl, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkoxy carbonyl group, hydroxyl C1-C6 alkyl, C1-C6 alcoxyl
Base C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthalene, furyl, thienyl, thiazole
Base, pyridyl group, pyrimidine radicals and unsubstituted or alkyl-substituted by C1-C6It is unsubstituted or by C1-C6 alkyl, halogenated
Phenyl replaced at least one group in C1-C6 alkyl, halogen and C1-C6 alkoxy；
M representative-(C1-C6) alkyl-R ,-halogenated (C1-C6) alkyl-R,
R is represented
R3Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base
C1-C6 alkyl and it is unsubstituted or by C1-C6 alkyl, C1-C6 alkoxy, halogen and halogenated C1-C6 alkyl at least
Phenyl replaced one group, naphthalene, benzyl,
R4、R5、R6Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring
Alkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxy carbonyl and it is unsubstituted or by be selected from C1-C6 alkyl, C1-C6 alkane
Phenyl replaced at least one group in oxygroup, halogen and halogenated C1-C6 alkyl, naphthalene, benzyl,
R ' represents C1-C6 alkyl, halogenated C1-C6 alkyl；
X represent amino, C1-C6 alkyl amino, C1-C6 alkyl-carbonyl-amino, benzylcarbonylamino, benzylamino, it is unsubstituted or
The halogenated alkyl-substituted furanylmethylenyl amino of C1-C6.
5. pyridine oxygroup carboxylic ester derivative according to claim 4, which is characterized in that
A, B separately represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl；
C represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl；
Q represent methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, acetenyl, fluorine, chlorine, bromine, cyano, amino, nitro,
Formoxyl, methoxyl group, methyl mercapto, methoxycarbonyl group, chloromethyl, a methyl fluoride, difluoromethyl, trifluoromethyl, 2- chloroethyl, 2,
2,2- trifluoroethyl, hydroxymethyl,Benzyl, naphthalene, furyl,
Thienyl, thiazolyl, pyridyl group, pyrimidine radicals and unsubstituted or methyl substitutedIt is unsubstituted or by methyl, three
Phenyl replaced at least one group in methyl fluoride, chlorine and methoxyl group；
R ' represents methyl, ethyl, difluoromethyl；
M is represented
X represents NH2、
6. pyridine oxygroup carboxylic ester derivative according to claim 5, which is characterized in that it is any one in table 1
It is a.
7. a kind of preparation method of pyridine oxygroup carboxylic ester derivative as claimed in any one of claims 1 to 6, feature exist
In, comprising the following steps:
General formula III compound represented is carried out to react obtained general formula I compound represented with II compound represented of general formula；Its
Reaction equation is as follows:
Wherein, W represents alkali metal, preferably K, Na；Hal represents halogen, preferably Br, Cl；The reaction is in catalysts and solvents
In the presence of carry out, it is preferable that the catalyst is TBAB, and the solvent is one of DCM, DCE, ACN, THF, DMF or more
Kind combination；
Or when X represents NR1R2(R1、R2Simultaneously it is not hydrogen) when, by general formula I-1 compound representedWith
Corresponding halides carry out reaction and are made；
Wherein, the preferred chloro thing of halides or bromo-derivative；The reaction carries out in the presence of alkali and solvent, and the alkali is selected from hydrogen
One or more of sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate；Solvent be selected from THF,
One of 1,4- dioxane, toluene, 1,2- dichloroethanes, ethyl acetate, acetonitrile, DMF, acetone, methylene chloride and chloroform
Or multiple combinations；Catalyst, preferably DMAP can also be added in the reaction process.
8. a kind of Herbicidal combinations, which is characterized in that including (i) pyridine oxygroup carboxylic acid as claimed in any one of claims 1 to 6
At least one of ester derivant；It preferably, further include (ii) one or more other herbicides and/or safener；It is more excellent
Selection of land further includes acceptable formulation auxiliary agents on (iii) agriculture chemistry.
9. a kind of method for controlling weeds, which is characterized in that including described in the claim 1-6 any one by herbicidally effective amount
At least one of pyridine oxygroup carboxylic ester derivative or herbicidal composition use according to any one of claims 8 on plant or
Person weed regions, it is preferable that the plant is rice (such as japonica rice, long-grained nonglutinous rice), soybean, and the weeds are grass family (such as barnyard grass, horse
Tang), broadleaf weeds (such as Monochoria vaginalis, piemarker, clearvers) and sedge weed (such as cyperus iria).
10. at least one of pyridine oxygroup carboxylic ester derivative as claimed in any one of claims 1 to 6 or claim 8
Purposes of the herbicidal composition on control weeds, it is preferable that be used for the pyridine oxygroup carboxylic ester derivative
Prevent and kill off the weeds in useful crop, the useful crop is genetically modified crops or the processed crop of genome editing technique,
It is highly preferred that the crop is rice (such as japonica rice, long-grained nonglutinous rice), soybean, the weeds are grass family (such as barnyard grass, herba digitariae), broad-leaved
Weeds (such as Monochoria vaginalis, piemarker, clearvers) and sedge weed (such as cyperus iria).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811610231.9A CN109438333B (en) | 2018-12-27 | 2018-12-27 | Pyridyloxycarboxylate derivative, preparation method thereof, weeding composition and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811610231.9A CN109438333B (en) | 2018-12-27 | 2018-12-27 | Pyridyloxycarboxylate derivative, preparation method thereof, weeding composition and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109438333A true CN109438333A (en) | 2019-03-08 |
| CN109438333B CN109438333B (en) | 2021-01-05 |
Family
ID=65538274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811610231.9A Active CN109438333B (en) | 2018-12-27 | 2018-12-27 | Pyridyloxycarboxylate derivative, preparation method thereof, weeding composition and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109438333B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943867A (en) * | 2020-06-28 | 2020-11-17 | 上海抚佳精细化工有限公司 | Dimethylglyoxime polyoxyethylene ether and preparation method and application thereof |
| CN112273395A (en) * | 2019-07-27 | 2021-01-29 | 青岛清原化合物有限公司 | Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof |
| WO2021017817A1 (en) * | 2019-07-27 | 2021-02-04 | 青岛清原化合物有限公司 | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof |
| WO2021036251A1 (en) * | 2019-08-27 | 2021-03-04 | 青岛清原化合物有限公司 | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivatives and application thereof |
| RU2807159C2 (en) * | 2019-07-27 | 2023-11-10 | Циндао Кингагрут Кемикал Компаунд Ко., Лтд. | Herbicidal composition containing r-pyridyloxycarboxylic acid and derivative, and its use |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755339A (en) * | 1971-07-26 | 1973-08-28 | Dow Chemical Co | Esters of aminohalopyridyloxy acids |
| US3761486A (en) * | 1971-07-26 | 1973-09-25 | Dow Chemical Co | Aminohalopyridyloxy acids and derivatives thereof |
| US4108629A (en) * | 1973-03-19 | 1978-08-22 | The Dow Chemical Company | Herbicidal use of esters of aminohalopyridyloxy acids |
| US4110104A (en) * | 1973-03-19 | 1978-08-29 | The Dow Chemical Company | Herbicidal use of aminohalopyridyloxy acids and derivatives thereof |
| CN104592103A (en) * | 2015-01-30 | 2015-05-06 | 大连世慕化学有限公司 | Method for synthesizing fluroxypyr ester |
-
2018
- 2018-12-27 CN CN201811610231.9A patent/CN109438333B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755339A (en) * | 1971-07-26 | 1973-08-28 | Dow Chemical Co | Esters of aminohalopyridyloxy acids |
| US3761486A (en) * | 1971-07-26 | 1973-09-25 | Dow Chemical Co | Aminohalopyridyloxy acids and derivatives thereof |
| US4108629A (en) * | 1973-03-19 | 1978-08-22 | The Dow Chemical Company | Herbicidal use of esters of aminohalopyridyloxy acids |
| US4110104A (en) * | 1973-03-19 | 1978-08-29 | The Dow Chemical Company | Herbicidal use of aminohalopyridyloxy acids and derivatives thereof |
| CN104592103A (en) * | 2015-01-30 | 2015-05-06 | 大连世慕化学有限公司 | Method for synthesizing fluroxypyr ester |
Non-Patent Citations (1)
| Title |
|---|
| 郭保国等: "《有机合成重要单元反应》", 30 June 2009, 黄河水利出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112273395A (en) * | 2019-07-27 | 2021-01-29 | 青岛清原化合物有限公司 | Herbicidal composition comprising R-type pyridyloxycarboxylic acid derivatives and use thereof |
| WO2021017502A1 (en) * | 2019-07-27 | 2021-02-04 | 青岛清原化合物有限公司 | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof |
| WO2021017817A1 (en) * | 2019-07-27 | 2021-02-04 | 青岛清原化合物有限公司 | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof |
| JP2022549554A (en) * | 2019-07-27 | 2022-11-28 | チンタオ、キングアグルート、ケミカル、コンパウンド、カンパニー、リミテッド | Herbicidal compositions comprising R-pyridyloxycarboxylic acids and derivatives and their application |
| EP4005384A4 (en) * | 2019-07-27 | 2023-07-19 | Qingdao KingAgroot Chemical Compound Co., Ltd. | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivative and use thereof |
| RU2807159C2 (en) * | 2019-07-27 | 2023-11-10 | Циндао Кингагрут Кемикал Компаунд Ко., Лтд. | Herbicidal composition containing r-pyridyloxycarboxylic acid and derivative, and its use |
| RU2807159C9 (en) * | 2019-07-27 | 2023-12-26 | Циндао Кингагрут Кемикал Компаунд Ко., Лтд. | Herbicidal composition containing r-pyridyloxycarboxylic acid and derivative, and its use |
| JP7494285B2 (en) | 2019-07-27 | 2024-06-03 | チンタオ、キングアグルート、ケミカル、コンパウンド、カンパニー、リミテッド | Herbicidal compositions comprising R-pyridyloxycarboxylic acids and derivatives and methods of application thereof |
| WO2021036251A1 (en) * | 2019-08-27 | 2021-03-04 | 青岛清原化合物有限公司 | Herbicidal composition containing r-type pyridyloxy carboxylic acid derivatives and application thereof |
| CN112438265A (en) * | 2019-08-27 | 2021-03-05 | 青岛清原化合物有限公司 | Weeding composition containing R-type pyridyloxycarboxylic acid derivative and application thereof |
| CN111943867A (en) * | 2020-06-28 | 2020-11-17 | 上海抚佳精细化工有限公司 | Dimethylglyoxime polyoxyethylene ether and preparation method and application thereof |
| CN111943867B (en) * | 2020-06-28 | 2023-03-10 | 上海抚佳精细化工有限公司 | Dimethylglyoxime polyoxyethylene ether and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109438333B (en) | 2021-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105218449B (en) | Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes | |
| CN105503728B (en) | Pyrazole compounds or salts thereof and preparation method thereof, and weedicide composition and application thereof | |
| CN107629035A (en) | A kind of pyrazolone compound or its salt, herbicidal composition and purposes | |
| CN109535070A (en) | Pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application | |
| CN113105405B (en) | Carboxylic acid derivative substituted imino aryl compound, preparation method thereof, herbicidal composition and application | |
| CN109438333A (en) | A kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application | |
| CN108586357B (en) | Substituted pyrimidineformyl oxime derivatives, preparation method thereof, herbicidal composition and application | |
| CN105399674B (en) | Pyrazole compound or salt thereof, and preparation method, herbicide composition and application thereof | |
| CN112778289A (en) | Substituted isoxazoline-containing aromatic compound, preparation method thereof, weeding composition and application | |
| CN109721546B (en) | Substituted pyrimidine aryl ester derivative and preparation method, herbicidal composition and application thereof | |
| CN110343102A (en) | A kind of substituted pyrazolyl-pyrazole sulfonyl urea compound or its as the acceptable salt of pesticide, composition and application thereof | |
| CN113149975B (en) | Isoxazoline oxime formate compound, preparation method thereof, weeding composition and application | |
| CN107353238B (en) | Substituted benzoylcyclohexan cyclohexadione compounds or its tautomer, salt, preparation method, Herbicidal combinations and application | |
| BR112021012415B1 (en) | PYRIDYLOXYCARBOXYLATE DERIVATIVE, HERBICIDAL COMPOSITION COMPRISING THE SAME, METHOD FOR PREPARING THE SAME, AS WELL AS METHOD AND USE OF SAID DERIVATIVE TO CONTROL WEED | |
| CN109400526A (en) | Pyridine oxygroup thioes derivatives and preparation method thereof, Herbicidal combinations and application | |
| CN112110852B (en) | Substituted picolinic acid pyridine methylene ester derivative and preparation method, herbicidal composition and application thereof | |
| CN113024531A (en) | Isoxazoline-containing compound, preparation method thereof, herbicidal composition and application | |
| CN112778296B (en) | Substituted thiazole aromatic ring compound, preparation method thereof, weeding composition and application | |
| RU2777594C2 (en) | Substituted pyrimidinylformyloxime derivative, its production method, its herbicidal composition, and use | |
| CN118515618A (en) | Benzene ring substituted pyrimidine carboxylic acid compound, preparation method thereof, weeding composition and application | |
| CN118530217A (en) | Pyrimidine ring substituted aromatic compound, preparation method thereof, weeding composition and application | |
| BR112021012577B1 (en) | PYRIDYLOXY THIOESTER DERIVATIVES, METHOD OF PREPARATION OF THE PYRIDYLOXY THIOESTER DERIVATIVE, HERBICIDAL COMPOSITION, METHOD FOR CONTROLING A WEED AND USE OF AT LEAST ONE OF THE PYRIDYLOXY THIOESTER DERIVATIVES | |
| BR112021012431B1 (en) | PYRIDYLOXYCARBOXYLATE DERIVATIVES, METHOD OF PREPARING THE PYRIDYLOXYCARBOXYLATE DERIVATIVE, HERBICIDAL COMPOSITION, METHOD FOR CONTROLING A WEED AND USE OF AT LEAST ONE OF THE PYRIDYLOXYCARBOXYLATE DERIVATIVES | |
| CN109832277A (en) | Nitrogenous hetero-aromatic ring formic acid imines ester derivant replaced and preparation method thereof, Herbicidal combinations and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |