CN102464630B - Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof - Google Patents
Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof Download PDFInfo
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- CN102464630B CN102464630B CN201010554434.8A CN201010554434A CN102464630B CN 102464630 B CN102464630 B CN 102464630B CN 201010554434 A CN201010554434 A CN 201010554434A CN 102464630 B CN102464630 B CN 102464630B
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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
-
- 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
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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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- Dentistry (AREA)
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- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a nitrogen heterocyclic substituent-containing benzoyl compound or a stereoisomer thereof shown as general formula I, wherein each substituent group in the formula is defined in the description. The compound of general formula I has very high herbicidal activity, can effectively control weeds, such as barnyard grass, digitaria sanguinalis, abutilon, green bristlegrass, zinnia elegans and the like, and can serve as a weedicide in agriculture; and a very good weed-removing effect can be achieved by a small amount of the compound.
Description
Technical field
The invention belongs to field of agricultural herbicide.Be specifically related to the cyclosubstituted benzoyl compounds of a kind of nitrogen-containing hetero and application thereof.
Background technology
Have a lot about benzoyl compounds as the report of weedicide, such as patent DE10301110, WO2001032636, WO2001010850, WO2000037437, DE19846792, 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.
However, still need to continually develop new herbicidal compound, to meet the demand of agriculture production.
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, 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 as C=O, C=NR
1or C=NOR
1when 2-position, 3-position can not be N or S;
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-
c6 alkyl-carbonyls, 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, 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;
Y is selected from C, N, O or S;
Z is selected from C, N, O, S, SO, SO
2or C=O;
As p=2 and Z and/or Y is selected from C time, 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, 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 methoxyl group: 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.
The comparatively preferred compound of the present invention is: in general formula I
Het is selected from one of group shown in Het-1 to Het-18;
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, 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, PYRIDYLCARBONYL, 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;
Q is selected from Q
1-Q
3one of shown group;
Wherein:
R
2be selected from C
1-C
3alkyl, C
3-C
6cycloalkyl, C
1-C
3alkoxyl group, C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl, C
1-C
3alkoxy carbonyl, C
1-C
3alkylthio or phenyl; P=0-4;
Y is selected from C, N, O or S;
Z is selected from C, N, O, S, SO, SO
2or C=O;
As p=2 and Z and/or Y is selected from C time, 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, O, O (CH
2)
2o, O (CH
2)
3o, S (CH
2)
2s or S (CH
2)
3s;
R
3, R
6be selected from hydroxyl, C
1-C
3alkoxyl group, C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkylthio, C
1-C
3alkyl sulphonyl oxygen base, C
2-C
4alkene oxygen base, halo C
2-C
4alkene oxygen base, C
2-C
4alkynyloxy group, 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, benzoyloxy, benzenesulfonyl oxygen base, pyridyloxy or benzoyl C
1-C
3alkoxyl group: 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;
R
4be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, benzyl or pyridyl: 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;
R
5be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
3alkyl, C
3-C
6cycloalkyl, C
1-C
3alkyl-carbonyl, C
1-C
3alkoxy carbonyl, phenyl that is unsubstituted or that be independently selected from following group replace by 1-3: 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
3alcoxyl;
R
7be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
3alkyl, C
3-C
6cycloalkyl, phenyl or halogenophenyl;
R
8be selected from hydrogen, cyano group, formamyl, C
1-C
3alkyl, halo C
1-C
3alkyl, C
3-C
6cycloalkyl, C
1-C
3alkoxyl group or C
1-C
3alkoxy carbonyl;
Or its hydrochloride, phosphoric acid salt, formate, acetate, trifluoroacetic acid, oxalate, benzene sulfonate, Citrate trianion or malate.
Preferred compound is further: in general formula I
Het is selected from one of group shown in Het-3 to Het-16;
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
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, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, pyridyl, benzyloxy, pyridylmethyl oxygen base, benzoyl-amido, BENZENESUFONYLAMINO, benzylamino or pyridylmethylaminojphenyl: 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
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, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, pyridyl, benzoyl, PYRIDYLCARBONYL, benzenesulfonyl, benzyl or picolyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical;
Q is selected from Q
1-1or Q
2one of shown group:
R
2be selected from C
1-C
3alkyl, C
3-C
6cycloalkyl, C
1-C
3alkoxyl group, C
1-C
3alkoxy C
1-C
3alkyl, C
1-C
3alkyl-carbonyl, C
1-C
3alkoxy carbonyl, C
1-C
3alkylthio, phenyl; P=0-4;
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, O, O (CH
2)
2o, O (CH
2)
3o, S (CH
2)
2s or S (CH
2)
3s;
R
3, R
6be selected from hydroxyl, C
1-C
3alkoxyl group, C
1-C
3alkyl-carbonyl oxygen base, C
1-C
3alkyl sulphonyl oxygen base, C
2-C
4alkene oxygen base, halo C
2-C
4alkene oxygen base, unsubstituted or that be independently selected from following group replace by 1-3 phenoxy group, benzyl oxygen base, benzoyloxy, benzenesulfonyl oxygen base or benzoyl methoxyl group: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy;
R
4be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
6alkyl, C
3-C
6cycloalkyl, 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 or trifluoromethoxy;
R
5be selected from hydrogen, C
1-C
3alkyl, halo C
1-C
3alkyl, C
3-C
6cycloalkyl, phenyl or the phenyl replaced by 1-3 fluorine, chlorine or bromine.
Further preferred compound is: in general formula I
Het is selected from one of group shown in Het-5 to Het-9;
R is selected from fluorine, chlorine, bromine, cyano group, hydroxyl, carboxyl, amino, methyl, ethyl, n-propyl, sec.-propyl, trifluoromethyl, methoxyl group, oxyethyl group, trifluoromethoxy, methylamino-, ethylamino, allyl group oxygen base, halogenated allyl oxygen base, allyl amino, halogenated allyl is amino, methoxycarbonyl, ethoxy carbonyl, amino-carbonyl, B aminocarbonyl, methoxymethyl, ethoxyl methyl, trifluoromethoxy methyl, formyl radical oxygen ylmethyl, ethanoyl oxygen ylmethyl, methoxymethoxy, oxyethyl group methoxyl group, trifluoromethoxy methoxyl group, methoxyvarbonyllnethoxy, ethoxycarbonyl methoxy, formyl radical oxygen base, ethanoyl oxygen base, Formylamino, acetylamino, methyl sulphonyl oxygen base, ethylsulfonyl oxygen base, Methylsulfonylamino, ethylsulphsulphonylamino, phenyl that is unsubstituted or that be independently selected from following group replace by 1-3, pyridyl, benzyloxy, pyridylmethyl oxygen base, benzylamino or pyridylmethylaminojphenyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical, n=0-4,
R
1be selected from hydrogen, methyl, trifluoromethyl, allyl group, halogenated allyl, methoxymethyl, ethoxyl methyl, trifluoromethoxy methyl, formyl radical, ethanoyl, fluoroform acyl group, methyl sulphonyl, ethylsulfonyl, phenyl that is unsubstituted or that be independently selected from following group replace by 1-3, pyridyl, benzoyl, PYRIDYLCARBONYL, benzenesulfonyl, benzyl or picolyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical,
Q is selected from one of group shown in Q1-1 or Q2:
R
2be selected from methyl, ethyl, cyclopropyl, methoxyl group, methoxymethyl, methylthio group, phenyl, p=0-2;
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, O, O (CH
2)
2o, O (CH
2)
3o, S (CH
2)
2s or S (CH
2)
3s;
R
3, R
6be selected from hydroxyl, methoxyl group, oxyethyl group, methanoyl, acetoxyl group, methyl sulphonyl oxygen base, ethylsulfonyl oxygen base, allyl group oxygen base, halogenated allyl oxygen base, unsubstituted or that be independently selected from following group replace by 1-3 phenoxy group, benzyl oxygen base, benzoyloxy, benzenesulfonyl oxygen base or benzoyl methoxyl group: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy;
R
4be selected from hydrogen, methyl, ethyl, trifluoromethyl, cyclopropyl, 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 or trifluoromethoxy;
R
5be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, chlorine methyl fluoride, cyclopropyl, phenyl or rubigan.
Preferred compound is further again: in general formula I
Het is selected from one of group shown in Het-5 to Het-9;
R is selected from fluorine, chlorine, bromine, cyano group, methyl, ethyl, methoxyl group, methylamino-, allyl group oxygen base, halogenated allyl oxygen base, allyl amino, halogenated allyl amino, methoxymethyl, methoxymethoxy, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, benzyloxy, pyridylmethyl oxygen base, benzylamino or pyridylmethylaminojphenyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical, n=0-2;
R
1be selected from methyl, allyl group, halogenated allyl, methoxymethyl, formyl radical, ethanoyl, fluoroform acyl group, methyl sulphonyl, ethylsulfonyl, unsubstituted or that be independently selected from following group replace by 1-3 phenyl, pyridyl, benzoyl, PYRIDYLCARBONYL, benzenesulfonyl, benzyl or picolyl: fluorine, chlorine, bromine, nitro, cyano group, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formyl radical;
Q is selected from Q
1-1-1, Q
1-1-2or Q
2-1one of shown group:
R
4select methyl or ethyl;
R
5be selected from hydrogen, methyl, ethyl, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, chlorine methyl fluoride, cyclopropyl, phenyl or rubigan.
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.
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.
Alkyl sulphonyl: refer to straight or branched alkyl through alkylsulfonyl (-SO
2-) be connected in structure, as methyl sulphonyl.
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.
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.
Alkylamino: straight or branched alkyl is connected in structure through nitrogen-atoms.
Haloalkane is amino: straight or branched alkylamino, the hydrogen atom on alkylamino can partly or entirely replace by halogen.
Thiazolinyl: straight or branched also can exist the unsaturated alkyl of double bond in any position, such as vinyl or allyl group.
Haloalkenyl group: hydrogen moiety or all the thiazolinyl that replaces by halogen atom.
Alkene oxygen base: straight or branched also can exist the unsaturated alkyl of double bond in any position, be connected in structure through Sauerstoffatom.
Haloalkene oxygen base: hydrogen moiety or all the thiazolinyl that replaces by halogen atom, be connected in structure through Sauerstoffatom
Enamino: straight or branched also can exist the unsaturated alkyl of double bond in any position, link in structure through nitrogen-atoms key.
Haloalkene is amino: hydrogen moiety or all the thiazolinyl that replaces by halogen atom, be connected in structure through nitrogen-atoms
Alkynyloxy group: straight or branched also can exist the unsaturated alkyl of triple bond in any position, be connected in structure through Sauerstoffatom.
Aryl moiety in aryl and aryloxy, aryl carbonyl and aryloxycarbonyl etc. comprises phenyl or naphthyl etc.
Heteroaryl is containing the heteroatomic five-ring of one or more N, O, S or hexa-atomic aromatic ring.Such as pyridyl, furyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, pyrazolyl, thiazolyl etc.
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.
In compound of the present invention, because tautomerism can exist multiple tautomer, the present invention includes the mixture of all tautomers and any ratio thereof.
Part of compounds in the present invention can illustrate by the particular compound listed in table 1-table 5, but these particular compound do not limit the present invention.
Table 1
| Sequence number | R 3 | (R)n | Sequence number | R 3 | (R)n |
| Ia-1 | OH | H | Ia-14 | OH | 3-CH 2CONHCH 3 |
| Ia-2 | OH | 2-CH 3 | Ia-15 | OCH 3 | / |
| Ia-3 | OH | 3-CH 3 | Ia-16 | OCH 3 | 3，5-2CH 3 |
| Ia-4 | OH | 3，5-2CH 3 | Ia-17 | OCOCH 3 | / |
| Ia-5 | OH | 2-CH 2OCH 3 | Ia-18 | OCOCH 3 | 3，5-2CH 3 |
| Ia-6 | OH | 3-CH 2OCH 3 | Ia-19 | OSO 2CH 3 | / |
| Ia-7 | OH | 2-(CH 2) 2OCH 3 | Ia-20 | OSO 2CH 3 | 3，5-2CH 3 |
| Ia-8 | OH | 3-(CH 2) 2OCH 3 | Ia-21 | OSO 2Ph | / |
| Ia-9 | OH | 2-CONHCH 3 | Ia-22 | OSO 2Ph-4-CH 3 | / |
| Ia-10 | OH | 3-CONHCH 3 | Ia-23 | OCH 2COPh | / |
| Ia-11 | OH | 2-CONHC 2H 5 | Ia-24 | OCH 2COPh-4-CH 3 | / |
| Ia-12 | OH | 3-CONHC 2H 5 | Ia-25 | ONa | / |
| Ia-13 | OH | 2-CH 2CONHCH 3 | Ia-26 | OK | / |
Note: "/" represents unsubstituted, lower same.
Table 2
Table 3
| Sequence number | R 4 | R 5 | R 6 | (R)n |
| Ic-1 | CH 3 | H | OH | / |
| Ic-2 | CH 3 | H | OH | 3，5-2CH 3 |
| Ic-3 | CH 3 | CH 3 | OH | / |
| Ic-4 | CH 3 | CH 3 | OH | 3，5-2CH 3 |
| Ic-5 | C 2H 5 | H | OH | / |
| Ic-6 | C 2H 5 | H | OH | 3，5-2CH 3 |
| Ic-7 | C 2H 5 | CH 3 | OH | / |
| Ic-8 | C 2H 5 | CH 3 | OH | 3，5-2CH 3 |
| Ic-9 | CH 3 | H | OSO 2Ph | / |
| Ic-10 | CH 3 | CH 3 | OSO 2Ph | / |
| Ic-11 | C 2H 5 | H | OSO 2Ph | / |
| Ic-12 | C 2H 5 | CH 3 | OSO 2Ph | / |
| Ic-13 | CH 3 | H | OSO 2Ph-4-CH 3 | / |
| Ic-14 | CH 3 | CH 3 | OSO 2Ph-4-CH 3 | / |
| Ic-15 | C 2H 5 | H | OSO 2Ph-4-CH 3 | / |
| Ic-16 | C 2H 5 | CH 3 | OSO 2Ph-4-CH 3 | / |
| Ic-17 | CH 3 | H | OCH 2COPh | / |
| Ic-18 | CH 3 | CH 3 | OCH 2COPh | / |
| Ic-19 | C 2H 5 | H | OCH 2COPh | / |
| Ic-20 | C 2H 5 | CH 3 | OCH 2COPh | / |
| Ic-21 | CH 3 | H | OCH 2COPh-4-CH 3 | / |
| Ic-22 | CH 3 | CH 3 | OCH 2COPh-4-CH 3 | / |
| Ic-23 | C 2H 5 | H | OCH 2COPh-4-CH 3 | / |
| Ic-24 | C 2H 5 | CH 3 | OCH 2COPh-4-CH 3 | / |
Table 4
In table 4, each substituting group of Compound I d-1 to Id-26 is same as each substituting group of Compound I a-1 to Ia-26 in table 1 respectively.
Table 5
In table 5, each substituting group of Compound I e-1 to Ie-62 is same as each substituting group of Ib-1 to Ib-62 in table 2 respectively.
Compound of Formula I of the present invention can be prepared in accordance with the following methods:
Compound of Formula I can by the compound shown in general formula I I and the substituted benzoic acid shown in general formula III or its corresponding derivative (as corresponding carboxylic acid halides, acyl cyanogen or ester), and under dewatering agent and one or more auxiliary agents exist, reaction is obtained.
In above-mentioned reaction formula, the definition of Q, Het, R and n is the same.
React and carry out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, methylene dichloride, chloroform, acetonitrile, toluene, dimethylbenzene, benzene, acetone or butanone etc.
The suitable optional dicyclohexylcarbodiimide of dewatering agent (DCC), also can be selected from other reagent as 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) or N, N '-carbonyl dimidazoles (CDI) etc.
Suitable auxiliary agent is selected from as sodium cyanide, potassium cyanide, acetone cyanohydrin, cyano group trimethyl silane 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.
Raw material II has commercially available, also can refer to the method self-control in patent EP0283261, WO2005080344.Raw material II I can make 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.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.Meanwhile, compound of Formula I of the present invention to crop safety, such as, has good security to corn.Therefore the present invention also comprises compound of Formula I for controlling the purposes of weeds.
Present invention also offers a kind of herbicidal composition, containing the compound of Formula I as active ingredient in said composition, in composition, the weight percentage of active ingredient is 0.1-99%.Therefore the present invention also comprises said composition for controlling the purposes of weeds.
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%.
Compound tool of the present invention has the following advantages:
Because compound of Formula I of the present invention not only has good weeding activity, and to crop, there is good security, therefore can be used for preventing and treating weeds in various crop, be applicable to the weeds of preventing and kill off in corn field especially.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.
Synthetic example
The preparation of example 1: Compound I a-1
Get morpholine Va-1 0.28g (3.22mmol, commercially available) and salt of wormwood 0.44g (3.22mmol) in reaction flask, add 20ml acetonitrile and stir 20min, add intermediate VI 1.0g (2.93mmol, method self-control according in patent US6376429), 5h is reacted under room temperature, TLC monitoring reaction is complete, filter, filtrate decompression precipitation, column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 3) purifying obtains intermediate compound IV a-1, from look 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 compound IV a-1 0.5g (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 salt is surveyed without starting material left, neutrality is adjusted to hydrochloric acid, decompression precipitation, drying, intermediate III a-1 crude product, need not purify, be directly used in next step reaction.
1 is added in intermediate III a-1 crude product upward, hydroresorcinol II-1 0.16g (1.44mmol, commercially available) and 20ml acetonitrile, DCC 0.37 (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, 10ml water and 0.5g hydrochloric acid is added in residue, extraction into ethyl acetate 3 times, aqueous phase sodium hydroxide is adjusted to neutrality, extraction into ethyl acetate, organic phase is dry, precipitation, obtain clear yellow viscous thing, add sherwood oil grinding and occur solid, filter to obtain Compound I a-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).
Example 2: the preparation of compounds ib-1
Intermediate Vb-1 can adopt the known method preparation of those skilled in the art with piperazine and 2,3-bis-chloro-5-trifluoromethylpyridine (all having commercially available).
According to method described in example 1, by the obtained intermediate compound IV b-1 of intermediate Vb-10.78g (2.93mmol) and intermediate VI 1.0g (2.93mmol), from look 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 example 1, by the obtained compounds ib-1 of intermediate compound IV b-10.5g (0.95mmol) and hydroresorcinol II-1 0.11g (0.95mmol), 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).
Example of formulations
Be metered into after active ingredient folding hundred in formula, all percentage compositions are weight percentage.
Example 3 35% missible oil
Compound I a-1 35%
Phosphorous acid 10%
Ethoxylated triglycerides 15%
Pimelinketone complements to 100%
Phosphorous acid is dissolved in pimelinketone, then adds Compound I a-1 and ethoxylated triglycerides, obtain transparent solution.
Example 4 60% wettable powder
Compound I a-1 60%
Dodecyl sodium naphthalene sulfonate 2%
Sodium lignosulfonate 9%
Kaolin complements to 100%
Compound I a-1, dodecyl sodium naphthalene sulfonate, sodium lignosulfonate and kaolin (being solid) are mixed, pulverizes in pulverizer, until particle reaches standard.
Example 5 30% aq suspension
Compounds ib-1 30%
Dodecyl sodium naphthalene sulfonate 4%
Hemicellulose 2%
Propylene oxide 8%
Water complements to 100%
By compounds ib-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.
Example 6 40% suspension agent
Compounds ib-1 40%
Ethylene glycol 10%
Nonoxynol-9 6%
Sodium lignosulfonate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
75% silicone oil water miscible liquid 0.8%
Water complements to 100%
Compounds ib-1 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 example 7
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 EngineerResearch Ltd. 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 to lady's-grass is as follows:
When drug concentration is 40g a.i./ha, the activity of Compound I a-1 is 100, and the activity of compounds ib-1 is 80%.
When drug concentration is 20g a.i./ha, the activity of Compound I a-1 is 100, and the activity of compounds ib-1 is 80%.
When drug concentration is 10g a.i./ha, the activity of Compound I a-1 is 90, and the activity of compounds ib-1 is 75%.
Compound I a-1 with contrast medicament sulphur humulone (15% aqua, Shenyang Sciencreat Chemicals Co., Ltd. produce) and carry out Herbicidal simultaneously, to the activity data of youth-and-old-age, piemarker, Herba Setariae Viridis and barnyard grass in table 6.
Table 6
The indoor corn of example 8, Security of rice measure
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 corn, rice paddy seed are 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), treat that corn, paddy growth are to the 2-4 leaf phase, carry out cauline leaf spraying process (spray pressure 1.95kg/cm by test design dosage track type crops sprayer (Britain Engineer Research Ltd. 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 the situation of growing of corn, paddy rice, periodical visual inspection investigation reagent agent is to the security of corn, paddy rice.Safety classification standard: 0 represents to crop without any damage, 100% for killing crop completely or seriously suppressing, and partial test the results are shown in Table 7.
Table 7
Claims (7)
1. the cyclosubstituted benzoyl compounds of nitrogen-containing hetero or its steric isomer, as shown in general formula I:
In formula:
Het is selected from one of group shown in Het-5 to Het-7;
R is selected from C
1-C
3alkyl; N=0-4;
R
1be selected from pyridyl that is unsubstituted or that be independently selected from following group replace by 1-3: fluorine, chlorine, bromine or trifluoromethyl;
Q is selected from Q
1-1one of shown group:
R
2be selected from C
1-C
3alkyl; P=0-4;
As p=2, be positioned at two R on different C atom
2cH can be connected into
2or (CH
2)
2;
R
3be selected from hydroxyl;
2. compound according to claim 1, is characterized in that: in general formula I
Het is selected from one of group shown in Het-6 or Het-7;
R is selected from methyl; N=0-2;
R
1be selected from the pyridyl being independently selected from following group replacing by 1-3: chlorine or trifluoromethyl;
Q is selected from Q
1-1one of shown group:
R
2be selected from methyl; P=0-2;
As p=2, be positioned at two R on different C atom
2cH can be connected into
2or (CH
2)
2;
R
3be selected from hydroxyl;
3. compound according to claim 2, is characterized in that: in general formula I
Het is selected from the group shown in Het-6;
R is selected from methyl, n=0-2;
Q is selected from Q
1-1-1:
4. one kind according to compound of Formula I according to claim 1 for controlling the purposes of weeds.
5. according to a purposes according to claim 4, it is characterized in that: compound of Formula I is for controlling the purposes of corn field weed.
6. 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%.
7. a herbicidal composition according to claim 6 is for controlling the purposes of weeds.
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| CN201010554434.8A CN102464630B (en) | 2010-11-19 | 2010-11-19 | Nitrogen heterocyclic substituent-containing benzoyl compound and application thereof |
| CN201180035270.0A CN103025718B (en) | 2010-11-19 | 2011-11-18 | Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof |
| PCT/CN2011/082436 WO2012065573A1 (en) | 2010-11-19 | 2011-11-18 | Nitrogen heterocyclic substituted benzoyl compound and use thereof |
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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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| 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 |
| CN1416422A (en) * | 2000-03-06 | 2003-05-07 | 拜尔公司 | Substituted benzoylcyclohexenones |
| 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 |
| CN1630643A (en) * | 1999-12-24 | 2005-06-22 | 拜尔公司 | Substituted benzoylcyclohexane diones for use as herbicides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL85659A (en) * | 1987-03-17 | 1992-03-29 | Nissan Chemical Ind Ltd | 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them |
| MX9706382A (en) * | 1995-02-24 | 1997-11-29 | Basf Ag | Herbicidal benzoyl derivatives. |
| CA2257196A1 (en) * | 1996-06-06 | 1997-12-11 | Morris Padgett Rorer | 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 |
| US6924251B1 (en) * | 1998-07-24 | 2005-08-02 | Bayer Aktiengesellschaft | Substituted benzoylcyclohexandiones |
| DE10106420A1 (en) * | 2001-02-12 | 2002-08-14 | Bayer Ag | Selective herbicides based on substituted aryl ketones and safeners |
| DE10301110A1 (en) * | 2003-01-09 | 2004-07-22 | Bayer Cropscience Gmbh | Substituted benzoyl derivatives as herbicides |
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2010
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- 2011-11-18 WO PCT/CN2011/082436 patent/WO2012065573A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1630643A (en) * | 1999-12-24 | 2005-06-22 | 拜尔公司 | Substituted benzoylcyclohexane diones for use as herbicides |
| CN1416422A (en) * | 2000-03-06 | 2003-05-07 | 拜尔公司 | Substituted benzoylcyclohexenones |
| 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 |
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| WO2012065573A1 (en) | 2012-05-24 |
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| CN103025718A (en) | 2013-04-03 |
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Effective date of registration: 20160120 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, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |