CN103025718B - Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof - Google Patents
Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof Download PDFInfo
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- CN103025718B CN103025718B CN201180035270.0A CN201180035270A CN103025718B CN 103025718 B CN103025718 B CN 103025718B CN 201180035270 A CN201180035270 A CN 201180035270A CN 103025718 B CN103025718 B CN 103025718B
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- oxygen base
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- 0 C*C(CCC1)=C(C(c(ccc(*)c2C*(C)=IC)c2N)=C2CC2)C1=C Chemical compound C*C(CCC1)=C(C(c(ccc(*)c2C*(C)=IC)c2N)=C2CC2)C1=C 0.000 description 9
- VSGJHHIAMHUZKF-UHFFFAOYSA-N CC(C(CCC1)=O)C1=O Chemical compound CC(C(CCC1)=O)C1=O VSGJHHIAMHUZKF-UHFFFAOYSA-N 0.000 description 1
- YQYVOGFWLVVXMM-UHFFFAOYSA-N COC(c(c(Cl)c1CBr)ccc1S(C)(=O)=O)=O Chemical compound COC(c(c(Cl)c1CBr)ccc1S(C)(=O)=O)=O YQYVOGFWLVVXMM-UHFFFAOYSA-N 0.000 description 1
- NTWWBTLULYJDPO-UHFFFAOYSA-N CS(c(cc1)c(CNCCO)c(Cl)c1C(C(C(CCC1)=O)=C1O)=O)(=O)=O Chemical compound CS(c(cc1)c(CNCCO)c(Cl)c1C(C(C(CCC1)=O)=C1O)=O)(=O)=O NTWWBTLULYJDPO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- A01N43/34—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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
A kind of cyclosubstituted benzoyl compounds of nitrogen-containing hetero or its steric isomer, as shown in general formula I:
Description
Technical field
The invention belongs to field of agricultural herbicide.Be specifically related to cyclosubstituted benzoyl compounds of a kind of nitrogen-containing hetero and uses thereof.
Background technology
Have a lot about benzoyl compounds as the report of weedicide, such as patent DE10301110, WO2001032636, WO2001010850, DE19921732, WO9907688, JP10265432 all have announcement to the purposes that this compounds is used as weedicide or plant-growth regulator.
In addition, report in patent DE19962923 on the phenyl ring shown in following general formula and be used as weedicide with nitrogenous substituent benzoyl compounds:
Report in patent WO2002090336 on the phenyl ring shown in following general formula and be used as weedicide with the benzoyl compounds of nitrogen-containing side chains:
Although you can well imagine and following general formula compound at patent WO2000021924A1, WO2000037437A1 decile, wherein there is no R
1and R
2can the compound of makeup ring with N:
The development need of modern agricultural production continually develops new herbicidal compound.In prior art, 3-bit strip benzoyl compounds having nitrogen heterocyclic ring methylene substituent as shown in general formula I of the present invention and uses thereof has no report.
Summary of the invention
In order to meet agriculturally to the new demand that weedicide constantly proposes; the invention provides a kind of cyclosubstituted benzoyl compound of nitrogen-containing hetero of novel structure, this compounds can effectively control the weeds such as barnyard grass, lady's-grass, black nightshade, piemarker, Herba Setariae Viridis, youth-and-old-age as weedicide.
Technical scheme of the present invention is as follows:
The invention provides the cyclosubstituted benzoyl compounds of a kind of nitrogen-containing hetero, as shown in general formula I:
In formula:
Het is selected from three to eight yuan of heterocycles, except containing except the atom N on C and 1-position on this ring, also containing 0-3 following atom or the group integral part as ring: O, NR
1, S, SO, SO
2, C=O, C=NR
1or C=NOR
1, and C=O, C=NR
1or C=NOR
1not in 2-position;
Y is selected from fluorine, chlorine, bromine, iodine or nitro;
R is selected from halogen, cyano group, hydroxyl, carboxyl, amino, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
1-C
6alkylamino, C
2-C
6alkene oxygen base, halo C
2-C
6alkene oxygen base, C
2-C
6enamino, halo C
2-C
6enamino, C
1-C
6alkyl-carbonyl, halo C
1-C
6alkyl-carbonyl, C
1-C
6alkoxy carbonyl, C
1-C
6alkyl amino-carbonyl, C
1-C
6alkoxy C
1-C
6alkyl, halo C
1-C
6alkoxy C
1-C
6alkyl, C
1-C
6alkyl-carbonyl oxygen base C
1-C
6alkyl, C
1-C
6alkoxy C
1-C
6alkoxyl group, halo C
1-C
6alkoxy C
1-C
6alkoxyl group, C
1-C
6alkoxy carbonyl C
1-C
6alkoxyl group, C
1-C
6alkyl-carbonyl oxygen base, halo C
1-C
6alkyl-carbonyl oxygen base, C
1-C
6alkyl-carbonyl-amino, C
1-C
6alkyl sulphonyl oxygen base, C
1-C
6alkyl sulfonyl-amino, C
1-C
6alkyl-carbonyl C
1-C
6alkoxyl group, unsubstituted or by 1-3 be independently selected from aryl, heteroaryl, aryloxy, heteroaryl oxygen base, aryl carbonyl oxygen base, aryl sulfonyl oxygen base, arylmethyl oxygen base, hetervaromatic methyl oxygen base, aryl-amino-carbonyl, arlysulfonylamino that following group replaces, arylmethyl is amino or hetervaromatic methyl is amino: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group or C
1-C
6alkyl-carbonyl; N=0-4;
R
1be selected from hydrogen, C
1-C
6alkyl, halo C
1-C
6alkyl, C
2-C
6thiazolinyl, halo C
2-C
6thiazolinyl, C
1-C
6alkoxy C
1-C
6alkyl, halo C
1-C
6alkoxy C
1-C
6alkyl, C
1-C
6alkyl-carbonyl, halo C
1-C
6alkyl-carbonyl, C
1-C
6alkyl sulphonyl, C
1-C
6alkoxy carbonyl, C
1-C
6alkyl amino-carbonyl, C
1-C
6alkyl-carbonyl C
1-C
6alkyl, C
1-C
6alkoxy carbonyl C
1-C
6alkyl, C
1-C
6alkyl amino-carbonyl C
1-C
6alkyl, unsubstituted or that be independently selected from following group replace by 1-3 aryl, heteroaryl, aryl carbonyl, Heteroarylcarbonyl, aryl sulfonyl, arylmethyl or hetervaromatic methyl: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group or C
1-C
6alkyl-carbonyl;
Q is selected from Q
1-Q
4one of shown group:
Wherein:
R
2be selected from C
1-C
6alkyl, C
3-C
6cycloalkyl, C
1-C
6alkoxyl group, C
1-C
6alkoxy C
1-C
6alkyl, C
1-C
6alkyl-carbonyl, C
1-C
6alkoxy carbonyl, C
1-C
6alkylthio, aryl or halogenated aryl, p=0-6;
As p=2, be positioned at two R on different C atom
2cH can be connected into
2; Or as p=2, be positioned at two R on same C or different C atom
2following group can be connected into: (CH
2)
2, (CH
2)
3, (CH
2)
4, (CH
2)
5, (CH
2)
6, O, O (CH
2)
2o, O (CH
2)
3o, O (CH
2)
4o, S (CH
2)
2s or S (CH
2)
3s;
R
3, R
6be selected from hydroxyl, halogen, C
1-C
6alkoxyl group, C
1-C
6alkyl-carbonyl oxygen base, C
1-C
6alkylthio, C
1-C
6alkyl sulphonyl oxygen base, C
2-C
6alkene oxygen base, halo C
2-C
6alkene oxygen base, C
2-C
6alkynyloxy group, C
1-C
6alkoxy carbonyl C
1-C
6alkoxyl group, C
1-C
6alkyl amino-carbonyl C
1-C
6alkoxyl group, unsubstituted or that be independently selected from following group replace by 1-3 aryloxy, arylthio, arylmethyl oxygen base, aryl carbonyl oxygen base, aryl sulfonyl oxygen base, heteroaryl oxygen base or aryl carbonyl methyl oxygen base: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group or halo C
1-C
6alkoxyl group;
R
4be selected from hydrogen, C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, unsubstituted or that be independently selected from following group replace by 1-3 aryl, arylmethyl or heteroaryl: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group or halo C
1-C
6alkoxyl group;
R
5, R
9be selected from hydrogen, halogen, cyano group, formamyl, thiocarbamoyl, C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, C
1-C
6alkoxyl group, C
1-C
6alkyl-carbonyl, C
1-C
6alkoxy carbonyl, C
1-C
6alkylthio, C
1-C
6alkyl sulphonyl, aryl that is unsubstituted or that be independently selected from following group replace by 1-3: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group or halo C
1-C
6alkoxyl group;
R
7be selected from hydrogen, C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, aryl or halogenated aryl;
R
8be selected from hydrogen, halogen, cyano group, formamyl, C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, C
1-C
6alkoxyl group, C
1-C
6alkoxy carbonyl, C
1-C
6alkylthio or C
1-C
6alkyl sulphonyl;
R
10be selected from hydroxyl, C
1-C
6alkoxyl group, C
1-C
6alkyl-carbonyl oxygen base or C
1-C
6alkyl sulphonyl oxygen base;
Or its salt.
In the definition of the general formula compound provided, collect term definition used as follows above:
Halogen (element): refer to fluorine, chlorine, bromine or iodine.Alkyl: straight or branched alkyl, such as methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl etc.Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl.Substituting group is as methyl, halogen etc.Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely replace by halogen atom.Such as, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl etc.Alkyl sulphonyl: refer to straight or branched alkyl through alkylsulfonyl (-SO
2-) be connected in structure, as methyl sulphonyl etc.Alkoxyl group: straight or branched alkyl is connected in structure through Sauerstoffatom.Halogenated alkoxy: straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely replace by halogen.Such as, chlorine methoxyl group, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.Alkylthio: straight or branched alkyl is connected in structure through sulphur atom.Halogenated alkylthio: straight or branched alkylthio, the hydrogen atom on these alkylthios can partly or entirely replace by halogen atom.Such as, chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.Alkylamino: straight or branched alkyl is connected in structure, as-NHCH through nitrogen-atoms
3,-NHCH
2cH
3,-N (CH
3)
2deng.Haloalkane is amino: straight or branched alkylamino, the hydrogen atom on alkyl can partly or entirely replace by halogen.Alkyl-carbonyl: alkyl is connected in structure, as-COCH through carbonyl
3,-COCH
2cH
3deng.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely replace by halogen atom, as-COCF
3deng.Alkoxy carbonyl: alkoxyl group is connected in structure through carbonyl.As-CO
2cH
3,-CO
2cH
3cH
2deng.Alkyl amino-carbonyl: alkylamino is connected in structure through carbonyl.As-CONHCH
3,-CON (CH
3)
2deng.Alkyl-carbonyl-amino: alkyl-carbonyl is connected in structure, as-NHCOCH through nitrogen-atoms
3,-NHCOCH
2cH
3deng.Alkyl sulphonyl oxygen base: alkyl sulphonyl is connected in structure, as-OSO through Sauerstoffatom
2cH
3,-OSO
2cH
2cH
3deng.Alkyl sulfonyl-amino: alkyl sulphonyl is connected in structure, as-NHSO through nitrogen-atoms
2cH
3,-NHSO
2cH
2cH
3deng.Thiazolinyl: straight or branched alkene class, such as vinyl, 1-propenyl, 2-propenyl and different butenyls, pentenyl and hexenyl isomers.Thiazolinyl also comprises polyenoid class, as 1,2-propadiene base and 2,4-hexadienyl.Haloalkenyl group: straight or branched thiazolinyl, the hydrogen atom on these thiazolinyls can partly or entirely replace by halogen atom.Alkene oxygen base: straight or branched thiazolinyl, is connected in structure through Sauerstoffatom.Haloalkene oxygen base: straight or branched alkene oxygen base, the hydrogen atom on these alkene oxygen bases can partly or entirely replace by halogen.Enamino: straight or branched thiazolinyl, links in structure through nitrogen-atoms key.Haloalkene is amino: straight or branched enamino, the hydrogen atom on these alkene oxygen bases can partly or entirely replace by halogen.Alkynyloxy group: straight or branched alkynyl, is connected in structure through Sauerstoffatom.Aryl moiety in aryl and aryloxy, aryl carbonyl and arylmethyl etc. comprises phenyl or naphthyl etc.Aryloxy: aryl is connected in structure, as phenoxy group, naphthyloxy etc. through Sauerstoffatom.Heteroaryl is containing the heteroatomic five-ring of one or more N, O, S or hexa-atomic aromatic ring.Such as furyl, pyrazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl etc.Heteroaryl oxygen base: heteroaryl is connected in structure through Sauerstoffatom, as pyridine-2-base oxygen base, pyridin-3-yl oxygen base or pyrimidine-2-yloxy etc.The atom N that described salt comprises on compound of Formula I heterocycle 1-position reacts with acid (example hydrochloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, Phenylsulfonic acid, citric acid or oxysuccinic acid etc.) salt formed, and the hydroxyl and the alkali (as triethylamine, lithium, sodium, potassium etc.) that also comprise its enol form react the salt formed.
In compound of the present invention, because configuration difference can form steric isomer (respectively with R and S to represent different configurations), the present invention includes the mixture of R type isomer and S type isomer and any ratio thereof; Because ketone/tautomerism can exist multiple tautomer, the present invention includes the mixture of all tautomers and any ratio thereof.
The comparatively preferred technical scheme of the present invention is, in the cyclosubstituted benzoyl compounds of the nitrogen-containing hetero shown in general formula I or its steric isomer, Q is selected from Q
1and the compound of p=0, as shown in general formula I-1:
In formula:
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, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group, halo C
1-C
3alkoxyl group, C
1-C
3alkylamino, C
2-C
4alkene oxygen base, halo C
2-C
4alkene oxygen base, C
2-C
4enamino, halo C
2-C
4enamino, C
1-C
3alkyl-carbonyl, halo C
1-C
3alkyl-carbonyl, C
1-C
3alkoxy carbonyl, C
1-C
3alkyl amino-carbonyl, C
1-C
3alkoxy C
1-C
3alkyl, halo C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl oxygen base C
1-C
3alkyl, C
1-C
3alkoxy C
1-C
3alkoxyl group, halo C
1-C
3alkoxy C
1-C
3alkoxyl group, C
1-C
3alkoxy carbonyl C
1-C
3alkoxyl group, C
1-C
3alkyl-carbonyl oxygen base, halo C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkyl-carbonyl-amino, C
1-C
3alkyl sulphonyl oxygen base, C
1-C
3alkyl sulfonyl-amino, C
1-C
3alkyl-carbonyl C
1-C
3alkoxyl group, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, pyridyl, phenoxy group, pyridyl oxygen base, benzoyl oxygen base, benzenesulfonyl oxygen base, benzyloxy, pyridylmethyl oxygen base, benzoyl-amido, BENZENESUFONYLAMINO, benzylamino or pyridylmethylaminojphenyl: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group, halo C
1-C
3alkoxyl group or C
1-C
3alkyl-carbonyl; N=0-4;
R
1be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
3alkyl, C
2-C
4thiazolinyl, halo C
2-C
4thiazolinyl, C
1-C
3alkoxy C
1-C
3alkyl, halo C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl, halo C
1-C
3alkyl-carbonyl, C
1-C
3alkyl sulphonyl, C
1-C
3alkoxy carbonyl, C
1-C
3alkyl amino-carbonyl, C
1-C
3alkyl-carbonyl C
1-C
3alkyl, C
1-C
3alkoxy carbonyl C
1-C
3alkyl, C
1-C
3alkyl amino-carbonyl C
1-C
3alkyl, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, pyridyl, benzoyl, picolinoyl, benzenesulfonyl, benzyl or picolyl: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group, halo C
1-C
3alkoxyl group or C
1-C
3alkyl-carbonyl;
R
3be selected from hydroxyl, chlorine, bromine, C
1-C
3alkoxyl group, C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkylthio, C
1-C
3alkyl sulphonyl oxygen base, C
1-C
3alkoxy carbonyl C
1-C
3alkoxyl group, C
1-C
3alkyl amino-carbonyl C
1-C
3alkoxyl group, unsubstituted or that be independently selected from following group replace by 1-3 phenoxy group, thiophenyl, benzyl oxygen base, benzoyl oxygen base, benzenesulfonyl oxygen base, pyridyloxy or benzoylmethyl oxygen base: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group or halo C
1-C
3alkoxyl group;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
Preferred compound is further: in general formula I-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, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group, halo C
1-C
3alkoxyl group, C
1-C
3alkylamino, C
1-C
3alkoxy carbonyl, C
1-C
3alkyl amino-carbonyl, C
1-C
3alkoxy C
1-C
3alkyl, halo C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl oxygen base, halo C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkyl-carbonyl-amino, C
1-C
3alkyl sulphonyl oxygen base, C
1-C
3alkyl sulfonyl-amino, unsubstituted or by 1-3 be independently selected from following group replace phenoxy group or pyridyl oxygen base: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical; N=0-4;
R
1be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxy C
1-C
3alkyl, halo C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl, halo C
1-C
3alkyl-carbonyl, C
1-C
3alkyl sulphonyl, unsubstituted or by 1-3 be independently selected from following group replace phenyl or pyridyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical;
R
3be selected from hydroxyl, chlorine, bromine, C
1-C
3alkoxyl group, C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkylthio, C
1-C
3alkyl sulphonyl oxygen base, unsubstituted or by 1-3 be independently selected from following group replace phenoxy group or thiophenyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
Further preferred compound is: in general formula I-1
Het is selected from one of group shown in Het-4 to Het-6;
R is selected from fluorine, chlorine, bromine, cyano group, methyl, methoxyl group, methylamino-, methoxycarbonyl, amino-carbonyl, ethanoyl oxygen base, acetylamino, phenoxy group, pyridyl oxygen base, 2-chloro-4-trifluoromethyl oxygen base or the chloro-5-trifluoromethylpyridin of 3--2-base oxygen base, n=0-2;
R
1be selected from methyl, ethanoyl, phenyl, pyridyl, 2-chloro-4-trifluoromethyl or the chloro-5-trifluoromethylpyridin of 3--2-base;
R
3be selected from hydroxyl;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
Preferred compound is further again: in general formula I-1
Het is selected from one of group shown in Het-4 to Het-6;
R is selected from methyl or the chloro-5-trifluoromethylpyridin of 3--2-base oxygen base, n=0-2;
R
1be selected from the chloro-5-trifluoromethylpyridin of 3--2-base;
R
3be selected from hydroxyl;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
The concrete structure of highly preferred compound is:
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
In formula of I of the present invention, part preferred compound can illustrate by the particular compound listed in table 1-table 7, but these particular compound do not limit the present invention.
Table 1
Note: "/" represents unsubstituted, lower same.
Table 2
Table 3
Table 4
Table 5
Table 6
In table 6, each substituting group of Compound I-3-1 to I-3-26 is same as each substituting group of Compound I-1-1 to I-1-26 in table 1 respectively.
Table 7
In table 7, each substituting group of Compound I-3-27 to I-3-88 is same as each substituting group of I-1-27 to I-1-88 in table 2 respectively.
Compound of Formula I of the present invention can be prepared in accordance with the following methods:
When Q is selected from Q
2or Q
4time, compound of Formula I can refer to the preparation of the method such as patent WO2002090336, US4885022, US6037312;
When Q is selected from Q
3time, compound of Formula I can refer to the method preparation in patent EP496630, US4741769.
When Q is selected from Q
1time, i.e. the present invention's preferred general formula I-1 compound, can prepare in accordance with the following methods:
First, obtained compound of formula III is reacted in the basic conditions by intermediate V and intermediate compound IV, compound of formula III hydrolysis under aqueous sodium hydroxide solution exists obtains the substituted benzoic acid shown in general formula I I, again by the substituted benzoic acid shown in general formula I I or its corresponding derivative (as corresponding carboxylic acid halides, acyl cyanogen or ester) and hydroresorcinol (Q
1a), under dewatering agent and one or more catalyzer exist the obtained R of reaction
3general formula I-1a the compound (keto-acid or enol form) of=OH; Then, general formula I-1a compound reacts to obtain R with halogenating agent again
3general formula I-1b the compound of=Hal; General formula I-1c compound (R
3≠ OH or Hal) preparation because of R
3difference in two kinds of situation:
The first situation: work as R
3for C
1-C
6alkoxyl group, C
1-C
6alkylthio, C
2-C
6alkene oxygen base, halo C
2-C
6alkene oxygen base, C
2-C
6alkynyloxy group, C
1-C
6alkoxy carbonyl C
1-C
6alkoxyl group, C
1-C
6alkyl amino-carbonyl C
1-C
6alkoxyl group, and replace or unsubstituted aryloxy, arylthio, arylmethyl oxygen base or heteroaryl oxygen base time, general formula I-1b react with the compound of hydroxyl or sulfydryl when having alkali or alkali-free and obtains;
The second situation: work as R
3for C
1-C
6alkyl-carbonyl oxygen base, C
1-C
6alkyl sulphonyl oxygen base, and when substituted or unsubstituted aryl carbonyl oxygen base, aryl sulfonyl oxygen base or aryl carbonyl methoxyl group, general formula I-1a compound and halides (as carboxylic acid halides, SULPHURYL CHLORIDE etc.) are reacted in the basic conditions and can directly obtain.
In above-mentioned reaction formula, Hal is halogen, and other each group definition are the same,
Above-mentioned each step reaction is all carried out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, methylene dichloride, chloroform, acetonitrile, toluene, dimethylbenzene, benzene, acetone or butanone etc.Temperature of reaction between room temperature to solvent boiling point temperature, can be generally room temperature.Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.
The suitable optional dicyclohexylcarbodiimide of dewatering agent (DCC) related in above-mentioned reaction, also other reagent can be selected from as 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) or N, N '-carbonyl dimidazoles (CDI) etc.Suitable catalyzer is selected from as sodium cyanide, potassium cyanide, acetone cyanohydrin or cyano group trimethyl silane etc.The suitable optional oxalyl chloride of halogenating agent or oxalyl bromine etc.Suitable alkali can be selected from triethylamine, sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide etc.
Raw material Q
1anamely hydroresorcinol has commercially available.Raw material II can be made by oneself according to the method for US6376429.
The salt of compound of Formula I of the present invention can comprise inorganic salt (example hydrochloric acid salt, phosphoric acid salt, sodium salt, sylvite etc.) or organic salt (as formate, acetate, trifluoroacetic acid, benzene sulfonate, oxalate, Citrate trianion or malate etc.).Prepare above-mentioned salt by compound of Formula I and can adopt the known method of those skilled in the art.
Bioactivity screening test shows that compound of Formula I of the present invention has good weeding activity.Especially general formula I-1 compound and 3-bit strip have compared with the nitrogenous substituent benzoyl compounds of chain, and weeding activity is more excellent.Contriver has synthesized that two more close with the compounds of this invention structure according to the related compound that patent WO2000021924, WO2000037437 report but 3-bit strip has the nitrogenous substituent benzoyl compounds (code name compd A and B) of chain compound in contrast, carries out weeding activity measure of merit.Test-results further demonstrates compound of the present invention and has more advantage.The structure of control compound A and B is as follows:
Compound of the present invention can control the weeds such as barnyard grass, lady's-grass, piemarker effectively, under low dosage, just can obtain good effect.Therefore the present invention also comprises compound of Formula I for controlling the purposes of weeds.Meanwhile, compound of Formula I of the present invention has good security to corn, is therefore preferred for the weeds controlling corn field.
Present invention also offers a kind of herbicidal composition, containing as the compound of Formula I of active ingredient in said composition, is 0.1-99% as the weight percentage of the compound of Formula I of active ingredient in composition.Therefore the present invention also comprises said composition for controlling the purposes of weeds, and particularly preferably said composition is for controlling the purposes of corn field weed.
Composition of the present invention can adopt the known method preparation of those skilled in the art.This composition can contain the mixture of single compound of the present invention or several compound.
Carrier system in the present composition meets the material of following condition: it and activeconstituents are convenient to be applied to pending site after preparing, such as, can be plant, seed or soil; Or be conducive to storage, transport or operation.Carrier can be solid or liquid, comprises and is generally gas but the material being compressed into liquid, and in preparation herbicidal composition, carrier used all can use usually.
Suitable solid carrier comprises clay that is natural and that synthesize and silicate, such as diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Calcium carbonate; Calcium sulfate; Ammonium sulfate; The silicon oxide of synthesis and synthetic calcium silicate or pure aluminium silicate; Element is as carbon and sulphur; Resin that is natural and synthesis as coumarone resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax as beeswax, paraffin.
Suitable liquid vehicle comprises water; Alcohol is as Virahol and ethanol; Ketone is as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons is as benzene,toluene,xylene; Petroleum fractions is as kerosene and mineral oil; Hydrochloric ether is as tetracol phenixin, tetrachloroethylene and trieline.Usually, the mixture of these liquid is also suitable.
Composition is usually processed into the form of enriched material and with this for transport, is diluted before administration by user.Having of a small amount of supporting surfactant helps dilution.Like this, according to having at least a kind of carrier to be preferably tensio-active agent in composition of the present invention.Such as composition can contain at least two kinds of carriers, and wherein at least one is tensio-active agent.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be tensio-active agent that is non-ionic or ion.The example of suitable tensio-active agent comprises sodium salt or the calcium salt of polyacrylic acid and lignosulfonic acid; Containing the lipid acid of at least 12 carbon atoms or the condenses of aliphatic amide or acid amides and oxyethane and/or propylene oxide in molecule.The condenses of glycol, sorbyl alcohol, sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; Fatty alcohol or alkylphenol are as paraoctyl phenol or the condenses to octyl group cresylol and oxyethane and/or propylene oxide; The vitriol of these condensation products and sulfonate; In the molecule at least containing the sulfuric acid of 10 carbon atoms or the basic metal of sulphonate or alkaline earth salt, particular certain cancers, such as sulfuric acid laurate sodium, the secondary alkyl ester sodium of sulfuric acid, sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium, as pelopon A.
The example of composition of the present invention is wettable powder, pulvis, granule, aqua, emulsible enriching agent, emulsion, aerosol and smoke substance.Wettable powder usually containing 25-75% wt. Active ingredient, and usually except solid inert carrier except, also contains the dispersion agent of 3-10% weight, and if desired can add the stablizer of 0-10% weight and/or other additive as permeate agent or tackiness agent.Pulvis can be usually has the composition similar to wettable powder but the pulvis enriching agent not having dispersion agent, more further with solid carrier dilution, obtains usually containing the composition of 0.5-10% weight activity component.Granula is prepared into usually has 10 to 100 orders (1.676-0.152mm) size, and available agglomerating or implantttion technique preparation.Usual granula containing the activeconstituents of 0.5-75% weight and 0-10% weight additive as stablizer, tensio-active agent, slowly-releasing modifying agent.Can emulsion concentrate in addition to the solvents, when needed usually containing cosolvent, 1-50%W/V activeconstituents, 2-20%W/V emulsifying agent and other additive of 0-20%W/V are as stablizer, permeate agent and corrosion inhibitor.The dispersion agent of the activeconstituents of suspension enriching agent usually containing 10-75% weight, 0.5-15% weight, other additive of 0.1-10% weight are as defoamer, corrosion inhibitor, stablizer, permeate agent and tackiness agent.
Water dispersant and emulsion, such as, by the composition that dilute with water obtains according to wettable powder of the present invention or enriched material, also list the scope of the invention in.Said emulsion can have water-in-oil or oil-in-water two types.
By adding other one or more weedicides in the composition, the activity of more wide spectrum can be had than independent compound of Formula I.In addition, other weedicide the weeding activity of mutual-through type I can have synergism, also can by compound of Formula I and other herbicide mixture, and in mixture, the content scope of effective constituent is very large, in mixture, active constituent content is generally at 1%-95%, and comparatively suitable content is at 5%-60%.
The known insecticide-applying way of those skilled in the art can be adopted to use containing the composition of compound of Formula I of the present invention as active ingredient, reach the object controlling weeds.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.(except as otherwise indicate outside, raw materials used all have commercially available)
Synthetic example
The preparation of embodiment 1 Compound I-1-1
Morpholine IV-1-10.28g (3.22mmol) and salt of wormwood 0.44g (3.22mmol) is in reaction flask, add 20mL acetonitrile and stir 20min, add intermediate V1.0g (2.93mmol, method self-control according in patent US6376429), 5h is reacted under room temperature, TLC monitoring reaction is complete, filter, filtrate decompression precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to column chromatography, volume ratio is 1: 3) purifying obtains intermediate III-1-1, white solid 0.78g, fusing point 118-120 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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 III-1-10.5g (1.44mmol) is dissolved in 10mL methyl alcohol, add the 5mL aqueous solution of 0.12g (3mmol) sodium hydroxide, stirring at room temperature 3h, TLC monitoring is without starting material left, neutrality is adjusted to hydrochloric acid, decompression precipitation, drying, intermediate II-1-1 crude product, need not purify, be directly used in next step reaction.
Hydroresorcinol Q is added in above-mentioned intermediate II-1-1 crude product
1a0.16g (1.44mmol) and 20mL acetonitrile, DCC0.37g (1.8mmol) is added under stirring, 10h is reacted under room temperature, then triethylamine 0.29g (2.88mmol) and two acetone cyanohydrins are added, 3h is reacted under continuing room temperature, filter, filtrate decompression precipitation, adds 10mL water and 0.5g hydrochloric acid in residue, extraction into ethyl acetate 3 times, aqueous phase sodium hydroxide is adjusted to neutrality, extraction into ethyl acetate, and organic phase is dry, precipitation, obtain clear yellow viscous thing, add sherwood oil grinding and occur solid, filter to obtain Compound I-1-1, yellow solid 0.23g.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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).
The preparation of embodiment 2 Compound I-1-4
According to the method described in embodiment 1, by intermediate compound IV-1-40.92g (8.0mmol) and intermediate V2.5g (7.31mmol) obtained intermediate III-1-4, colorless oil 2.3g.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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, 1H), 8.16 (d, 1H).
According to method described in embodiment 1, the sour II-1-4 obtained after being hydrolyzed by intermediate III-1-41.0g (2.66mmol) and hydroresorcinol 0.3g (2.66mmol) reacts, obtained Compound I-1-4, colorless oil 0.64g.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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).
The preparation of embodiment 3 Compound I-1-27
Intermediate compound IV-1-27 can adopt the method preparation of patent EP370560 with piperazine and 2,3-bis-chloro-5-trifluoromethylpyridine.
According to method described in embodiment 1, intermediate compound IV-1-270.78g (2.93mmol) and intermediate V1.0g (2.93mmol) react obtained intermediate III-1-27, white solid 1.3g, fusing point 131-133 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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 method described in embodiment 1, the sour II-1-27 obtained after being hydrolyzed by intermediate III-1-270.5g (0.95mmol) and hydroresorcinol 0.11g (0.95mmol) reacts obtained Compound I-1-27, yellow solid 0.11g.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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, 1H), 7.76 (s, 1H), 8.16 (d, 1H), 8.38 (s, 1H).
The preparation of embodiment 4 Compound I-1-98
Intermediate compound IV-1-98 can be prepared with reference to the method 4-hydroxy piperidine introduced in patent WO2005095362 and 2,3-bis-chloro-5-trifluoromethylpyridine.
According to method described in embodiment 1, intermediate compound IV-1-981.23g (4.38mmol) and intermediate V1.5g (4.38mmol) react obtained intermediate III-1-98, white solid 1.32g, fusing point 140-142 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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, 1H), 7.71 (d, 1H), 7.84 (d, 1H), 8.17 (d, 1H), 8.29 (s, 1H).
According to method described in embodiment 1, the sour II-1-98 obtained after intermediate III-1-980.58g (1.07mmol) hydrolysis and hydroresorcinol 0.11g (1.07mmol) reacts obtained Compound I-1-98, white solid 0.10g.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (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, 1H), 7.25 (d, 1H), 7.3 (d, 1H), 8.15 (d, 1H), 8.29 (s, 1H).
Example of formulations
Be metered into after active ingredient folding hundred in formula, all percentage compositions are weight percentage.
Embodiment 535% missible oil
Phosphorous acid is dissolved in cyclohexanone, then adds Compound I-1-1 and ethoxylated triglycerides, obtain transparent solution.
Embodiment 660% wettable powder
Compound I-1-4, dodecyl sodium naphthalene sulfonate, sodium lignosulfonate and kaolin (being solid) are mixed, pulverizes in pulverizer, until particle reaches standard.
Embodiment 730% aq suspension
By Compound I-1-1 with answer 80% of amount of water and dodecyl sodium naphthalene sulfonate in ball mill in (1mm pearl) together with pulverize.Hemicellulose and propylene oxide are dissolved in all the other water of 20%, then stir and add said components.
Embodiment 840% suspension agent
Compound I-1-27 and other components are fully mixed, the suspension agent obtained thus, dilute with water gained suspension agent can obtain the diluent of any desired concn.
Biological activity determination
The indoor Herbicidal of embodiment 9
The former medicinal a small amount of acetone solution of testing compound, then be diluted to required concentration with the water containing 0.1% tween 80.Quantitative weed seed is sowed at respectively diameter be 7cm be equipped with in the dixie cup of Nutrition Soil, broadcast rear earthing 1cm, in hot-house culture after suppression, trickle, thinning after emerging, field planting (gramineous weeds 10-20 strain/cup, broadleaf weeds 2-4 strain/cup), treat the gramineous weeds 2-3 leaf phase, broadleaf weeds grows to 2-4 leaf period, carries out cauline leaf spraying process (spray pressure 1.95kg/cm by test design dosage track type crops sprayer (Britain EngineerResearchLtd. designs production)
2, spouting liquid 50mL/m
2, crawler track speeds 1.48km/h).3 repetitions are established in test.After liquid natural air drying, be placed in greenhouse and manage according to a conventional method, the situation of growing of routine observation examination material, and according to practical situation, periodical visual inspection investigation reagent agent is to the preventive effect of weeds after process.Preventive effect grade scale: 0 is invalid, 100% for killing weeds completely or seriously suppressing.
The activity data of part of compounds is in Table 7-table 11.
Part of compounds to the activity data of lady's-grass in table 7.
Table 7
Compound I-1-1 with contrast medicament sulphur humulone (15% aqua, Shenyang Sciencreat Chemicals Co., Ltd. produce, lower with) activity data in table 8.
Table 8
Compound I-1-1 with contrast medicament mesotrione (95% former medicine, self-control, lower with) activity data in table 9.
Table 9
Compound I-1-1 to the activity data of lamb's-quarters, Siberian cocklebur, Eclipta prostrata in table 10.
Table 10
Part of compounds and control compound A and B to the activity data of barnyard grass and Setaria glauca in table 11.
Table 11
Embodiment 10 indoor security measures
The former medicinal a small amount of acetone solution of testing compound, then be diluted to required concentration with the water containing 0.1% tween 80.The seed of quantitative corn, paddy rice, wheat, soybean and cotton is sowed at respectively diameter be 7cm be equipped with in the dixie cup of Nutrition Soil, broadcast rear earthing 1cm, in hot-house culture after suppression, trickle, thinning after emerging, field planting (1-2 strain/cup), the 2-4 leaf phase to be grown into, carry out cauline leaf spraying process (spray pressure 1.95kg/cm by test design dosage track type crops sprayer (Britain EngineerResearchLtd. designs production)
2, spouting liquid 50mL/m
2, crawler track speeds 1.48km/h), 3 repetitions are established in test.After liquid natural air drying, be put in greenhouse and manage according to a conventional method, observe crop growth situation, periodical visual inspection investigation reagent agent is to the security of crop.Safety classification standard: 0 represents crop without any damage, 100% for killing crop completely or seriously suppressing, the comparative test result of Compound I-1-1 and control compound sulphur humulone is in table 12, and the comparative test result of Compound I-1-1 and control compound mesotrione is in table 13.
Table 12
Table 13
Claims (9)
1. the cyclosubstituted benzoyl compounds of nitrogen-containing hetero or its tautomer, as shown in general formula I-1:
In formula:
Het is selected from one of group shown in Het-5 or Het-6;
R is selected from C
1-C
3alkyl; N=0-4;
R
1be selected from C
1-C
3alkyl, unsubstituted or by 1-3 be independently selected from following group replace phenyl or pyridyl: fluorine, chlorine, bromine or trifluoromethyl;
R
3be selected from hydroxyl;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
2. compound according to claim 1, is characterized in that: in general formula I-1
Het is selected from one of group shown in Het-5 or Het-6;
R is selected from methyl, n=0-2;
R
1be selected from the chloro-5-trifluoromethylpyridin of 3--2-base;
R
3be selected from hydroxyl;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
3. compound according to claim 2, is characterized in that: in general formula I-1
Het is selected from the group shown in Het-5;
R is selected from methyl, n=0-2;
R
3be selected from hydroxyl;
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
4. compound according to claim 3, is characterized in that: the concrete structure of compound is
Or its sodium salt, sylvite, hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetate, oxalate, benzene sulfonate, Citrate trianion or malate.
5. a compound of Formula I according to claim 1 is for controlling the purposes of weeds.
6. a purposes according to claim 5, is characterized in that: for controlling the purposes of corn field weed.
7. a herbicidal composition, is characterized in that: containing compound of Formula I according to claim 1 as active ingredient, and the weight percentage of the active ingredient in composition is 0.1-99%.
8. a herbicidal composition according to claim 7 is for controlling the purposes of weeds.
9. a purposes according to claim 8, is characterized in that: for controlling the purposes of corn field weed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201180035270.0A CN103025718B (en) | 2010-11-19 | 2011-11-18 | Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010554434.8A CN102464630B (en) | 2010-11-19 | 2010-11-19 | Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof |
| CN201010554434.8 | 2010-11-19 | ||
| PCT/CN2011/082436 WO2012065573A1 (en) | 2010-11-19 | 2011-11-18 | Nitrogen heterocyclic substituted benzoyl compound and use thereof |
| CN201180035270.0A CN103025718B (en) | 2010-11-19 | 2011-11-18 | Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof |
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| CN103025718A CN103025718A (en) | 2013-04-03 |
| CN103025718B true CN103025718B (en) | 2016-01-20 |
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| CN201180035270.0A Active CN103025718B (en) | 2010-11-19 | 2011-11-18 | Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof |
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| WO (1) | WO2012065573A1 (en) |
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| CN105766944B (en) * | 2014-12-22 | 2018-12-14 | 沈阳中化农药化工研发有限公司 | A kind of herbicide and its application |
| CN105794796B (en) * | 2014-12-30 | 2019-01-04 | 沈阳中化农药化工研发有限公司 | A kind of herbicidal composition and application |
| 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 |
| CN112939953B (en) * | 2019-12-10 | 2024-04-23 | 沈阳中化农药化工研发有限公司 | Benzamide compound and application thereof as herbicide |
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| CN1179778A (en) * | 1995-02-24 | 1998-04-22 | 巴斯福股份公司 | Herbicidal benzoyl derivatives |
| WO2001047894A1 (en) * | 1999-12-24 | 2001-07-05 | Bayer Aktiengesellschaft | Substituted benzoylcyclohexane diones for use as herbicides |
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| DE10301110A1 (en) * | 2003-01-09 | 2004-07-22 | Bayer Cropscience Gmbh | Substituted benzoyl derivatives as herbicides |
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| IL85659A (en) * | 1987-03-17 | 1992-03-29 | Nissan Chemical Ind Ltd | 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them |
| WO1997046530A1 (en) * | 1996-06-06 | 1997-12-11 | E.I. Du Pont De Nemours And Company | Herbicidal pyridinyl and pyrazolylphenyl ketones |
| AR012142A1 (en) * | 1997-03-24 | 2000-09-27 | Dow Agrosciences Llc | 1-ALKYL-4-BENZOIL-5-HYROXYPYRAZOLE COMPOUNDS, HERBICIDE COMPOSITIONS CONTAINING THEM; METHOD FOR CONTROLLING UNWANTED VEGETATION AND USEFUL INTERMEDIATE COMPOUNDS TO PREPARE SUCH COMPOUNDS |
| AR027575A1 (en) * | 2000-03-06 | 2003-04-02 | Bayer Ag | SUBSTITUTED BENZOILCICLOHEXENONAS |
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2010
- 2010-11-19 CN CN201010554434.8A patent/CN102464630B/en active Active
-
2011
- 2011-11-18 CN CN201180035270.0A patent/CN103025718B/en active Active
- 2011-11-18 WO PCT/CN2011/082436 patent/WO2012065573A1/en active Application Filing
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| CN1179778A (en) * | 1995-02-24 | 1998-04-22 | 巴斯福股份公司 | Herbicidal benzoyl derivatives |
| CN1310714A (en) * | 1998-07-24 | 2001-08-29 | 拜尔公司 | Substituted benzoylcyclohexandiones |
| CN1323292A (en) * | 1998-10-10 | 2001-11-21 | 阿温提斯作物科学有限公司 | Benzoylcyclohexandiones, method for the production and use thereof as herbicides and plant growth regulators |
| WO2001047894A1 (en) * | 1999-12-24 | 2001-07-05 | Bayer Aktiengesellschaft | Substituted benzoylcyclohexane diones for use as herbicides |
| CN1466582A (en) * | 2000-07-29 | 2004-01-07 | 拜尔农作物科学股份公司 | Substituted aryl ketones and their use as herbicides |
| WO2002063957A2 (en) * | 2001-02-12 | 2002-08-22 | Bayer Cropscience Ag | Selective substituted aryl ketone and safener based herbicides |
| DE10301110A1 (en) * | 2003-01-09 | 2004-07-22 | Bayer Cropscience Gmbh | Substituted benzoyl derivatives as herbicides |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012065573A1 (en) | 2012-05-24 |
| CN102464630A (en) | 2012-05-23 |
| CN103025718A (en) | 2013-04-03 |
| CN102464630B (en) | 2015-05-13 |
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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 |