CN1168668A - Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur - Google Patents

Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur Download PDF

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CN1168668A
CN1168668A CN 95196565 CN95196565A CN1168668A CN 1168668 A CN1168668 A CN 1168668A CN 95196565 CN95196565 CN 95196565 CN 95196565 A CN95196565 A CN 95196565A CN 1168668 A CN1168668 A CN 1168668A
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fluorine
chlorine
alkoxy
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K·H·穆勒
K·柯尼希
H·J·沙图尔
M·多林格
K·斯滕策尔
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

New sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur have the formula (I), in which n equals 0, 1 or 2; R<1> stands for hydrogen or an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl, aralkyl; R<2> stands for an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl; and R<3> stands for an optionally substituted rest from the group alkyl, aralkyl, aryl, heteroaryl. Certain nine compounds having the formula (I) but already disclosed in EP-A 431291, are excluded. Also disclosed are salts of the new compounds having the formula (I), several processes and various new intermediate products for preparing the new compounds and their use - possibly as salts - as herbicides and fungicides.

Description

Pass through oxygen and the sulfonyl-amino-carbnyl triazolinone of sulphur combination substituent
Pass through oxygen and the sulfonyl-amino-carbnyl triazolinone of sulphur combination substituent, its several method and a variety of intermediates for preparing, and its purposes as herbicide and bactericide the present invention relates to new.
Some known sulfonyl-amino-carbnyl triazolinones have an activity of weeding, such as compound 4- amino -5- methyl mercaptos -2- (2- trifluoromethoxies-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone (referring to：EP-A 341489；EP-A 422469；EP-A 425948；EP-A431291).Had been disclosed in a latter piece in above-mentioned document some by the sulfonyl-amino-carbnyl triazolinone of oxygen and sulphur combination substituent (referring to：Following compounds abandoned).But, the activity of above-mentioned formerly known compound can not be satisfactory in all respects.
It has been found that the salt of the new sulfonyl-amino-carbnyl triazolinone and formula (I) compound by oxygen and sulphur combination substituent of logical formula (I)
Figure A9519656500151
Wherein n is 0,1 or 2, R1The optional substituted substituent included for hydrogen or the following group：Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl and aralkyl, R2The optional substituted substituent included for the following group：Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, cycloalkyl-alkyl, aralkyl and aryl, and R3The optional substituted substituent included for the following group：Alkyl, aralkyl, aryl and heteroaryl, and by abandoning excluding published following compounds in EP-A431291：4- methoxyl group -5- methyl mercaptos -2- (2- methoxycarbonvl-phenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- ethylmercapto groups -2- [2- (N- methoxyl groups)-methylaminosulfonyl-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- propoxyl group -5- allyl sulfenyls -2- (2- methylphenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- methoxyl group -5- methyl mercaptos -2- (2- methoxycarbonyls-thiene-3-yl-sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- methyl mercaptos -2- (2- methoxyl groups-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- ethylmercapto groups -2- [2- (the chloro- ethyoxyls of 2-)-phenyl sulfonyl-amino carbonyl] -2,4- dihydros -3H-1,2,4- triazole -3- ketone 4- allyloxy -5- ethylmercapto groups -2- (2- fluoro-phenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- methoxyl group -5- ethylmercapto groups -2- (3- amino-sulfonyls-pyridine -2- bases-sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone and 4- methoxyl group -5- ethylmercapto groups -2- (2,6- difluorophenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone.
The new preparation by oxygen and the sulfonyl-amino-carbnyl triazolinone of sulphur combination substituent of logical formula (I) is selectively in the presence of reaction promoter and selectable in the presence of diluent by (a), leads to the Triazolinones of formula (II) and is reacted with the sulfonylisocyanates of logical formula (III)
Figure A9519656500161
Wherein n, R1And R2It is as defined above,
               R3-SO2- N=C=O (IU) wherein R3For above-mentioned definition or selectively in the presence of acid acceptor and selectable in the presence of diluent by (b), the sulphonyl ammonia of the triazolinones derivative and logical formula (V) of leading to formula (IV) reacts
Figure A9519656500171
Wherein n, R1And R2As defined above, Z is halogen, alkoxy, aralkoxy or aryloxy group
R3-SO2-NH2(V) wherein R3It is for above-mentioned definition or selectively in the presence of acid acceptor and selectable in the presence of diluent by (c), lead to the Triazolinones of formula (II) and reacted with the sulphonic-acid-amide derivative of logical formula (VI)Wherein n, R1And R2It is as defined above,
R3-SO2- NH-CO-Z (VI) wherein R3For above-mentioned definition Z be halogen, alkoxy, aralkoxy or aryloxy group or by (d) selectively in the presence of reaction promoter and selectively in the presence of diluent, the Triazolinones of logical formula (II) and the sulfonic acid halide of logical formula (VII), and with the metal cyanate reactant salt of logical formula (VIII)Wherein n, R1And R2It is as defined above,
                 R3-SO2- X (VII) wherein R3It is halogen for above-mentioned definition X,
MOCN (VIII) wherein M is the alkaline-earth metal of alkali metal or equivalence,
And formula (I) compound prepared by method (a), (b), (c) or (d) can selectively be changed into by salt by conventional method.
If the R in formula (I), (II) and (IV) noval chemical compound2It is propargyl, by using alkali process, can be isomerizated into as wherein R2For allene (=propyl- 1,2- dialkylenes) respective compound (referring to：Prepare embodiment).
The new sulfonyl-amino-carbnyl triazolinone by oxygen and sulphur combination substituent of logical formula (I) is that it has weeding and Fungicidally active on one side.
Surprisingly; the noval chemical compound of formula (I) the known in the art representation compound similar than structure; for example; known 4- amino -5- methyl mercaptos -2- (2- trifluoromethoxies-phenyl sulfonyl-amino carbonyl) -2; 4- dihydros -3H-1; 2,4- triazole -3- ketone have relatively strong activity of weeding.
It is 0,1 or 2, R present invention advantageously provides formula (I) compound wherein n1For hydrogen, by fluorine, chlorine, bromine, cyano group, C1-C4Alkoxy, C1-C4- alkyl-carbonyl or C1-C4The C of substitution may be selected in-alkoxy-carbonyl1-C6Alkyl, the C that substitution each may be selected by fluorine, chlorine and/or bromine2-C6- alkenyl or C2-C6Alkynyl group, each can be by fluorine, chlorine, bromine and/or C1-C4The C of substitution may be selected in alkyl3-C6Cycloalkyl or C5-C6Cycloalkenyl group each can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy and/or C1-C4The phenyl or phenyl-C of substitution may be selected in-alkoxy-carbonyl1-C3- alkyl, R2For by fluorine, chlorine, bromine, cyano group, C3-C6- cycloalkyl, C1-C4Alkoxy, C1-C4Alkylthio group or C1-C4The C of substitution may be selected in-alkoxy-carbonyl1-C6Alkyl, the C that substitution each may be selected by fluorine, chlorine and/or bromine2-C6- alkenyl or C2-C6Alkynyl group, each can be by fluorine, chlorine, bromine and/or C1-C4The C of substitution may be selected in alkyl3-C6Cycloalkyl, C5-C6Cycloalkenyl group or C3-C6- cycloalkyl-C1-C3- alkyl, can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy and/or C1-C4Phenyl-the C of substitution may be selected in-alkoxy-carbonyl1-C3- alkyl each can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy, fluoro- and/or chloro- substituted C1-C3- alkoxy, C1-C4- alkylthio group, fluoro- and/or chloro- substituted C1-C3- alkylthio group, C1-C4- alkyl-sulfinyl, C1-C4- alkyl sulphonyl and/or C1-C4The phenyl of substitution, R may be selected in-alkoxy-carbonyl3For group
Figure A9519656500191
Wherein
R4And R5It is identical or different and for hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-C6(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkyl1-C4- alkoxy carbonyl group, C1-C4- alkylamino-carbonyl, two-(C1-C4- alkyl) amino-carbonyl, hydroxyl, C1-C4- alkoxy, formyloxy, C1-C4- alkyl-carbonyloxy group, C1-C4- alkoxy-carbonyloxy group, C1-C4- alkyl amino-carbonyloxy group, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl, C1-C4- alkyl sulphonyl, two-(C1-C4- alkyl)-amino-sulfonyl, C3-C6Substitution may be selected in-cycloalkyl or phenyl), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, C for-alkenyl1-C4Substitution may be selected in-alkoxy-carbonyl, carboxyl or phenyl), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, C for-alkynyl group1-C4Substitution may be selected in-alkoxy-carbonyl, carboxyl or phenyl), C1-C4(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkoxy1-C4- alkoxy-carbonyl, C1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl may be selected substitution), C1-C4(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkylthio group1-C4- alkoxy-carbonyl, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl may be selected substitution), C2-C6(it can be by fluorine, chlorine, bromine, cyano group or C for-alkenyloxy1-C4- alkoxy-carbonyl may be selected substitution), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, nitro, C for-alkenyl thio1-C3- alkylthio group or C1-C4- alkoxy carbonyl may be selected substitution), C3-C6- chain oxy-acetylene, C3-C6- sulfur-based chain acetylene or group S (O)p-R6, wherein
P is 1 or 2 Hes
R6For C1-C4(it can be by fluorine, chlorine, bromine, cyano group or C for-alkyl1-C4- alkoxy-carbonyl may be selected substitution), C3-C6- alkenyl, C3-C6- alkynyl group, C1-C4- alkoxy, C1-C4- alkoxy -C1-C4- alkylamino, C1-C4- alkylamino, two-(C1-C4- alkyl)-amino, phenyl or group-NHOR7, wherein
