CN1349382A - Use of N-substituted heterocycloalkylamines as herbicides, and novel N-substituted thienylamines - Google Patents
Use of N-substituted heterocycloalkylamines as herbicides, and novel N-substituted thienylamines Download PDFInfo
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- CN1349382A CN1349382A CN00807002A CN00807002A CN1349382A CN 1349382 A CN1349382 A CN 1349382A CN 00807002 A CN00807002 A CN 00807002A CN 00807002 A CN00807002 A CN 00807002A CN 1349382 A CN1349382 A CN 1349382A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/58—Radicals substituted by nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Abstract
The invention relates to N-substituted heterocyclylalkylamines of general formula as herbicidesThe use of agents, and novel N-substituted thienylalkylamines and processes for their preparation, wherein A represents a single bond or represents an alkanediyl group, R1Represents optionally substituted alkyl, R2Represents hydrogen, amino or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino, Y represents cyano or nitro and Z represents optionally substituted heterocyclyl.
Description
The present invention relates to the purposes of the Heterocyclylalkyl amine of N-replacement as weed killer herbicide, and the thiophene alkylamine of new N-replacement and their preparation method.
The Heterocyclylalkyl amine that known some N-replaces has insecticidal activity (referring to EP-A-364844, EP-A-418199, JP-A-08231524-draws from Chem.Abstracts125:300813).Yet, the activity of weeding of above-claimed cpd openly not so far.
And the aralkyl guanidine of known some replacement have influence plant growing effect (referring to DE-A-3345281, US-A-4639268).
The Heterocyclylalkyl amine of finding the N-replacement of general formula (I) at present has very strong activity of weeding
Wherein
A represents singly-bound or represents alkane two bases,
R
1The optional alkyl that replaces of representative,
R
2Represent hydrogen, amino or represent optional alkyl, alkoxyl, alkylthio group, alkyl amino or the dialkyl amido that replaces under every kind of situation,
Y represent cyano group or nitro and
The optional heterocyclic radical that replaces of Z representative.
Saturated or undersaturated alkyl as alkyl or alkenyl, can be a straight or branched under every kind of situation as possible, also comprises combining with hetero atom forming as alkoxyl.
The optional group that replaces can be single or polysubstituted, and under the wherein polysubstituted situation, substituting group can be identical or different.
General formula of the present invention (I) compound contains the two keys of at least one carbon-nitrogen, therefore can have different E-and Z-configurational isomer.The invention still further relates to the single E-of use general formula (I) compound and the mixture of Z-configurational isomer and these isomeric compounds.
General formula of the present invention (I) compound contains the carbon atom of at least one asymmetric replacement, therefore can have different enantiomter (R-and S-configuration) or diastereomeric form.The invention still further relates to the different possible single enantiomter of use general formula (I) compound or the mixture of stereoisomer and these isomeric compounds.
The preferred substituents or the group range of group is as described below above and in the hereinafter listed general formula.
On behalf of singly-bound or representative, A preferably have alkane two bases of 1-4 carbon atom.
R
1Preferred representative optional by cyano group-, halogen-or C
1-C
4The alkyl with 1-6 carbon atom of-alkoxyl-replacement.
R
2Preferred represent hydrogen, amino or represent choose wantonly under every kind of situation by cyano group-, halogen-, C
1-C
4-alkoxyl-, C
1-C
4-alkylthio group-, C
1-C
4-alkyl sulphinyl-or C
1-C
4The alkyl, alkoxyl, alkylthio group, alkyl amino or the dialkyl amido that have 1-6 carbon atom under every kind of situation of-alkyl sulphonyl-replacement at moieties.
Z preferably represents the heterocyclic radicals optional monocycle that replaces or two rings, and heterocyclic radical is furyl, tetrahydrofuran base, benzofuranyl, dihydro benzo furyl, isobenzofuran-base, thienyl, tetrahydro-thienyl, benzothienyl, dihydrobenzo thienyl, pyrrole radicals, indyl, isoindolyl, pyrazolyl, indazolyl, imidazole radicals, benzimidazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, pyridine radicals, quinolyl, isoquinolyl, pyrimidine radicals, quinazolyl.
Wherein preferred substituents is selected from nitro, cyano group, carboxyl, carbamoyl, thiocarbamoyl, sulfamoyl, halogen, C
1-C
4-alkyl, C
1-C
4-haloalkyl, C
1-C
4-alkoxyl, C
1-C
4-halogenated alkoxy, C
1-C
4-alkylthio group, C
1-C
4-halogenated alkylthio, C
1-C
4-alkyl sulphinyl, C
1-C
4-haloalkyl sulfinyl, C
1-C
4-alkyl sulphonyl, C
1-C
4-halogenated alkyl sulfonyl, C
1-C
4-alkyl-carbonyl, C
1-C
4-alkoxyl-carbonyl, C
1-C
4-alkyl amino-carbonyl, two-(C
1-C
4-alkyl)-amino-carbonyl, C
1-C
4-alkyl amino-sulfonyl, two-(C
1-C
4-alkyl) amino-sulfonyl, phenyl.
A especially preferably represents singly-bound, represents methylene (CH
2-), dimethylene (ethane-1,2-two bases ,-CH
2CH
2-), ethylidene (ethane-1,1-two bases ,-CH (CH
3)-), trimethylene (propane-1,3-two bases ,-CH
2CH
2CH
2-) or propane-1,2-two base (CH
2CH (CH
3)-).
R
1Under every kind of situation of preferred especially representative optional by cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of ethyoxyl-replacement, ethyl, just or isopropyl, just, different, second month in a season or the tert-butyl group.
R
2Especially preferably represent hydrogen; amino, represent under every kind of situation optional by cyano group-; fluoro-; chloro-; methoxyl group-; ethyoxyl-; methyl mercapto-; ethylmercapto group-; methylsulfinyl-; the ethyl sulfinyl-; methyl sulphonyl-or the methyl of ethylsulfonyl-replacement; ethyl; just or isopropyl; just; different; the second month in a season or the tert-butyl group; methoxyl group; ethyoxyl; just or isopropoxy; just; different; the second month in a season or tert-butoxy; methyl mercapto; ethylmercapto group; just or different rosickyite base; just; different; the second month in a season or uncle's butylthio; methylamino; ethylamino; just or isopropyl amino; just; different; the second month in a season or tert-butyl group amino; dimethylamino; diethylamino or dipropyl amino.
Z especially preferably represents the heterocyclic radicals optional monocycle that replaces or two rings, heterocyclic radical is a furyl, tetrahydrofuran base, benzofuranyl, dihydro benzo furyl, isobenzofuran-base, thienyl, tetrahydro-thienyl, benzothienyl, the dihydrobenzo thienyl, pyrrole radicals, indyl, isoindolyl, pyrazolyl, indazolyl, imidazole radicals, benzimidazolyl oxazolyl benzoxazolyl isoxazolyl, thiazolyl, benzothiazolyl, pyridine radicals, quinolyl, isoquinolyl, pyrimidine radicals, quinazolyl
Wherein particularly preferred substituting group is selected from nitro; cyano group; carboxyl; carbamoyl; thiocarbamoyl; sulfamoyl; fluorine; chlorine; bromine; iodine; methyl; ethyl; just or isopropyl; just; different; the second month in a season or the tert-butyl group; difluoromethyl; dichloromethyl; trifluoromethyl; trichloromethyl; chlorodifluoramethyl-; the fluorine dichloromethyl; methoxyl group; ethyoxyl; just or isopropoxy; difluoro-methoxy; trifluoromethoxy; methyl mercapto; ethylmercapto group; just or different rosickyite base; just; different; the second month in a season or uncle's butylthio; the difluoro methyl mercapto; trifluoromethylthio; methylsulfinyl; the ethyl sulfinyl; just or the isopropyl sulfinyl; the trifluoromethyl sulphinyl base; methyl sulphonyl; ethylsulfonyl; just or the isopropyl sulfonyl; trifluoromethyl sulfonyl; acetyl group; propiono; just or isobutyryl; methoxycarbonyl; ethoxy carbonyl; just or isopropoxy-carbonyl; the methylamino carbonyl; the ethylamino carbonyl; just or the isopropyl amino carbonyl; the dimethylamino carbonyl; the diethylamino carbonyl; the methylamino sulfonyl; the ethylamino sulfonyl; just or the isopropyl amino-sulfonyl; the dimethylamino sulfonyl; the diethylamino sulfonyl; phenyl.
The more preferred singly-bound of A or represent dimethylene (CH
2CH
2-).
R
1More preferred represent methylidene, ethyl, just or isopropyl.
R
2More especially preferably represent hydrogen, amino, methyl, ethyl, just or isopropyl, methoxyl group, ethyoxyl, just or isopropoxy, methyl mercapto, ethylmercapto group, just or different rosickyite base, methylamino, ethylamino, just or isopropyl amino, dimethylamino or diethylamino.
Optional thienyl or the benzothienyl that replaces under every kind of situation of the more preferred representative of Z.
Wherein more particularly preferred substituting group is selected from nitro; cyano group; carbamoyl; thiocarbamoyl; fluorine; chlorine; bromine; methyl; ethyl; just or isopropyl; difluoromethyl; dichloromethyl; trifluoromethyl; trichloromethyl; chlorodifluoramethyl-; the fluorine dichloromethyl; methoxyl group; ethyoxyl; just or isopropoxy; difluoro-methoxy; trifluoromethoxy; methyl mercapto; ethylmercapto group; just or different rosickyite base; the difluoro methyl mercapto; trifluoromethylthio; methylsulfinyl; the ethyl sulfinyl; just or the isopropyl sulfinyl; the trifluoromethyl sulphinyl base; methyl sulphonyl; ethylsulfonyl; just or the isopropyl sulfonyl; trifluoromethyl sulfonyl; acetyl group; propiono; just or isobutyryl; methoxycarbonyl; ethoxy carbonyl; just or isopropoxy-carbonyl.
The above-mentioned general or preferred group range of definition both had been applicable to the end-product of general formula (I), also correspondingly was applicable to be used to prepare required starting material or intermediate under every kind of situation.The definition of these groups can be mutually combination arbitrarily, promptly comprise the combination between the preferable range of giving.
The present invention preferably includes by the general formula of above-mentioned preferred definition combination (I) compound as weed killer herbicide.
The present invention preferably includes general formula (I) compound of above-mentioned special preferred definition combination especially as weed killer herbicide.
More special general formula (I) compound of above-mentioned more special preferred definition combination that preferably includes of the present invention is as weed killer herbicide.
Minority general formula (I) compound is known (referring to EP-A-364844, EP-A-418199, EP-A-483062, JP-A-08231524-draws from Chem.Abstracts125:300813) or as in first to file but there is not the part (referring to DE-A-19 832 447) of disclosed following application formerly.
So far a large amount of relatively general formula (I) compounds is also not open.Wherein, it should be noted that following new general formula (I) compound especially, the following compound that in first to file, proposes as an example of optional thienyl that replaces or benzothienyl under every kind of situation of Z representative-do not comprise wherein: N '-cyano group-N-[1-methyl-3-(3-thienyl)-propyl group]-ethyleneimine acid amides (ethanimidamid), N '-cyano group-N-[1-ethyl-3-(3-thienyl)-propyl group] the ethyleneimine acid amides, N '-cyano group-N-[1-methyl-3-(2-thienyl)-propyl group] the ethyleneimine acid amides, N '-cyano group-N-[1-(2-thienyl)-ethyl] 1-ethyleneimine acid amides and N '-cyano group-N-[1-(3-thienyl)-ethyl]-ethyleneimine acid amides (referring to DE-A-19 832 447).
Therefore, the claimed noval chemical compound of the present invention be following general formula (I) compound wherein
On behalf of singly-bound or representative, A have alkane two bases of 1-4 carbon atom,
R
1Representative optional by cyano group-, halogen-or C
1-C
4The alkyl with 1-6 carbon atom of-alkoxyl-replacement,
R
2Represent hydrogen, amino or represent under every kind of situation optional by cyano group-, halogen-, C
1-C
4-alkoxyl-, C
1-C
4-alkylthio group-, C
1-C
4-alkyl sulphinyl or C
1-C
4The alkyl, alkoxyl, alkylthio group, alkyl amino or the dialkyl amido that have 1-6 carbon atom under every kind of situation of-alkyl sulphonyl-replacement at moieties,
Y represents cyano group or nitro, and
Optional thienyl or the benzothienyl that replaces under every kind of situation of Z representative,
Wherein possible substituting group is selected from nitro, cyano group, carboxyl, carbamoyl, thiocarbamoyl, sulfamoyl, halogen, C
1-C
4-alkyl, C
1-C
4-haloalkyl, C
1-C
4-alkoxyl, C
1-C
4-halogenated alkoxy, C
1-C
4-alkylthio group, C
1-C
4-halogenated alkylthio, C
1-C
4-alkyl sulphinyl, C
1-C
4-haloalkyl sulfinyl, C
1-C
4-alkyl sulphonyl, C
1-C
4-halogenated alkyl sulfonyl, C
1-C
4-alkyl-carbonyl, C
1-C
4-alkoxyl-carbonyl, C
1-C
4-alkyl amino-carbonyl, two-(C
1-C
4-alkyl)-amino-carbonyl, C
1-C
4-alkyl amino-sulfonyl, two-(C
1-C
4-alkyl) amino-sulfonyl, phenyl,
Do not comprise following compound: N '-cyano group-N-[1-methyl-3-(3-thienyl)-propyl group]-the ethyleneimine acid amides, N '-cyano group-N-[1-ethyl-3-(3-thienyl)-propyl group] the ethyleneimine acid amides, N '-cyano group-N-[1-methyl-3-(2-thienyl)-propyl group] the ethyleneimine acid amides, N '-cyano group-N-[1-(2-thienyl)-ethyl]-ethyleneimine acid amides and N '-cyano group-N-[1-(3-thienyl)-ethyl]-ethyleneimine acid amides (referring to DE-A-19 832 447).
A, R
1, R
2Preferably has above-mentioned given preferred definition with the substituting group of listed Z.
General formula of the present invention (I) examples for compounds is listed in each following group.Except structural formula shown in the table, also can there be E and Z isomer and composition thereof in each case by all cpds of these structural formula representatives.
Group 1
Here, A, R
1, R
2For example has listed definition in the following table with Y.
Group 2
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 3
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 4
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 5
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 6
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 7
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 8
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 9
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 10
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 11
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 12
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 13
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 14
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 15
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 16
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 17
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 18
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 19
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 20
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 21
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 22
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 23
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.Group 24
| A | R 1 | R 2 | Y | ?A | ?R 1 | R 2 | ?Y | |
| - | CH 3 | H | CN | - | ?CH 3 | H | NO 2 | |
| - | CH 3 | CH 3 | CN | - | ?CH 3 | CH 3 | NO 2 | |
| - | CH 3 | C 2H 5 | CN | - | ?CH 3 | C 2H 5 | NO 2 | |
| - | CH 3 | C 3H 7-n | CN | - | ?CH 3 | C 3H 7-n | NO 2 | |
| - | CH 3 | C 3H 7-i | CN | - | ?CH 3 | C 3H 7-i | NO 2 | |
| - | CH 3 | OCH 3 | CN | - | ?CH 3 | OCH 3 | NO 2 | |
| - | CH 3 | OC 2H 5 | CN | - | ?CH 3 | OC 2H 5 | NO 2 | |
| - | CH 3 | OC 3H 7-n | CN | - | ?CH 3 | OC 3H 7-n | NO 2 | |
| - | CH 3 | OC 3H 7-i | CN | - | ?CH 3 | OC 3H 7-i | NO 2 | |
| - | CH 3 | SCH 3 | CN | - | ?CH 3 | SCH 3 | NO 2 | |
| - | CH 3 | SC 2H 5 | CN | - | ?CH 3 | SC 2H 5 | NO 2 | |
| - | CH 3 | SC 3H 7-n | CN | - | ?CH 3 | SC 3H 7-n | NO 2 | |
| - | CH 3 | SC 3H 7-i | CN | - | ?CH 3 | SC 3H 7-i | NO 2 | |
| - | CH 3 | NH 2 | CN | - | ?CH 3 | NH 2 | NO 2 | |
| - | CH 3 | NHCH 3 | CN | - | ?CH 3 | NHCH 3 | NO 2 | |
| - | CH 3 | NHC 2H 5 | CN | - | ?CH 3 | NHC 2H 5 | NO 2 | |
| - | CH 3 | NHC 3H 7-n | CN | - | ?CH 3 | NHC 3H 7-n | NO 2 | |
| - | CH 3 | NHC 3H 7-i | CN | - | ?CH 3 | NHC 3H 7-i | NO 2 | |
| - | CH 3 | N(CH 3) 2 | CN | - | ?CH 3 | N(CH 3) 2 | NO 2 | |
| - | CH 3 | N(C 2H 5) 2 | CN | - | ?CH 3 | N(C 2H 5) 2 | NO 2 |
| A | ?R 1 | R 2 | Y | A | ?R 1 | R 2 | Y | |
| - | C 2H 5 | H | CN | - | ?C 2H 5 | H | NO 2 | |
| - | C 2H 5 | CH 3 | CN | - | ?C 2H 5 | CH 3 | NO 2 | |
| - | C 2H 5 | C 2H 5 | CN | - | ?C 2H 5 | C 2H 5 | NO 2 | |
| - | C 2H 5 | C 3H 7-n | CN | - | ?C 2H 5 | C 3H 7-n | NO 2 | |
| - | C 2H 5 | C 3H 7-i | CN | - | ?C 2H 5 | C 3H 7-i | NO 2 | |
| - | C 2H 5 | OCH 3 | CN | - | ?C 2H 5 | OCH 3 | NO 2 | |
| - | C 2H 5 | OC 2H 5 | CN | - | ?C 2H 5 | OC 2H 5 | NO 2 | |
| - | C 2H 5 | OC 3H 7-n | CN | - | ?C 2H 5 | OC 3H 7-n | NO 2 | |
| - | C 2H 5 | OC 3H 7-i | CN | - | ?C 2H 5 | OC 3H 7-i | NO 2 | |
| - | C 2H 5 | SCH 3 | CN | - | ?C 2H 5 | SCH 3 | NO 2 | |
| - | C 2H 5 | SC 2H 5 | CN | - | ?C 2H 5 | SC 2H 5 | NO 2 | |
| - | C 2H 5 | SC 3H 7-n | CN | - | ?C 2H 5 | SC 3H 7-n | NO 2 | |
| - | C 2H 5 | SC 3H 7-i | CN | - | ?C 2H 5 | SC 3H 7-i | NO 2 | |
| - | C 2H 5 | NH 2 | CN | - | ?C 2H 5 | NH 2 | NO 2 | |
| - | C 2H 5 | NHCH 3 | CN | - | ?C 2H 5 | NHCH 3 | NO 2 | |
| - | C 2H 5 | NHC 2H 5 | CN | - | ?C 2H 5 | NHC 2H 5 | NO 2 | |
| - | C 2H 5 | NHC 3H 7-n | CN | - | ?C 2H 5 | NHC 3H 7-n | NO 2 | |
| - | C 2H 5 | NHC 3H 7-i | CN | - | ?C 2H 5 | NHC 3H 7-i | NO 2 | |
| - | C 2H 5 | N(CH 3) 2 | CN | - | ?C 2H 5 | N(CH 3) 2 | NO 2 | |
| - | C 2H 5 | N(C 2H 5) 2 | CN | - | ?C 2H 5 | N(C 2H 5) 2 | NO 2 | |
| -CH 2CH 2- | CH 3 | H | CN | -CH 2CH 2- | ?CH 3 | H | NO 2 | |
| -CH 2CH 2- | CH 3 | CH 3 | CN | -CH 2CH 2- | ?CH 3 | CH 3 | NO 2 | |
| -CH 2CH 2- | CH 3 | C 2H 5 | CN | -CH 2CH 2- | ?CH 3 | C 2H 5 | NO 2 | |
| -CH 2CH 2- | CH 3 | C 3H 7-n | CN | -CH 2CH 2- | ?CH 3 | C 3H 7-n | NO 2 | |
| -CH 2CH 2- | CH 3 | C 3H 7-i | CN | -CH 2CH 2- | ?CH 3 | C 3H 7-i | NO 2 | |
| -CH 2CH 2- | CH 3 | OCH 3 | CN | -CH 2CH 2- | ?CH 3 | OCH 3 | NO 2 | |
| -CH 2CH 2- | CH 3 | OC 2H 5 | CN | -CH 2CH 2- | ?CH 3 | OC 2H 5 | NO 2 | |
| -CH 2CH 2- | CH 3 | OC 3H 7-n | CN | -CH 2CH 2- | ?CH 3 | OC 3H 7-n | NO 2 | |
| -CH 2CH 2- | CH 3 | OC 3H 7-i | CN | -CH 2CH 2- | ?CH 3 | OC 3H 2-i | NO 2 |
| A | R 1 | R 2 | Y | A | R 1 | ?R 2 | Y | |
| -CH 2CH 2- | CH 3 | SCH 3 | CN | -CH 2CH 2- | CH 3 | ?SCH 3 | NO 2 | |
| -CH 2CH 2- | CH 3 | SC 2H 5 | CN | -CH 2CH 2- | CH 3 | ?SC 2H 5 | NO 2 | |
| -CH 2CH 2- | CH 3 | SC 3H 7-n | CN | -CH 2CH 2- | CH 3 | ?SC 3H 7-n | NO 2 | |
| -CH 2CH 2- | CH 3 | SC 3H 7-i | CN | -CH 2CH 2- | CH 3 | ?SC 3H 7-i | NO 2 | |
| -CH 2CH 2- | CH 3 | NH 2 | CN | -CH 2CH 2- | CH 3 | ?NH 2 | NO 2 | |
| -CH 2CH 2- | CH 3 | NHCH 3 | CN | -CH 2CH 2- | CH 3 | ?NHCH 3 | NO 2 | |
| -CH 2CH 2- | CH 3 | NHC 2H 5 | CN | -CH 2CH 2- | CH 3 | ?NHC 2H 5 | NO 2 | |
| -CH 2CH 2- | CH 3 | NHCC 3H 7-n | CN | -CH 2CH 2- | CH 3 | ?NHC 3H 7-n | NO 2 | |
| -CH 2CH 2- | CH 3 | NHC 3H 7-i | CN | -CH 2CH 2- | CH 3 | ?NHC 3H 7-i | NO 2 | |
| -CH 2CH 2- | CH 3 | N(CH 3) 2 | CN | -CH 2CH 2- | CH 3 | ?N(CH 3) 2 | NO 2 | |
| -CH 2CH 2- | CH 3 | N(C 2H 5) 2 | CN | -CH 2CH 2- | CH 3 | ?N(C 2H 5) 2 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | H | CN | -CH 2CH 2- | C 2H 5 | ?H | NO 2 | |
| -CH 2CH 2- | C 2H 5 | CH 3 | CN | -CH 2CH 2- | C 2H 5 | ?CH 3 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | C 2H 5 | CN | -CH 2CH 2- | C 2H 5 | ?C 2H 5 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | C 3H 7-n | CN | -CH 2CH 2- | C 2H 5 | ?C 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 2H 5 | C 3H 7-i | CN | -CH 2CH 2- | C 2H 5 | ?C 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 2H 5 | OCH 3 | CN | -CH 2CH 2- | C 2H 5 | ?OCH 3 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | OC 2H 5 | CN | -CH 2CH 2- | C 2H 5 | ?OC 2H 5 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | OC 3H 7-n | CN | -CH 2CH 2- | C 2H 5 | ?OC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 2H 5 | OC 3H 7-i | CN | -CH 2CH 2- | C 2H 5 | ?OC 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 2H 5 | SCH 3 | CN | -CH 2CH 2- | C 2H 5 | ?SCH 3 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | SC 2H 5 | CN | -CH 2CH 2- | C 2H 5 | ?SC 2H 5 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | SC 3H 7-n | CN | -CH 2CH 2- | C 2H 5 | ?SC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 2H 5 | SC 3H 7-i | CN | -CH 2CH 2- | C 2H 5 | ?SC 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 2H 5 | NH 2 | CN | -CH 2CH 2- | C 2H 5 | ?NH 2 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | NHCH 3 | CN | -CH 2CH 2- | C 2H 5 | ?NHCH 3 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | NHC 2H 5 | CN | -CH 2CH 2- | C 2H 5 | ?NHC 2H 5 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | NHC 3H 7-n | CN | -CH 2CH 2- | C 2H 5 | ?NHC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 2H 5 | NHC 3H 7-i | CN | -CH 2CH 2- | C 2H 5 | ?NHC 3H 7-i | NO 2 |
| ?A | R 1 | R 2 | Y | ?A | R 1 | R 2 | ?Y | |
| -CH 2CH 2- | C 2H 5 | N(CH 3) 2 | CN | -CH 2CH 2- | C 2H 5 | N(CH 3) 2 | NO 2 | |
| -CH 2CH 2- | C 2H 5 | N(C 2H 5) 2 | CN | -CH 2CH 2- | C 2H 5 | N(C 2H 5) 2 | NO 2 | |
| - | C 3H 7-i | H | CN | - | C 3H 7-i | H | NO 2 | |
| - | C 3H 7-i | CH 3 | CN | - | C 3H 7-i | CH 3 | NO 2 | |
| - | C 3H 7-i | C 2H 5 | CN | - | C 3H 7-i | C 2H 5 | NO 2 | |
| - | C 3H 7-i | C 3H 7-n | CN | - | C 3H 7-i | C 3H 7-n | NO 2 | |
| - | C 3H 7-i | C 3H 7-i | CN | - | C 3H 7-i | C 3H 7-i | NO 2 | |
| - | C 3H 7-i | OCH 3 | CN | - | C 3H 7-i | OCH 3 | NO 2 | |
| - | C 3H 7-i | OC 2H 5 | CN | - | C 3H 7-i | OC 2H 5 | NO 2 | |
| - | C 3H 7-i | OC 3H 7-n | CN | - | C 3H 7-i | OC 3H 7-n | NO 2 | |
| - | C 3H 7-i | OC 3H 7-i | CN | - | C 3H 7-i | OC 3H 7-i | NO 2 | |
| - | C 3H 7-i | SCH 3 | CN | - | C 3H 7-i | SCH 3 | NO 2 | |
| - | C 3H 7-i | SC 2H 5 | CN | - | C 3H 7-i | SC 2H 5 | NO 2 | |
| - | C 3H 7-i | SC 3H 7-n | CN | - | C 3H 7-i | SC 3H 7-n | NO 2 | |
| - | C 3H 7-i | SC 3H 7-i | CN | - | C 3H 7-i | SC 3H 7-i | NO 2 | |
| - | C 3H 7-i | NH 2 | CN | - | C 3H 7-i | NH 2 | NO 2 | |
| - | C 3H 7-i | NHCH 3 | CN | - | C 3H 7-i | NHCH 3 | NO 2 | |
| - | C 3H 7-i | NHC 2H 5 | CN | - | C 3H 7-i | NHC 2H 5 | NO 2 | |
| - | C 3H 7-i | NHC 3H 7-n | CN | - | C 3H 7-i | NHC 3H 2-n | NO 2 | |
| - | C 3H 7-i | NHC 3H 7-i | CN | - | C 3H 7-i | NHC 3H 7-i | NO 2 | |
| - | C 3H 7-i | N(CH 3) 2 | CN | - | C 3H 7-i | N(CH 3) 2 | NO 2 | |
| - | C 3H 7-i | N(C 2H 5) 2 | CN | - | C 3H 7-i | N(C 2H 5) 2 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | H | CN | -CH 2CH 2- | C 3H 7-i | H | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | CH 3 | CN | -CH 2CH 2- | C 3H 7-i | CH 3 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | C 2H 5 | CN | -CH 2CH 2- | C 3H 7-i | C 2H 5 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | C 3H 7-n | CN | -CH 2CH 2- | C 3H 7-i | C 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | C 3H 7-i | CN | -CH 2CH 2- | C 3H 7-i | C 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | OCH 3 | CN | -CH 2CH 2- | C 3H 7-i | OCH 3 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | OC 2H 5 | CN | -CH 2CH 2- | C 3H 7-i | OC 2H 5 | NO 2 |
| A | R 1 | ?R 2 | ?Y | A | R 1 | R 2 | Y | |
| -CH 2CH 2- | C 3H 7-i | ?OC 3H 7-n | ?CN | -CH 2CH 2- | C 3H 7-i | OC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?OC 3H 7-i | ?CN | -CH 2CH 2- | C 3H 7-i | OC 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?SCH 3 | ?CN | -CH 2CH 2- | C 3H 7-i | SCH 3 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?SC 2H 5 | ?CN | -CH 2CH 2- | C 3H 7-i | SC 2H 5 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?SC 3H 7-n | ?CN | -CH 2CH 2- | C 3H 7-i | SC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?SC 3H 7-i | ?CN | -CH 2CH 2- | C 3H 7-i | SC 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?NH 2 | ?CN | -CH 2CH 2- | C 3H 7-i | NH 2 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?NHCH 3 | ?CN | -CH 2CH 2- | C 3H 7-i | NHCH 3 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?NHC 2H 5 | ?CN | -CH 2CH 2- | C 3H 7-i | NHC 2H 5 | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?NHC 3H 7-n | ?CN | -CH 2CH 2- | C 3H 7-i | NHC 3H 7-n | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?NHC 3H 7-i | ?CN | -CH 2CH 2- | C 3H 7-i | NHC 3H 7-i | NO 2 | |
| -CH 2CH 2- | C 3H 7-i | ?N(CH 3) 2 | ?CN | -CH 2CH 2- | C 3H 7-i | N(CH 3) 2 | NO 2 |
Here, A, R
1, R
2Has listed definition in for example above-mentioned the 1st group table with Y.
Heterocyclic radical amine when general formula (II)
Wherein
A, R
1As above define with Z
Imino-compound with general formula (III)
Wherein
R
2As above define with Y and
X representation alkoxy or alkylthio group,
During reaction, can there be thinner, obtains general formula (I) compound as needs.
If for example use, 1-(5-fluoro-2-thienyl)-ethamine and (dimethoxy methene amido)-(nitrilo-)-methane are as starting material, and the course of reaction of the inventive method can be represented with following reaction scheme so:
General formula (II) provides the Heterocyclylalkyl amine of General Definition, prepares the starting material of general formula (I) compound method used as the present invention.In general formula (II), A, R
1Preferably have those definition that the front has provided with Z, and in conjunction with in general formula (I) compound as preferably, preferred especially or more particularly preferred A, R
1Description with Z.
The Heterocyclylalkyl amine of general formula (II) is known and/or can be by known method preparation own (referring to DE-A-19744232/LeA 32589, DE-A-19816055).
General formula (III) provides the imino-compound of General Definition, and it is further prepared the starting material of general formula (I) compound method as the present invention.In general formula (III), R
2Preferably have those definition that the front has provided with Y, and in conjunction with in general formula of the present invention (I) compound as preferably, preferred especially or more particularly preferred R
2Description with Y; X represents particularly C
1-C
4-alkoxyl or C
1-C
4-alkylthio group, particularly methoxyl group, ethyoxyl, methyl mercapto or ethylmercapto group.
The imino-compound of general formula (III) is known and/or can be by known method preparation own (referring to Chem.Ber.100 (1967), 2604-2615; J.Am.Chem.Soc.76 (1954), 1877-1879; J.Org.Chem.26 (1961), 3347-3350; Loc.cit.28 (1963), 1816-1821; Loc.cit.35 (1970), 2067-2069; Synthesis1975,332-334; Tetrahedron Lett.1968,5523-5526; US-A-3910928).
The preparation method of general formula of the present invention (I) compound preferably carries out under the condition of using thinner.Be suitable for preparation method's of the present invention thinner, except water, inert organic solvents particularly.These organic solvents in particular comprise aliphatic series, alicyclic or aromatics, and optional halogenated hydrocarbons, as gasoline, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, benzinum, hexane, cyclohexane, carrene, chloroform, carbon tetrachloride; Ethers such as ether, Di Iso Propyl Ether, diox, oxolane or glycol dimethyl ether or ethylene glycol diethyl ether; Ketone such as acetone, butanone or methylisobutylketone; Nitrile such as acetonitrile, propionitrile or butyronitrile; Acid amides such as N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formailide, N-Methyl pyrrolidone or HMPA; Ester class such as methyl acetate or ethyl acetate; Sulfoxide such as dimethyl sulfoxide (DMSO); Alcohols such as methyl alcohol, ethanol, just or isopropyl alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the mixture or the pure water of they and water.
In preparation method of the present invention, reaction temperature can change in the scope of broad.Generally, the inventive method is at 0 ℃ to 150 ℃, carries out under preferred 10 ℃ to 120 ℃.
Usually the inventive method is under atmospheric pressure carried out.Yet the inventive method also can boosted or reduce pressure, and generally carries out under 0.1bar to 10bar condition.
When adopting preparation method of the present invention, starting material uses approximate equimolar amounts usually.Yet, can also wherein a kind of component of excessive use.Usually, be reflected at and have reaction promoter and in the thinner that is fit to, carry out, and usually reactant mixture was stirred several hours down temperature required.Handle (referring to preparation embodiment) by conventional method.
Reactive compound of the present invention can be used as defoliant, and desiccant removes culm agent, particularly weed killer herbicide.In broad terms, weeds are interpreted as being grown in all plants that are not suitable for the place.Whether material of the present invention is to determine according to its usage amount as go out natural disposition or selective herbicide basically.
Reactive compound of the present invention for example can be used for following corresponding plants:
Broadleaf weed belongs to: Europe sinapsis alba, pepper grass, clearvers, chickweed, german chamomile, yellow chamomile, root of bidentate achyranthes chrysanthemum, lamb's-quarters, nettle, climbing groundsel, amaranth, kitchen garden, Siberian cocklebur, japanese bearbind, sweet potato, knotweed, sesbania, artemisiifolia, Ji, welted thistle, common sow thistle, black nightshade ， Han dish, Chinese deciduous cypress leaf, Brittle Falsepimpernel Herb, white dead nettle, Veronica, piemarker, thorn garden sorrel, datura, violet, weasel hemp nettle, opium poppy, cornflower, trefoil and buttercup, dandelion.
Dicotyledonous crops belongs to: cotton, soybean, beet, carrot, Kidney bean, pea, eggplant, flax, sweet potato, common vetch, tobacco, tomato, peanut, wild cabbage, lettuce, cucumber and cucurbit.
Monocotyledon weed belongs to: barnyard grass, green foxtail, broomcorn millet, lady's-grass, timothy grass, annual bluegrass, fescue grass, eleusine indica, arm shape grass, perennial ryegrass, bromegrass, oat, nutgrass flatsedge, chinese sorghum, wheatgrass, Bermuda grass, Monochoria vaginalis, dichotomous fimbristylis herb, arrowhead, pin Lin, the sugarcane grass, ditch millet, Ischaemum, cusp flower, Egyptian grass, cut a gang Ying, amur foxtail, wind grass (Apera), goatweed and Phalaris grass.
Monocot crops belongs to: paddy rice, corn, wheat, barley, oat, rye, Chinese sorghum, broomcorn millet, sugarcane, pineapple, asparagus and green onion.
, the application of reactive compound of the present invention is not limited in the above-mentioned genus, and they also have identical effect to other plant.
According to its concentration, reactive compound of the present invention is controlling weeds with being suitable for going out natural disposition, for example at industrial area and rail, plants tree or road or the square of the tree that has no guts.Equally, The compounds of this invention also can be used to prevent and treat the weeds in the perennial cultivation crop, and controlling weeds in annual raise crop optionally, the perennial cultivation crop for example is a forest, ornamental trees and shrubs, orchard, the vineyard, citrus garden, nut garden, banana garden, coffee garden, tea place, the rubber plantation, oil palm garden, but Keyuan Garden, berry plantation and hop growing district, turf, lawn and herbage.
When formula of the present invention (I) compound is applied to the acrial part of soil and plant, show very strong activity of weeding and action spectrum wide.To a certain extent, formula of the present invention (I) compound also is suitable in unifacial leaf and dicotyledonous crops, optionally prevents and treats unifacial leaf and broadleaf weed before seedling or behind the seedling.
To a certain extent, general formula of the present invention (I) compound is also to insect, and particularly nematode has very strong activity.
According to the present invention, can handle all plants and plant each several part.Plant is interpreted as all plants and plant community such as needs and unwanted wild plant or crop (comprising the crop that nature grows) herein.Crop can be by conventional breeding and optimization method or by biotechnology and genetic engineering method or said method in conjunction with the plant that obtains, comprise genetically modified plants and comprise the plant cultivation kind that obtains or do not obtain plant breeder's certificate protection (Sortenschutzrechte).The each several part of plant can be regarded as all on the ground and under ground portion and plant tissue such as stem, leaf, Hua Hegen, and the example that can mention is blade, needle, branch, trunk, flower, fruit body, fruit and seed and root, stem tuber and root-like stock.The plant each several part also comprises plant and asexual and sexual propagation material, for example seedling, stem tuber, root-like stock, cutting and the seed of results.
The processing of using reactive compound of the present invention to carry out plant and plant each several part is to handle by them were directly used or acted on to conventional treatment method environment, habitat or storage area, for example floods, sprays, fumigates, atomizing, broadcasts sowing, brushes and particularly can also carry out one or more layers dressing under the situation of seed at propagating materials.
Reactive compound of the present invention can be converted to the preparation into routine, as liquor, and emulsion, wetting powder, suspending agent, pulvis, pulvis subtilis, paste, solvable pulvis, granule, dense suspended emulsion is with natural and the synthetic material and the microcapsules in polymer of reactive compound dipping.
These preparations are produced with known method, and for example, by with active component and extender, promptly liquid flux and/or solid carrier mix and produce, and can selectively use surfactant in the preparation arbitrarily, i.e. emulsifier and/or dispersant, and/or blowing agent.
Under the situation that makes water as extender, for example, also can be with an organic solvent as cosolvent.Suitable liquid flux mainly contains: aromatics, and as dimethylbenzene, toluene or Fluhyzon, chloro aromatics and chloro fat hydro carbons, as chlorobenzene, dichloroethane or carrene, fat hydrocarbon is as cyclohexane or alkane, for example petroleum cuts, mineral oil and vegetable oil, alcohols is as butanols or ethylene glycol and ether and ester class, ketone, as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone, intensive polar solvent such as dimethyl formamide and dimethyl sulfoxide (DMSO), and water.
Suitable solid carrier has: for example, ammonium salt and natural minerals powder, as kaolin, clay, talcum, chalk, quartz, Attagel, imvite or diatomite and synthetic mineral powder, as high dispersive silica, aluminium oxide and silicate; The solid carrier that is fit to granule has: for example, the natural rock of pulverizing and classification, as calcite, marble, float stone, sepiolite and dolomite, and inorganic synthetic particle and organic dust, with the particle such as the sawdust of organic material, shuck, corn ears and stems and tobacco stem; Suitable emulsifier and/or blowing agent have: for example nonionic and anion emulsifier, and as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkaryl polyglycol ether for example, alkylsulfonate, alkyl sulfate, arylsulphonate and protein hydrolysate; The dispersant that is fit to has: for example lignin sulfinic acid waste liquid and methylcellulose.
In preparation, also can use sticker such as carboxymethyl cellulose and powder, particle or the natural or synthetic polymer of latex shape, as gum Arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid such as cephalin and lecithin, and synthetic phospholipid.Other sticker can be mineral oil and vegetable oil.
Colouring agent that may use such as inorganic pigment, iron oxide for example, titanium oxide and Prussia orchid, and organic dyestuff, as alizarin dyes, azo dyes and metal phthalocyanine dyestuff and trace nutrients such as slaine, for example, iron, manganese, boron, copper, cobalt, molybdenum and zinc salt.
Usually contain 0.1%-95% by weight in the preparation, the preferred reactive compound of 0.5%-90% by weight.
When controlling weeds, reactive compound of the present invention can itself or dosage form use, can also use with the form of mixtures of the material (" safener ") of known weed killer herbicide and/or improvement and crop compatibility, wherein, a finished product preparation or the mixed form of bucket are possible.Can also mix with the weed killer herbicide that comprises one or more known weed killer herbicides and safener.
To the admissible known weed killer herbicide of said mixture be, Acetochlor for example, acifluorfen, aclonifen, alachlor, alloxydimsodium, ametryn, elder generation's alachlor, amidosulfuron, anilofos, the spirit of sulphur grass, atrazine, azoles pyridine alkynes grass, azimsulfuron, BAS-662H, benazolin, benfuresate, bensulfuron-methyl, bentazon, Benzobicyclon, benzofenap, suffer, bialaphos, bifenox, two careless ethers, bromobutide, bromofenoxim, Brominal, butachlor, fourth oxygen cyclic ketones, butylate, the benzophenone azoles, the quinone oximes grass, carbetamide, fluorine ketazolam grass, chlomethoxyfen, chloramben, Pynamin, chlorimuronethyl, Mo 9 granular, chlorine sulphur is grand, chlortoluron, Cinidon (ethyl), cinmethylin, ether is yellow grand, Clefoxydim, clethodim, alkynes oxalic acid, clomazone, clomeprop, clopyralid, Clopyrasulfuron (methyl), the phonetic sulfanilamide (SN) salt of azoles, Cumyluron, cyanazine, Cybutryne, cycloate, AC322140, cycloxydim, cyhalofop-butyl, 2,4-drips, 2, the 4-Embutox, 2,4-drips propionic acid, desmedipham, Avadex, dicamba, diclofop-methyl, the phonetic sulfanilamide (SN) of azoles, acetyl alachlor, difenzoquat, diflufenican, the difluoro pyrrole is grand, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, Dimexyflam, dinitramine, diphenamide, diquat, the pyridine of fluorine sulphur grass, diuron, daimuron, Epropodan, Eptam (EPTC), esprocarb, ethalfluralin, ethametsulfuron, ethofumesate, Ethoxyfen, ethoxysulfuron, diphenyl, fenoxapropPethyl, Fentrazamide, flampropisopropyl, flampropisopropyl-L, flampropmethyl, flazasulfuron, Florasulam, efficient fluazifop, Fluazolate, Flucarbazone, Flufenacet, the fluorine ethofumesate, Flumiclorac pentyl, flumioxazin, Flumipropyn, Flumetsulam, fluometuron, fluorochloridone, fluoroglycofen-ethyl, flupoxam, Flupropacil, Flurpyrsulfuron (methyl,-sodium), flurenol, fluridone, fluroxypyr, the phonetic alcohol of fluorine, flurtamone, reach careless fluorine, thiazole oxamide, fomesafen, grass ammonium phosphine, glyphosate isopropyl amine salt, fluorine nitre sulfonamide, the spirit of fluorine pyrrole second standing grain, haloxyfop-methyl, hexazinone, miaow grass ester, Imazamethapyr, imazamox, Imazapic, imidazoles nicotinic acid, imazaquin, imazethapyr, the miaow pyrazosulfuron, Iodosulfuron (methyl, sodium), ioxynil, isopropalin, isoproturon, isouron Yi Evil grass amine, Isoxachlortole Yi Evil fluorine grass, isoxapyrifop, lactofen, lenacil, lorox, 2 first, 4 chlorine, Thistrol, mefenacet, Mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (α-) isopropyl methoxalamine, metosulam, metoxuron, the piperazine humulone, metsulfuron-methyl, molinate, afesin, naproanilide, napropamide, neburea, nicosulfuron, norflurazon, orbencarb, oryzalin Que Bing oxazole grass, Lonster, encircle the grand Lv oxazine grass of the third oxygen sulphur, Oxyfluorfen, paraquat, n-nonanoic acid, pendimethalin, Pendralin Wu oxazole grass, phenmedipham, Picolinafon, piperophos, the third careless amine, primisulfuronmethyl, prometryn, propachlor, Stam F-34, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, the fluorine carfentrazone, pyrazolate, pyrazosulfuron, pyrazoxyfen, Pyribenzoxim, pyributicarb, pyridate, oxime pyridine grass, pyrithiobac-sodium, dichloro quinolinic acid, quinmerac, quinoclamine, Quizalotop-ethyl, quinoline standing grain sugar ester, rimsulfuron, sethoxydim, Simanex, symetryne, the sulphur humulone, sulfentrazone, sulfometuronmethyl, grass sulphur phosphorus, lead ethyl xanthate is yellow grand, tebutam, tebuthiuron, Tepraloxydim, Garagard, terbutryn, P DimethenamidP, Thiafluamide, thrizopyr, thiadiazoles amine, thifensulfuronmethyl, benthiocarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron-methyl, trichlopyr, tridiphane, trefanocide, Trifloxysulfuron, triflusulfuronmethyl and Tritosulfuron.
With other known activity compound such as fungicide, insecticide, miticide, nematocide, bird repellent, the mixture of plant nutrient agent and soil structure conditioner also are possible.
Reactive compound of the present invention can itself or its dosage form, or the application form of further dilution preparation uses, as now using solution, suspension, emulsion, pulvis, paste or granule.Can use above-mentioned preparation in a usual manner, for example sprinkle and water, spraying, atomizing or dispersion.
Can use reactive compound of the present invention before plantling or behind the seedling.Also can prior to seeding reactive compound be sneaked into soil.
The amount of the reactive compound that uses can change in quite wide scope.This mainly determines according to the character of required effect.Usually, consumption is that per hectare table soil is used 1g to 10kg reactive compound, preferred per hectare 5g to 5kg reactive compound.
The preparation of reactive compound of the present invention and application can be referring to following embodiment.
Preparation embodiment:
Embodiment 1
N-cyano group-thiol acetimidic acid methyl esters of 2.0g (20mmol) is added in the mixture that is formed by 2.0g (20mmol) 1-(3-thienyl)-ethamine (racemic) and 60ml methyl alcohol, and with reactant mixture (about 20 ℃) stirring at room temperature 15 hours.Under reduced pressure, solvent is distilled carefully then.
Obtain amorphous residue thus, N '-cyano group-N-[1-(3-thienyl)-ethyl of 3.9g (theoretical value 100%)]-ethyleneimine acid amides (racemic), refractive index is n
20 D=1.5572.
Embodiment 2
With 2.0g (20mmol) 1-(3-thienyl)-ethamine (racemic), the mixture of 2.7g (20mmol) S-methyl-N-nitro-isothiourea and 80ml ethanol heated 8 hours under reflux temperature.After the cooling, obtain the crystalloid product by the vacuumizing filtration separation.
Obtain N '-nitro-N-[1-(3-thienyl)-ethyl of 3.1g (theoretical value 72%) thus]-guanidine (racemate), fusing point is 167 ℃.
Embodiment 3
With 3.4g (20mmol) S-[1-ethyl-3-(2-thienyl)-propyl group]-amine, the mixture of 2.9g (20mmol) N-cyano group-dithiocarbonimide dimethyl phthalate and 50ml acetonitrile heated 2 hours under reflux temperature.After the cooling, mixture is vibrated with carrene then with the dilution of 80ml water.Isolate organic facies, with dried over sodium sulfate and filtration.Water pump vacuumizes concentrated filtrate under the condition, floods residue with benzinum, and the vacuumizing filtration separation obtains the crystalloid product.
Obtain 2-((3S)-3-{[(cyanoimino)-(methyl sulfane base (sulfanyl))-methyl of 4.2g (theoretical value 78%) thus]-amino }-amyl group)-thiophene, fusing point is 104 ℃.
Embodiment 4
With 1.7g (10mmol) 1-ethyl-3-(2-thienyl)-propyl group-amine (racemic), 1.2g (10mmol) (dimethoxy methene amido)-(nitrilo-)-methane and 60ml methanol mixture stirred 18 hours down in room temperature (about 20 ℃).Under reduced pressure, solvent is distilled carefully then.
Obtain amorphous residue thus, 2-(3-{[(cyanoimino)-(methoxyl group)-methyl of 2.4g (theoretical value 96%)]-amino }-amyl group)-thiophene (racemate), refractive index is n
20 D=1.5400.
Be similar to embodiment 1-4, and the general description of method produced according to the present invention, listed general formula (I) compound in all right preparation example such as the following table 1.
Table 1: general formula (I) examples for compounds.
The logP value that provides in the table 1 is to use reversed-phase column (C18) according to EEC Directive79/831 Annex V.A8 method by HPLC (high performance liquid chromatography), temperature: determine under 43 ℃ of conditions.
(a) flowing phase that under acid condition, is used to measure: 0.1% phosphate aqueous solution, acetonitrile; The linear gradient of 10% acetonitrile to 90% acetonitrile-corresponding measurement result with
A)Mark is listed in the table 1.
(b) flowing phase that under neutrallty condition, is used to measure: 0.01 mole of phosphoric acid salt buffer, acetonitrile; The linear gradient of 10% acetonitrile to 90% acetonitrile-corresponding measurement result
B)Mark is listed in the table 1.
Use the unbranched alkane-2-ketone (3-16 carbon atom) of known logP value to calibrate (retention time by the linear interpolation between two continuous alkane ketones is measured the logP value).
Use the UV spectrum of 200-400nm in the chromatographic signal maximum, to determine the λ maximum.General formula (II) starting material:
Embodiment (II-1)
Step 1
At 140 ℃-160 ℃, under stirring 150ml formic acid is dropwise joined in the mixture of 100g (0.79mol) 2-acetyl group-thiophene and 300ml formamide, reactant mixture was stirred 2 hours at 160 ℃.After being cooled to room temperature, with the about twice of mixture diluted to initial volume, wash twice with toluene with water, dried over sodium sulfate is also filtered.Vacuumize at water pump and from filtrate, to distill solvent under the condition carefully.
Obtain amorphous residue thus, N-(1-thiophene-2-base-ethyl)-formamide (racemic) of 78g (theoretical value 64%).
Step 2
With N-(1-thiophene-2-base-ethyl)-formamide of 75g (0.48mol), the mixture of 120ml concentrated hydrochloric acid and 50ml water under refluxad heated 3 hours, vacuumized concentrated then by water pump.The vibration of residue water/carrene transfers to alkalescence with water and vibrates with toluene with the 2N sodium hydrate aqueous solution.Dried over sodium sulfate toluene also filters mutually.Filtrate is carried out decompression distillation and is handled.
Obtain 1-(thiophene-2-yl)-ethamine (racemate) of 24.8g (theoretical value 41%) thus, boiling point is 40 ℃ under the 0.8mbar.
Embodiment (II-2)
With 160g (1.25mol) 1-(thiophene-2-yl)-ethamine (racemate), the 140g methoxy menthyl acetate, the mixture that 15g Novenzym-435 and 1 liter of methyl tertiary butyl ether(MTBE) form stirred 24 hours, and then added 5g Novenzym-435, stirred 24 hours under 60 ℃ again.Then mixture is filtered, vacuumize concentrated filtrate by water pump, and residue is dissolved in the 500ml carrene, and vibrate with 1 liter of 10% aqueous hydrochloric acid solution.Isolate organic facies and as described below the processing.Add concentrated sodium hydroxide aqueous solution adjusting water and be alkalescence, and use dichloromethane extraction.With dried over sodium sulfate organic extract liquid and filtration.By decompression distillation by separate targets product in the filtrate.
Obtain S-1-(2-thienyl)-ethamine of 35.5g (theoretical value 44%) thus, boiling point is 50 ℃ (0.8mbar).
After the above-mentioned reaction in processing procedure isolated organic facies with dried over sodium sulfate and filter.From filtrate, distill solvent under the reduced pressure carefully.Obtain solid residue thus, R-(N-methoxyl group acetyl group)-1-(2-thienyl)-ethamine of 100g (theoretical value 84%), fusing point is about 30 ℃.
The R-of 60g (0.30mol) (N-methoxyl group acetyl group)-1-(2-thienyl)-ethamine and 200ml water and 200ml concentrated hydrochloric acid reflux and heated 8 hours down.After the cooling, with diethyl ether extracting said mixture, and by decompression distillation processing organic facies.
Obtain R-1-(2-thienyl)-ethamine of 28.5g (theoretical value 75%) thus, boiling point is 55 ℃ (2mbar).
Embodiment (II-3)
With N-(1-methyl-4-(thiophene-2-yl)-butyl)-formamide of 9.8g (50mmol), the mixture that 100ml concentrated hydrochloric acid and 40ml water form refluxes and heated 90 minutes down.Then mixture is vacuumized by water pump and fully concentrate and stir with ether and residue.Decant falls the ether phase, and vacuumizes by water pump to distill solvent carefully from residue.
Obtain dark oil thus, 2-amino-5-(thiophene-2-yl)-pentane hydrochloride of 8.5g (theoretical value 83%).
Be similar to example II-1 to II-3, listed general formula (II) compound in all right preparation example such as the following table 2.
Table 2: general formula (II) examples for compounds.
Application Example:
Embodiment A
Seedling pre-treatment test
Solvent: 5 weight portion acetone
Emulsifier: 1 weight portion alkaryl polyglycol ether
For preparing suitable active agent preparations, with the solvent of 1 weight portion reactive compound and above-mentioned amount, and the emulsifier that adds above-mentioned amount is diluted with water to desired concn with concentrate then.
With the planting seed of test plants in normal soil.After about 24 hours, with active agent preparations spraying soil so that can use required a certain amount of reactive compound on the per unit area under every kind of situation.Select spray liquid concentration so that under every kind of situation required a certain amount of reactive compound use with per hectare 1000 premium on currency.
After three weeks, compare the extent of injury of estimating plant with the developmental state of untreated control, with % injury expression.
Following numeral:
0%=does not have effect (being similar to untreated control)
100%=all kills
In above-mentioned test, the compound that for example prepares embodiment 5 and 18 shows very strong activity of weeding, and some crops for example corn, soybean and wheat have good tolerance to these compounds.
Embodiment B
Seedling post processing test
Solvent: 5 weight portion acetone
Emulsifier: 1 weight portion alkaryl polyglycol ether
For preparing suitable active agent preparations, with the solvent of 1 weight portion reactive compound and above-mentioned amount, and the emulsifier that adds above-mentioned amount is diluted with water to desired concn with concentrate then.
To grow to the high test plants of 5-15cm with active agent preparations spraying so that can use required a certain amount of reactive compound on the per unit area under every kind of situation.Select spray liquid concentration so that under every kind of situation required a certain amount of reactive compound use with 1000 premium on currency/hectares.
After three weeks, compare the extent of injury of estimating plant with the developmental state of untreated control, with % injury expression.
Following numeral:
0%=does not have effect (being similar to untreated control)
100%=all kills
In above-mentioned test, the compound that for example prepares embodiment 5 and 44 shows very strong activity of weeding, and some crops for example barley, corn and wheat have good tolerance to these compounds.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19919790A DE19919790A1 (en) | 1999-04-30 | 1999-04-30 | Use of N-substituted heterocyclyalkylamines as herbicides and new N-substituted thienylaklylamines |
| DE19919790.3 | 1999-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1349382A true CN1349382A (en) | 2002-05-15 |
Family
ID=7906473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00807002A Pending CN1349382A (en) | 1999-04-30 | 2000-04-18 | Use of N-substituted heterocycloalkylamines as herbicides, and novel N-substituted thienylamines |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1198172A1 (en) |
| JP (1) | JP2002543099A (en) |
| KR (1) | KR20020008830A (en) |
| CN (1) | CN1349382A (en) |
| AU (1) | AU761304B2 (en) |
| BR (1) | BR0010686A (en) |
| CA (1) | CA2372031A1 (en) |
| DE (1) | DE19919790A1 (en) |
| HK (1) | HK1043916A1 (en) |
| MX (1) | MXPA01011007A (en) |
| PL (1) | PL351589A1 (en) |
| WO (1) | WO2000065916A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10303883A1 (en) * | 2003-01-31 | 2004-08-12 | Bayer Cropscience Ag | Substituted pyrimidines |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639268A (en) * | 1985-07-29 | 1987-01-27 | American Cyanamid Company | Nitro- and cyanoguanidines as selective preemergence herbicides and plant defoliants |
| ATE266631T1 (en) * | 1998-07-18 | 2004-05-15 | Bayer Cropscience Ag | IMIDAMIDE DERIVATIVES |
-
1999
- 1999-04-30 DE DE19919790A patent/DE19919790A1/en not_active Withdrawn
-
2000
- 2000-04-18 HK HK02105506.4A patent/HK1043916A1/en unknown
- 2000-04-18 CN CN00807002A patent/CN1349382A/en active Pending
- 2000-04-18 JP JP2000614812A patent/JP2002543099A/en active Pending
- 2000-04-18 EP EP00929377A patent/EP1198172A1/en not_active Withdrawn
- 2000-04-18 MX MXPA01011007A patent/MXPA01011007A/en unknown
- 2000-04-18 KR KR1020017012958A patent/KR20020008830A/en not_active Withdrawn
- 2000-04-18 PL PL00351589A patent/PL351589A1/en not_active Application Discontinuation
- 2000-04-18 AU AU47490/00A patent/AU761304B2/en not_active Ceased
- 2000-04-18 CA CA002372031A patent/CA2372031A1/en not_active Abandoned
- 2000-04-18 WO PCT/EP2000/003496 patent/WO2000065916A1/en not_active Ceased
- 2000-04-18 BR BR0010686-0A patent/BR0010686A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU4749000A (en) | 2000-11-17 |
| AU761304B2 (en) | 2003-06-05 |
| BR0010686A (en) | 2002-02-05 |
| EP1198172A1 (en) | 2002-04-24 |
| MXPA01011007A (en) | 2002-07-22 |
| KR20020008830A (en) | 2002-01-31 |
| DE19919790A1 (en) | 2000-11-02 |
| HK1043916A1 (en) | 2002-10-04 |
| CA2372031A1 (en) | 2000-11-09 |
| WO2000065916A1 (en) | 2000-11-09 |
| PL351589A1 (en) | 2003-05-05 |
| JP2002543099A (en) | 2002-12-17 |
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