CN103025718A - Nitrogen heterocyclic substituted benzoyl compound and use thereof - Google Patents
Nitrogen heterocyclic substituted benzoyl compound and use thereof Download PDFInfo
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- CN103025718A CN103025718A CN2011800352700A CN201180035270A CN103025718A CN 103025718 A CN103025718 A CN 103025718A CN 2011800352700 A CN2011800352700 A CN 2011800352700A CN 201180035270 A CN201180035270 A CN 201180035270A CN 103025718 A CN103025718 A CN 103025718A
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- 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
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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- 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
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- 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
- A01N43/44—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom three- or four-membered rings
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- 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
- A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- 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
- A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
- C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
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Abstract
A nitrogen heterocyclic substituted benzoyl compound or a stereoisomer thereof, as represented by Formula (I): See the description for the definition of each of the substituents in the formula. The compound represented by Formula (I) has herbicidal activity, is capable of controlling effectively weeds such as barnyard grass, crabgrass, black nightshade, velvetleaf, setaria, and zinnia, and can be used agriculturally as a herbicide.
Description
Cyclosubstituted benzoyl base class compound of nitrogen-containing hetero and application thereof
Technical field
The invention belongs to field of agricultural herbicide.Specifically related to a kind of cyclosubstituted benzoyl base class compound of nitrogen-containing hetero and application thereof.Background technology
Have much as the report of herbicide on benzoyl base class compound, such as patent DE10301110,
WO2001032636 WO2001010850, DE19921732, WO9907688, JP 10265432 have announcement to the purposes that such compound is used as herbicide or plant growth regulator.
In addition, the benzoyl base class compound with nitrogenous substituent on the phenyl ring shown in below formula is reported in patent DE19962923 is used as herbicide：
The benzoyl base class compound with nitrogen-containing side chains on the phenyl ring shown in below formula is reported in patent WO2002090336 and is used as herbicide：
Although you can well imagine and below formula compound in patent WO2000021924Al, WO2000037437A1 decile, without with N
The development need of modern agricultural production continually develops new herbicides compounds.In the prior art, the 3- bit strips as shown in formula I of the present invention have benzoyl base class compound of nitrogen heterocyclic ring methylene substituent and application thereof to have no report.
The content of the invention
In order to meet new demand agriculturally to the continuous proposition of herbicide; the invention provides a kind of novel cyclosubstituted benzoyl compound of nitrogen-containing hetero of structure, such compound can effectively control the weeds such as barnyard grass, lady's-grass, black nightshade, piemarker, green bristlegrass, youth-and-old-age as herbicide.
Technical scheme is as follows：
The present invention provides a kind of nitrogen heterocyclic ring and taken as shown in formula I：
Het is selected from three to eight circle heterocycles, in addition to the N atoms on the ring on containing C and 1- positions, also contains 0-3 individual following atoms or group as the part of ring： 0、 N i^ S、 SO、 S02, C=0, C=N i ^ C=NO i, and C=0, C=N i
Or C=NOR is not at 2-；
Y is selected from fluorine, chlorine, bromine, iodine or nitro；
R is selected from halogen, cyano group, hydroxyl, carboxyl, amino, d-C6Protective embankment base, halo C C6Protective embankment base, C C6Protective embankment epoxide, halo C C6Protective embankment epoxide, C C6Protective embankment amino, ^-^ alkenyloxy groups, ^ are for ^-^ alkenyloxy groups, ^-^ enaminos, ^ for C2-C6Enamino, C C6Protective embankment base carbonyl, for d-C6Protective embankment base carbonyl, C C6Protective embankment Epoxide carbonyl, d-C6Protective embankment amino carbonyl, C C6
Ci-c6¾¾S Ci-C !' c ,S Ci-c6¾¾S Ci-C6 Ci-c6¾¾S Ci-C6 Ί C\-C ' Ci-C !' c ,S Ci-C6¾¾ftS Ci-C6¾¾ftS S Ci-C6¾¾ftS Ci-C6Protective embankment base carbonyl epoxide, halo d-c ^ base carbonyls epoxide, d-c ^ bases carbonylamino, d-c6Protective embankment base sulfonyl epoxide, d-c6Protective embankment base sulfuryl amino, d-C ^ base carbonyl d-C ^ epoxides, aryl, heteroaryl, aryloxy group, heteroaryl epoxide, aryl carbonyl epoxide, aryl sulfonyl epoxide, arylmethyl epoxide, hetervaromatic methyl epoxide, aryl-amino-carbonyl, arlysulfonylamino, arylmethyl amino or hetervaromatic methyl amino unsubstituted or that be independently selected from following substituent group by 1-3：Halogen, nitro, cyano group, C C6Protective embankment base, halo d-C6Protective embankment base, C C6Protective embankment epoxide, halo d-C6Protective embankment epoxide or C C6Protective embankment base carbonyl； n=0-4;
Ri is selected from hydrogen, Ci-Co protective embankments base, ^ for ^-^ protective embankments base, C2-C6Alkenyl, ^ are for ^-^ alkenyls, d-C6Protective embankment epoxide d-C6Protective embankment base, ^ are for ^-^ protective embankment epoxides d-C6Protective embankment base, d-C6Protective embankment base carbonyl, ^ are for ^-^ protective embankment bases carbonyl, d-C6Protective embankment base sulphonyl
¾、 Ci-C6 Ci-C6¾¾ S S Ci-C6 Ci-c6¾¾S Ci-c6 Ci-c6Protective embankment base, d-C6Protective embankment amino carbonyl d-C6Protective embankment base, aryl, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl sulfonyl, arylmethyl or hetervaromatic methyl unsubstituted or that be independently selected from following substituent group by 1-3：Halogen, nitro, cyano group, d-C6Protective embankment base, halo d-C6Protective embankment base, d-C6Protective embankment epoxide, halo d-C6Protective embankment epoxide or ^-^ protective embankment base carbonyls；
One：
Wherein-
R2From C1-C6¾l¾、 C3-C6 Ci-C6 Ci-C6¾¾ftS Ci-C6¾¾S Ci-C6S carbonyls, d-C6Protective embankment Epoxide carbonyl, C C6Protective embankment sulfenyl, aryl or halogenated aryl, p=0-6;
As p=2, two on different C atoms can connect into CH2;Or as p=2, two on same C or difference C atoms can connect into following group：（CH2)2、 （CH2)3、 （CH2)4、 （CH2)5、 （CH2)6、 0、 0(CH2)20、 0(CH2)30、 0(CH2)40、 S(CH2)2S or S (CH2)3S;
, selected from hydroxyl, halogen, C C6Protective embankment epoxide, C C6Protective embankment base carbonyl epoxide, C C6Protective embankment sulfenyl, C C6Protective embankment base sulfonyl epoxide, ^-^ alkenyloxy groups, ^ are for ^-^ alkenyloxy groups, ^-^ alkynyloxy groups, d-C6Protective embankment Epoxide carbonyl d-C6Protective embankment epoxide, d-C6Protective embankment amino carbonyl d-C ^ epoxides, aryloxy group, arylthio, arylmethyl epoxide, aryl carbonyl epoxide, aryl sulfonyl epoxide, heteroaryl epoxide or aryl carbonyl methyl epoxide unsubstituted or that be independently selected from following substituent group by 1-3：Halogen, nitro, cyano group, d-C6Protective embankment base, halo d-C6Protective embankment base, d-C6Protective embankment epoxide or halo C C6Protective embankment epoxide；
Selected from hydrogen, d-C6Protective embankment base, halo d-C6Protective embankment base, ^-^ ring protective embankments base, aryl, arylmethyl or heteroaryl unsubstituted or that be independently selected from following substituent group by 1-3：Halogen, nitro, cyano group, d-C6Protective embankment base, halo d-C6Protective embankment base, d-C6Protective embankment epoxide or halo d-C6Protective embankment epoxide；
R5、 R9Selected from hydrogen, halogen, cyano group, carbamoyl, thiocarbamoyl, d-C6Protective embankment base, halo C C6
C3-C6J^¾I¾、 Ci-C ^ Ci-C Ci-C6¾¾ftS S Ci-c6 Ci-c6Protective embankment base sulfonyl, aryl that is unsubstituted or being independently selected from following substituent group by 1-3：Halogen, nitro, cyano group, d-C6Protective embankment base, halo d-C6Protective embankment base, d-C6Protective embankment epoxide or halo d-C6Protective embankment epoxide；
R7Selected from hydrogen, d-C6Protective embankment base, halo d-C6Protective embankment base, C3-C6Ring protective embankment base, aryl or halogenated aryl；
Selected from hydrogen, halogen, cyano group, carbamoyl, d-C6Protective embankment base, halo d-C6Protective embankment base, C3-C6Ring protective embankment base, d-C6
Protective embankment epoxide, d-C6Protective embankment Epoxide carbonyl, d-C ^ sulfenyls or C C6Protective embankment base sulfonyl；
R1()Selected from hydroxyl, d-C6Protective embankment epoxide, C C6Protective embankment base carbonyl epoxide or C C6Protective embankment base sulfonyl epoxide；
Or its salt.
In the definition of general formula compound given above, collect term used and be defined as follows：
Halogen（Element）：Refer to fluorine, chlorine, bromine or iodine.Protective embankment base：Straight or branched protective embankment base, such as methyl, ethyl, propyl group, isopropyl or the tert-butyl group.Ring protective embankment base：Substituted or unsubstituted ring-type protective embankment base, such as cyclopropyl, cyclopenta or cyclohexyl.Substituent such as methyl, halogen etc..Halo protective embankment base：Straight or branched protective embankment base, the hydrogen atom on these protective embankment bases partly or entirely can be replaced by halogen atom.For example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl etc..Protective embankment base sulfonyl：Refer to straight or branched protective embankment base through sulfonyl（-S02-) be connected in structure, such as methyl sulphonyl.Protective embankment epoxide：Straight or branched protective embankment base is connected in structure through oxygen atom.Halo protective embankment epoxide：Straight or branched protective embankment epoxide, the hydrogen atom in these protective embankment epoxides partly or entirely can be replaced by halogen.For example, chloromethane epoxide, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc..Protective embankment sulfenyl：Straight or branched protective embankment base is connected in structure through sulphur atom.Halo protective embankment sulfenyl：Straight or branched protective embankment sulfenyl, the hydrogen atom on these protective embankment sulfenyls partly or entirely can be replaced by halogen atom.For example, chloromethane sulfenyl, dichloro methyl mercapto, trichloro-methylthio, fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, chlorine fluorine methyl mercapto etc..Protective embankment amino：Straight or branched protective embankment base is connected in structure through nitrogen-atoms, such as-NHCH3、 -NHCH2CH3、 -N(CH3)2Deng.Halo protective embankment amino：Hydrogen atom on straight or branched protective embankment amino, protective embankment base partly or entirely can be replaced by halogen.Protective embankment base carbonyl：Protective embankment base is connected in structure through carbonyl, such as-COCH3、 -COC¾CH3Deng.Halo protective embankment base carbonyl：Hydrogen atom on the protective embankment base of protective embankment base carbonyl partly or entirely can be replaced by halogen atom, such as-COCF3Deng.Protective embankment Epoxide carbonyl：Protective embankment epoxide is connected in structure through carbonyl.Such as-C02CH3、 -C02CH3CH2Deng.Protective embankment amino carbonyl：Protective embankment amino is connected in structure through carbonyl.Such as-CONHCH3、 -CON(CH3)2Deng.Protective embankment base carbonylamino：Protective embankment base carbonyl is connected in structure through nitrogen-atoms, such as-NHCOCH3、 -NHCOC¾CH3Deng.Protective embankment base sulfonyl epoxide：Protective embankment base sulfonyl is connected in structure through oxygen atom, such as-OS02CH3、 -OS02C¾CH3Deng.Protective embankment base sulfuryl amino：Protective embankment base sulfonyl is connected in structure through nitrogen-atoms, such as-NHS02CH3、 -NHS02CH2CH3Deng.Alkenyl：Straight or branched alkenes, such as vinyl, 1- acrylic, 2- acrylic and different cyclobutenyls, pentenyl and hexenyl isomers.Alkenyl also includes many alkenes, such as 1,2- allene base and 2,4- hexadienyl.Haloalkenyl group：Straight or branched alkenyl, the hydrogen atom on these alkenyls partly or entirely can be replaced by halogen atom.Alkenyloxy group：Straight or branched alkenyl, is connected in structure through oxygen atom.Halo alkenyloxy group：Straight or branched alkenyloxy group, the hydrogen atom in these alkenyloxy groups partly or entirely can be replaced by halogen.Enamino：Straight or branched alkenyl, is connected in structure through nitrogen-atoms key.Halo enamino：Straight or branched enamino, the hydrogen atom in these alkenyloxy groups partly or entirely can be replaced by halogen.Alkynyloxy group：Straight or branched alkynyl, is connected in structure through oxygen atom.Aryl moiety in aryl and aryloxy group, aryl carbonyl and arylmethyl etc. is including phenyl or naphthyl etc..Aryloxy group：Aryl is connected in structure through oxygen atom, such as phenoxy group, naphthoxy.Heteroaryl is containing one or more N, 0, the heteroatomic five-membered rings of S or hexa-atomic aromatic ring.Such as furyl, pyrazolyl, thiazolyl, pyridine radicals, pyrimidine radicals, pyrazinyl, pyridazinyl, triazine radical, quinolyl.Heteroaryl epoxide：Heteroaryl is connected in structure through oxygen atom, such as pyridine -2- bases epoxide, pyridin-3-yl epoxide or pyrimidine-2-yloxy.Described salt includes N atoms and acid on compound of Formula I heterocycle 1- positions（Such as hydrochloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, benzene sulfonic acid, citric acid or malic acid）The salt formed is reacted, includes the hydroxyl and alkali of its enol form（Such as triethylamine, lithium, sodium, potassium）React the salt formed.
In the compound of the present invention, because configuration difference can form stereoisomer（Different configurations is represented with R and S respectively）, it is of the invention to include R types isomers and S types isomers and its mixture of any ratio；Because ketone/tautomerism may have a variety of dynamic isomers, mixture of the present invention including all dynamic isomers and its any ratio.
The present invention more preferred technical scheme is that Q is selected from the cyclosubstituted benzoyl base class compound of the nitrogen-containing hetero shown in formula I or its stereoisomer（^ and=0 compound, as shown in formula 1-1-
In formula：One
Het is selected from one of group shown in Het-1 to Het-14:
R is selected from fluorine, chlorine, bromine, cyano group, hydroxyl, carboxyl, amino, d-C3Protective embankment base, halo d-C3Protective embankment base, d-C3Protective embankment epoxide, for ^3Protective embankment epoxide, d-C3Protective embankment amino, C2-C4Alkenyloxy group, for ^4Alkenyloxy group, C2-C4Enamino, halo C2-C4Enamino, d-C3Protective embankment base carbonyl, for d-C3Protective embankment base carbonyl, d-C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C3Protective embankment epoxide d-C3Protective embankment base, generation-protective embankment epoxide d-C3Protective embankment base, d-C3Protective embankment base carbonyl epoxide d-C3Protective embankment
¾、 Ci-c3¾¾ftS Ci-c3¾¾ftS Ci-c3¾¾ftS Ci-c3FtS C1-C3 C1-C3 epoxides, d-C3Protective embankment base carbonyl epoxide, halo d-C3Protective embankment base carbonyl epoxide, d-C3Protective embankment base carbonylamino, d-C3Protective embankment base sulfonyl epoxide, d-C3Protective embankment base sulfuryl amino, d-C3Protective embankment base carbonyl-protective embankment epoxide, phenyl, pyridine radicals, phenoxy group, pyridine radicals epoxide, benzoyl epoxide, benzenesulfonyl epoxide, benzyloxy, pyridylmethyl epoxide, benzoyl-amido, BENZENESUFONYLAMINO, benzylamino or pyridylmethylaminojphenyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, d-C3Protective embankment base, halo d-C3Protective embankment base, d-C3Protective embankment epoxide, halo d-C3Protective embankment epoxide or3Protective embankment base carbonyl； n=0-4;
Ri is selected from hydrogen, C C3Protective embankment base, ^ are for ^-^ protective embankments base, C2-C4Alkenyl, generation4Alkenyl, C C3Protective embankment epoxide C C3Protective embankment base, generation-protective embankment epoxide C C3Protective embankment base, C C3Protective embankment base carbonyl, generation-protective embankment base carbonyl, C C3Protective embankment base sulfonyl, d-C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C^l base carbonyls d-C3Protective embankment base, d-C3Protective embankment Epoxide carbonyl d-C3Protective embankment base, d-C3Protective embankment amino carbonyl C C3Protective embankment base, phenyl, pyridine radicals, benzoyl, picolinoyl, benzenesulfonyl, benzyl or picolyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, C C3Protective embankment base, halo C C3Protective embankment base ,-protective embankment epoxide, halo-protective embankment epoxide or C C3Protective embankment base carbonyl；
Selected from hydroxyl, chlorine, bromine, d-C3Protective embankment epoxide, C C3Protective embankment base carbonyl epoxide, C C3Protective embankment sulfenyl, C C3Protective embankment base sulfonyl epoxide, d-C3Protective embankment Epoxide carbonyl-protective embankment epoxide, d-C3Protective embankment amino carbonyl-protective embankment epoxide, phenoxy group, thiophenyl, benzyl epoxide, benzoyl epoxide, benzenesulfonyl epoxide, pyridine epoxide or benzoylmethyl epoxide unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, d-C3Protective embankment base, halo d-C3Protective embankment base, C C3Protective embankment epoxide or for-protective embankment epoxide；
Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.
Further preferred compound is：In formula 1-1
Het is selected from one of group shown in Het-4 to Het-8；
R is selected from fluorine, chlorine, bromine, cyano group, hydroxyl, carboxyl, amino, d-C3Protective embankment base, halo d-C3Protective embankment base, d-C3Protective embankment epoxide, halo d-C3Protective embankment epoxide, d-C3Protective embankment amino, d-C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C3Protective embankment epoxide ^3Protective embankment base, generation3Protective embankment epoxide d-C3Protective embankment base, d-C3Protective embankment base carbonyl epoxide, generation-protective embankment base carbonyl epoxide, d-C3Protective embankment base carbonylamino, d-C3Protective embankment base sulfonyl epoxide, d-C3Protective embankment base sulfuryl amino, it is unsubstituted or by 1-3 solely
Vertical phenoxy group or pyridine radicals epoxide selected from following substituent group：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formoxyl； n=0-4;
Selected from hydrogen, C C3Protective embankment base, halo d-C3Protective embankment base, CrC3Protective embankment epoxide C C3Protective embankment base, halo C C3Protective embankment epoxide C C3Protective embankment base, C C3Protective embankment base carbonyl, halo d-C3Protective embankment base carbonyl, C C3Protective embankment base sulfonyl, phenyl or pyridine radicals unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formoxyl；
Selected from hydroxyl, chlorine, bromine, d-C3Protective embankment epoxide, C C3Protective embankment base carbonyl epoxide, C C3Protective embankment sulfenyl, C C3Protective embankment base sulfonyl epoxide, phenoxy group or thiophenyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy；
Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.
Compound still more preferably is:In one formula 1-1
Het is selected from one of group shown in Het-4 to Het-6；
Selected from fluorine, chlorine, bromine, cyano group, methyl, methoxyl group, methylamino, methoxycarbonyl, amino-carbonyl, acetyl group epoxide, acetyl-amino, phenoxy group, pyridine radicals epoxide, the chloro- 4- trifluoromethyls epoxides of 2- or the chloro- 5- trifluoromethylpyridins -2- base epoxides of 3-, n=0-2;
Selected from methyl, acetyl group, phenyl, pyridine radicals, the chloro- 4- trifluoromethyls of 2- or the chloro- 5- trifluoromethylpyridins -2- bases of 3-；
Selected from hydroxyl；
Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.
Compound still further preferably is:In one formula 1-1
Het is selected from one of group shown in Het-4 to Het-6；
R is selected from methyl or the chloro- 5- trifluoromethylpyridins -2- base epoxides of 3-, n=0-2;
Selected from the chloro- 5- trifluoromethylpyridins -2- bases of 3-；
Selected from hydroxyl；
Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.
The concrete structure of highly preferred compound for-
Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.
Part preferred compound can be illustrated with the particular compound listed in table 1- tables 7 in formula of I of the present invention, but these particular compounds do not limit the present invention.
Note："/", represents unsubstituted, similarly hereinafter(
Table 2
/3/: O 980nil£ Pss90iAV
Table 4
Sequence number R5 Re (R)n
1-2-1 CH3 H OH 1
1-2-2 CH3 H OH 3,5-2CH3
1-2-3 CH3 CH3 OH 1
1-2-4 CH3 CH3 OH 3,5-2CH3
1-2-5 C2H5 H OH 1
1-2-6 C2H5 H OH 3,5-2CH3
1-2-7 C2H5 CH3 OH 1
1-2-8 C2H5 CH3 OH 3,5-2CH3
1-2-9 CH3 H OS02Ph 1
1-2-10 CH3 CH3 OS02Ph 1
1-2-11 C2H5 H OS02Ph 1
1-2-12 C2H5 CH3 OS02Ph 1
1-2-13 CH3 H OSO2PI1-4-CH3 1
1-2-14 CH3 CH3 OSO2PI1-4-CH3 1
1-2-15 C2H5 H OSO2PI1-4-CH3 1
1-2-16 C2H5 CH3 OSO2PI1-4-CH3 1
1-2-17 CH3 H OCH2COPh 1
1-2-18 CH3 CH3 OCH2COPh 1
1-2-19 C2H5 H OCH2COPh 1
1-2-20 C2H5 CH3 OCH2COPh 1
1-2-21 CH3 H OCH2COPh-4-CH3 1
1-2-22 CH3 CH3 OCH2COPh-4-Cl 1
1-2-23 C2H5 H OCH2COPh-2,4-2Cl 1
1-2-24 C2H5 CH3 OCH2COPh-4-CH3 1
Each substituents of compound 1-3-1 to 1-3-26 are same as each substituent of compound 1-1-1 to 1-1-26 in table 1 respectively in table 6t
Each substituents of compound 1-3-27 to 1-3-88 are same as each substituent of 1-1-27 to 1-1-88 in table 2 respectively in table 7tCompound of Formula I of the present invention can be prepared in accordance with the following methods：
When Q is selected from Q2Or during Q4, compound of Formula I can refer to the preparation of the methods such as patent WO2002090336, US4885022, US6037312；
When Q is selected from Q3When, it is prepared by the method that compound of Formula I can refer in patent EP496630, US4741769.
When Q is selected from, i.e., currently preferred formula 1-1 compounds can be prepared in accordance with the following methods：
First, obtained formula Ι Π compounds are reacted by intermediate V and intermediate compound IV in the basic conditions, formula Ι Π compounds hydrolyze the substituted benzoic acid obtained shown in formula II in the presence of sodium hydrate aqueous solution, then as the substituted benzoic acid shown in formula II or its corresponding derivative（Such as corresponding carboxylic acid halides, acyl cyanogen or ester）With hydroresorcinol（Qla), reacted in the presence of dehydrating agent and one or more catalyst R be made3=OH formula I-la compounds（Keto-acid or enol form）；Then, formula I-la compounds reacted again with halogenating agent R3=Hal formula I-lb compounds；Formula I-lc compounds（R3≠ OH or Hal) preparation because it is different in two kinds of situation：
The first situation：When for d-C6Protective embankment epoxide, d-C6Protective embankment sulfenyl, C2-C6Alkenyloxy group, halo C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, d-C6Protective embankment Epoxide carbonyl d-C6Protective embankment epoxide, d-C6Protective embankment amino carbonyl d-C6Protective embankment epoxide, and when substitution or unsubstituted aryloxy, arylthio, arylmethyl epoxide or heteroaryl epoxide, formula I-lb is reacted in the case where having alkali or alkali-free with the compound of hydroxyl or sulfydryl and is made；
Second of situation：When for d-C6Protective embankment base carbonyl epoxide, d-C6Protective embankment base sulfonyl epoxide, and when substituted or unsubstituted aryl carbonyl epoxide, aryl sulfonyl epoxide or aryl carbonyl methoxyl group, by formula I-la compounds and halides（Such as carboxylic acid halides, sulfonic acid chloride）Reaction can directly be made in the basic conditions.
I -lb (R3=Hal) I -lc ( R3≠OH, Hal)
Hal is halogen in above-mentioned reaction equation, and other each group definitions are the same,
Above-mentioned each step reaction is carried out in suitable solvent, the optional tetrahydrofuran freely of suitable solvent, dichloromethane protective embankment, chloroform, acetonitrile, toluene, dimethylbenzene, benzene, acetone or butanone etc..Reaction temperature can be in room temperature between solvent boiling point temperature, usually room temperature.Reaction time is 30 minutes to 20 hours, usual 1 ~ 10 hour.
The optional dicyclohexylcarbodiimide of suitable dehydrating agent being related in above-mentioned reaction（DCC), also selected from other reagents such as 1-(3- dimethylamino-propyls)-3- ethyl carbodiimides（EDC) or N, N ,-carbonyl dimidazoles（CDI) etc..Suitable catalyst is selected from such as Cymag, potassium cyanide, acetone cyanohydrin or cyano group trimethyl silicane protective embankment.The optional oxalyl chloride of suitable halogenating agent or oxalyl bromine etc..Suitable alkali may be selected from triethylamine, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide etc..
Raw material QlaI.e. hydroresorcinol is commercially available.Raw material II can make by oneself according to US6376429 method.
The salt of compound of Formula I of the present invention can include inorganic salts（Such as hydrochloride, phosphate, sodium salt, sylvite）Or organic salt（Such as formates, acetate, trifluoroacetic acid, benzene sulfonate, oxalates, citrate or malate）.Method well known to those skilled in the art can be used by preparing above-mentioned salt by compound of Formula I.
Bioactivity screening test shows that the compound of Formula I of the present invention has good activity of weeding.Especially formula 1-1 compounds have the benzoyl base class compound phase ratio of the nitrogenous substituent of chain with 3- bit strips, and activity of weeding is more excellent.The related compound that inventor reports according to patent WO2000021924, WO2000037437 has synthesized that two more close with the compounds of this invention structure but 3- bit strips have the benzoyl base class compound of the nitrogenous substituent of chain（Code name compound A and B) as control compound, carry out activity of weeding measure of merit.Result of the test further demonstrates the compound more advantage of the present invention.Control compound A and B structure are as follows：
The compound of the present invention can efficiently control the weeds such as barnyard grass, lady's-grass, piemarker, and good effect is obtained with low dosage.Therefore it is used for the purposes for controlling weeds present invention additionally comprises compound of Formula I.Meanwhile, compound of Formula I of the invention has good security to corn, therefore is preferred for controlling the weeds of corn field.
Present invention also offers a kind of Herbicidal combinations, the weight percentage that the compound of Formula I in the compound of Formula I as active component, composition as active component is contained in said composition is 0.1-99%.Therefore it is used for the purposes for controlling weeds present invention additionally comprises said composition, particularly preferred said composition is used for the purposes for controlling corn field weed.
The composition of the present invention can be prepared using method well known to those skilled in the art.This composition can contain the single compound of the present invention or the mixture of several compounds.
Carrier system in the present composition meets the material of following conditions：It is easy to be applied to pending site after preparing with active component, for example, can be plant, seed or soil；Or be conducive to storing, transport or operating.Carrier can be solid or liquid, including be usually gas but be compressed into the material of liquid, and generally carrier used in Herbicidal combinations are prepared can be used.
Suitable solid carrier includes natural and synthesis clay and silicate, for example diatomite, talcum, Attagel, alumina silicate (；Kaolin), montmorillonite and mica；Calcium carbonate；Calcium sulfate；Ammonium sulfate；The silica and synthetic calcium silicate or alumina silicate of synthesis；Element such as carbon and sulphur；Natural and synthesis resin such as cumarone resin, polyvinyl chloride and styrene polymer and copolymer；Solid polystream phenol；Pitch；Wax such as beeswax, paraffin.
Suitable liquid-carrier includes water；Alcohol such as isopropanol and ethanol；Ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone；Ether；Aromatic hydrocarbons such as benzene,toluene,xylene；Oil leavened point such as kerosene and mineral oil；Chlorohydrocarbon such as carbon tetrachloride, perchloroethylene and trichloro ethylene.Generally, the mixture of these liquid is also suitable.
Composition is generally processed into the form of concentrate and is used to transport with this, is diluted before administration by user.The presence of a small amount of supporting surfactant contributes to dilution.So, it is preferably surfactant according at least a kind of carrier in the composition of the present invention.For example composition can contain at least two carriers, and wherein at least one is surfactant.
Surfactant can be emulsifying agent, dispersant or wetting agent；It can be non-ionic or ion surfactant.The example of suitable surfactant includes the sodium salt or calcium salt of polyacrylic acid and lignin sulfonic acid；Aliphatic acid or fatty amine or acid amides and epoxy second protective embankment and/or the condensation product of the protective embankment of epoxy third containing at least 12 carbon atoms in molecule.The condensation product of glycol, sorbierite, sucrose or pentaerythritol fatty ester and these esters and epoxy second protective embankment and/or the protective embankment of epoxy third；Fatty alcohol or protective embankment base phenol such as POP or to octyl group cresols and epoxy second protective embankment and/or the condensation product of the protective embankment of epoxy third；The sulfate and sulfonate of these condensation products；At least alkali metal or alkali salt of the sulfuric acid containing 10 carbon atoms or sulphonic acid ester, such as particular certain cancers, sulfuric acid laurate sodium in the molecule, the secondary protective embankment base ester sodium of sulfuric acid, sulfonated castor oil sodium salt, such as sulfonic acid protective embankment base aryl ester sodium, 12 protective embankment base benzene sulfonic acid sodium salts.
The example of the composition of the present invention is wettable powder, pulvis, granule, aqua, emulsifiable concentrating agents, emulsion, aerosol and smoke agent.Wettable powder generally wt. Active ingredient containing 25-75%, and generally in addition to solid inert carrier, the also dispersant containing 3-10% weight, and if desired can add the stabilizer and/or other additives such as bleeding agent or sticker of 0-10% weight.Pulvis generally can be with the composition similar to wettable powder but the pulvis concentrating agents without dispersant, further be diluted with solid carrier, obtain the composition of the usual component of weight activity containing 0.5-10%.Granula is generally prepared as having 10 to 100 mesh（1.676-0.152 mm) size, and can be prepared with agglomerating or injection technique.The active component and 0-10% weight additive of usual granula weight containing 0.5-75% such as stabilizer, surfactant, sustained release modifying agent.Emulsifiable concentrating agents in addition to the solvents, usually contains cosolvent, 1-50%W/V active components, 2-20%W/V emulsifying agents and the other additives of 0-20%W/V such as stabilizer, bleeding agent and corrosion inhibitor when needed.Suspension concentrating agents usually contains the active component of 10-75% weight, the dispersant of 0.5-15% weight, other additives such as defoamer, corrosion inhibitor, stabilizer, bleeding agent and the sticker of 0.1-10% weight.
Water dispersant and emulsion, the composition for example obtained by the wettable powder or concentrate that are diluted with water according to the present invention, are also included in the scope of the invention.Described emulsion can have two types of Water-In-Oil or oil-in-water.
By adding other one or more herbicides in the composition, there can be broader spectrum of activity than single compound of Formula I.In addition, other herbicides can the activity of weeding of mutual-through type I there is synergistic effect, also can be by compound of Formula I and other herbicide mixtures, the changes of contents scope of active ingredient is very big in mixture, active constituent content is general in 1%-95% in mixture, and convenient content is in 5%-60%.
It can be applied using insecticide-applying way well known to those skilled in the art and contain the logical compound of formula I of the present invention as the composition of active component, reach the purpose of control weeds.