R7For C1-C12(it can be by fluorine, chlorine, cyano group, C for-alkyl1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl, C1-C4- alkyl sulphonyl, C1-C4- alkyl-carbonyl, C1-C4- alkoxy-carbonyl, C1-C4- alkylamino-carbonyl or two-(C1-C4- alkyl)-amino-carbonyl may be selected substitution), C3-C6- alkenyl (substitution can may be selected by fluorine, chlorine or bromine in it), C3-C6- alkynyl group, C3-C6- cycloalkyl, C3-C6- cycloalkyl-C1-C2- alkyl, phenyl-C1-C2(it can be by fluorine, chlorine, nitro, cyano group, C for-alkyl1-C4- alkyl, C1-C4- alkoxy or C1-C4Substitution may be selected in-alkoxy-carbonyl), (it can be by fluorine, chlorine, nitro, cyano group, C for benzhydryl or phenyl1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy, C1-C2- Fluoroalkyloxy, C1-C4- alkylthio group, trifluoromethylthio or C1-C4Substitution may be selected in-alkoxy-carbonyl), R4And/or R5Also it is phenyl or phenoxy group, C1-C4- alkyl-carbonylamino, C1-C4- alkoxy-carbonyl amino, C1-C4- alkylamino-carbonyl-amino, two-(C1-C4- alkyl)-amino-carbonyl amino or group-CO-R8, wherein
R8For hydrogen, C1-C6- alkyl, C3-C6- cycloalkyl, C1-C6- alkoxy, C3-C6- cycloalkyloxy, C3-C6- alkenyloxy, C1-C4- alkylthio group, C1-C4- alkyl amino, C1-C4- alkoxy amino, C1-C4- alkoxy -C1-C4- alkyl amino or two-(C1-C4- alkyl)-amino (substitution can may be selected by fluorine and/or chlorine in it), or R4And/or R5Also it is trimethyl silyl, thiazolinyl, C1-C4- alkylsulfonyloxy, two-(C1-C4- alkyl)-aminosulfonyl amino or group
- CH=N-R9, wherein
R9For by fluorine, chlorine, cyano group, carboxyl, C1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4The C of substitution may be selected in-alkyl sulphonyl1-C6- alkyl, the benzyl of substitution may be selected by fluorine or chlorine, the C of substitution each may be selected by fluorine or chlorine3-C6- alkenyl or C3-C6- alkynyl group, can be by fluorine, chlorine, bromine, C1-C4- alkyl, C1-C4- alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio may be selected the phenyl of substitution, the C of substitution can each be may be selected by fluorine and/or chlorine1-C6- alkoxy, C3-C6- alkenyloxy, C3-C6- chain oxy-acetylene or benzyloxy, amino, C1-C4- alkyl amino, two-(C1-C4- alkyl)-amino, phenyl amino, C1-C4- alkyl-carbonylamino, C1-C4- alkoxy-carbonyl amino, C1-C4- alkyl sulfonyl-amino or the phenylsulfonyl-amido or R that substitution can be may be selected by fluorine, chlorine, bromine or methyl3For group
Figure A9519656500211
Wherein
R10For hydrogen or C1-C4- alkyl and
R11And R12It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), carboxyl, C1-C4- alkoxy carbonyl, Dimethylaminocarbonyl, C1-C4- alkyl sulphonyl or two-(C1-C4- alkyl) amino-sulfonyl, or R3For group
Figure A9519656500221
Wherein
R13And R14It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it) or C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), or R3For group
Wherein
R15And R16It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it), amino-sulfonyl, list-(C1-C4- alkyl)-amino-sulfonyl, two-(C1-C4- alkyl)-amino-sulfonyl, C1-C4- alkoxy-carbonyl or Dimethylaminocarbonyl or R3For group
Wherein
R17And R18It is identical or different and for hydrogen, fluorine, chlorine, bromine, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it) or two-(C1-C4- alkyl)-amino-sulfonyl, or R3For group
Figure A9519656500231
Wherein
R19And R20It is identical or different and for hydrogen, fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it), two-(C1-C4- alkyl)-amino-sulfonyl, C1-C4- alkoxy-carbonyl or Dimethylaminocarbonyl, and A are oxygen, sulphur or group N-Z1, wherein
Z1For hydrogen, C1-C4- alkyl (substitution can may be selected by fluorine, chlorine, bromine or cyano group in it), C3-C6- cycloalkyl, benzyl, phenyl (substitution can may be selected by fluorine, chlorine, bromine or nitro in it), C1-C4- alkyl-carbonyl, C1-C4- alkoxy carbonyl or two-(C1-C4- alkyl)-amino carbonyl, or R3For group
Figure A9519656500232
Wherein
R21And R22It is identical or different and for hydrogen, C1-C4- alkyl, halogen, C1-C4- alkoxy carbonyl, C1-C4- alkoxy or C1-C4- halogenated alkoxy, and
Y1For sulphur or group N-R23, wherein
R23For hydrogen or C1-C4- alkyl, or R3For group
Wherein
R24For hydrogen, C1-C4- alkyl, benzyl, pyridine radicals, quinolyl or benzyl,
R25For hydrogen, halogen, cyano group, nitro, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), dioxolanyl or C1-C4- alkoxy-carbonyl, and
R26For hydrogen, halogen or C1-C4- alkyl, or R3For following radicals：
Figure A9519656500242
Except the above-mentioned compound for abandoning excluding.
The present invention preferably provides the sodium, potassium, magnesium, calcium, ammonium, C of formula (I) compound1-C4- alkyl-ammonium, two-(C1-C4- alkyl)-ammonium, three-(C1-C4- alkyl)-ammonium, four-(C1-C4- alkyl)-ammonium, three-(C1-C4- alkyl)-sulfonium, C5Or C6- cycloalkyl-ammonium and two-(C1-C2- alkyl)-benzyl-ammonium salt, wherein n, R1、R2And R3For the above-mentioned definition provided.
Invention especially provides formula (I) compound, wherein n is 0,1 or 2, R1For each can by fluorine, chlorine, cyano group, methoxy or ethoxy may be selected substitution methyl, ethyl, n- or i-propyl or the N-, iso-, sec- or tert-butyl group, each can by fluorine, chlorine or bromine may be selected substitution acrylic, cyclobutenyl, propinyl or butynyl, each can by fluorine, chlorine, bromine, methyl or ethyl may be selected substitution cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl, each can by fluorine, chlorine, bromine, cyano group, methyl, trifluoromethyl or methoxyl group may be selected substitution benzyl or phenyl, R2For each can be by fluorine, chlorine, cyano group, methoxyl group, ethyoxyl, the methyl of substitution may be selected in methyl mercapto or ethylmercapto group, ethyl, n- or i-propyl is n-, it is iso-, sec- or the tert-butyl group, each can be by fluorine, chlorine, or the acrylic of substitution may be selected in bromine, cyclobutenyl, propinyl, butynyl or pi-allyl, each can be by fluorine, chlorine, bromine, the cyclopropyl of substitution may be selected in methyl or ethyl, cyclobutyl, cyclopenta, cyclohexyl, Cvclopropvlmethvl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl, each can be by fluorine, chlorine, bromine, cyano group, methyl, the benzyl or phenyl of substitution may be selected in trifluoromethyl or methoxyl group, and R3For group
Wherein
R4For fluorine, chlorine, bromine, methyl, ethyl, propyl group, trifluoromethyl, butoxy, allyloxy, propynyloxy base, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, difluoro-methoxy, trifluoromethoxy, the chloro- ethyoxyls of 2-, 2- Mehtoxy-ethoxies, C1-C3- alkylthio group, C1-C3- alkyl sulphinyl, C1-C3- alkyl sulphonyl, dimethylamino-sulfonyl, diethylamino sulfonyl, N- methoxy-. N-methyls amino-sulfonyl, Methoxyamino sulfonyl, phenyl, phenoxy group or C1-C3- alkoxy carbonyl group, and
R5For hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R3For group
Figure A9519656500252
Wherein R10For hydrogen
R11For fluorine, chlorine, bromine, methyl, methoxyl group, difluoro-methoxy, trifluoromethoxy, ethyoxyl, methoxycarbonyl group, carbethoxyl group, methyl sulphonyl or dimethylamino-sulfonyl, and
R12For hydrogen, or R3For group
Figure A9519656500261
Wherein R is C1-C4- alkyl or R3For group
Figure A9519656500262
Wherein
R24For C1-C3- alkyl, phenyl or pyridine radicals,
R25For hydrogen, fluorine, chlorine or bromine and
R26For fluorine, chlorine, bromine or C1-C3Except-alkoxy carbonyl, the above-mentioned compound for abandoning excluding.
The above-mentioned total or preferred group definition listed is applied to the end-product of formula (I) and the corresponding starting material or intermediate of its preparation.These group definitions can be engaged one another while, including the combination between the preferred definition.
The alkyl addressed in group definition, such as alkyl, alkenyl or alkynyl group, and its group combined to form with hetero atom, such as alkoxy, alkylthio group or alkylamino, are straight or brancheds, when not representing directly also in this way.
Halogen is usually fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly fluorine or chlorine.
If for example, 2- trifluoromethoxies-phenylsulphonylisocyanate and 4- methoxyl group -5- rosickyite base -2,4- dihydros -3H-1,2,4- triazole -3- ketone are used as starting material, following formula can be generalized into according to the course of reaction of the inventive method (a)：
Figure A9519656500271
If for example, 2- ethylmercapto groups-benzsulfamide and 2- chlorocarbonyl -4- ethyoxyl -5- methyl sulphonyl -2,4- dihydros -3H-1,2,4- triazole -3- ketone are used as starting material, following formula can be generalized into according to the course of reaction of the inventive method (b)：
Figure A9519656500272
If for example, N- methoxycarbonyl groups -2- methoxyl groups-phenyl-sulfamide and 5- ethylsulfinyl -4- propoxyl group -2,4- dihydros -3H-1,2,4- triazole -3- ketone are used as starting material, following formula can be generalized into according to the course of reaction of the inventive method (c)：
If for example, the chloro- 6- methylphenyls sulfonic acid chlorides of 2-, 4- allyloxy -5- benzylthio -2,4- dihydros -3H-1,2,4- triazole -3- ketone and Zassol are used as starting material, following formula can be generalized into according to the course of reaction of the inventive method (d)：
Figure A9519656500274
In the method (a) of formula produced according to the present invention (I) compound, the Triazolinones of starting material are used as in (c) and (d) for defined in formula (II).
In formula (II), n, R1And R2Preferred or particularly preferred definition, be described according to relevant preferred or the particularly preferred n, R of formula (I) compound of the present invention1And R2Definition in.
The Triazolinones of logical formula (II) are unknown in document, and they are provided in the present patent application as novel substance.
The preparation of the new Triazolinones of formula (II) is the mercapto-triazole quinoline ketone by formula (II), or the metal salt of formula (IX) compound reacts with the compound of logical formula (X)
Figure A9519656500281
Wherein R1It is as defined above
             X-R2    (X)R2It is halogen or-O-SO for above-mentioned definition and X2-OR2,
Reaction is selectively in acid acceptor, such as potassium hydroxide, in the presence of potassium tert-butoxide or potassium carbonate, selectively in diluent, for example in the presence of methanol or ethanol, carried out at a temperature of 0 DEG C to 100 DEG C, then selectively oxidation product turns into sulfoxide or sulfone in conventional manner (referring to embodiment is prepared).
In formula (X), R1Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention1Definition in.
Alkali metal salt and alkali salt, particularly sodium, potassium, magnesium and calcium salt, are the metal salts of preferred formula (IX) compound.
It is unknown in the mercapto-triazole quinoline ketone-and its metal salt of logical formula (IX)-be document；Also provided in the application as novel substance.
The preparation of the new mercapto-triazole quinoline ketone of formula (IX) is the semicarbazide derivative by formula (XI)
Figure A9519656500291
Wherein R1As defined above and Y is halogen, imidazole radicals, alkoxy, aralkoxy or aryloxy group,
It is selectable in the presence of the reaction promoter of such as potassium carbonate, and selectable in the presence of the diluent of such as methanol or ethanol, reaction at 20 DEG C to 150 DEG C (referring to embodiment is prepared).
In formula (XI), R1Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention1Definition in；Y is preferably fluorine, chlorine, bromine, iodine, methoxyl group, ethyoxyl, benzyloxy or phenoxy group, particularly methoxyl group or phenoxy group.
The semicarbazide derivative of formula (XI) is unknown in document；Also provided in the application as novel substance.
The preparation of the new semicarbazide derivative of formula (XI) is to be reacted by the semicarbazides of formula (XII) with the acylting agent of formula (XIII)
Figure A9519656500292
Wherein R1For above-mentioned definition
          X1- CS-Y (XIII) wherein Y is above-mentioned definition and X1For halogen
Reaction is selectable in the presence of the acid acceptor of such as triethylamine and selectable in the presence of the diluent of such as dichloromethane, is carried out at a temperature of 0 DEG C to 100 DEG C (referring to embodiment is prepared).
The precursor of formula (XII) is known and/or prepared by known method by prior art (referring to J.Prakt.Chem.313 (1971), 636-641；DE-A2044834；Prepare embodiment).
The precursor of formula (XIII) is known synthesis of chemicals.
The alkylating reagent that preparing the starting material of formula (II) needs has carried out total definition in formula (X).In formula (X), R2Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention2Definition in；X is preferably fluorine, chlorine, bromine or iodine, particularly chlorine, bromine or iodine
The compound of formula (X) is known synthesis of chemicals.
In the method (a) of formula produced according to the present invention (I) compound, total definition of the sulfonylisocyanates as starting material is the definition in formula (III).
In formula (III), R3Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention3Definition in.
The starting material of formula (III) be known and/or prepared by known method of the prior art (referring to：
US-P 4127405, US-P 4169719, US-P 4371391,
EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139,
EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322,
EP-A 70041, EP-A 173312)
In the method (b) of logical formula (I) compound produced according to the present invention, total definition of the triazolinones derivative as starting material is the definition in formula (IV).In formula (IV), n, R1And R2Preferred or particularly preferred definition, be described according to relevant preferred or the particularly preferred n, R of formula (I) compound of the present invention1And R2Definition in；Z is preferably fluorine, chlorine, bromine, methoxyl group, ethyoxyl, benzyloxy, phenoxy group, halo-phenoxy or nitro-phenoxy, particularly methoxyl group, phenoxy group or 4- nitro-phenoxies.
The starting material of formula (IV) is unknown in document；They are provided as novel substance in this application.
The preparation of the noval chemical compound of formula (IV) is reacted by leading to the carbonic acid derivative of the Triazolinones of formula (II) and formula (XIV)
Figure A9519656500311
Wherein n, R1And R2It is as defined above,
                 Z-CO-Z1(XIV) wherein Z is above-mentioned definition and Z1For halogen, alkoxy, aralkoxy or aryloxy group,
Reaction is selectable in the presence of such as acid acceptor of tert-butyl group potassium and selectable in the presence of the diluent of such as tetrahydrofuran or dimethoxy-ethane, is carried out at a temperature of 0 DEG C to 100 DEG C.
In the method (b) of logical formula (I) compound produced according to the present invention, total definition of the sulfonamide as starting material is the definition in formula (V).In formula (V), R3Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention3Definition in.
The starting material of formula (V) be it is known and/or be prepared by known methods (referring to：
US-P 4127405, US-P 4169719, US-P 4371391,
EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139,
EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322,
EP-A 70041, EP-A 173312)
In the method (c) of logical formula (I) compound produced according to the present invention, total definition of the sulfamide derivative as starting material is the definition in formula (VI).In formula (VI), R3Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention3Definition in；Z is preferably fluorine, chlorine, bromine, methoxyl group, ethyoxyl, benzyloxy or phenoxy group, particularly methoxyl group or phenoxy group.
The starting material of formula (VI) is known and/or can prepared by known method of the prior art.
In the method (d) of logical formula (I) compound produced according to the present invention, total definition of the sulfonic acid halide as starting material is the definition in formula (VII).In formula (VII), R3Preferred or particularly preferred definition, be described according to the relevant preferred or particularly preferred R of formula (I) compound of the present invention3Definition in；X is preferably fluorine, chlorine or bromine, particularly chlorine.
The starting material of formula (VII) is known and/or can prepared by known method of the prior art.
The method (a) of logical formula (I) compound produced according to the present invention, (b), (c) and (d) is preferably carried out under using diluent, and workable diluent is various inert organic solvents in practice.Above-mentioned organic solvent preferably includes that the aliphatic series of halo and aromatic hydrocarbon such as pentane, hexane, heptane, hexamethylene, petroleum ether, volatile oil, ligroin, benzene,toluene,xylene, dichloromethane, dichloroethanes, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorohenzene may be selected, ethers such as ether, butyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, tetrahydrofuran He dioxane, ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK).Esters such as methyl acetate and ethyl acetate, nitrile acetonitrile and propionitrile, amide-type such as dimethylformamide, such as dimethyl acetamide and 1-METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO), sulfolane and hexamethyl phosphoramide.
In the method according to the invention (a), (b), (c) reaction promoter that uses or acid acceptor can be any conventional acid acceptor used in above-mentioned reaction and in (d), suitable preparation be preferably alkali metal hydroxide such as, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxide such as calcium hydroxide, alkali carbonate and alcoholates such as sodium carbonate and potassium carbonate and sodium tert-butoxide and potassium tert-butoxide, and basic nitrogen compound such as Trimethylamine, triethylamine, tripropylamine, tri-butylamine, diisobutyl amine, dicyclohexylamine, ethyl diisopropyl amine, ethyl dicyclohexylamine, N, N- dimethyl benzyl amine, DMA, pyridine, 2- methyl-, 3- methyl, 4- methyl-, 2,4- dimethyl-, 2,6- methyl-, 2- ethyls-, 4- ethyls-and 5- Ethyl-2-Methyls-pyridine, 1,5- diazabicylo [4.3.0.]-nonyl- 5- alkene (DBU), carbon -7- the alkene (DBU) of 1,8- diazabicylo-[5.4.0]-ten one and Isosorbide-5-Nitrae-diazabicylo-[2.2.2]-octane (DABCO).
The method according to the invention (a), (b), the reaction temperature of (c) and (d) can change in comparatively wide scope.Reaction is preferably carried out generally at -20 DEG C to 100 DEG C at a temperature of 0 DEG C to+80 DEG C.
The method according to the invention (a), (b), (c) and (d) is generally carried out at ambient pressure, but they can also be carried out under the pressure for improving or reducing.
In order to carry out the method according to the invention (a), (b), (c) and (d), it usually needs using the appropriate starting material of about equimolar amounts, but, it can also make the considerable excess of a kind of composition therein.Reaction is generally carried out in appropriate diluent, in the presence of acid acceptor, also, reactant mixture can be stirred into a few hours at appropriate required temperature.The method according to the invention (a), (b), the working process (referring to embodiment is prepared) of (c) and (d) are carried out by appropriate conventional method.
It is selectable, it can prepare salt from according to the logical formula (I) compound of the present invention.Above-mentioned salt can be obtained by conventional salinization method, such as by the way that formula (I) compound is dissolved or dispersed in the solvent such as dichloromethane, acetone, t-butyl methyl ether or toluene, and add suitable alkali.Then salt is separated by concentration or suction strainer, if it is desired, separated after long agitation.
According to the active material of the present invention can be used as defoliant, drier, herbicide and particularly herbicide, from broadly understanding that weeds are any plant for being grown in inappropriate place.Whether it is used as going out natural disposition or selective herbicide mainly according to its usage amount according to the material of the present invention.
For example it is may be used on following plants according to the active material of the present invention：Broadleaf weed belongs to：Mustard belongs to, separate row Vegetable spp, Bedstraw, Stellaria, Matricaria, Anthemis, smallflower galinsoga herb belongs to, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, japanese bearbind genus, sweet potato genus, Polygonum, Daubentonia, Ambrosia, Cirsium, bristlethistle, sonchus, Solanum, Lepidium, Chinese deciduous cypress leaf belongs to, Matricaria, lamium, Veronica, fiber crops category, bur belongs to, Datura, Viola, galeopsis, papaver, bachelor's-button, Clover, the blunt category of hair, Dandelion.Dicotyledonous crops belong to：Cotton, soybean, beet, carrot, Kidney bean, pea, eggplant, flax, sweet potato, vetch, tobacco, tomato, peanut, rape, lettuce, cucumber, cucurbit.Monocotyledon weed belongs to：Echinochloa, setaria, Panicum, knotgrass, careless category, Poa L., Festuca, yard grass category, Brachiaria, Lolium, Brome, Avena, Cyperus, sorghum, Agropyron, Cynodon, Monochoria vaginalis category, genus fimbristylis, arrowhead category, comet shepherd's purse category, careless category, Paspalum, Ischaemum, sphenoclea, talon eria, cut that Gu Ying, which belongs to, amur foxtail belongs to, wind is careless belongs to.Monocot crops belongs to：Paddy rice, corn, wheat, barley, oat, rye, sorghum, broomcorn millet, sugarcane, pineapple, asparagus, green onion.
But, it is not limited according to the application of active material of the present invention in above-mentioned category, other plants is may also act in the same way.
According to its concentration, this compound is also suitable for the natural disposition control of weeds that goes out, for example, regardless of whether trees are planted, in industrial area, rail both sides and roadside and other areas.This compound can be additionally used in the control of weeds of perennial crop, such as forest, ornamental crops, orchard, vineyard, mandarin tree, nut, banana, coffee, tea, rubber, oil palm, cocoa and strawberry cultivating garden and hop field, and lawn, sports turf and pasture, this compound can also in annual crop optionally controlling weeds.
According to formula (I) compound of the present invention, no matter in before seedling processing or after seedling processing, the broadleaf weed in monocot crops is particularly suitable for preventing and treating.
Moreover, also there is the interesting fungicidal action to phytopathogenic fungi, particularly scab of apple, and the rice blast on preventing and treating paddy rice to a certain extent according to formula (I) compound of the present invention.
This active material can be converted into conventional preparation, such as liquor, emulsion, wettable powder, suspending agent, pulvis, pulvis subtilis, paste, solvable pulvis, granule, dense suspended emulsion/emulsion, the natural and synthetic material and fine polymer capsule impregnated with reactive compound.
These preparations are produced in a known manner, for example, produced, selectable usable surfactant in preparation by the way that active component and filler, i.e. liquid flux and/or solid carrier are mixed, i.e. emulsifying agent and/or dispersant and/or foam agent.
In the case where using water as filler, for example, it is possible to use organic solvent is used as cosolvent.Appropriate liquid flux mainly has：Arene, such as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatic hydrocarbons class and chloralkane, such as chlorobenzene, dichloroethanes or dichloromethane, fat hydrocarbon, such as hexamethylene or alkane, such as mineral oil fractions, mineral oil and vegetable oil, alcohols, such as butanol or ethylene glycol and its ether and esters, ketone, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone, intensive polar solvent, such as dimethylformamide and dimethyl sulfoxide (DMSO), Yi Jishui.
Appropriate solid carrier has：
For example, ammonium salt and natural minerals powder, such as kaolin, clay, talcum, chalk, quartz, Attagel, montmorillonite or diatomite, and synthetic mineral powder, such as high dispersive silica, aluminum oxide and silicate；Being adapted to the solid carrier of granule has：For example, crush and classification natural rock, such as calcite, marble, float stone, sepiolite and dolomite, and inorganic synthesis particle and organic dust, and organic material particle such as sawdust, shuck, corn ears and stems and tobacco stem；Appropriate emulsifying agent and/or foam agent has：Such as nonionic and anion emulsifier, such as polyoxyethylene fatty acid ester, such as polyoxyethylene aliphatic alcohol ether, alkylaryl polyglycol ether, alkylsulfonate, alkyl sulfate, arylsulphonate and protein hydrolysate；Suitable dispersant has：Such as lignin sulfinic acid waste liquid and methylcellulose.
It it is also possible to use that sticker such as carboxymethyl cellulose and powder, particle or latex shape be natural and synthetic polymer, such as gum arabic, polyvinyl alcohol and polyvinyl acetate in the formulation, and natural phospholipid such as cephalin and lecithin, and synthetic phospholipid.Other stickers can be mineral oil and vegetable oil.
The colouring agent that may be used such as inorganic pigment, such as iron oxide, titanium oxide and Prussian blue, and organic dyestuff, such as alizarin dyes, azo dyes and metallized phthalocyanine dye, and trace nutrients such as metal salt, for example, iron, manganese, boron, copper, cobalt, molybdenum and zinc salt.
0.1%-95% by weight is usually contained in preparation, preferably 0.5%-90% reactive compound by weight.
It can be used, can also be used with the form of mixtures of the herbicide of known controlling weeds, possible composition can be final preparation or bucket mixture with itself or its dosage form according to the reactive compound of the present invention.
Known herbicide, such as phenyl amines such as Diflufenican and propanil can be contained in mixture；Aryl carboxylic acid class such as lontrel, Mediben and picloram；Aryloxy group carboxylic acid such as 2,4- drops, 2,4- Embutoxs, 2,4- drops propionic acid, fixed fluorine grass, MCPA,MCP,methoxone, MCPA,MCP,methoxone propionic acid and triclopyr；Arylphenoxy carboxylate such as diclofop-methyl, fenoxaprop-P, fluazifop, the spirit of pyrrole fluorine second grass and quizalofop-ethyl, azine ketone such as pyrazon and monometflurazone；Carbamates such as chlorpropham, different phenmedipham, enemy's gram grass and Chem hoe；Chloracetophenone amine such as alachlor, acetochlor, butachlor, metazachlor, isopropyl methoxalamine, pretilachlor and propachlor；Dinitroaniline such as Huang disappears grass, pendimethalin and trefanocide；Diphenyl ether such as acifluorfen, bifenox, fluoroglycofen-ethyl, Fomesafen, gram wealthy pleasure, lactofen and Oxyfluorfen；Ureas such as chlorine wheat is grand, diuron, fluometuron, isoproturon, linuron and methabenz thiazuron；Azanol class for example it is withered kill reach, clethodim, cycloxydim, sethoxydim and tralkoxydim；The careless ester of imidazolone type such as Imazethapyr, miaow, Arsenal and Scepter；Phenyl amines such as Brominal, dichlobenil and ioxynil, oxyacetamide such as mefenacet；Sulfonylurea such as amidosulfuron, benzyl ethyl methyl, chlorimuron, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, chlorimuron, pyrazosulfuron, thiophene methyl, triasulfuron and tribenuron-methyl；Thiocarbamates such as butylate, cycloate, Avadex, Eptam, esprocarb, Hydram, prosulfocarb, benthiocarb and tri-allate；Triazines such as Atrazine, bladex, Simanex, symetryne, terbutryn and Garagard；Triazolineone such as Hexazinone, benzene thiophene grass and metribuzin；With other classes of herbicides such as aminotriazole(ATA), benfuresate, bentazone, cinmethlin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, Glufosinate, glyphosate, isoxaben, pyridate, quinclorac, quinoline dogstail, sulphosate and tridiphane.
It can also be mixed according to the active material of the present invention with other known active component, other active components such as fungicide, insecticide, acaricide, nematicide, birds repellent agent, plant nutrient substance and soil conditioner.
This active material can be used with its own or dosage form or by the type of service for further diluting preparation, such as now miscible fluid, suspension, emulsion, pulvis, paste and granule.Above-mentioned preparation can be used in a usual manner, for example, pouring by sprinkling, spraying (large volume or small size administration) or broadcasting sowing.
Plant can be used in the way of before seedling processing or after seedling processing according to the active material of the present invention.They can be also admixed in soil prior to seeding.
The consumption of active material can change in comparatively wide scope.It depends on required type of action.Amount of application is usually per hectare soil surface 10g to 10Kg active component, preferably per hectare 50g to 5Kg.
Following embodiments have listed the preparation and application according to active material of the present invention.Prepare embodiment：Embodiment 1(ten thousand methods (a))
By 1.9g (10mmol) 4- ethyoxyl -5- ethylmercapto group -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 2.7g (11mmol) 2- methoxycarbonvl-phenyls sulfonylisocyanates and 50ml acetonitrile, stirred 16 hours at 20 DEG C.After water spray reduced under vacuum, residue is extracted with ether, and pass through suction strainer fractional crystallization product.Obtain 3.9g (the 91% of theoretical value) 4- ethyoxyl -5- ethylmercapto groups -2- (2- methoxycarbonyl-phenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 162 DEG C of fusing point.Embodiment 2
Figure A9519656500372
(isomerization)
By 2.8g (6mmol) 4- ethyoxyl -5- alkynes rosickyite bases -2- (2- methoxycarbonyl groups phenyl sulfonyl-amino carbonyl) -2; 4- dihydros -3H-1; 2; 4- triazole -3- ketone (8); 50ml dichloromethane; 50ml water, 0.3g (7.5mmol) sodium hydroxide and 50mg Tetrabutylammonium bromide, are stirred 16 hours at 20 DEG C.Then it is acidified with 2N hydrochloric acid, separates organic phase, dried and filtered with magnesium sulfate.Filtrate is concentrated, residue, the separating obtained crystallized product of suction strainer are extracted with ether.Obtain 2.0g (the 71% of theoretical value) 4- ethyoxyls -5- (propyl- 1,2- diene sulphur) -2- (2- methoxycarbonvl-phenyls sulfonyl-amino carbonyl -2,4- dihydro -3H-1,2,4- triazole -3- ketone, 144 DEG C of fusing point.Embodiment 3(method (d))
By 3.2g (20mmol) 4- methoxyl group -5- methyl mercaptos -2; 4- dihydros -3H-1; 2; 4- triazole -3- ketone; 7.6 g (24mmol) 2- (N- methoxy-. N-methyls amino-sulfonyl)-benzene sulfonyl chloride (95%), 2.6g (40mmol) Zassol, 1.2g (15mmol) pyridine; with 50ml acetonitrile, stirred 2 days at 20 DEG C.After water spray reduced under vacuum, residue is absorbed with methylene chloride/water, is adjusted with 2N hydrochloric acid to PH3.Then organic phase is separated, is dried and filtered with sodium sulphate.In water spray reduced under vacuum filtrate, residue is crystallized with methyl alcohol process.
Thus 5.7g (the 61% of theoretical value) 4- methoxyl group -5- methyl mercaptos -2- [2- (N- methoxy-. N-methyls-amino-sulfonyl)-phenyl sulfonyl-amino carbonyl] -2 is obtained; 4- dihydros -3H-1; 2,4- triazole -3- ketone, 185 DEG C of fusing point.
Formula (I) compound being shown in below in table 1 is also to prepare, such as is prepared similar to above-described embodiment and according to total description to preparation method of the present invention.
Figure A9519656500382
Table 1：The preparation EXAMPLE Example n R of formula (I) compound1       R2                      R3The C of physical data 402H5    CH3                       m.p.：179℃     5       0      C2H5    C3H7-n           
Figure A9519656500392
       m.p.：150℃     6       0      C2H5    CH(CH3)2                  m.p.：124C   7       0      C2H5    CH2- CH=CH2              m.p.：142℃     8       0      C2H5    CH2-C≡CH                  m.p.：133℃     9       0      C2H5    CH3                          m.p.：163℃   10      0      C2H5    CH3               
Figure A9519656500397
               m.p.：193℃   11      0      C2H5    CH3                           m.p.：165 DEG C of (Continued) Example No. n R of table 11     R2              R3The C of physical data 12 02H5   CH3         
Figure A9519656500401
            m.p.：188℃   13        0    C2H5   CH3       
Figure A9519656500402
       m.p.：156℃   14        0    C2H5   CH3        
Figure A9519656500403
      m.p.：108℃   15        0    C2H5   CH3      
Figure A9519656500404
           m.p.：140℃   16        0    C2H5   CH3       
Figure A9519656500405
          m.p.：188℃   17        0    C2H5   CH3       
Figure A9519656500406
          m.p.：147℃   18        0    C2H5   CH3      
Figure A9519656500407
             m.p.：134℃   19        0    C2H5   C2H5             m.p.：143 DEG C of (Continued) Example No. n R of table 11      R2            R3The C of physical data 20 02H5   C2H5      
Figure A9519656500411
             m.p.：163℃   21       0    C2H5   C2H5               m.p.：141℃   22       0    C2H5   C2H5       
Figure A9519656500413
       m.p.：92℃   23       0    C2H5   C2H5             m.p.：95℃   24       0    C2H5   C2H5        
Figure A9519656500415
          m.p.：132℃   25       0    C2H5   C2H5                  m.p.：138℃   26       0    C2H5   C2H5                 m.p.：180℃   27       0    C2H5   C2H5                 m.p.：143℃   28       0    CH3      C3H7-n     
Figure A9519656500419
       m.p.：129 DEG C of (Continued) Example No. n R of table 11     R2                    R3The CH of physical data 29 03     CH3      
Figure A9519656500421
            m.p.：159℃   30         0   C2H5   C2H5                           m.p.：157℃   31         0   CH3     CH3                       m.p.：178℃   32         0   CH3     CH3         
Figure A9519656500424
           m.p.：148℃   33         0   CH3     CH3                                m.p.：183℃   34         0   CH3     CH3         
Figure A9519656500426
                    m.p.：185℃   35         0   CH3     CH3                            m.p.：160℃   36         0   CH3     CH3                            m.p.：149℃   37         0   CH3     CH3         
Figure A9519656500429
                 m.p.：175 DEG C of (Continued) Example No. n R of table 11    R2                R3The CH of physical data 38 03   CH3        
Figure A9519656500431
               m.p.：192℃   39       0   CH3   CH3       
Figure A9519656500432
               m.p.：144℃   40       0   CH3   CH3       
Figure A9519656500433
               m.p.：159℃   41       0   CH3   CH3                          m.p.：130℃   42       0   CH3   CH3       
Figure A9519656500435
        m.p.：151℃   43       0   CH3   CH3                           m.p.：168℃   44       0   CH3   CxH7-i     
Figure A9519656500437
            m.p.：156℃   45       0   CH3   CH3        
Figure A9519656500438
                m.p.：170 DEG C of (Continued) Example No. n R of table 11      R2                 R3The CH of physical data 46 03  CH2- CH=CH2  
Figure A9519656500441
         m.p.：126℃   47      0   CH3    C2H5       
Figure A9519656500442
          m.p.：151℃   48      0   CH3    C2H5                 m.p.：129℃   49      0   CH3    C2H5                 m.p.：105℃   50      0   CH3    C2H5                       m.p.：137℃   51      0   CH3    C2H5       
Figure A9519656500446
               m.p.：150℃   52      0   CH3    C2H5       
Figure A9519656500447
             m.p.：135℃   53      0   CH3    C2H5       
Figure A9519656500448
             m.p.：158℃   54      0   CH3    C2H5       
Figure A9519656500449
             m.p.：164 DEG C of (Continued) Example No. n R of table 11     R2                R3The CH of physical data 55 03    C2H5       
Figure A9519656500451
         m.p.：172℃   56      0   CH3    C2H5        
Figure A9519656500452
         m.p.：148℃   57      0   CH3    C2H5                  m.p.：127℃   58      0   CH3    C2H5                    m.p.：124℃   59      0   CH3    C2H5           m.p.：161℃   60      0   CH3    C2H5        
Figure A9519656500456
               m.p.：138℃   61      0   CH3    C2H5        
Figure A9519656500457
               m.p.：124℃   62      0   CH3    C2H5        
Figure A9519656500458
         m.p.：153 DEG C of (Continued) Example No. n R of table 11        R2                    R3The CH of physical data 63 03       CH3              
Figure A9519656500461
          m.p.：146℃    64      0       CH3       CH3              
Figure A9519656500462
                 m.p.：156℃    65      0       CH3       CH2-C≡CH                      m.p.：110℃    66      0       CH3       CH2-CH2-F       
Figure A9519656500464
            m.p.：148℃    
Figure A9519656500465
             
Figure A9519656500466
                           m.p.：130℃      68      0       CH3       CH2-CH2-CI                    m.p.：100℃    69      0       CH3       CH2CI           
Figure A9519656500468
               m.p.：142℃    70      0       CH3       C2H5                          m.p.：153 DEG C of (Continued) Example No. n R of table 11        R2                 R3The CH of physical data 71 03       C2H5                m.p.：124℃     72        0       CH3       C2H5            m.p.：136℃     73        0       CH3       C2H5      
Figure A9519656500473
               m.p.：149℃   74        0     -C(CH3)3    CH3                   m.p.：139℃    75        0     -C(CH3)3    C2H5     
Figure A9519656500475
          m.p.：133 DEG C of preparations by the compound being listed in the embodiment 62 of table 1 list as follows：
Figure A9519656500481
(method b)
By 3.8g (13mmol) 5- ethylmercapto group -4- methoxyl group -2- phenyloxycarbonyls -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 2.9g (13.1mmol) 2- methoxycarbonyl groups-thiophene -3- sulfonamide, 2.0g (13.2mmol) diazabicylo endecatylene (DBU) and 50ml acetonitrile, is stirred 3 days at 20 DEG C.In the mixture for being subsequently poured into dichloromethane and aqueous hydrochloric acid solution (about 10%), and it is sufficiently stirred for.Organic phase is separated, is washed with water, is dried and concentrated.Residue is crystallized from ether.2.0g (the 36.5% of theoretical value) 5- ethylmercapto group -4- methoxyl groups -2- (2- methoxycarbonyl groups-thiene-3-yl-sulfonyl amino carbonyl) -2,4- dihydros -3H-1 is obtained, 2,4- triazole -3- ketone are colourless crystallization, 153 DEG C of fusing point.The preparation of formula (II) starting material：Embodiment (II-1)
Figure A9519656500482
By 4.0g (20mmol) 4- ethyoxyl -5- sulfydryl -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 4.3g (30mmol) methyl iodide and 50ml methanol are stirred 16 hours at 20 DEG C, then concentrated.Residue is absorbed with methylene chloride/water, and separates organic phase, is dried and filtered with magnesium sulfate.Filtrate is concentrated, residue is diluted with ether, the crystallized product obtained is separated by suction strainer.Thus 1.8g (the 51% of theoretical value) 4- ethyoxyl -5- methyl mercapto -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 99 DEG C of fusing point are obtained.
For example, similar to embodiment (II-1), being also prepared for formula (II) compound being shown in table 2.Table 2：The example of formula (II) compound
Figure A9519656500491
Example No. n R1      R2    R3The C of physical data II-2 02H5      C2H5            m.p.：83℃   II-3     0        C2H5      C3H7-n          (amorphous)  II-4     0        C2H5      C3H7-i          (amorphous)  II-5     0        C2H5      CH2- CH=CH2     m.p.：30℃  II-6     0        C2H5      CH2-CH≡CH        m.p.：77℃  II-7     0         CH3       CH3               m.p.：156℃  II-8     0         CH3       C2H5             m.p.：135℃  II-9     0         CH3       C3H7-n           m.p.：90℃  II-10    0         CH3       C3H7-i             m.p.：89℃  II-11    0         CH3       CH2- CH=CH2      m.p.：70℃  II-12    0         CH3       CH2-C≡CH          m.p.：134℃  II-13    0         CH3       CH2The (Continued) Example No. n R of-F tables 21      R2       R3The CH of physical data II-14 03         CH2-Cl       m.p.：94℃ II-15    0         CH3        CH2-CH2-F    m.p.：96℃ II-16    0         CH3        CH2-CH2-Cl    m.p.：152℃ II-17    0         CH3           CHF2 II-18    0         CH3         CH2-CHF2 II-19    0         CH3         CH2-CF3 II-20    0         CH3        CH2-CH2-CF3 II-21    0         C2H5        CH2-F II-22    0         C2H5        CH2-Cl II-23    0         C2H5        CHF2 II-24    0         C2H5     CH2-CH2-F II-25    0         C2H5     CH2-CH2-Cl II-26    0         C2H5     CH2-CHF2 II-27    0         C2H5      CH2-CF3 II-28    0         C3H7-n      CH3 II-29    0         C3H7-i      CH3 II-30    0         C4H9-n      CH3 II-31    0      CH2- CH=CH2    CH3The (Continued) Example No. n R of table 21       R2      R3The C of physical data II-32 03H7-n       C2H5 II-33    0     C3H7-i       C2H5 II-34    0     C4H9-n       C2H5 II-35    0  CH2- CH=CH2     C2H5 II-36    1      CH3           CH3 II-37    2      CH3           CH3 II-38    1      CH3           C2H5 II-39    2      CH3           C2H5 II-40    1     C2H5         CH3 II-41    2     C2H5         C2H5 II-42    0     CH3                   m.p.：108℃ II-43    0     C2H5      
Figure A9519656500512
 II-44    0    C3H7-n        II-45    0     C3H7-i    
Figure A9519656500514
 II-46    0  CH2- CH=CH2     Formula (IX) starting material embodiment (IX-1)
By 25.5g (100mmol) 4- ethyoxyls -1- (benzene oxygen thiocarbonyl group)-semicarbazides, 6.9g (50mmol) potassium carbonate and the mixture of 150ml methanol flow back about 10 minutes.Then concentrate, residue is extracted with isopropanol, pass through suction strainer fractional crystallization product.Thus 21g (the 100% of theoretical value) 4- ethyoxyl -5- sulfydryl -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 123 DEG C of fusing point are obtained.
For example, similar to embodiment (IX-1), being also prepared for formula (IX) compound being shown in table 3.Table 3：The EXAMPLE Example R of formula (IX) compound1Physical data IX-2 CH3(sylvite) m.p.：221℃IX-3    C3H7- n (sylvite) IX-4 C3H7- i (sylvite) IX-5 CH2- CH=CH2(sylvite) IX-6 C4H9- n (sylvite) IX-7 C4H9- i (sylvite) IX-8 C4H9- s (sylvite) IX-9
Figure A9519656500531
The starting material embodiment (XI-1) of formula (XI)
At 0 DEG C to 15 DEG C, by 70g (0.4mol) chloro- bamic acid phenylester, it is added dropwise to 47.6g (0.4mol) 4- ethyoxyls-semicarbazides, in 41g (0.4mol) triethylamine and the mixture of 400ml dichloromethane, then mixture is stirred for 16 hours at 15 DEG C to 20 DEG C.Then the crystallized product prepared is separated by suction strainer.4- ethyoxyls -1- (benzene oxygen thiocarbonyl group)-semicarbazides of thus obtained 85.7g (the 84% of theoretical value), 153 DEG C of fusing point.
For example, similar to embodiment (XI-1), being also prepared for formula (XI) compound being shown in table 4.The EXAMPLE Example R of the formula of table 4 (XI) compound1Y physical data XI-2 CH3                        
Figure A9519656500551
       m.p.：172℃  XI-3         C3H7-n                      
Figure A9519656500552
  XI-4         C3H7-i                         XI-5         C4H9-n                        XI-6        CH2- CH=CH2                  
Figure A9519656500555
  XI-7      
Figure A9519656500556
  XI-8          CH3                               Cl  XI-9          C2H5                            Cl  XI-10        C3H7-n                           Cl  XI-11        C3H7-i                           Cl  XI-12        C4H9-n                           Cl  XI-13      CH2- CH=CH2The (Continued) Example No. R of Cl tables 41Y physical data XI-14 CH3                           XI-15       C2H5                         XI-16       CH3                                OCH3 XI-17       C2H5                              OCH3 XI-18       CH3                                OC2H5 XI-19       C2H5                              OC2H5 XI-20       CH3                             
Figure A9519656500563
 XI-21       C2H5                          
Figure A9519656500564
 XI-22       C3H7-n                         
Figure A9519656500565
 XI-23       CH2- CH=CH2                   
Figure A9519656500566
 XI-24      
Figure A9519656500567
The starting material embodiment (XII-1) of formula (XII)
At 0 DEG C, with stirring, 31g (0.2mo1) phenyl chloroformate is added dropwise in 24.4g (0.2mol) amine ethoxylate (50% aqueous solution), 100ml ether, 28g (0.2mol) potassium carbonate and the mixture of 10ml water.After gas stops volatilizing, organic phase is separated, aqueous phase is extracted again with ethyl acetate and merging organic phase is fully dried with magnesium sulfate and is filtered.Filtrate is concentrated, residue is absorbed with 50ml ethanol, adds 10g (0.2mol) hydrazine hydrate.After backflow one hour, cool down reactant mixture and filter.Filtrate is concentrated, residue is extracted with Di Iso Propyl Ether, the crystallized product prepared is separated by suction strainer.Obtain 23.4g (the 98% of theoretical value) 4- ethyoxyls-semicarbazides, 83 DEG C of fusing point.
For example, similar to embodiment (XII-1), being also prepared for formula (XII) compound being shown in table 5.
Figure A9519656500572
The EXAMPLE Example R of the formula of table 5 (XII) compound1Physical data XII-2 CH3             m.p.：73℃ XII-3          C3H7-n XII-4          C3H7-i XII-5          C4H9-n XII-6        CH2- CH=CH2 XII-7          XII-8       The starting material embodiment (IV-1) of formula IV
Figure A9519656500583
At 20 DEG C, 17.2g (0.11mol) phenyl chloroformate is added dropwise to 16.2g (0.1mol) 4- methoxyl group -5- methyl mercaptos -2,4- dihydros -3H-1,2,4- triazole -3- ketone, 4.4g (0.11mol) sodium hydroxide, 100mg Tetrabutylammonium bromides, in the mixture of the thorough agitation of 250ml water and 500ml dichloromethane, reactant mixture is then stirred for 16 hours.Organic phase is separated, is rinsed, is dried and concentrated with water.Oil residue is crystallized from ether.24.0g (the 85% of theoretical value) 4- methoxyl group -5- methyl mercapto -2- phenyloxycarbonyl -2,4- dihydros -3H-1 are obtained, 2,4- triazole -3- ketone are colourless crystallization shape, 113 DEG C of fusing point.
For example, similar to embodiment (IV-1), being also prepared for formula (IV) compound being shown in table 6.Table 6：The wherein embodiment of n=0 formula (IV) compound
Figure A9519656500601
Example No. R1      R2Z physical data IV-2 CH3    C2H5        IV-3       CH3    C3H7-n    
Figure A9519656500603
 IV-4       CH3    C3H7-i    
Figure A9519656500604
 IV-5       CH3  CH2- CH=CH2   
Figure A9519656500605
 IV-6       CH3   CH2-C≡CH       IV-7       CH3     CH2-F      
Figure A9519656500607
 IV-8       CH3     CH2-Cl     
Figure A9519656500608
The (Continued) Example No. R of table 61     R2Z physical data IV-9 CH3    CHF2                
Figure A9519656500611
 IV-10       CH3    CH2-CH2-F           
Figure A9519656500612
 IV-11       CH3    CH2-CH2-Cl           
Figure A9519656500613
  IV-12       CH3    CH2-CHF2             
Figure A9519656500614
 IV-13       CH3    CH2-CF3                IV-14       CH3    CH2-CH2-CF3             IV-15       CH3CH=C=CH2                IV-16       CH3    
Figure A9519656500618
 IV-17       CH3     The (Continued) Example No. R of table 61       R2Z physical data IV-18 CH3      C4H9-n       
Figure A9519656500621
 IV-19     C2H5     C2H5     
Figure A9519656500622
 IV-20     C2H5     C3H7-n      
Figure A9519656500623
 IV-21     C2H5     C3H7-i      
Figure A9519656500624
 IV-22     C2H5     CH2- CH=CH2   
Figure A9519656500625
 IV-23     C2H5      CH2-C≡CH   
Figure A9519656500626
 IV-24     C2H5        CH2-F     
Figure A9519656500627
 IV-25     C2H5       CH2-Cl     
Figure A9519656500628
 IV-26     C2H5        CHF2      
Figure A9519656500629
The (Continued) Example No. R of table 61          R2Z physical data IV-27 C2H5     CH2-CH2-F         
Figure A9519656500631
 IV-28    C2H5     CH2-CH2-Cl         
Figure A9519656500632
 IV-29    C2H5     CH2-CHF2           
Figure A9519656500633
 IV-30    C2H5     CH2-CF3            
Figure A9519656500634
 IV-31    C2H5     CH2-CH2-CF3          IV-32    C2H5CH=C=CH2              IV-33    C2H5    
Figure A9519656500637
 IV-34    C2H5      IV-35    C2H5     C4H9-n                 
Figure A9519656500639
The (Continued) Example No. R of table 61         R2Z physical data IV-36 C2H5      C2H5         IV-37    C3H7-n    C3H7-n       
Figure A9519656500642
 IV-38    C3H7-n    C3H7-i       
Figure A9519656500643
 IV-39    C3H7-n    CH2- CH=CH2  
Figure A9519656500644
 IV-40    C3H7-n    CH2-C≡CH         IV-41    C3H7-n      CH2-F          IV-42    C3H7-n      CH2-Cl         IV-43    C3H7-n       CHF2       
Figure A9519656500648
 IV-44    C3H7-n    CH2-CH2-F      
Figure A9519656500649
The (Continued) Example No. R of table 61              R2Z physical data IV-45 C3H7-n       CH2-CH2-Cl           
Figure A9519656500651
 IV-46    C3H7-n        CH2-CHF2            
Figure A9519656500652
 IV-47    C3H7-n        CH2-CF3              
Figure A9519656500653
 IV-48    C3H7-n       CH2-CH2-CF3         
Figure A9519656500654
 IV-49    C3H7- n CH=C=CH2            
Figure A9519656500655
 IV-50    C3H7-n        IV-51    C3H7-n        IV-52    C3H7-n       C4H9-n                   IV-53    C3H7-n       C2H5                    
Figure A9519656500659
The (Continued) Example No. R of table 61             R2Z physical data IV-54 C3H7-n         C3H7-n              IV-55    CH2- CH=CH2    C3H7-i            
Figure A9519656500662
 IV-56    CH2- CH=CH2    CH2- CH=CH2        IV-57    CH2- CH=CH2    CH2-C≡CH              IV-58    CH2- CH=CH2    CH2-F                
Figure A9519656500665
 IV-59    CH2- CH=CH2    CH2-Cl                  IV-60    CH2- CH=CH2    CHF2                    IV-61    CH2- CH=CH2    CH2-CH2-F           
Figure A9519656500668
 IV-62    CH2- CH=CH2    CH2-CH2-Cl          
Figure A9519656500669
The (Continued) Example No. R of table 61             R2Z physical data IV-63 CH2- CH=CH2    CH2-CHF2                   
Figure A9519656500671
 IV-64    CH2- CH=CH2    CH2-CF3                  
Figure A9519656500672
 IV-65    CH2- CH=CH2    CH2-CH2-CF3               
Figure A9519656500673
 IV-66    CH2- CH=CH2CH=C=CH2                  
Figure A9519656500674
 IV-67    CH2- CH=CH2                   
Figure A9519656500676
 IV-68    CH2- CH=CH2    
Figure A9519656500677
 IV-69    CH2- CH=CH2    C4H9-n                    
Figure A9519656500678
Application Example：Following compounds：
Figure A9519656500681
I.e.; 4- amino -5- methyl mercaptos -2- (2- trifluoromethoxies-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2; 4- triazole -3- ketone (being disclosed in EP-A 431291/LeA 27156), is used as control compounds in following Application Examples.Embodiment A after seedling test solvents：5 pbw acetone emulsifying agents：1 parts by weight alkylaryl polyglycol ether
By mixing the active material of 1 parts by weight and the solvent of above-mentioned amount, the emulsifying agent for adding above-mentioned amount prepares the suitable preparation of active material, and concentrate is diluted with water to required concentration.
By in the preparation spraying of active material to test plant high 5-15cm, to be distributed the desired amount of active material on per unit area.The concentration of spraying mixture is selected, make the desired amount of active material is distributed as 20001 water/ha.After three weeks, the development with untreated plant is contrasted, and is evaluated the extent of damage of plant, is represented with % loss ratios.0%=is eliminated completely without effect (such as untreated control) 100%=
In this test, for example, preparing the compatibility that has all existed to crop, such as wheat of compound ratio known compound (A) of embodiment 1,2,4,5,6,7 and 8, but there is good active function to weeds.It is also identical (being shown in Table A) using the compound results for preparing embodiment 22,29,31 and 48.Table A：After seedling experiment/greenhouse activity material amount of application wheat amaranth lamb's-quarters sunflower german chamomile black nightshade Siberian cocklebur
                                            (g/ha)
Figure A9519656500691
       125         0       0     0        0      0     0     0
Figure A9519656500692
125 0 95 95 100 95 90 95 Table A (Continued) active material amount of application wheat amaranth lamb's-quarters sunflower german chamomile black nightshade Siberian cockleburs
                                             (g/ha)
Figure A9519656500701
       125        10    95    95      100    95    95    95125 5 95 95 100 90 50 95 Table A (Continued)
Active material amount of application wheat amaranth lamb's-quarters sunflower german chamomile black nightshade Siberian cocklebur
                                                  (g/ha)       125      5     80    95    100     80    90    80
Figure A9519656500712
125 0 80 80 100 40 50 Table A (Continued)
Active material amount of application wheat amaranth lamb's-quarters sunflower german chamomile black nightshade Siberian cocklebur
                                                    (g/ha)        125      5     70   90   100     40    90    90125 0 70 60 70 70 50 80 Table A (Continued) active material (preparation Example No.) amount of application wheat amaranth lamb's-quarters sunflower german chamomile black nightshade Siberian cockleburs
                      (g/ha)
    (22)                60     10    95    80    100    90    90    100
    (29)                60     10    80    90    90     80    95     -
    (31)                60      5    80    80    70     -     95     -
(48) 125 10 80 80 100 90 80 100 embodiment B before seedling test solvents：5 pbw acetone emulsifying agents：1 parts by weight alkylaryl polyglycol ether
By mixing the active material of 1 parts by weight and the solvent of above-mentioned amount, the emulsifying agent for adding above-mentioned amount prepares the suitable preparation of active material, and concentrate is diluted with water to required concentration.
The seed of test plant is sowed in normal soil.After 24 hours, sprinkled with the aqueous solution of active substance preparation and pour soil, the water of per unit area is preferably consistent.The concentration of active material in the formulation is unimportant, and determinant is only the amount of application of per unit area active material.After three weeks, the development with untreated plant is contrasted, and is evaluated the extent of damage of plant, is represented with % loss ratios.
0%=is without effect (such as untreated control)
100%=is eliminated completely
In this test, for example, preparing embodiment Isosorbide-5-Nitrae, there is good active function to weeds in 5,6,7 and 8 compound ratio known compound (A).It is also identical (being shown in Table B) using the compound results for preparing embodiment 11,12,22,29,31,33,34,35 and 47.Table B：Before seedling experiment/greenhouse
Active material amount of application clearvers smallflower galinsoga herb german chamomile mustard black nightshade chickweed
                                       (g/ha)       250      0    0    0      30    20     0
Figure A9519656500752
125 90 95 95 90 95 90 table B (Continued)
Active material amount of application clearvers smallflower galinsoga herb german chamomile Si mustard black nightshade chickweeds
                                   (g/ha)     125        80   95   95      95     90     95
Figure A9519656500762
125 90 95 95 90 80 90 table B (Continued)
Active material amount of application clearvers smallflower galinsoga herb german chamomile mustard black nightshade chickweed
                                    (g/ha)
Figure A9519656500771
      125       70   95   90      90    80    90
Figure A9519656500772
125 70 95 95 80 70 80 table B (Continued)
Active material amount of application clearvers smallflower galinsoga herb german chamomile S mustard black nightshade chickweeds
                                                         (g/ha)
Figure A9519656500781
125 50 90 80 60 80 60 table B (Continued) active material (preparation Example No.) amount of application clearvers smallflower galinsoga herb german chamomile mustard black nightshade chickweeds
                    (g/ha)
    (11)              125      -    95   95     95   95   95
    (12)              125      -    95   95     90   95   -
    (22)              250      95   95   95     70   95   95
    (29)              125      -    95   95     95   95   95
    (31)              125      -    100  100    95   95   70
    (33)              250      -    80   90     95   80   -
    (34)              125      -    100  95     95   95   90
    (35)              125      -    95   95     95   95   95
(47) 125-95 95 90 95 95 embodiment C scabs test (apple)/protective effect solvent：4.7 pbw acetone emulsifying agents：0.3 parts by weight alkylaryl polyglycol ether
By mixing the active material of 1 parts by weight and the solvent of above-mentioned amount, the emulsifying agent for adding above-mentioned amount prepares the suitable preparation of active material, and concentrate is diluted with water to required concentration.
In order to test protective effect, with the preparation spraying seedling of active material, until it soaks.After the dry tack free of spraying, with the pathomycete Venturia inaequalis of scab of apple conidium aqueous to plant inoculating, then in raising chamber, under conditions of 20 DEG C and relative humidity 100%, place 1 day.
Hereafter, plant is placed in the greenhouse of 20 DEG C and relative humidity 70%.
Evaluate within 12 days after inoculation.
In this test, embodiment Isosorbide-5-Nitrae is for example prepared, 5 and 6 compound, in the case where active material concentration is 10ppm, shows 100% effectiveness.Table C：When scab experiment (apple)/protective effect active substance material concentration is 10ppm, the % effect compared with untreated control
Figure A9519656500811

Claims (10)

1. the salt for the sulfonyl-amino-carbnyl triazolinone and formula (I) compound that logical formula (I) passes through oxygen and sulphur combination substituent
Figure A9519656500021
Wherein n is 0,1 or 2, R1The optional substituted substituent included for hydrogen or the following group：Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl, aryl and aralkyl, R2The optional substituted substituent included for the following group：Alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl, cycloalkyl-alkyl, aralkyl and aryl, and R3The optional substituted substituent included for the following group：Alkyl, aralkyl, aryl and heteroaryl, and by abandoning excluding published following compounds in EP-A431291：4- methoxyl group -5- methyl mercaptos -2- (2- methoxycarbonvl-phenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- ethylmercapto groups -2- [2- (N- methoxyl groups)-methylaminosulfonyl-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- propoxyl group -5- allyl sulfenyls -2- (2- methylphenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- methoxyl group -5- methyl mercaptos -2- (2- methoxycarbonyls-thiene-3-yl-sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- methyl mercaptos -2- (2- methoxyl groups-phenyl sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- ethyoxyl -5- ethylmercapto groups -2- [2- (the chloro- ethyoxyls of 2-)-phenyl sulfonyl-amino carbonyl] -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- allyloxy -5- ethylmercapto groups -2- (2- fluoro-phenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone,4- methoxyl group -5- ethylmercapto groups -2- (3- amino-sulfonyls-pyridine -2- bases-sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone and 4- methoxyl group -5- ethylmercapto groups -2- (2,6- difluorophenyls sulfonyl-amino carbonyl) -2,4- dihydros -3H-1,2,4- triazole -3- ketone.
2. (I) compound according to claim 1 is wherein, it is characterised in that n is 0,1 or 2, R1For hydrogen, by fluorine, chlorine, bromine, cyano group, C1-C4Alkoxy, C1-C4- alkyl-carbonyl or C1-C4The C of substitution may be selected in-alkoxy-carbonyl1-C6Alkyl, the C that substitution each may be selected by fluorine, chlorine and/or bromine2-C6- alkenyl or C2-C6Alkynyl group, each can be by fluorine, chlorine, bromine and/or C1-C4The C of substitution may be selected in alkyl3-C6Cycloalkyl or C5-C6Cycloalkenyl each can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy and/or C1-C4The phenyl or phenyl-C of substitution may be selected in-alkoxy-carbonyl1-C3- alkyl, R2For by fluorine, chlorine, bromine, cyano group, C3-C6- cycloalkyl, C1-C4Alkoxy, C1-C4Alkylthio group or C1-C4The C of substitution may be selected in-alkoxy-carbonyl1-C6Alkyl, the C that substitution each may be selected by fluorine, chlorine and/or bromine2-C6- alkenyl or C2-C6Alkynyl group, each can be by fluorine, chlorine, bromine and/or C1-C4The C of substitution may be selected in alkyl3-C6Cycloalkyl, C5-C6Cycloalkenyl or C3-C6- cycloalkyl-C1-C3- alkyl, can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy and/or C1-C4Phenyl-the C of substitution may be selected in-alkoxy-carbonyl1-C3- alkyl each can be by fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy, fluoro- and/or chloro- substituted C1-C3- alkoxy, C1-C4- alkylthio group, fluoro- and/or chloro- substituted C1-C3- alkylthio group, C1-C4- alkyl-sulfinyl, C1-C4- alkyl sulphonyl and/or C1-C4The phenyl of substitution, R may be selected in-alkoxy-carbonyl3For groupWherein
R4And R5It is identical or different and for hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-C6(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkyl1-C4- alkoxy carbonyl group, C1-C4- alkylamino-carbonyl, two-(C1-C4- alkyl) amino-carbonyl, hydroxyl, C1-C4- alkoxy, formyloxy, C1-C4- alkyl-carbonyloxy group, C1-C4- alkoxy-carbonyloxy group, C1-C4- alkyl amino-carbonyloxy group, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl, C1-C4- alkyl sulphonyl, two-(C1-C4- alkyl)-amino-sulfonyl, C3-C6Substitution may be selected in-cycloalkyl or phenyl), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, C for-alkenyl1-C4Substitution may be selected in-alkoxy-carbonyl, carboxyl or phenyl), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, C for-alkynyl group1-C4Substitution may be selected in-alkoxy-carbonyl, carboxyl or phenyl), C1-C4(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkoxy1-C4- alkoxy-carbonyl, C1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl may be selected substitution), C1-C4(it can be by fluorine, chlorine, bromine, cyano group, carboxyl, C for-alkylthio group1-C4- alkoxy-carbonyl, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl may be selected substitution), C2-C6(it can be by fluorine, chlorine, bromine, cyano group or C for-alkenyloxy1-C4- alkoxy-carbonyl may be selected substitution), C2-C6(it can be by fluorine, chlorine, bromine, cyano group, nitro, C for-alkenyl thio1-C3- alkylthio group or C1-C4- alkoxy carbonyl may be selected substitution), C3-C6- chain oxy-acetylene, C3-C6- sulfur-based chain acetylene or group S (O)p-R6, wherein
P is 1 or 2 Hes
R6For C1-C4(it can be by fluorine, chlorine, bromine, cyano group or C for-alkyl1-C4- alkoxy-carbonyl may be selected substitution), C3-C6- alkenyl, C3-C6- alkynyl group, C1-C4- alkoxy, C1-C4- alkoxy -C1-C4- alkylamino, C1-C4- alkylamino, two-(C1-C4- alkyl)-amino, phenyl or group-NHOR7, wherein
R7For C1-C12(it can be by fluorine, chlorine, cyano group, C for-alkyl1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl, C1-C4- alkyl sulphonyl, C1-C4- alkyl-carbonyl, C1-C4- alkoxy-carbonyl, C1-C4- alkylamino-carbonyl or two-(C1-C4- alkyl)-amino-carbonyl may be selected substitution), C3-C6- alkenyl (substitution can may be selected by fluorine, chlorine or bromine in it), C3-C6- alkynyl group, C3-C6- cycloalkyl, C3-C6- cycloalkyl-C1-C2- alkyl, phenyl-C1-C2(it can be by fluorine, chlorine, nitro, cyano group, C for-alkyl1-C4- alkyl, C1-C4- alkoxy or C1-C4Substitution may be selected in-alkoxy-carbonyl), (it can be by fluorine, chlorine, nitro, cyano group, C for benzhydryl or phenyl1-C4- alkyl, trifluoromethyl, C1-C4- alkoxy, C1-C2- Fluoroalkyloxy, C1-C4- alkylthio group, trifluoromethylthio or C1-C4Substitution may be selected in-alkoxy-carbonyl), R4And/or R5Also it is phenyl or phenoxy group, C1-C4- alkyl-carbonylamino, C1-C4- alkoxy-carbonyl amino, C1-C4- alkylamino-carbonyl-amino, two-(C1-C4- alkyl)-amino-carbonyl amino or group-CO-R8, wherein
R8For hydrogen, C1-C6- alkyl, C3-C6- cycloalkyl, C1-C6- alkoxy, C3-C6- cycloalkyloxy, C3-C6- alkenyloxy, C1-C4- alkylthio group, C1-C4- alkyl amino, C1-C4- alkoxy amino, C1-C4- alkoxy -C1-C4- alkyl amino or two-(C1-C4- alkyl)-amino (substitution can may be selected by fluorine and/or chlorine in it), or R4And/or R5Also it is trimethyl silyl, thiazolinyl, C1-C4- alkylsulfonyloxy, two-(C1-C4- alkyl)-aminosulfonyl amino or group-CH=N-R9, wherein
R9For by fluorine, chlorine, cyano group, carboxyl, C1-C4- alkoxy, C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4The C of substitution may be selected in-alkyl sulphonyl1-C6- alkyl, the benzyl of substitution may be selected by fluorine or chlorine, the C of substitution each may be selected by fluorine or chlorine3-C6- alkenyl or C3-C6- alkynyl group, can be by fluorine, chlorine, bromine, C1-C4- alkyl, C1-C4- alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio may be selected the phenyl of substitution, the C of substitution can each be may be selected by fluorine and/or chlorine1-C6- alkoxy, C3-C6- alkenyloxy, C3-C6- chain oxy-acetylene or benzyloxy, amino, C1-C4- alkyl amino, two-(C1-C4- alkyl)-amino, phenyl amino, C1-C4- alkyl-carbonylamino, C1-C4- alkoxy-carbonyl amino, C1-C4- alkyl sulfonyl-amino or the phenylsulfonyl-amido or R that substitution can be may be selected by fluorine, chlorine, bromine or methyl3For group
Figure A9519656500051
Wherein
R10For hydrogen or C1-C4- alkyl and
R11And R12It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), carboxyl, C1-C4- alkoxy carbonyl, Dimethylaminocarbonyl, C1-C4- alkyl sulphonyl or two-(C1-C4- alkyl) amino-sulfonyl, or R3For group
Figure A9519656500061
Wherein
R13And R14It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it) or C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), or R3For group
Figure A9519656500062
Wherein
R15And R16It is identical or different and for hydrogen, fluorine, chlorine, bromine, nitro, cyano group, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it), amino-sulfonyl, list-(C1-C4- alkyl)-amino-sulfonyl, two-(C1-C4- alkyl)-amino-sulfonyl, C1-C4- alkoxy-carbonyl or Dimethylaminocarbonyl or R3For group
Wherein
R17And R18It is identical or different and for hydrogen, fluorine, chlorine, bromine, C1-C4- alkyl (substitution can may be selected by fluorine and/or bromine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it) or two-(C1-C4- alkyl)-amino-sulfonyl, or R3For group
Wherein
R19And R20It is identical or different and for hydrogen, fluorine, chlorine, bromine, cyano group, nitro, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkylthio group, C1-C4- alkyl sulphinyl or C1-C4- alkyl sulphonyl (substitution can may be selected by fluorine and/or chlorine in it), two-(C1-C4- alkyl)-amino-sulfonyl, C1-C4- alkoxy-carbonyl or Dimethylaminocarbonyl, and A are oxygen, sulphur or group N-Z1, wherein
Z1For hydrogen, C1-C4- alkyl (substitution can may be selected by fluorine, chlorine, bromine or cyano group in it), C3-C6- cycloalkyl, benzyl, phenyl (substitution can may be selected by fluorine, chlorine, bromine or nitro in it), C1-C4- alkyl-carbonyl, C1-C4- alkoxy carbonyl or two-(C1-C4- alkyl)-amino carbonyl, or R3For group
Wherein
R21And R22It is identical or different and for hydrogen, C1-C4- alkyl, halogen, C1-C4- alkoxy carbonyl, C1-C4- alkoxy or C1-C4- halogenated alkoxy, and
Y1For sulphur or group N-R23, wherein
R23For hydrogen or C1-C4- alkyl, or R3For group
Wherein
R24For hydrogen or C1-C4- alkyl, benzyl, pyridine radicals, quinolyl or phenyl,
R25For hydrogen, halogen, cyano group, nitro, C1-C4- alkyl (substitution can may be selected by fluorine and/or chlorine in it), C1-C4- alkoxy (substitution can may be selected by fluorine and/or chlorine in it), dioxolanyl or C1-C4- alkoxy-carbonyl, and
R26For hydrogen, halogen or C1-C4- alkyl, or R3For one of following radicals：
Figure A9519656500082
Except the compound that exclusion is abandoned in claim 1.
3. formula (I) compound according to claim 1, it is characterised in that n is 0,1 or 2, R1For each can by fluorine, chlorine, cyano group, methoxy or ethoxy may be selected substitution methyl, ethyl, n- or i-propyl or N-, iso-, sec- or tert-butyl, each can by fluorine, chlorine or bromine may be selected substitution acrylic, cyclobutenyl, propinyl or butynyl, each can by fluorine, chlorine, bromine, methyl or ethyl may be selected substitution cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl, each can by fluorine, chlorine, bromine, cyano group, methyl, trifluoromethyl or methoxyl group may be selected substitution benzyl or phenyl, R2For each can be by fluorine, chlorine, cyano group, methoxyl group, ethyoxyl, the methyl of substitution may be selected in methyl mercapto or ethylmercapto group, ethyl, n- or i-propyl is n-, it is iso-, sec- or the tert-butyl group, each can be by fluorine, chlorine, or the acrylic of substitution may be selected in bromine, cyclobutenyl, propinyl, butynyl or allene base, each can be by fluorine, chlorine, bromine, the cyclopropyl of substitution may be selected in methyl or ethyl, cyclobutyl, cyclopenta, cyclohexyl, Cvclopropvlmethvl, cyclobutylmethyl, cyclopentyl-methyl or cyclohexyl methyl, each can be by fluorine, chlorine, bromine, cyano group, methyl, the phenyl or benzyl of substitution may be selected in trifluoromethyl or methoxyl group, and R3For group
Figure A9519656500091
Wherein
R4For fluorine, chlorine, bromine, methyl, ethyl, propyl group, trifluoromethyl, butoxy, allyloxy, propynyloxy base, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, difluoro-methoxy, trifluoromethoxy, the chloro- ethyoxyls of 2-, 2- Mehtoxy-ethoxies, C1-C3- alkylthio group, C1-C3- alkyl sulphinyl, C1-C3- alkyl sulphonyl, dimethylamino-sulfonyl, diethylamino sulfonyl, N- methoxy-. N-methyls amino-sulfonyl, Methoxyamino sulfonyl, phenyl, phenoxy group or C1-C3- alkoxy carbonyl group, and
R5For hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R3For group
Wherein
R10For hydrogen
R11For fluorine, chlorine, bromine, methyl, methoxyl group, difluoro-methoxy, trifluoromethoxy, ethyoxyl, methoxycarbonyl group, carbethoxyl group, methyl sulphonyl or dimethylamino-sulfonyl, and
R12For hydrogen, or R3For group
Wherein
R is C1-C4- alkyl or R3For group
Wherein
R24For C1-C3- alkyl, phenyl or pyridine radicals,
R25For hydrogen, fluorine, chlorine or bromine and
R25For fluorine, chlorine, bromine or C1-C3Except the compound that exclusion is abandoned in-alkoxy carbonyl, claim 1.
4. the preparation method of formula (I) compound according to claim 1; it is characterized in that (a) is selectively in the presence of reaction promoter and selectable in the presence of diluent, leads to the Triazolinones of formula (II) and reacted with the sulfonylisocyanates of logical formula (III)
Figure A9519656500103
Wherein n, R1And R2It is as defined above,
R3-SO2- N=C=O (III) wherein R3For defined in claim 1 or selectively in the presence of acid acceptor and selectable in the presence of diluent by (b), the triazolinones derivative of logical formula (IV) and the sulphonyl ammonia reaction of logical formula (V)
Figure A9519656500111
Wherein n, R1And R2As defined above, Z is halogen, alkoxy, aralkoxy or aryloxy group
                  R3-SO2-NH2(V) wherein R3For above-mentioned definition or selectively in the presence of acid acceptor and selectable in the presence of diluent by (c), the sulphonic-acid-amide derivative of the triazolinones derivative and logical formula (VI) of leading to formula (II) reactsWherein n, R1And R2It is as defined above,
                R3-SO2- NH-CO-Z (VI) wherein R3It is halogen, alkoxy, aralkoxy or aryloxy group for above-mentioned definition Z, or by (d) selectively in the presence of reaction promoter and selectively in the presence of diluent, the triazolinones derivative of logical formula (II) and the sulfonic acid halide of logical formula (VII), and with the metal cyanate reactant salt of logical formula (VIII)
Figure A9519656500121
Wherein n, R1And R2It is as defined above,
              R3-SO2- X (VII) wherein R3It is halogen for above-mentioned definition X,
MOCN (VIII) wherein M is the alkaline-earth metal of alkali metal or equivalence,
Formula (I) compound prepared by method (a), (b), (c) or (d) can selectively be changed into by salt by conventional method.
5. weeding and Fungicidal composition, it is characterised in that it contains at least one formula according to claim 1 (I) compound.
6. the compound control undesired plant growth and/or phytopathogenic fungi of the logical formula (I) of application.
7. the Triazolinones of logical formula (II)
Figure A9519656500131
Wherein n is 0,1 or 2, R1The group of substitution may be selected for hydrogen or the following group, wherein including alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl and aralkyl and R2The group of substitution may be selected for the following group, wherein including alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, cycloalkyl-alkyl, aralkyl and aryl.
8. the triazolinones derivative of logical formula (IV)
Figure A9519656500132
Wherein n is 0,1 or 2, R1The group of substitution may be selected for hydrogen or the following group, wherein including alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl and aralkyl and R2The group of substitution may be selected for the following group, wherein comprising alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, cycloalkyl-alkyl, aralkyl and aryl, and Z is halogen, alkoxy, aralkoxy or aryloxy group.
9. sulfydryl-Triazolinones of logical formula (IX) and the metal salt of formula (IX) compoundWherein R1The group of substitution may be selected for hydrogen or the following group, wherein including alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl and aralkyl.
10. the semicarbazide derivative of formula (XI)
Figure A9519656500142
Wherein R1The group of substitution may be selected for hydrogen or the following group, wherein being halogen, imidazole radicals, alkoxy, aralkoxy or aryloxy group comprising alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl group, aryl and aralkyl and Y.
CN 95196565 1994-10-05 1995-09-22 Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur Pending CN1168668A (en)

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Publication number Priority date Publication date Assignee Title
CN110734433A (en) * 2018-07-19 2020-01-31 东莞市东阳光农药研发有限公司 Triazole compound and application thereof in agriculture
CN110734433B (en) * 2018-07-19 2020-09-11 东莞市东阳光农药研发有限公司 Triazole compound and application thereof in agriculture

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