Embodiment
Specific examples below is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.（It is outer except as otherwise indicating, it is raw materials used to be commercially available）
Synthetic example
It is real
Morpholine IV-1-1 0.28g (3.22mmol) and potassium carbonate 0.44g (3.22mmol) are in reaction bulb, power Jie 20mL acetonitriles stir 20min, adding intermediate V l.Og, (2.93mmol makes by oneself according to the method in patent US6376429）, 5h is reacted at room temperature, and TLC monitoring reactions are finished, filtered, filtrate decompression precipitation, and (eluant, eluent is ethyl acetate and petroleum ether to column chromatography（60-90 °C of boiling range), volume ratio is 1:3) intermediate Ι Π -1-1, white solid 0.78g, 118-120 °C of fusing point are purified to obtain.1H-NMR (300MHz, internal standard TMS, solvent C DC13) S(ppm): 2.64 (t, 4H), 3.58 (s, 3H), 3.65 (t, 4H), 3.98 (s, 3H), 4.33 (s, 2H), 7.71 (d, 1H), 8.16 (d, 1H)。
Intermediate Ι Π -1-l 0.5g (1.44mmol) are dissolved in lOmL methanol, add 0.12g Gmmol) the 5mL aqueous solution of sodium hydroxide, 3h is stirred at room temperature, TLC is monitored without starting material left, neutrality is adjusted to hydrochloric acid, depressurize precipitation, drying, obtain intermediate Π -1-l crude products, it is not necessary to purify, be directly used in next step reaction.
1 is added into above-mentioned intermediate Π -1-l crude products, hydroresorcinol Qia 0.16g (1.44mmol) and 20mL acetonitriles, stirring is lower to add the g of DCC 0.37 (1.8mmol), 10h is reacted at room temperature, then the drop acetone cyanohydrins of triethylamine 0.29g (2.88mmol) and two are added, 3h is reacted in continuation at room temperature, filtering, filtrate decompression precipitation, 10mL water and 0.5g hydrochloric acid are added in residue, ethyl acetate is extracted 3 times, aqueous phase is adjusted to neutrality with sodium hydroxide, ethyl acetate is extracted, organic phase is dried, precipitation, obtain clear yellow viscous thing, plus there is solid in petroleum ether grinding, filter to obtain compound 1-1-1, yellow solid 0.23go1H-NM (300MHz, internal standard TMS, solvent C DC13) 8(ppm):2.07 (m, 2H), 2.43 (t, 2H), 2.64 (t, 4H), 2.82 (t, 2H), 3.59 (s, 3H), 3.66 (t, 4H), 4.28 (s, 2H), 7.23 (d, 1H), 8.15 (d, 1H).
It is real
1-1-4
According to the method described in embodiment 1, by intermediate 1$-1-4 0.92§Intermediate Ι Π -1-4, colorless oil 2.3g is made in (8.01^^1) and intermediate $ 2.5g (7.31mmol).1H-NMR (300MHz, internal standard TMS, solvent C DC13) 8(ppm): 1.16(d, 6H), 2.02-2.15 (m, 2H), 2.73-2.77 (m, 2H), 3.52-3.58 (m, 5H), 3.98 (s, 3H), 4.29 (s, 2H), 7.72 (d,
According to the methods described of embodiment 1, the sour Π -1-4 and 1,3- obtained after intermediate Ι Π -1-4 l.Og (2.66mmol) hydrolysis
Cyclohexanedione 0.3g (2.66mmol) reacts, and compound 1-1-4, colorless oil 0.64g is made.1H-NMR (300MHz, internal standard TMS, solvent C DC13) 5(ppm):1.17 (d, 6H), 1.96-2.10 (m, 4H), 2.41-2.43 (m, 2H), 2.80-2.84 (m, 4H), 3.53-3.57 (m, 5H), 4.25 (s, 2H), 7.25 (d, 1H), 8.16 (d, 1H), 16.78 (s, 1H).
Intermediate compound IV -1-27 can be prepared with piperazine and the chloro-5-trifluoromethylpyridines of 2,3- bis- using patent EP370560 method.According to the methods described of embodiment 1, intermediate Ι Π -1-27, white solid 1.3g, 131-133 °C of fusing point is made in intermediate compound IV-l-27 0.78g (2.93mmol) and intermediate V l .Og (2.93mmol) reactions.^-NMR (300MHz, internal standard TMS, solvent C DC13) 8(ppm): 2.80 (t, 4H), 3.44 (t, 4H), 3.58 (s, 3H), 3.99 (s, 3H), 4.40 (s, 2H), 7.73 (d, 1H), 7.77 (s, 1H), 8.18 (d, 1H), 8.38 (s, 1H)。
According to the methods described of embodiment 1, sour Π-the 1-27 and 1 obtained after intermediate Ι Π -1-27 0.5g (0.95mmol) are hydrolyzed, compound 1-1-27, yellow solid 0.11g is made in hydroresorcinol O. l lg (0.95mmol) reactions.1H-NMR (300MHz, internal standard TMS, solvent C DC13) 5(ppm):2.08 (m, 2H), 2.45 (t, 2H), 2.86 (m, 6H), 3.44 (t, 4H), 3.52 (s, 3H), 4.41 (s, 2H), 7.26 (d, IH), 7.76 (s, 1H), 8.16 (d, 1H), 8.38 (s, 1H).
Real 4 compound 1-1-98 preparation
The method that intermediate compound IV -1-98 is referred to introduce in patent WO2005095362 is prepared with 4- hydroxy piperidines and the chloro-5-trifluoromethylpyridines of 2,3- bis-.
According to the methods described of embodiment 1, intermediate Ι Π -1-98, white solid 1.32g, 140-142 °C of fusing point is made in intermediate compound IV -1-98 1.23g (4.38mmol) and intermediate V 1.5g (4.38mmol) reactions.1H-NMR (300MHz, internal standard TMS, solvent C DC13) 8(ppm): 1.75-1.83 (m, 2H), 1.95-2.05 (bs, 2H), 2.54-2.60 (m, 2H), 2.88-2.95 (m, 2H), 3.61 (s, 3H), 3.98 (s, 3H), 4.35 (s, 2H), 5.18-5.25 (m, IH), 7.71 (d, IH), 7.84 (d, IH), 8.17 (d, IH), 8.29 (s, 1H)。
According to the methods described of embodiment 1, sour Π-the 1-98 and 1 obtained after intermediate Ι Π -1-98 0.58g (1.07mmol) hydrolysis, compound 1-1-98, white solid 0.10g is made in 3- cyclohexanediones O.llg (1.07mmol) reactions.1H-NM (300MHz, internal standard TMS, solvent C DC13) 8(ppm): 1.78-1.92 (bs, 2H), 2.00-2.10 (m, 2H), 2.39-2.45 (m, 2H), 2.59-2.70 (bs, 2H), 2.78-2.85 (m, 2H), 2.90-3.15 (bs, 2H), 3.60 (s, 3H), 4.35 (s, 2H), 5.25 (s, IH), 7.25 (d, IH), 7.3 (d, IH), 8.15 (d, IH), 8.29 (s, 1H)。
Example of formulations
Active component folding hundred is post-dised in formula, and all percentage compositions are weight percentage.
The missible oil of embodiment 5 35%
Compound 1-1-1 35%
Phosphorous acid 10%
Ethoxylated triglycerides 15%
Cyclohexanone complements to 100%
Phosphorous acid is dissolved in cyclohexanone, compound 1-1-1 and ethoxylated triglycerides are added, transparent solution is obtained.
The wettable powder of embodiment 6 60%
Compound 1-1-4 60%
12 protective embankment base sodium naphthalene sulfonates 2%
Sodium lignin sulfonate 9%
Kaolin complements to 100%
By compound 1-1-4,12 protective embankment base sodium naphthalene sulfonates, sodium lignin sulfonate and kaolin（It is solid）Mix, crushed in pulverizer, until particle reaches standard.
The aqueous suspension of embodiment 7 30%
Compound 1-1-1 30%
12 protective embankment base sodium naphthalene sulfonates 4%
Hemicellulose 2%
The third protective embankment of epoxy 8%
Water complements to 100%
By compound 1-1-1 and answer amount of water 80% and 12 protective embankment base sodium naphthalene sulfonate in ball mill（1mm pearls）In crush together.Hemicellulose and the protective embankment of epoxy third are dissolved in remaining 20% water, and then stirring adds said components.
The suspending agent of embodiment 8 40%
Compound 1-1-27 40%
Ethylene glycol 10%
Nonoxynol-9 6%
Sodium lignin sulfonate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
75% silicone oil aqueous emulsion 0.8%
Water complements to 100%
Compound 1-1-27 and other components are sufficiently mixed, thus obtained suspending agent, the dilution that gained suspending agent can obtain any required concentration is diluted with water.
Biological activity determination
Herbicidal in the Room of embodiment 9
The a small amount of acetone solution of testing compound active compound, then it is diluted to the water containing 0.1% Tween 80 required concentration.Quantitative weed seed is sowed in a diameter of 7cm dixie cup equipped with Nutrition Soil respectively, rear earthing lcm is broadcast, in hot-house culture after suppression, water drenching, thinning, field planting after emerging（10-20 plants/cup of grassy weed, 2-4 plants/cup of broad leaved weed）, treat the grassy weed 2-3 leaf phases, broad leaved weed length to 2-4 leaf periods, by experimental design dosage crawler type crops sprayer（Britain Engineer Research Ltd. design productions）Carry out cauline leaf spraying treatment（Atomisation pressure 1.95kg/cm2, spouting liquid 50mL/m2, crawler track speeds 1.48km/h) o experiment set 3 repetitions.After after decoction natural air drying, it is placed in greenhouse and manages according to a conventional method, routine observation tries the situation of growing of material, and according to actual conditions, in preventive effect of the periodical visual inspection tune Check reagent agents to weeds after processing.Preventive effect grade scale：0 is invalid, and 100% is to kill weeds completely or seriously suppress.
The activity data of part of compounds is shown in Table 7_ tables 11.
Part of compounds is shown in Table 7 to the activity data of lady's-grass.
Table 7
Compound 1-1-1 and comparison medicament sulphur humulone（15% aqua, Shenyang Sciencreat Chemicals Co., Ltd.'s production, similarly hereinafter）Activity data be shown in Table 8.
Table 8
Compound I-l-l and comparison medicament mesotrione（95% active compound, self-control, similarly hereinafter）Activity data be shown in Table 9.
Table 9
Compound 1-1-1 to lamb's-quarters, Siberian cocklebur,
Part of compounds is shown in Table 11 with control compound A and B to the activity data of barnyard grass and Setaria glauca.
Table 11
The indoor security of embodiment 10 is determined
The a small amount of acetone solution of testing compound active compound, then it is diluted to the water containing 0.1% Tween 80 required concentration.Quantitative corn, paddy rice, wheat, soybean and the seed of cotton are sowed in a diameter of 7cm dixie cup equipped with Nutrition Soil respectively, rear earthing l cm are broadcast, in hot-house culture after suppression, water drenching, thinning, field planting after emerging（1-2 plants/cup）, it is to be generated to grow to the 2-4 leaf phases, by experimental design dosage crawler type crops sprayer（Britain Engineer Research Ltd. design productions）Carry out cauline leaf spraying treatment (atomisation pressure 1.95kg/cm2, the mL/m of spouting liquid 502, crawler track speeds 1.48km/h), experiment sets 3 repetitions.After after decoction natural air drying, it is put in greenhouse and manages according to a conventional method, observes crop growth situation, security of the periodical visual inspection tune Check reagent agents to crop.Safety classification standard：0 represents to crop without any damage, 100% is to kill crop completely or seriously suppress, the comparative test result of compound 1-1-1 and control compound sulphur humulone is shown in Table 12, and compound 1-1-1 and control compound mesotrione comparative test result are shown in Table 13.
Table 12
Table 13
Claims (8)
- Claims1st, a kind of cyclosubstituted benzoyl base class compound of nitrogen-containing hetero or its stereoisomer, as shown in formula 1-1:In formula：OneHet is selected from one of group shown in Het-1 to Het-14:R 、 d-C3Protective embankment halo d-C3Protective embankment epoxide, d-C3Protective embankment amino, C2-C4Alkenyloxy group, halo C2-C4Alkenyloxy group, C2-C4Enamino, generation4Enamino, CrC3Protective embankment base carbonyl, generation-protective embankment base carbonyl, C C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C3Protective embankment epoxide C C3Protective embankment base, ^ are for d-C3Protective embankment epoxide C C3Protective embankment base, d-C3Protective embankment base carbonyl epoxide C C3Protective embankment base, d-C3Protective embankment epoxide C C3Protective embankment epoxide, ^ are for d-C3Protective embankment epoxide C C3Protective embankment epoxide, d-C3Protective embankment Epoxide carbonyl C C3Protective embankment epoxide ,-protective embankment base carbonyl epoxide, halo-protective embankment base carbonyl epoxide ,-protective embankment base carbonylamino ,-protective embankment base sulfonyl epoxide, d-C3Protective embankment base sulfuryl amino ,-protective embankment base carbonyl-protective embankment epoxide, phenyl, pyridine radicals, phenoxy group, pyridine radicals epoxide, benzoyl epoxide, benzenesulfonyl epoxide, benzyloxy, pyridylmethyl epoxide, benzoyl-amido, BENZENESUFONYLAMINO, benzylamino or pyridylmethylaminojphenyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, d-C3Protective embankment base, halo d-C3Protective embankment base, C C3Protective embankment epoxide, halo d-C3Protective embankment epoxide or C C3Protective embankment base carbonyl； n=0-4;Ri is selected from hydrogen, C C3Protective embankment base, ^ are for ^-^ protective embankments base, C2-C4Alkenyl, generation4Alkenyl, C C3Protective embankment epoxide C C3Protective embankment base, generation-protective embankment epoxide C C3Protective embankment base, C C3Protective embankment base carbonyl, generation-protective embankment base carbonyl, C C3Protective embankment base sulfonyl, d-C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C^l base carbonyls d-C3Protective embankment base, d-C3Protective embankment Epoxide carbonyl d-C3Protective embankment base, d-C3Protective embankment amino carbonyl C C3Protective embankment base, phenyl, pyridine radicals, benzoyl, picolinoyl, benzenesulfonyl, benzyl or picolyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, C C3Protective embankment base, halo C C3Protective embankment base ,-protective embankment epoxide, halo-protective embankment epoxide or C C3Protective embankment base carbonyl；R3Selected from hydroxyl, chlorine, bromine ,-C3 protective embankments epoxide, d-C3Protective embankment base carbonyl epoxide, d-C3Protective embankment sulfenyl, d-C3Protective embankment base sulfonyl epoxide, d-C3Protective embankment Epoxide carbonyl d-C3Protective embankment epoxide, d-C3Protective embankment amino carbonyl d-C3Protective embankment epoxide, phenoxy group, thiophenyl, benzyl epoxide, benzoyl epoxide, benzenesulfonyl epoxide, pyridine epoxide or benzoylmethyl epoxide unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, d-C3Protective embankment base, halo d-C3Protective embankment base, d-C3 Protective embankment epoxide or for-protective embankment epoxide；Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.2nd, compound according to claim 1, it is characterised in that：In formula 1-1Het is selected from one of group shown in Het-4 to Het-8；R is selected from fluorine, chlorine, bromine, cyano group, hydroxyl, carboxyl, amino, d-C3Protective embankment base, halo CrC3Protective embankment base, C C3Protective embankment epoxide, halo d-C3Protective embankment epoxide, d-C3Protective embankment amino, C C3Protective embankment Epoxide carbonyl, d-C3Protective embankment amino carbonyl, d-C3Protective embankment epoxide C C3Protective embankment base, generation-protective embankment epoxide d-C3Protective embankment base ,-protective embankment base carbonyl epoxide, generation-protective embankment base carbonyl epoxide, ^- protective embankment bases carbonylamino, d-C3Protective embankment base sulfonyl epoxide, d-C3Protective embankment base sulfuryl amino, phenoxy group or pyridine radicals epoxide unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formoxyl； n=0-4;Selected from hydrogen, C C3Protective embankment base, halo d-C3Protective embankment base, CrC3Protective embankment epoxide C C3Protective embankment base, halo C C3Protective embankment epoxide d-C3Protective embankment base, d-C3Protective embankment base carbonyl, halo d-C3Protective embankment base carbonyl, d-C3Protective embankment base sulfonyl, phenyl or pyridine radicals unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formoxyl；Selected from hydroxyl, chlorine, bromine, d-C3Protective embankment epoxide, d-C3Protective embankment base carbonyl epoxide, d-C3Protective embankment sulfenyl, d-C3Protective embankment base sulfonyl epoxide, phenoxy group or thiophenyl unsubstituted or that be independently selected from following substituent group by 1-3：Fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy；Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.3rd, compound according to claim 2, it is characterised in that：In formula 1-1Het is selected from one of group shown in Het-4 to Het-6；Selected from fluorine, chlorine, bromine, cyano group, methyl, methoxyl group, methylamino, methoxycarbonyl, amino-carbonyl, acetyl group epoxide, acetyl-amino, phenoxy group, pyridine radicals epoxide, the chloro- 4- trifluoromethyls epoxides of 2- or the chloro- 5- trifluoromethylpyridins -2- base epoxides of 3-, n=0-2;Selected from methyl, acetyl group, phenyl, pyridine radicals, the chloro- 4- trifluoromethyls of 2- or the chloro- 5- trifluoromethylpyridins -2- bases of 3-；Selected from hydroxyl；Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.4th, compound according to claim 3, it is characterised in that：In formula 1-1Het is selected from one of group shown in Het-4 to Het-6；R is selected from methyl or the chloro- 5- trifluoromethylpyridins -2- base epoxides of 3-, n=0-2;Selected from the chloro- 5- trifluoromethylpyridins -2- bases of 3-；Selected from hydroxyl；Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, Chinese catalpa lemon tenth of the twelve Earthly Branches wheat salt or apple tenth of the twelve Earthly Branches wheat salt.5th, compound according to claim 4, it is characterised in that：Or its sodium salt, sylvite, hydrochloride, phosphate, formates, acetate, trifluoroacetate, oxalates, benzene sulfonate, citrate or malate.6th, a kind of compound of Formula I according to claim 1 is used for the purposes for controlling weeds.7th, a kind of purposes according to claim 6, it is characterised in that：Purposes for controlling corn field weed.8th, a kind of Herbicidal combinations, it is characterised in that：Contain compound of Formula I described in claim 1 as active component, the weight percentage of the active component in composition is 0.1-99%.9th, a kind of Herbicidal combinations according to claim 8 are used for the purposes for controlling weeds.10th, a kind of purposes according to claim 9, it is characterised in that：Purposes for controlling corn field weed.
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| CN107353238B (en) * | 2017-08-17 | 2019-09-03 | 青岛清原化合物有限公司 | Substituted benzoylcyclohexan cyclohexadione compounds or its tautomer, salt, preparation method, Herbicidal combinations and application |
| CN112300092B (en) * | 2019-07-31 | 2023-06-09 | 东莞市东阳光农药研发有限公司 | Heterocyclylalkyl-substituted dichlorobenzoyl compounds and application thereof |
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| CN102464630A (en) | 2012-05-23 |
| WO2012065573A1 (en) | 2012-05-24 |
| CN103025718B (en) | 2016-01-20 |
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Effective date of registration: 20160114 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031, Beijing, Xicheng District, Beijing, China Xicheng District Fuxing Avenue, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |