CA2318096A1 - Substituted aminoalkylidenamino triazines as herbicides - Google Patents
Substituted aminoalkylidenamino triazines as herbicides Download PDFInfo
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- CA2318096A1 CA2318096A1 CA002318096A CA2318096A CA2318096A1 CA 2318096 A1 CA2318096 A1 CA 2318096A1 CA 002318096 A CA002318096 A CA 002318096A CA 2318096 A CA2318096 A CA 2318096A CA 2318096 A1 CA2318096 A1 CA 2318096A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to novel substituted aminoalkylidenamino triazines of formula (I), wherein R1 represents the grouping A-Z, wherein A represents optionally substituted straight-chain or branched alkane diyl, which contains oxygen, sulphur, imino (NH) or alkylimino either initially or finally or inside the akane diyl chain, and Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping such as phenyl, naphthyl, benzofuryl, dihydrobenzofuryl, pyridyl and thienyl, R2 represents hydrogen, cyano, halogen or respectively and optionally substituted alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkythio, alkyl sulfinyl, alkenyl, alkinyl or cycloalkyl, R3 represents hydrogen or alkyl, R4 represents hydrogen or alkyl and R5 represents alkyl. The invention also relates to a method for the production and use thereof as herbicides.
Description
. - Le A 32 819-Foreign countries Bi/Kr/NT
i' r Substituted aminoalkylideneaminotriazines The invention relates to novel substituted aminoalkylideneaminotriazines, to a process for their preparation and to their use as herbicides.
A number of substituted 2,4-diamino-triazines is already known from the (patent) literature (cf. US 3816419, US 393? 167, EP 191496, EP ?73328. EP 41 1 1 ~3 /
WO
90/09378, WO 97/0024, WO 97/08156). However, these compounds have hitherto not attained any particular importance.
This invention, accordingly, provides the novel substituted aminoalkylideneamino-triazines of the general formula (I) RZ
~V~N R3 W ~R' (1) N N N N
R' RS
- l~
in which R~ represents the grouping -A-Z, in which A represents optionally substituted straight-chain or branched alkanedivl which optionally contains at the be~~innin~~ or at the end or within the alkanedivl chain an o~y~len atom. a Sulphur atom. an imino (NH) or an alkvlimino ( ~
? ~ alkyl) '=roup, and Le A 32 819-Foreign countries Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, di-hydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benz-oxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, R'- represents hydrogen, cyano, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkyl-sulphinyl, alkylsulphonyl, alkenyl, alkinyl or cycloalkyl, R' represents hydrogen or alkyl, R4 represents hydrogen or alkyl, and R~ represents alkyl.
The novel substituted aminoalkylideneaminotriazines of the general formula (I) are obtained when substituted aminotriazines of the general formula (II) N~N
(II>
N N N
I, I
R' H
in which Le A 32 819-Foreign countries R~ and R2 are as defined above, are reacted with substituted amino compounds of the general formula (III) RO'~N~R4 (III) R
in which R', R4 and R~ are as defined above and R represents alkyl, if appropriate in the presence of a diluent.
The novel substituted aminoalkylideneaminotriazines of the general formula (I) have strong and selective herbicidal activity.
To a certain extent, the compounds of the formula (I) also have fungicidal and insecticidal activity.
The compounds of the general formula (I) accordin~~ to the invention may contain asymmetrically substituted carbon atoms, in which case they can be present in different enantiomeric (R- and S-configured forms) or diastereomeric forms.
The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the ~~encra.l ti>rmula (1) and to the mixtures of these isomeric compounds.
Le A 32 819-Foreign countries In the definitions, the hydrocarbon chains, such as alkyl - including in combination with heteroatoms, such as in alkoxy or alkylthio - are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which l0 R ~ represents the grouping -A-Z, in which A represents optionally cyano- or halogen-substituted straight-chain or 1 S branched alkanediyl having 1 to 6 carbon atoms, which optionally contains at the beginning or at the end or within the alkanediyl chain oxygen, sulphur, imino (NH) or C 1-C4-alkylimino, and Z represents an optionally substituted monocyclic or bicyclic, carbo-20 cyclic or heterocyclic grouping from the series consisting of cyclo-pentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzo-thienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, 25 indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thia-zolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thia-diazolyl, pyrazolyl, pyridinyl, pyri~:midinyl, pyrazinyl, pyridazinyl, quinolvl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinvl.
30 where the possible substituents of these radicals are in each case preferably selected from the followin~~ group:
Le A 32 819-Foreign countries a hydroxyl, cyano, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, Cl-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, R'- represents hydrogen, cyano, halogen, represents in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C 1-C4-alkoxy-, C 1-C4-alkylthio-, C 1-C4-alkylsulphinyl- or C 1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkyl-carbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C 1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R' represents hydrogen or alkyl having 1 to 6 carbon atoms, R't represents hydrogen or alkyl having 1 to 6 carbon atoms, and R~ represents alkyl having 1 to 6 carbon atoms.
2~ Among the compounds of the fornmla (I) defined above as being preferred ("preferably"), particular emphasis is given to the following groups:
(A) the compounds of the formula (I) in which A, R~', R'. R~ and R' are as defined above and Z represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are as defined above;
Le A 32 819-Foreign countries (B) the compounds of the formula (I) in which A, R2, R3, R4 and RS are as defined above and Z represents optionally substituted heterocyclyl, where the possible heterocyclyl groupings and the possible substituents are as defined above.
The invention relates in particular to compounds of the formula (I) in which R ~ represents the ~~roupin~~ -A-Z , in which A represents in each case optionally cyano-, fluorine- or chlorine-substituted methylene (-CH,-), dimethylene (ethane-1,2-diyl, -CH~CH~-), ethylidene (ethane-1,1-diyl, -CH(CH;)-), trimethylene (propane-1,3-diyl, -CH-,CH~CH-,-), propylidene (propane-l,l-diyl, -CH(C~H~)-), propane-2,3-diyl (-CH(CH3)CH~-), 2-methyl-propane-1,3-diyl (-CH~CH(CH~)CH~-), 3-oxa-propane-1,3-diyl (-CH~CH~O-), 2-oxa-propane-1,3-diyl (-CH~OCH-,-), tetramethylene (butane-1,4-diyl -CH~CH-,CH~CH~-), butane-2,4-diyl (-CH(CH3)CH~CH-,-), butane-2,3-diyl (-CH(CH;)CH(CH~)-), 3-methyl-butane-2,4-diyl (-CH(CH~)CH(CH~)CH~-), 4-oxa-butane-2,4-diyl (-CH(CH~)CH~O-), pentane-3,5-diyl (-CH(C-,H~)CH~C.'H-,-), 5-oxa-pentane-3,~-diyl (-CH(C~H~)CH-,O-), 4-oxa-pentane-2,5-diyl (-CH(CH~)CH-,OCH~-) or 5-oxa-hexane-3,6-diyl (-CH(C-,HS)CH-,OCH~-), and Z represents an optionally substituted monocyclic or bicyclic, carbo-cyclic or heterocyclic grouping from the series consisting of cyclo-pentyl, cvclohexyl, phenyl, naphthyl, tetralinyl. dccalinyl, indanvl, indenvl, furyl. benzofuryl, dihydrobenzofuryl. thienyl, benzothienyl, dihydrobc:nzothicnvl. isobenzofuryl. dihydroisobmzofuryl, isobenzo-thienyl. dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinvl, isoindolinyl, bcn zodioxolyl, oxazolyl, benzoxazolyl, thia-Le A 32 819-Foreign countries _7.
zolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thia-diazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, where the possible substituents of these radicals are in each case preferably selected from the group below:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- and/or chlorine-substituted methyl-carbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- or t-butoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butyl-thio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy-or trifluoromethoxy-substiuted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, R-' represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, n- or i-butyroyl, methoxy-carbonyl, ethoxvcarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n-or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, rnethylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents in each Le A 32 819-Foreign countries _g_ case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R' represents hydrogen, methyl or ethyl, R4 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, and RS represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.
Group 1 CH3 N ~ N H
CH
N~N~N~\N~ 3 I I
Here. R' has. for example, tl meanin~~s given below:
Le A 32 819-Foreign countries n _9_ methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, fluoromethyl, difluoromethyl, tri-fluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromo-methyl, chlorodifluoromethyl, fluorodichloromethyl, bromodifluoromethyl, trichloro-methyl, 1-fluoroethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 1-chloro-1-fluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-bromopropyl, I-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl, 1-fluoro-1-methyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-I-ethyl-propyl, I-fluoro-2-methyl-propyl, 1-chloro-2-methyl-propyl, 2-chloro-I-methyl-ethyl, 1,l-difluoroethyl, 1,2-difluoroethyl, 1,1-dichloroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl, 1,1-difluoropropyl, 1,1-dichloropropyl, perfluoropropyl, 1-fluorobutyl, 1-chlorobutyl, perfluorobutyl, per-fluoropentyl, perfluorohexyl, 1-hydroxy-ethyl, 1-hydroxy-1-methyl-ethyl, 1-hydroxy-propyl, methoxymethyl, ethoxymethyl, dimethoxy-methyl, 1-methoxyethyl, 2-methoxy-ethyl, 1,1-dirnethoxy-ethyl, 1-ethoxyethyl, 2-ethoxy-ethyl, 2,2-dimethoxy-ethyl, 2,2-diethoxy-ethyl, 2-methoxy-1-methyl-ethyl, 2-methoxy-1-ethylethyh 2-ethoxy-1-methylethyl, 2-ethoxy-1-ethylethyl, 2,2-bis-methoxymethyl, methylthio-methyl, ethylthiomethyl, 1-methylthio-ethyl, 2-methylthioethyl, !-ethylthioethyl, 2-ethylthioethyl, methylsulphinylmethyl, ethylsulphinylmethyl, methylsulphonyl-methyl, ethylsulphonylmethyl, vinyl, 1-chlorovinyl, 2-chlorovinyl, 1-fluorovinyl, 2-fluorovinyl, 1-bromovinyl, 2-bromovinyl, 1,2-dichlorovinyl, 1,2-dibromovinyl, 1,2-difluorovinyl, 2,2-dichlorovinyl, 2,2-difluoro-vinyl, 2,2-dibromovinyl, 1-chloro-2-fluorovinyl, 1-fluoro-2-chlorovinyl, 2-bromo-1-chlorovinyl, 2-bromo-2-chlorovinyl, l-bromo-2-fluorovinyl, 1-fluoro-2-bromovinyl, 1-bromo-2-chlorovinyl, trichloro-vinyl, trifluorovinyl, tribromovinyl, 1-fluoro-2,2-dichlorovinyl, 1-bromo-2,2-dichlorovinyl, 1-fluoro-2,2-dibromovinyl, 1-chloro-2,2-difluorovinyl, 1-chloro-2,2-dibromovinyl, 1-bromo-2,2-difluorovinyl, 2-fluoro-1.2-dichlorovinyl, 2-chloro-1,2-difluorovinyl, 2-bromo-1.2-difluorovinyl, 2-bromo-~1,2-dichlorovinyl, 2-chloro-1,2-dibromovinyl, 2-tluoro-1,2-dibromovinyl, 2-bromo-1-chloro-2-fluorovinyl, ?-methoxyvinyl, 2-ethoxwinyl, allyl, 2-chloroallyl, 3-chloro-allvl, 3.3-dichloroallyl, propen-1-yl, propen-2-yl, 1-chloropropen-I-yl, 1-bromo-propen-1-yl, 1-tluoropropen-2-yl, 1-chloropropen-2-yl, 1-bromopropen-2-yl, ?-methoxypropen-1-yL, 2 Le A 32 819-Foreign countries ethoxypropen-1-yl, 3,3,3-trifluoropropen-1-yl, 3,3,3-trifluoropropen-2-yl, 1-chloropropen-2-yl, 1-fluoropropen-2-yl, 1-bromoprapen-2-yl, 1,2-dichloropropen-yl, 1,2-dibromopropen-1-yl, 1,2-difluoropropen-1-yl, 1,1-dichloropropen-2-yl, 1,1-dibromopropen-2-yl, 1,1-difluoropropen-2-yl, 1-chloro-2-fluoropropen-1-yl, I-chloro-2-bromopropen-1-yl, 1-bromo-2-chloropropen-1-yl, 1-bromo-2-fluoropropen I-yl, 1-chloro-3,3,3-trifluoropropen-2-yl, 1-bromo-3,3,3-trifluoropropen-2-yl, I-fluoro-3,3,3-trichloropropen-1-yl, 1,3,3,3-tetrafluoropropen-1-yl, 1,3,3,3-tetra-fluoropropen-2-yl, 1-bromo-2-chloro-3,3,3-trifluoropropen-1-y(, I ,1,3,3,3-penta-fluoropropen-2-yl, 1,2,3,3,3-pentafluoropropen-I-yl, 1,1-dichloro-3,3,3-trifluoropropen-2-yl, 1,2-dichloro-3,3,3-trifluoropropen-2-yl, I,1-dibromo-3,3,3-trifluoropropen-2-yl, 1,2-dibromo-3,3,3-trifluoropropen-2-yl, 1-chloro-2,3,3,3-tetra-fluoro-1-propen-1-yl, 2-methyl-propen-I-yl, 1-chloro-2-methyl-propen-1-yl, 1-bromo-2-methyl-propen-I-yl, I-fluoro-2-methyl-propen-1-yl, 1-bromo-2-methyl-3,3,3-trifluoropropen-1-yl, 1-chloro-3,3,3-trifluoro-2-trifluoromethyl-propen-I-yl, 1-bromo-3,3,3-trifluoro-2-trifluoromethyl-propen-I-yl, I-chloro-3,3,3-trifluoropropen-I-yl, 1-bromo-3,3,3-trifluoropropen-1-yl, 1-chloro-2,3,3,3-tetrafluoropropen-I-yl, 1-chloro-2-bromo-3,3,3-trifluoropropen-1-yl, I-chloro-2-methyl-3,3,3-trifluoropropen-1-yl, 1-bromo-2-fluoropropen- I -yl, 1-buten-1-yl, 1-buten-2-yl, 2-buten-1-yl, 2-buten-2-yl, I -chloro-1-buten-1-yl, I -bromo-1-buten-1-yl, I -fluoro-1-buten-1-yl, 1-chloro-1-buten-2-yl, 1-fluoro- I -buten-2-yl, I -bromo- I -buten-2-yl, 1,2-difluoro- I -buten-1-yl, I ,2-dichloro-1-buten- I -yl, 1,2-dibromo- I -buten-1-yl, 1-bromo-2-fluoro- I -buten-1-yl, 3-methyl-2-buten-2-yl, I-chloro-2-fluoro-I-buten-1-yl, I-bromo-2-chloro-I-buten-I-yl, 1,1,1-trifluoro-2-methyl-2-buten-2-yl, 4,4,4-trifluoro-2-methyl-buten-2-yl, 4,4,4-trifluoro-3-trifluoromethyl-2-buten-2-yl, I-chloro-2-methyl-3,3,3-trifluoropropen-1-yl, 3-chloro-2-buten-2-yl, 3-bromo-2-buten-2-yl, 3-fluoro-2-buten-2-yl, I-chloro-2-methyl- I -buten- I -yl, 1-bromo-2-methyl-1-buten- I -yl, I -fluoro-2-methyl-I -buten- I -yl, 1-fluoro-3-methyl-1-buten-1-yl, 1-chloro- 3-methyl-1-buten-1-yl, 2-methoxy-buten-1-yl, 2-ethoxy- I -buten-1-vl, l , l -dichloro-1-buten-2-yl, l , l -dibromo-1-buten-2-yl, 1,1-dit7uoro-1-buten-2-yl. I-chloro-2-fluoro-1-buten-1-yl. I-chloro-2-bromo-1-buten-1-yl, I -chloro-2-tritluoromethyl- l -buten-1-yl, 1,1,1-tritluoro-2-buten-2-yl, 4,4,4-tritluoro-2-buten-2-yl. 4,4,4-tritluoro-3-methyl-2-buten-2-yl, l,l,l-trifluoro-3-. Le A 32 819-Foreign countries methyl-2-penten-2-yl, 1,1;1-trifluoro-3-ethyl-2-penten-2-yl, 1,1,1,4,4,4-hexafluoro-2-buten-2-yl, 1-chloro-2-ethyl-1-buten-1-yl, 1-bromo-2-ethyl-1-buten-1-yl, I -fluoro-2-ethyl-I-buten-1-yl, 2-penten-2-yl, 2-penten-3-yl, 2-chloro-2-penten-3-yl, 2-bromo-2-penten-3-yl, 2-fluoro-2-penten-3-yl, 3-chloro-2-penten-2-yl, 3-bromo-2-penten-2-yl, 3-fluoro-2-penten-2-yl, 3-trifluoromethyl-2-penten-2-yl, 1, I , l -trifluoro-2-penten-3-yl, 1,1,1-trifluoro-2-penten-2-yl, 1, l,1-trifluoro-3-methyl-2-penten-2-yl, 2-methyl-2-penten-3-yl, 3-methyl-2-penten-2-yl, 1,1,I-trifluoro-2-trifluoromethyl-2-penten-3-yl, 4-methyl-3-hexen-3-yl, 4-fluoro-3-hexen-3-yl, 4-chloro-3-hexen-3-yl, 4-bromo-3-hexen-3-yl, 1, l, I-trifluoro-2-methyl-2-hexen-3-yl, 4-ethyl-3-hexen-3-yl, ethinyl, 2-chloroethinyl, 2-bromoethinyl, propin-I-yl, propin-3-yl, 3,3,3-trifluoropropin-I-yl, 1-butin-1-yl, 1-butin-3-yl, 3-methyl-1-butin- I -yl, 1-pentin- I -yl, cyclopropyl, 1-cyano cyclopropyl, 1-fluorocyclopropyl, 1-chlorocyclopropyl, 2-cyanocyclopropyl, 2 fluorocyclopropyl, 2-chlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dichlorocyclo propyl, cyclobutyl, 2,2-difluorocyclobutyl, 2,2,3-trifluorocyclobutyl, 2,2-difluoro-3 chlorocyclobutyl, cyclopentyl, cyclohexyl.
Group 2 CZHS N ~ N H
~CH3 N~N~N~N
I I
Here, R'- has, for example, the meanin~~s ~~iven above in group 1.
Le A 32 819-Foreign countries Group 3 Rz CZHS N-/ _N H
CH
~N N N N~
CI
Here, R'- has, for example, the meanin~~s given above in group 1.
Group 4 CH3 N~N H
N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 5 Rz N~N~.N~N~CH3 I I
Here, R-' has. for example, the meanings given above in ~~roup 1.
Le A 32 819-Foreign countries Grou 6 Rz C2H5 N~N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 7 RZ
CzHs N~N H
H3C ~ N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 8 Rz CH3 N~N H
H3C ~ N~N~N~N~CH3 I I
Is Here, R'- has, for example, the meanin~~s given above in 'croup 1.
Le A 32 819-Foreign countries Group 9 Rz CH3 CH3 N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group l .
Group 10 CH3 CzHs N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 11 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
l~
Here, R' has, for example. the meanings given above in ~~roup I .
Le A 32 819-Foreign countries Group 12 Rz C3H~-i N-/ _N H
N~N~N~N~CH3 I I
S Here, R'- has, for example, the meanings given above in group I .
Group 13 Rz C3Hz-i N_/ _N H
N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group I .
Group 14 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
1 ~ CI
Here, R~' has. for example, the meanin';s ~~iven above in 'Troup 1.
Le A 32 819-Foreign countries Group 15 Rz CH3 N~N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 16 Rz CzHs N~N H
N~N~~N~N~CH3 I
Here, R'- has, for example, the meanings given above in group 1.
Group 17 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
l~
Eiere, R'- has. for example. the mcanin~~s ~~ivcn above in ~'roup 1.
Le A 32 819-Foreign countries Group 18 Rz C3H~-i N-/ _N H
\ N~N~N~N~CH3 I I
Here, R-' has, for example, the meanings given above in group 1.
Group 19 RZ
\ CH3 N-/ _N H
~CH3 \ N~N~N~N
I I
Here, R' has, for example, the meanings given above in group 1.
Group 20 Rz CH3 N~N H
\ \ N~N~~N~N~CH3 I I
is Here, R-' has, ter example. the meanin~,s <~iven above in 'croup l .
Le A 32 819-Foreign countries Grog 21 Rz CH3 N~N H
CI \ N~N~N J\N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 22 RZ
CZHS N / _N H
CI \ N~N~~~N~CH3 i I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 23 RZ
CZHS N~N H
HsC \ N~N~.N~N~CH3 I I
I~ H3C
Here, R' has, for example, the meanin~~s ~Tiven above in group I .
Le A 32 819-Fore~yn countries Group 24 Rz CH3 N~N H
H3C \ N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 2J
Rz CH3 N_/ _N H
F \ ~N~N~N~N~CH3 I I
F
Here, R'- has, for example, the meanings given above in group 1.
Group 26 Rz CzHs N~N H
F \ N~N~N~N~CH3 I I
l~
Here. R'- has, for example. the meanings given above in group 1.
Le A 32 819-Foreign countries Groin 27 Rz CH3 N-/ _N H
H3C ~ N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 28 CH3 N-/ _N H
CI \ N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 29 CH3 N~N H
\ N~N~N~N~CH3 I I
l~
Here, R-' has, for example, the meanin~~s ~,iven above in ~~roup 1.
Le A 32 819-Foreien countries Group 30 Rz CZHS N_/ _N H
N~N~N~N~CH3 I f F
Here, R'- has, for example, the meanings given above in group 1.
Group 31 Rz CH3 N-/ _N H
N~N~N~N~CH3 Here, R' has, for example, the meanings given above in group 1.
Group 32 Rz CH3 N~N H
N~N~.N~N~CH3 l~
Here, R' has. for example, the meaning; riven abovf: in ~~roup 1.
Le A 32 819-Fore countries Groin 33 Rz CH3 N-/ _N H
N~N~N~N~CH3 t I I
Here, R-' has, for example, the meanings given above in group 1.
Grou~34 Rz CZHS N~N H
N~N~N~N~CH3 l I I
Here, R' has, for example, the meanings given above in group 1.
Group 35 Rz CZHS N-/ _N H
~CH3 ~N N N N
I
H~C
l Here. R-' has, for example. the meanings given above in group I .
Le A 32 819-Foreign countries =23-Group 36 RZ
CH3 N_/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 37 RZ
CH3 N~N H
H C ~ N~N~\N~N/CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 38 C2H5 N~N H
N~N~~N~N~CH3 H3C ~~ 'I I
Here, R~ has, for example. the meanin~~s ~~iv~n above in ~~roup 1.
Le A 32 819-Foreign countries Group 39 Rz CH3 N-/ _N H
N~N~N~N~CH3 I I
CI
Here, R-' has, for example, the meanings given above in group 1.
Group 40 C H N H
z 5 ~ ~ ~CH3 ~N N N N
CI
Here, R' has, for example, the meanings given above in group 1.
Group 41 Rz CZHS N~N H
CI ~ N~N~N~N~CH
I I
1 ~ CI
Rz N
Here, R-' has, for example, the meanin«s riven above in ~Troup 1.
Le A 32 819-Foreiem countries Group 42 Rz CH3 N-/ _N H
\ ~ /~
CI ~ N~N~N~N'CH
I I
CI
Here, R-' has, for example, the meanings given above in group 1.
Group 43 Rz CH3 N-/ _N H
~\ ~ /~
N~N~N~N~CH
I I
Here, R'- has, for example, the meanings given above in group 1.
Group 44 Rz C2H5 N~N H
~CH3 N N N N
is Eiere, R~ has, for example. the meanin~~s ~~iven abov~° in ~~roup 1.
Le A 32 819-Foreign countries Group 45 CZHS N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 46 Rz CH3 N-/ _N H
/
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 47 Rz CH3 N~N H
w ~ ~CH3 N N N N
l~
Here. R-' has, for example. the mvaninV~s y~ivcn ahove in ~~roup I .
Le A 32 819-Foreign countries Group 48 CzHs N~N H
O~ ~ ~ ~ ~CH3 N N N N
Here, R' has, for example, the meanings given above in group 1.
Groin 49 CZHS N~N H
F3C \ O~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 50 Rz CH3 N~~N H
FsC W O~N~:N~N~N~CHs l~
Here. R'- has, for example. the meanin~~s given above in «roup I .
Le A 32 819-Foreign countries Group 51 Rz CH3 N-' _N H
H3C \ p~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Grou~52 Rz CzHs N~N H
H C ~ ~~N~~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 53 Rz CZHS N ~~N H
i \ p~N~.N~N~N~CH3 I I
l~
Here. R' has, for example, the meanings <~iven above in group 1.
Le A 32 819-Foreign countries Group 54 Rz CH3 N~N H
O~N~N~N~N~CHs Here, R'- has, for example, the meanings given above in group 1.
Group 55 Rz CH3 N~N H
H3C \ O~N~N~~~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Groin 56 Rz CZHS N~N H
HsC W O~N~~N~N~N~CH3 I I
H CH, Is Here, R~ has. for example. the meanings given above in ~Troup 1.
Le A 32 819-Foreign countries GrouQ57 Rz C2H5 N~N H
O~N~N~N~NiCHs F
Here, R'- has, for example, the meanings given above in group 1.
Group 58 Rz CH3 N~N H
O~ ~ ~ ~ ~CH3 N N N N
F
Here, R'- has, for example, the meanings given above in group 1.
Group 59 Rz CH3 N'~N H
O' ~ ~~ ~ ~ ~CH3 CI ~ v _N N N N
I I
1 ~ CI
Here, R' has, for example. the meanings given abov~° in groin 1.
Le A 32 819-Foreign countries Group 60 Rz CZHS N-/ _N H
CI ~ ~~N~N~N~N~CH' CI
Here, R'- has, for example, the meanings given above in group 1.
Group 61 Rz CzHs N~N H
F ~ O~N~N~N~N~CH3 I I
F
Here, R'- has, for example, the meanings given above in group 1.
Group 62 Rz CH3 N~\N H
F \ O~N~N~N~N~CH3 F
1>
Here. R~ has. for wample, the meanings given above in group 1.
Le A 32 819-Foreign countries Group 63 CH3 N~N H
H3C \ O~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 64 Rz CZHS N~N H
O' ~ ~ ~ ~ ~CH3 H3C ~ v _N N N N
Here, R'- has, for example, the meanings given above in group 1.
Group 65 CZHS N'~N H
CI ~ O~N~'N~N~N~CH3 CI
1>
E-lerc. R'- has, for example, the meanin~ls <~iven above in ~*r~up 1.
Le A 32 819-Foreign countries GrouQ 66 Rz CH3 N~N H
CI ~ ~~N~N~N~N~CH3 CI
Here, R-' has, for example, the meanings given above in group 1.
Group 67 Rz CH3 N-/ _N H
p~N~N~N~N~CH3 I
Here, R' has, for example, the meanings given above in group 1.
Group 68 Rz CZHS N~N H
p~N~Nj~N~N~CH3 l Here. R-' has, for example. the mennin'~s given above: in group 1.
Le A 32 819-Foreign countries Group 69 Rz CI CZHS N-/ _N H
O~N~N~N~N~CH3 i Here, R'- has, for example, the meanings given above in group 1.
Grog 70 CI CH3 N~N H
' ~ ~CH3 O~N N N ~N
I I
Here, R' has, for example, the meanings given above in group 1.
Group 71 CH3 N~N H
W I O~Ni~N~N~N~CH3 CI I i Here. R- ha;. ti>r example. the meanin~~s given above' in ~~roup 1.
Le A 32 819-Foreign countries Groin 72 Rz CZHS N-/ _N H
O~N~N~N~N~CH3 CI I I
Here, R'- has, for example, the meanings given above in group 1.
Group 73 RZ
CI CzHs N~N H
O~N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 74 Rz CI CH3 N~~N H
O~N~N~N~N~CH3 I I
1~
Here, R' has, for example, the meanin~Ts given above: in group 1.
Le A 32 819-Foreign countries Group 75 Rz CH3 CH3 N_/ _N H
O~N~N~N~N~CH3 I I
Hefe, R'- has, for example, the meanings given above in group 1.
Group 76 Rz CH3 CzHs N-/ _N H
O~N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 77 Rz H3C CzHs N~N H
I O~N~N~N~N~CH3 I I
Here. R' has, for example, the meanings given above, in <~roup l .
Le A 32 819-Foreigil countries Group 78 H C CH3 N-/ _N H
s ~ I O~N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 79 Rz CH3 N-/ _N H
I O~N,~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Gro ~ 80 Rz C2H5 N-/ _N H
W I O~N.~N~N~NiCHs 1-lere. R-' hay, for example, the meanin<~s ~Tiven above in <,roup 1.
Le A 32 819-Forei countries _3g_ Group 81 Rz CZHS N~N H
I p~N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group I .
Group 82 Rz CH3 N~N H
I p~N~Nj~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 83 Rz I p~N~N~N~N~CH3 I I
l~ H CH3 Here. R'- has, for example, the meanings <~iven above in group 1.
Le A 32 819-Foreign countries Group 84 Rz CzHs N-/ _N H
I p~N~N~N~N~CH3 I I
Flere, R'- has, for example, the meanings given above in group 1.
Group 85 Rz CH3 N-/ _N H
I p~N~N~N~N~CH3 CI
I I
Here, R2 has, for example, the meanings given above in group 1.
Group 86 Rz CH3 N~N H
CI ~ I C~N~~N~N~N~CH3 I I
1 ~ H CH3 Here, R'- has, for example, the meanings ~~iven abov~° in group 1.
Le A 32 819-Foreign countries Grou~87 Rz CH3 N~N H
S N~N~N~N~CH3 I I
Here, R-' has, for example, the meanings given above in group 1.
Groin 88 Rz CZHS N~N H
S N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 89 Rz CZHS N~N H
N~N~N~N~CH3 I I
lS
Here, R, has, for example. the meanings ~~iven above in group 1.
Le A 32 819-Foreign countries Group 90 Rz CH3 N~N H
N~N~N~N~CH3 S
Here, R' has, for example, the meanings given above in group 1.
Using, for example, 2-amino-4-(1-phenyl-ethylamino)-6-trifluoromethyl-1,3,5-triazine and N,N-diethyl-acetamide diethyl acetal as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme:
CH3 N~N .~ H C O~ C H CH3 N~N CH3 5 2 i 2 5 II 'I
\ ~ HsCzO N \ N~N~N~NiC2Hs ~N N NHz CzHS I H I
/ H i CzHS
The formula (II) provides a general definition of the substituted aminotriazines to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (II), R 1 and R2 preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R 1 and R2.
The starting materials of the y=eneral formula (II) are known and/or can be prepared by processes known per se (cf. US 3816419, US 3932167, EP 191496, EP 273328, EP 411153 / WO 90/09378, WO 97/00254, WO 97/08156, DE 19641691, DE
19641692, DE 19641693, DE 19711825, DE 19744 232, DE 1974471 1 ).
Le A 32 819-Foreign countries The formula (III) provides a general definition of the substituted amino compounds further to be used as starting materials for the process according to the invention. In the formula (III), R3, R4 and RS preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R3, R4 and R5; R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the ~~eneral formula (III) are known chemicals for synthesis.
The process according to the invention for preparing compounds of the general formula (I) is, if appropriate, carried out using a diluent. Suitable diluents are here especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, 1 ~ benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, disopropyl ether, dioxane, tetrahydrofttran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
When carryiny~ out the process according to the invention, the reaction temperatures can be varied within a relatively wide ran<~e. In general, the process is carried out at temperatures between 0°C an<l I ~0°C, preferably between 10°C and I 20°C.
>0 Le A 32 819-Foreign countries The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess.
The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the followin~~ plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver. Centaurea, Trifolium, Ranunculus. Taraxacum.
Dicotvledonous crops of the ~~enera: Gossypium, Gl:ycin~, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum. Ipomoea, Vicia, Nicotiana, Lvcopersicon, Arachis, Brassica, Lactuca, Cucumis, C'ucurbita.
Le A 32 819-Foreign countries Monocotyledonous weeds of the eg nera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or 1 ~ without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (1) according to the invention are particularly suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops, both by the pre-emergence and by the post-emergence 2~ method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wcttable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
Le A 32 819-Foreign countries These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example li'~nosulphite waste liquors and methylcellulose.
1'ackifiers, such as carboxymethvlcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and Le A 32 819-Foreign countries polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 9~ per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, 2~ chlorimuron(-ethyl), chlornitrofen, ehlorsulfuron, chlorotoluron, einmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxvdim, cyhalofop(-butyl), ?.4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, ditZufenican, diftufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitraminc, diphenamid, diquat, Le A 32 819-Foreign countries dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthi-acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate-(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, tritluralin and triflusulfuron.
A mixture with other known active compounds, such as fun'Ticides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
Le A 32 819-Foreign countries The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between l g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.
Le A 32 819-Foreign countries Preparation Examples:
Example 1 CF(CH3)2 CzHs N ~~ N H
~ i CH3 N~N~N~N~
I
A mixture of 2.0 g (0.8 mmol) of 2-amino-4-(1-fluoro-1-methyl-ethyl)-6-(1-thien-2-yl-propylamino)-1,3,5-triazine, 1.0 g (0.8 mmol) of N,N-dimethylformamide dimethyl acetal and 50 ml of methanol is stirred at from 50°C to 60°C for 5 hours.
The volatile components are subsequently carefully distilled off under waterpump vacuum.
This gives 2.4 g (99% of theory) of 2-dimethylaminomethyleneamino-4-(1-fluoro-methyl-ethyl)-6-(1-thien-2-yl-propylamino)-1,3,5-triazine as an oily residue with a refractive index np = 1.5995.
Analogously to Example 1, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
RZ
N~N R3 I
() H~ ~ ~ ~ ~Ra N N N N
R, Rs The stereochemical specifications in Table 1 refer to the '~roupin~~s defined under R~.
Le A 32 819-Foreign countries Table 1: Examples of the compounds of the formula (I) Ex. R~ R'- R3 R4 RS Physical data and stereochem.
No. specifications 2 ~2H5 CHFCH3 H CH3 CH3 (amorphous) s \ ~ (racemate) 3 ~ZHS CF(CH~)~ H CH3 CH3 np = 1.5606 s \ ~ (racemate) 4 c~ ~ CHFCH~ H CH3 CH3 m.p.:138°C
(racemate) N
5 0~ ~ CF(CH3)~ H CH3 CH3 m.p.: 185°C
(racemate) N
i' r Substituted aminoalkylideneaminotriazines The invention relates to novel substituted aminoalkylideneaminotriazines, to a process for their preparation and to their use as herbicides.
A number of substituted 2,4-diamino-triazines is already known from the (patent) literature (cf. US 3816419, US 393? 167, EP 191496, EP ?73328. EP 41 1 1 ~3 /
WO
90/09378, WO 97/0024, WO 97/08156). However, these compounds have hitherto not attained any particular importance.
This invention, accordingly, provides the novel substituted aminoalkylideneamino-triazines of the general formula (I) RZ
~V~N R3 W ~R' (1) N N N N
R' RS
- l~
in which R~ represents the grouping -A-Z, in which A represents optionally substituted straight-chain or branched alkanedivl which optionally contains at the be~~innin~~ or at the end or within the alkanedivl chain an o~y~len atom. a Sulphur atom. an imino (NH) or an alkvlimino ( ~
? ~ alkyl) '=roup, and Le A 32 819-Foreign countries Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, di-hydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benz-oxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, R'- represents hydrogen, cyano, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkyl-sulphinyl, alkylsulphonyl, alkenyl, alkinyl or cycloalkyl, R' represents hydrogen or alkyl, R4 represents hydrogen or alkyl, and R~ represents alkyl.
The novel substituted aminoalkylideneaminotriazines of the general formula (I) are obtained when substituted aminotriazines of the general formula (II) N~N
(II>
N N N
I, I
R' H
in which Le A 32 819-Foreign countries R~ and R2 are as defined above, are reacted with substituted amino compounds of the general formula (III) RO'~N~R4 (III) R
in which R', R4 and R~ are as defined above and R represents alkyl, if appropriate in the presence of a diluent.
The novel substituted aminoalkylideneaminotriazines of the general formula (I) have strong and selective herbicidal activity.
To a certain extent, the compounds of the formula (I) also have fungicidal and insecticidal activity.
The compounds of the general formula (I) accordin~~ to the invention may contain asymmetrically substituted carbon atoms, in which case they can be present in different enantiomeric (R- and S-configured forms) or diastereomeric forms.
The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the ~~encra.l ti>rmula (1) and to the mixtures of these isomeric compounds.
Le A 32 819-Foreign countries In the definitions, the hydrocarbon chains, such as alkyl - including in combination with heteroatoms, such as in alkoxy or alkylthio - are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which l0 R ~ represents the grouping -A-Z, in which A represents optionally cyano- or halogen-substituted straight-chain or 1 S branched alkanediyl having 1 to 6 carbon atoms, which optionally contains at the beginning or at the end or within the alkanediyl chain oxygen, sulphur, imino (NH) or C 1-C4-alkylimino, and Z represents an optionally substituted monocyclic or bicyclic, carbo-20 cyclic or heterocyclic grouping from the series consisting of cyclo-pentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzo-thienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, 25 indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thia-zolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thia-diazolyl, pyrazolyl, pyridinyl, pyri~:midinyl, pyrazinyl, pyridazinyl, quinolvl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinvl.
30 where the possible substituents of these radicals are in each case preferably selected from the followin~~ group:
Le A 32 819-Foreign countries a hydroxyl, cyano, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, Cl-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, R'- represents hydrogen, cyano, halogen, represents in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C 1-C4-alkoxy-, C 1-C4-alkylthio-, C 1-C4-alkylsulphinyl- or C 1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkyl-carbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C 1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R' represents hydrogen or alkyl having 1 to 6 carbon atoms, R't represents hydrogen or alkyl having 1 to 6 carbon atoms, and R~ represents alkyl having 1 to 6 carbon atoms.
2~ Among the compounds of the fornmla (I) defined above as being preferred ("preferably"), particular emphasis is given to the following groups:
(A) the compounds of the formula (I) in which A, R~', R'. R~ and R' are as defined above and Z represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are as defined above;
Le A 32 819-Foreign countries (B) the compounds of the formula (I) in which A, R2, R3, R4 and RS are as defined above and Z represents optionally substituted heterocyclyl, where the possible heterocyclyl groupings and the possible substituents are as defined above.
The invention relates in particular to compounds of the formula (I) in which R ~ represents the ~~roupin~~ -A-Z , in which A represents in each case optionally cyano-, fluorine- or chlorine-substituted methylene (-CH,-), dimethylene (ethane-1,2-diyl, -CH~CH~-), ethylidene (ethane-1,1-diyl, -CH(CH;)-), trimethylene (propane-1,3-diyl, -CH-,CH~CH-,-), propylidene (propane-l,l-diyl, -CH(C~H~)-), propane-2,3-diyl (-CH(CH3)CH~-), 2-methyl-propane-1,3-diyl (-CH~CH(CH~)CH~-), 3-oxa-propane-1,3-diyl (-CH~CH~O-), 2-oxa-propane-1,3-diyl (-CH~OCH-,-), tetramethylene (butane-1,4-diyl -CH~CH-,CH~CH~-), butane-2,4-diyl (-CH(CH3)CH~CH-,-), butane-2,3-diyl (-CH(CH;)CH(CH~)-), 3-methyl-butane-2,4-diyl (-CH(CH~)CH(CH~)CH~-), 4-oxa-butane-2,4-diyl (-CH(CH~)CH~O-), pentane-3,5-diyl (-CH(C-,H~)CH~C.'H-,-), 5-oxa-pentane-3,~-diyl (-CH(C~H~)CH-,O-), 4-oxa-pentane-2,5-diyl (-CH(CH~)CH-,OCH~-) or 5-oxa-hexane-3,6-diyl (-CH(C-,HS)CH-,OCH~-), and Z represents an optionally substituted monocyclic or bicyclic, carbo-cyclic or heterocyclic grouping from the series consisting of cyclo-pentyl, cvclohexyl, phenyl, naphthyl, tetralinyl. dccalinyl, indanvl, indenvl, furyl. benzofuryl, dihydrobenzofuryl. thienyl, benzothienyl, dihydrobc:nzothicnvl. isobenzofuryl. dihydroisobmzofuryl, isobenzo-thienyl. dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinvl, isoindolinyl, bcn zodioxolyl, oxazolyl, benzoxazolyl, thia-Le A 32 819-Foreign countries _7.
zolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thia-diazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, where the possible substituents of these radicals are in each case preferably selected from the group below:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- and/or chlorine-substituted methyl-carbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- or t-butoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butyl-thio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy-or trifluoromethoxy-substiuted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, R-' represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, n- or i-butyroyl, methoxy-carbonyl, ethoxvcarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n-or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, rnethylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents in each Le A 32 819-Foreign countries _g_ case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R' represents hydrogen, methyl or ethyl, R4 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, and RS represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.
Group 1 CH3 N ~ N H
CH
N~N~N~\N~ 3 I I
Here. R' has. for example, tl meanin~~s given below:
Le A 32 819-Foreign countries n _9_ methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, fluoromethyl, difluoromethyl, tri-fluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromo-methyl, chlorodifluoromethyl, fluorodichloromethyl, bromodifluoromethyl, trichloro-methyl, 1-fluoroethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 1-chloro-1-fluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-bromopropyl, I-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl, 1-fluoro-1-methyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-I-ethyl-propyl, I-fluoro-2-methyl-propyl, 1-chloro-2-methyl-propyl, 2-chloro-I-methyl-ethyl, 1,l-difluoroethyl, 1,2-difluoroethyl, 1,1-dichloroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl, 1,1-difluoropropyl, 1,1-dichloropropyl, perfluoropropyl, 1-fluorobutyl, 1-chlorobutyl, perfluorobutyl, per-fluoropentyl, perfluorohexyl, 1-hydroxy-ethyl, 1-hydroxy-1-methyl-ethyl, 1-hydroxy-propyl, methoxymethyl, ethoxymethyl, dimethoxy-methyl, 1-methoxyethyl, 2-methoxy-ethyl, 1,1-dirnethoxy-ethyl, 1-ethoxyethyl, 2-ethoxy-ethyl, 2,2-dimethoxy-ethyl, 2,2-diethoxy-ethyl, 2-methoxy-1-methyl-ethyl, 2-methoxy-1-ethylethyh 2-ethoxy-1-methylethyl, 2-ethoxy-1-ethylethyl, 2,2-bis-methoxymethyl, methylthio-methyl, ethylthiomethyl, 1-methylthio-ethyl, 2-methylthioethyl, !-ethylthioethyl, 2-ethylthioethyl, methylsulphinylmethyl, ethylsulphinylmethyl, methylsulphonyl-methyl, ethylsulphonylmethyl, vinyl, 1-chlorovinyl, 2-chlorovinyl, 1-fluorovinyl, 2-fluorovinyl, 1-bromovinyl, 2-bromovinyl, 1,2-dichlorovinyl, 1,2-dibromovinyl, 1,2-difluorovinyl, 2,2-dichlorovinyl, 2,2-difluoro-vinyl, 2,2-dibromovinyl, 1-chloro-2-fluorovinyl, 1-fluoro-2-chlorovinyl, 2-bromo-1-chlorovinyl, 2-bromo-2-chlorovinyl, l-bromo-2-fluorovinyl, 1-fluoro-2-bromovinyl, 1-bromo-2-chlorovinyl, trichloro-vinyl, trifluorovinyl, tribromovinyl, 1-fluoro-2,2-dichlorovinyl, 1-bromo-2,2-dichlorovinyl, 1-fluoro-2,2-dibromovinyl, 1-chloro-2,2-difluorovinyl, 1-chloro-2,2-dibromovinyl, 1-bromo-2,2-difluorovinyl, 2-fluoro-1.2-dichlorovinyl, 2-chloro-1,2-difluorovinyl, 2-bromo-1.2-difluorovinyl, 2-bromo-~1,2-dichlorovinyl, 2-chloro-1,2-dibromovinyl, 2-tluoro-1,2-dibromovinyl, 2-bromo-1-chloro-2-fluorovinyl, ?-methoxyvinyl, 2-ethoxwinyl, allyl, 2-chloroallyl, 3-chloro-allvl, 3.3-dichloroallyl, propen-1-yl, propen-2-yl, 1-chloropropen-I-yl, 1-bromo-propen-1-yl, 1-tluoropropen-2-yl, 1-chloropropen-2-yl, 1-bromopropen-2-yl, ?-methoxypropen-1-yL, 2 Le A 32 819-Foreign countries ethoxypropen-1-yl, 3,3,3-trifluoropropen-1-yl, 3,3,3-trifluoropropen-2-yl, 1-chloropropen-2-yl, 1-fluoropropen-2-yl, 1-bromoprapen-2-yl, 1,2-dichloropropen-yl, 1,2-dibromopropen-1-yl, 1,2-difluoropropen-1-yl, 1,1-dichloropropen-2-yl, 1,1-dibromopropen-2-yl, 1,1-difluoropropen-2-yl, 1-chloro-2-fluoropropen-1-yl, I-chloro-2-bromopropen-1-yl, 1-bromo-2-chloropropen-1-yl, 1-bromo-2-fluoropropen I-yl, 1-chloro-3,3,3-trifluoropropen-2-yl, 1-bromo-3,3,3-trifluoropropen-2-yl, I-fluoro-3,3,3-trichloropropen-1-yl, 1,3,3,3-tetrafluoropropen-1-yl, 1,3,3,3-tetra-fluoropropen-2-yl, 1-bromo-2-chloro-3,3,3-trifluoropropen-1-y(, I ,1,3,3,3-penta-fluoropropen-2-yl, 1,2,3,3,3-pentafluoropropen-I-yl, 1,1-dichloro-3,3,3-trifluoropropen-2-yl, 1,2-dichloro-3,3,3-trifluoropropen-2-yl, I,1-dibromo-3,3,3-trifluoropropen-2-yl, 1,2-dibromo-3,3,3-trifluoropropen-2-yl, 1-chloro-2,3,3,3-tetra-fluoro-1-propen-1-yl, 2-methyl-propen-I-yl, 1-chloro-2-methyl-propen-1-yl, 1-bromo-2-methyl-propen-I-yl, I-fluoro-2-methyl-propen-1-yl, 1-bromo-2-methyl-3,3,3-trifluoropropen-1-yl, 1-chloro-3,3,3-trifluoro-2-trifluoromethyl-propen-I-yl, 1-bromo-3,3,3-trifluoro-2-trifluoromethyl-propen-I-yl, I-chloro-3,3,3-trifluoropropen-I-yl, 1-bromo-3,3,3-trifluoropropen-1-yl, 1-chloro-2,3,3,3-tetrafluoropropen-I-yl, 1-chloro-2-bromo-3,3,3-trifluoropropen-1-yl, I-chloro-2-methyl-3,3,3-trifluoropropen-1-yl, 1-bromo-2-fluoropropen- I -yl, 1-buten-1-yl, 1-buten-2-yl, 2-buten-1-yl, 2-buten-2-yl, I -chloro-1-buten-1-yl, I -bromo-1-buten-1-yl, I -fluoro-1-buten-1-yl, 1-chloro-1-buten-2-yl, 1-fluoro- I -buten-2-yl, I -bromo- I -buten-2-yl, 1,2-difluoro- I -buten-1-yl, I ,2-dichloro-1-buten- I -yl, 1,2-dibromo- I -buten-1-yl, 1-bromo-2-fluoro- I -buten-1-yl, 3-methyl-2-buten-2-yl, I-chloro-2-fluoro-I-buten-1-yl, I-bromo-2-chloro-I-buten-I-yl, 1,1,1-trifluoro-2-methyl-2-buten-2-yl, 4,4,4-trifluoro-2-methyl-buten-2-yl, 4,4,4-trifluoro-3-trifluoromethyl-2-buten-2-yl, I-chloro-2-methyl-3,3,3-trifluoropropen-1-yl, 3-chloro-2-buten-2-yl, 3-bromo-2-buten-2-yl, 3-fluoro-2-buten-2-yl, I-chloro-2-methyl- I -buten- I -yl, 1-bromo-2-methyl-1-buten- I -yl, I -fluoro-2-methyl-I -buten- I -yl, 1-fluoro-3-methyl-1-buten-1-yl, 1-chloro- 3-methyl-1-buten-1-yl, 2-methoxy-buten-1-yl, 2-ethoxy- I -buten-1-vl, l , l -dichloro-1-buten-2-yl, l , l -dibromo-1-buten-2-yl, 1,1-dit7uoro-1-buten-2-yl. I-chloro-2-fluoro-1-buten-1-yl. I-chloro-2-bromo-1-buten-1-yl, I -chloro-2-tritluoromethyl- l -buten-1-yl, 1,1,1-tritluoro-2-buten-2-yl, 4,4,4-tritluoro-2-buten-2-yl. 4,4,4-tritluoro-3-methyl-2-buten-2-yl, l,l,l-trifluoro-3-. Le A 32 819-Foreign countries methyl-2-penten-2-yl, 1,1;1-trifluoro-3-ethyl-2-penten-2-yl, 1,1,1,4,4,4-hexafluoro-2-buten-2-yl, 1-chloro-2-ethyl-1-buten-1-yl, 1-bromo-2-ethyl-1-buten-1-yl, I -fluoro-2-ethyl-I-buten-1-yl, 2-penten-2-yl, 2-penten-3-yl, 2-chloro-2-penten-3-yl, 2-bromo-2-penten-3-yl, 2-fluoro-2-penten-3-yl, 3-chloro-2-penten-2-yl, 3-bromo-2-penten-2-yl, 3-fluoro-2-penten-2-yl, 3-trifluoromethyl-2-penten-2-yl, 1, I , l -trifluoro-2-penten-3-yl, 1,1,1-trifluoro-2-penten-2-yl, 1, l,1-trifluoro-3-methyl-2-penten-2-yl, 2-methyl-2-penten-3-yl, 3-methyl-2-penten-2-yl, 1,1,I-trifluoro-2-trifluoromethyl-2-penten-3-yl, 4-methyl-3-hexen-3-yl, 4-fluoro-3-hexen-3-yl, 4-chloro-3-hexen-3-yl, 4-bromo-3-hexen-3-yl, 1, l, I-trifluoro-2-methyl-2-hexen-3-yl, 4-ethyl-3-hexen-3-yl, ethinyl, 2-chloroethinyl, 2-bromoethinyl, propin-I-yl, propin-3-yl, 3,3,3-trifluoropropin-I-yl, 1-butin-1-yl, 1-butin-3-yl, 3-methyl-1-butin- I -yl, 1-pentin- I -yl, cyclopropyl, 1-cyano cyclopropyl, 1-fluorocyclopropyl, 1-chlorocyclopropyl, 2-cyanocyclopropyl, 2 fluorocyclopropyl, 2-chlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dichlorocyclo propyl, cyclobutyl, 2,2-difluorocyclobutyl, 2,2,3-trifluorocyclobutyl, 2,2-difluoro-3 chlorocyclobutyl, cyclopentyl, cyclohexyl.
Group 2 CZHS N ~ N H
~CH3 N~N~N~N
I I
Here, R'- has, for example, the meanin~~s ~~iven above in group 1.
Le A 32 819-Foreign countries Group 3 Rz CZHS N-/ _N H
CH
~N N N N~
CI
Here, R'- has, for example, the meanin~~s given above in group 1.
Group 4 CH3 N~N H
N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 5 Rz N~N~.N~N~CH3 I I
Here, R-' has. for example, the meanings given above in ~~roup 1.
Le A 32 819-Foreign countries Grou 6 Rz C2H5 N~N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 7 RZ
CzHs N~N H
H3C ~ N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 8 Rz CH3 N~N H
H3C ~ N~N~N~N~CH3 I I
Is Here, R'- has, for example, the meanin~~s given above in 'croup 1.
Le A 32 819-Foreign countries Group 9 Rz CH3 CH3 N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group l .
Group 10 CH3 CzHs N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 11 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
l~
Here, R' has, for example. the meanings given above in ~~roup I .
Le A 32 819-Foreign countries Group 12 Rz C3H~-i N-/ _N H
N~N~N~N~CH3 I I
S Here, R'- has, for example, the meanings given above in group I .
Group 13 Rz C3Hz-i N_/ _N H
N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group I .
Group 14 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
1 ~ CI
Here, R~' has. for example, the meanin';s ~~iven above in 'Troup 1.
Le A 32 819-Foreign countries Group 15 Rz CH3 N~N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 16 Rz CzHs N~N H
N~N~~N~N~CH3 I
Here, R'- has, for example, the meanings given above in group 1.
Group 17 Rz C3H~-nN~N H
N~N~N~N~CH3 I I
l~
Eiere, R'- has. for example. the mcanin~~s ~~ivcn above in ~'roup 1.
Le A 32 819-Foreign countries Group 18 Rz C3H~-i N-/ _N H
\ N~N~N~N~CH3 I I
Here, R-' has, for example, the meanings given above in group 1.
Group 19 RZ
\ CH3 N-/ _N H
~CH3 \ N~N~N~N
I I
Here, R' has, for example, the meanings given above in group 1.
Group 20 Rz CH3 N~N H
\ \ N~N~~N~N~CH3 I I
is Here, R-' has, ter example. the meanin~,s <~iven above in 'croup l .
Le A 32 819-Foreign countries Grog 21 Rz CH3 N~N H
CI \ N~N~N J\N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 22 RZ
CZHS N / _N H
CI \ N~N~~~N~CH3 i I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 23 RZ
CZHS N~N H
HsC \ N~N~.N~N~CH3 I I
I~ H3C
Here, R' has, for example, the meanin~~s ~Tiven above in group I .
Le A 32 819-Fore~yn countries Group 24 Rz CH3 N~N H
H3C \ N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 2J
Rz CH3 N_/ _N H
F \ ~N~N~N~N~CH3 I I
F
Here, R'- has, for example, the meanings given above in group 1.
Group 26 Rz CzHs N~N H
F \ N~N~N~N~CH3 I I
l~
Here. R'- has, for example. the meanings given above in group 1.
Le A 32 819-Foreign countries Groin 27 Rz CH3 N-/ _N H
H3C ~ N~N~N~N~CH3 I I
CI
Here, R'- has, for example, the meanings given above in group 1.
Group 28 CH3 N-/ _N H
CI \ N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 29 CH3 N~N H
\ N~N~N~N~CH3 I I
l~
Here, R-' has, for example, the meanin~~s ~,iven above in ~~roup 1.
Le A 32 819-Foreien countries Group 30 Rz CZHS N_/ _N H
N~N~N~N~CH3 I f F
Here, R'- has, for example, the meanings given above in group 1.
Group 31 Rz CH3 N-/ _N H
N~N~N~N~CH3 Here, R' has, for example, the meanings given above in group 1.
Group 32 Rz CH3 N~N H
N~N~.N~N~CH3 l~
Here, R' has. for example, the meaning; riven abovf: in ~~roup 1.
Le A 32 819-Fore countries Groin 33 Rz CH3 N-/ _N H
N~N~N~N~CH3 t I I
Here, R-' has, for example, the meanings given above in group 1.
Grou~34 Rz CZHS N~N H
N~N~N~N~CH3 l I I
Here, R' has, for example, the meanings given above in group 1.
Group 35 Rz CZHS N-/ _N H
~CH3 ~N N N N
I
H~C
l Here. R-' has, for example. the meanings given above in group I .
Le A 32 819-Foreign countries =23-Group 36 RZ
CH3 N_/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 37 RZ
CH3 N~N H
H C ~ N~N~\N~N/CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 38 C2H5 N~N H
N~N~~N~N~CH3 H3C ~~ 'I I
Here, R~ has, for example. the meanin~~s ~~iv~n above in ~~roup 1.
Le A 32 819-Foreign countries Group 39 Rz CH3 N-/ _N H
N~N~N~N~CH3 I I
CI
Here, R-' has, for example, the meanings given above in group 1.
Group 40 C H N H
z 5 ~ ~ ~CH3 ~N N N N
CI
Here, R' has, for example, the meanings given above in group 1.
Group 41 Rz CZHS N~N H
CI ~ N~N~N~N~CH
I I
1 ~ CI
Rz N
Here, R-' has, for example, the meanin«s riven above in ~Troup 1.
Le A 32 819-Foreiem countries Group 42 Rz CH3 N-/ _N H
\ ~ /~
CI ~ N~N~N~N'CH
I I
CI
Here, R-' has, for example, the meanings given above in group 1.
Group 43 Rz CH3 N-/ _N H
~\ ~ /~
N~N~N~N~CH
I I
Here, R'- has, for example, the meanings given above in group 1.
Group 44 Rz C2H5 N~N H
~CH3 N N N N
is Eiere, R~ has, for example. the meanin~~s ~~iven abov~° in ~~roup 1.
Le A 32 819-Foreign countries Group 45 CZHS N-/ _N H
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 46 Rz CH3 N-/ _N H
/
N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 47 Rz CH3 N~N H
w ~ ~CH3 N N N N
l~
Here. R-' has, for example. the mvaninV~s y~ivcn ahove in ~~roup I .
Le A 32 819-Foreign countries Group 48 CzHs N~N H
O~ ~ ~ ~ ~CH3 N N N N
Here, R' has, for example, the meanings given above in group 1.
Groin 49 CZHS N~N H
F3C \ O~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 50 Rz CH3 N~~N H
FsC W O~N~:N~N~N~CHs l~
Here. R'- has, for example. the meanin~~s given above in «roup I .
Le A 32 819-Foreign countries Group 51 Rz CH3 N-' _N H
H3C \ p~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Grou~52 Rz CzHs N~N H
H C ~ ~~N~~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 53 Rz CZHS N ~~N H
i \ p~N~.N~N~N~CH3 I I
l~
Here. R' has, for example, the meanings <~iven above in group 1.
Le A 32 819-Foreign countries Group 54 Rz CH3 N~N H
O~N~N~N~N~CHs Here, R'- has, for example, the meanings given above in group 1.
Group 55 Rz CH3 N~N H
H3C \ O~N~N~~~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Groin 56 Rz CZHS N~N H
HsC W O~N~~N~N~N~CH3 I I
H CH, Is Here, R~ has. for example. the meanings given above in ~Troup 1.
Le A 32 819-Foreign countries GrouQ57 Rz C2H5 N~N H
O~N~N~N~NiCHs F
Here, R'- has, for example, the meanings given above in group 1.
Group 58 Rz CH3 N~N H
O~ ~ ~ ~ ~CH3 N N N N
F
Here, R'- has, for example, the meanings given above in group 1.
Group 59 Rz CH3 N'~N H
O' ~ ~~ ~ ~ ~CH3 CI ~ v _N N N N
I I
1 ~ CI
Here, R' has, for example. the meanings given abov~° in groin 1.
Le A 32 819-Foreign countries Group 60 Rz CZHS N-/ _N H
CI ~ ~~N~N~N~N~CH' CI
Here, R'- has, for example, the meanings given above in group 1.
Group 61 Rz CzHs N~N H
F ~ O~N~N~N~N~CH3 I I
F
Here, R'- has, for example, the meanings given above in group 1.
Group 62 Rz CH3 N~\N H
F \ O~N~N~N~N~CH3 F
1>
Here. R~ has. for wample, the meanings given above in group 1.
Le A 32 819-Foreign countries Group 63 CH3 N~N H
H3C \ O~N~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Group 64 Rz CZHS N~N H
O' ~ ~ ~ ~ ~CH3 H3C ~ v _N N N N
Here, R'- has, for example, the meanings given above in group 1.
Group 65 CZHS N'~N H
CI ~ O~N~'N~N~N~CH3 CI
1>
E-lerc. R'- has, for example, the meanin~ls <~iven above in ~*r~up 1.
Le A 32 819-Foreign countries GrouQ 66 Rz CH3 N~N H
CI ~ ~~N~N~N~N~CH3 CI
Here, R-' has, for example, the meanings given above in group 1.
Group 67 Rz CH3 N-/ _N H
p~N~N~N~N~CH3 I
Here, R' has, for example, the meanings given above in group 1.
Group 68 Rz CZHS N~N H
p~N~Nj~N~N~CH3 l Here. R-' has, for example. the mennin'~s given above: in group 1.
Le A 32 819-Foreign countries Group 69 Rz CI CZHS N-/ _N H
O~N~N~N~N~CH3 i Here, R'- has, for example, the meanings given above in group 1.
Grog 70 CI CH3 N~N H
' ~ ~CH3 O~N N N ~N
I I
Here, R' has, for example, the meanings given above in group 1.
Group 71 CH3 N~N H
W I O~Ni~N~N~N~CH3 CI I i Here. R- ha;. ti>r example. the meanin~~s given above' in ~~roup 1.
Le A 32 819-Foreign countries Groin 72 Rz CZHS N-/ _N H
O~N~N~N~N~CH3 CI I I
Here, R'- has, for example, the meanings given above in group 1.
Group 73 RZ
CI CzHs N~N H
O~N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 74 Rz CI CH3 N~~N H
O~N~N~N~N~CH3 I I
1~
Here, R' has, for example, the meanin~Ts given above: in group 1.
Le A 32 819-Foreign countries Group 75 Rz CH3 CH3 N_/ _N H
O~N~N~N~N~CH3 I I
Hefe, R'- has, for example, the meanings given above in group 1.
Group 76 Rz CH3 CzHs N-/ _N H
O~N~N~N~N~CH3 I I
Here, R' has, for example, the meanings given above in group 1.
Group 77 Rz H3C CzHs N~N H
I O~N~N~N~N~CH3 I I
Here. R' has, for example, the meanings given above, in <~roup l .
Le A 32 819-Foreigil countries Group 78 H C CH3 N-/ _N H
s ~ I O~N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 79 Rz CH3 N-/ _N H
I O~N,~N~N~N~CH3 Here, R'- has, for example, the meanings given above in group 1.
Gro ~ 80 Rz C2H5 N-/ _N H
W I O~N.~N~N~NiCHs 1-lere. R-' hay, for example, the meanin<~s ~Tiven above in <,roup 1.
Le A 32 819-Forei countries _3g_ Group 81 Rz CZHS N~N H
I p~N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group I .
Group 82 Rz CH3 N~N H
I p~N~Nj~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 83 Rz I p~N~N~N~N~CH3 I I
l~ H CH3 Here. R'- has, for example, the meanings <~iven above in group 1.
Le A 32 819-Foreign countries Group 84 Rz CzHs N-/ _N H
I p~N~N~N~N~CH3 I I
Flere, R'- has, for example, the meanings given above in group 1.
Group 85 Rz CH3 N-/ _N H
I p~N~N~N~N~CH3 CI
I I
Here, R2 has, for example, the meanings given above in group 1.
Group 86 Rz CH3 N~N H
CI ~ I C~N~~N~N~N~CH3 I I
1 ~ H CH3 Here, R'- has, for example, the meanings ~~iven abov~° in group 1.
Le A 32 819-Foreign countries Grou~87 Rz CH3 N~N H
S N~N~N~N~CH3 I I
Here, R-' has, for example, the meanings given above in group 1.
Groin 88 Rz CZHS N~N H
S N~N~N~N~CH3 I I
Here, R'- has, for example, the meanings given above in group 1.
Group 89 Rz CZHS N~N H
N~N~N~N~CH3 I I
lS
Here, R, has, for example. the meanings ~~iven above in group 1.
Le A 32 819-Foreign countries Group 90 Rz CH3 N~N H
N~N~N~N~CH3 S
Here, R' has, for example, the meanings given above in group 1.
Using, for example, 2-amino-4-(1-phenyl-ethylamino)-6-trifluoromethyl-1,3,5-triazine and N,N-diethyl-acetamide diethyl acetal as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme:
CH3 N~N .~ H C O~ C H CH3 N~N CH3 5 2 i 2 5 II 'I
\ ~ HsCzO N \ N~N~N~NiC2Hs ~N N NHz CzHS I H I
/ H i CzHS
The formula (II) provides a general definition of the substituted aminotriazines to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (II), R 1 and R2 preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R 1 and R2.
The starting materials of the y=eneral formula (II) are known and/or can be prepared by processes known per se (cf. US 3816419, US 3932167, EP 191496, EP 273328, EP 411153 / WO 90/09378, WO 97/00254, WO 97/08156, DE 19641691, DE
19641692, DE 19641693, DE 19711825, DE 19744 232, DE 1974471 1 ).
Le A 32 819-Foreign countries The formula (III) provides a general definition of the substituted amino compounds further to be used as starting materials for the process according to the invention. In the formula (III), R3, R4 and RS preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R3, R4 and R5; R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the ~~eneral formula (III) are known chemicals for synthesis.
The process according to the invention for preparing compounds of the general formula (I) is, if appropriate, carried out using a diluent. Suitable diluents are here especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, 1 ~ benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, disopropyl ether, dioxane, tetrahydrofttran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
When carryiny~ out the process according to the invention, the reaction temperatures can be varied within a relatively wide ran<~e. In general, the process is carried out at temperatures between 0°C an<l I ~0°C, preferably between 10°C and I 20°C.
>0 Le A 32 819-Foreign countries The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess.
The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the followin~~ plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver. Centaurea, Trifolium, Ranunculus. Taraxacum.
Dicotvledonous crops of the ~~enera: Gossypium, Gl:ycin~, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum. Ipomoea, Vicia, Nicotiana, Lvcopersicon, Arachis, Brassica, Lactuca, Cucumis, C'ucurbita.
Le A 32 819-Foreign countries Monocotyledonous weeds of the eg nera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or 1 ~ without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (1) according to the invention are particularly suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops, both by the pre-emergence and by the post-emergence 2~ method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wcttable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
Le A 32 819-Foreign countries These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example li'~nosulphite waste liquors and methylcellulose.
1'ackifiers, such as carboxymethvlcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and Le A 32 819-Foreign countries polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 9~ per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, 2~ chlorimuron(-ethyl), chlornitrofen, ehlorsulfuron, chlorotoluron, einmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxvdim, cyhalofop(-butyl), ?.4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, ditZufenican, diftufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitraminc, diphenamid, diquat, Le A 32 819-Foreign countries dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthi-acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate-(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, tritluralin and triflusulfuron.
A mixture with other known active compounds, such as fun'Ticides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
Le A 32 819-Foreign countries The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between l g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.
Le A 32 819-Foreign countries Preparation Examples:
Example 1 CF(CH3)2 CzHs N ~~ N H
~ i CH3 N~N~N~N~
I
A mixture of 2.0 g (0.8 mmol) of 2-amino-4-(1-fluoro-1-methyl-ethyl)-6-(1-thien-2-yl-propylamino)-1,3,5-triazine, 1.0 g (0.8 mmol) of N,N-dimethylformamide dimethyl acetal and 50 ml of methanol is stirred at from 50°C to 60°C for 5 hours.
The volatile components are subsequently carefully distilled off under waterpump vacuum.
This gives 2.4 g (99% of theory) of 2-dimethylaminomethyleneamino-4-(1-fluoro-methyl-ethyl)-6-(1-thien-2-yl-propylamino)-1,3,5-triazine as an oily residue with a refractive index np = 1.5995.
Analogously to Example 1, and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
RZ
N~N R3 I
() H~ ~ ~ ~ ~Ra N N N N
R, Rs The stereochemical specifications in Table 1 refer to the '~roupin~~s defined under R~.
Le A 32 819-Foreign countries Table 1: Examples of the compounds of the formula (I) Ex. R~ R'- R3 R4 RS Physical data and stereochem.
No. specifications 2 ~2H5 CHFCH3 H CH3 CH3 (amorphous) s \ ~ (racemate) 3 ~ZHS CF(CH~)~ H CH3 CH3 np = 1.5606 s \ ~ (racemate) 4 c~ ~ CHFCH~ H CH3 CH3 m.p.:138°C
(racemate) N
5 0~ ~ CF(CH3)~ H CH3 CH3 m.p.: 185°C
(racemate) N
6 ~H3 CF(CH~)-, H CH3 CH3 °
[a]p =-109 \ w (S enantiomer) 7 czHS CF(CH~)-, H CH3 CH3 np = 1.5342 s \ ~ (S enantiomer) 8 c2"5 CF; H CH3 CH3 oil v ~ (racemate) s c_HS C-,H~ H CH; CHI oil (racemate) s Le A 32 819-Fore~n countries Table 1 (continued) Ex. R1 R2 R3 R4 RS Physical data No. and stereochem.
specifications 10 ~z"5 CF(CH~)~ H CH3 CH3 n; ° = I .5817 (racemate) s ci 11 ~z"5 CH~OCH~ H CH3 CH3 oil / " ~ (racemate) s 12 ~2"5 CHCI-, H CH3 CH3 oil / " ~ (racemate) s 13 ~5 CHC1CH~ H CH3 CH3 oil / ~ ~ (racemate) J
14 ~2"5 CFA H CH3 CH3 oil s (racemate) 15 ~Z"5 CH3 H CH3 CH3 oil / v ~ (racemate) s 16 ~z"5 CHCI, H CH3 CH3 oil s (racemate) 17 cZ"5 CHFCH~ H CHI CH3 oil /~ " ~ (racemate) s Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R' R3 R4 RS Physical data No. and stereochem.
specifications 18 cZHs CF(CH3)-, H CH3 CH3 oil v ~ (racemate) s 19 CH3 CHCICH~ H CH3 CH3 nD - 1.5961 (S enantiomer) /
[a]p -_128.35°
20 ~ CzHs CHC1CH~ H CH3 CH3 20 [a]p - -102.5 (S enantiomer) 21 CzHs CHBrCH~ H CH3 CH3 (amorphous) \ (racemate) /
CI
22 CzHs CHBrCH~ H CH3 CH3 n~~ = 1.5932 (racemate) /
23 CH3 CH(CH~)~ H CH3 CH3 nD = 1.6123 (racemate) /
~4 CH3 CF~CF~ H CH3 CH3 n~~~ = 1.5373 (racemate) /
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data No. and stereochem.
specifications 25 CH3 CHFCH3 H CH3 CH3 np = 1.5930 (racemate) /
26 CzHS CHFCH; H CH3 CH3 np = 1.5709 (S enantiomer) /
27 CzHs CF(CH3)? H CH3 CH3 (S enantiomer) /
28 CzHs CHFCH~ H CH3 CH3 np = 1.5932 (R enantiomer) /
29 CzHS CF(CH~)~ H CH3 CH3 np = 1.5820 (R enantiomer) /
30 CzHs CHC1CH~ H CH3 CH3 n~ = 1.5975 (R enantiomer) /
31 CzHs CHCI~ H CH3 CH3 n~~' = I
.6053 I ~ ~ ~ (R enantiomer) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data No. and stereochem.
specifications 32 CH3 CHCl2 H CH3 CH3 \ (racemate) CI
33 CH3 CH~OCH3 H CH3 CH3 \ \ (racemate) CI
34 CHs CHC1CH; H CH3 CH3 \ \ (racemate) /
CI
35 CH3 CHFCH~ H CH3 CH3 nD = 1.5999 \ ~ (S enantiomer) /
CI
36 CH3 CFA H CH3 CH3 n~ = 1.5871 \ ~ (S enantiomer) /
CI
37 CH3 CF~CF~ H CH3 CH3 \ \ (S enantiomer) /
CI
38 CH3 CHFCH~ H CH3 CH3 \ \ (R enantiomer) /
CI
Le A 32 819-Foreign countries Table 1 (continued) Ex.. R~ R2 R3 R4 RS Physical data and No.
stereochem.
specifications 39 CzHs CFA H CHI CHI (S enantiomer) \ w CI
40 CH3 CHFCH; H CH3 CH3 \ (S enantiomer) /
41 CH3 CF(CH~), H CH3 CH3 \ (S enantiomer) \ (S enantiomer) /
43 CH3 CHC1CH~ H CH3 CH3 \ (racemate) \ (S enantiomer) 4~ CH3 C-,H~ H CHI CH3 \ (S enantiomer) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R' R3 R4 R5 Physical data and stereochem.
specifications \ (S enantiomer) / /
47 CH3 CHFCH; H CH3 CH3 \ (S enantiomer) / /
48 CH3 CF(CH~)2 H CH3 CH3 \ (S enantiomer) / /
49 CH3 CF(CH3)2 H CH3 CH3 H3C ~ (racemate) /
50 CH3 CHFCH; H CH3 CH3 H3C ~ (racemate) ~ 1 CH3 CFA H CH3 CH3 H3C ~ (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 52 ~H3 CF3 H CH3 CH3 F
\ \ (racemate) F
53 ~H3 CHFCH~ H CH3 CH3 F \ (racemate) F
54 ~H3 CF(CH~)2 H CH3 CH3 F \ (racemate) /
F
55 ~H3 CF(CH3)~ H CH3 CH3 (racemate) 56 ~H3 CHFCH~ H CH3 CH3 (racemate) 57 ~zHs CHCI-, H CH3 CH3 (amorphous) \ \ (S enantiomer) I
I, ~8 CzHs CF; H CH3 CH3 (amorphous) \ (S enantiomer) I
I, /
I
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R' R4 RS Physical data and stereochem.
No. specifications 59 ~ZHS CF(CH3)2 H CH3 CH3 (amorphous) s (racemate) Br 60 ~ZHS C2H5 H CH3 CH3 nip' = 1.583?
H3~ ~ (racemate) s 61 CzHS CHFCH~ H CH3 CH3 np = 1.5745 H3~ ~ (racemate) s 62 ~H3 CF(CH~)~ H CH3 CH3 O (racemate) 63 CzHs CF(CH~)~ H CH3 CH3 S (racemate) 64 CzHs CHFCH~ H CH3 CH3 np = 1.5093 S (racemate) 6~ CzHs C~H~ H CH3 CH3 n« = 1.498?
S (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
N' specifications 66 CH3 CF(CH~)2 H CH3 CH3 S (racemate) 67 CH3 CHFCH~ H CH3 CH3 (racemate) 68 CH3 C2H~ H CH3 CH3 S (racemate) HsC
69 CH3 CF(CH~), H CH3 CH3 p = 1.5956 n H3C ~ ~ (racemate) S
70 CH3 CHFCH~ H CH3 CH3 np = 1.6049 H3C ~ ~ (racemate) S
71 CH3 C~H~ H CH3 CH3 (racemate) H3C / ~
S \
7? CH3 H H CH3 CH3 S (racemate) CI
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
No. specifications 73 CH3 CF(CH3)2 H CH3 CH3 (amorphous) S (racemate) CI
74 CH3 C~HS H CH3 CH3 (amorphous) S (racemate) CI
75 CH3 CHFCH~ H CH3 CH3 (amorphous) S (racemate) CI
76 CzHs CHC1CH~ H CH3 CH3 \ (racemate) 77 CZHS CHFCH~ H CH3 CH3 (racemate) CI
S
CI
78 c"3 CFA H CH3 CH3 (S enantiomer) i 79 ~z"5 CF(CH~)-, H CH3 CH3 (racemate) i 80 ~ ~" CF(CH~)-, H CH3 CHI
(racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 81 ~ I cH CHFCH3 H CH3 CH3 w (racemate) 82 ~ CF3 H CH3 CH3 (S enantiomer) i 83 ~ CHFCH; H CH3 CH3 (R enantiomer) i 84 ~5 CHFCH~ H CH3 CH3 (amorphous) ~o (racemate) i 85 ~5 C~H~ H CH3 CH3 ~o (racemate) i 86 cZHS CH(CH;)~ H CH3 CH3 F3C ~ O
(racemate) 87 cZ"5 CHFCH~ H CH3 CH3 F3C ~ O
(racemate) i 88 c2H5 CF(CH~)-, H CH3 CH3 F3C ~ O
(racemate) i 89 ~ CF(CH;)~ H CH3 CH3 (racemate) H,C
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
No. specifications 90 ~H3 CF(CH3)~ H CH3 CH3 log.P=3.33b>
H3C ~ O
(racemate) /
91 ~H3 CHFCH~ H CH3 CH3 H3C ~ O
( (racemate) /
92 ~H3 C~HS H CH3 CH3 H3C ~ O
(racemate) /
93 ~2H5 C2H~ H CH3 ~ CH3 H3C ~ O
(racemate) /
94 ~zHS CHC1CH; H CH3 CH3 H3C ~ O
(racemate) /
95 ~zHS CHFCH; H CH3 CH3 H3C ~ O
(racemate) /
96 ~2H5 CH(CH~)-, H CH3 CH3 H,C ~ O
( raCenlate Le A 32 819-Forei~ countries Table 1 (continued) Ex. R ~ R2 R3 R4 R5 Physical data and stereochem.
No. specifications 97 c2"5 CF(CH3)2 H CH3 CH3 ",c ~ o~
(racemate) /
CH, 98 cz"5 CF(CH3)-_, H CH3 CH3 log.P=3.09b>
F ~ O
(racemate) /
99 cz"5 CHFCH; H CH3 CH3 (amorphous) F \ O
(racemate) /
100 cz"5 CFA H CH3 CH3 F ~ O
(racemate) /
101 ~z"5 C,HS H CH3 CH3 F ~ O
(racemate) /
102 ~ CF(CH3)-, H CH3 CH3 s (racemate) 103 c,2H5 CF(CH~)~ H CH3 CH3 ~s (racemate) /
104 c"3 CF(CH~)~ H CH3 CH3 (amorphous) ci ~ s~
(racemate) / ci Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 105 ~ZHS CF(CH3)2 H CH3 CH3 H3C ~ S
(racemate) 106 , cH3 CF(CH3)~ H CH3 CH3 (amorphous) (racemate 107 , I cZHS CF(CH3)~ H CH3 CH3 (amorphous) racemate ( ) 108 ' c~ CHFCH~ H CH3 CH3 (amorphous) (racemate) 109 ~ c~ c H CHFCH~ H CH3 CH3 (amorphous) z 5 (racemate) 110 ~ ~~ c H CF(CH3)~ H CH3 CH3 (racemate 111 , c H CHFCH; H CH3 CH3 (amorphous) (racemate) 112 cH3 CF(CH~)~ H CH3 CH3 (amorphous) (racemate) 113 cH3 CH(CH~)-, H CH3 CH3 (racemate) 114 cH3 CHFCH~ H CH3 CH3 (amorphous) !, i cz"5 (racemate) I w ~ o~
Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R'- R3 R4 RS Physical data and stereochem.
No. specifications 115 c"3 CHC1CH~ H CH3 CH3 (racemate) ~o 116 , c"3 c " CHFCH~ H CH3 CH3 (amorphous) (racemate) 117 , c"3 c " CF(CH;)~ H CH3 CH3 (amorphous) w I o~ (racemate) 118 cz"5 CF(CH3)2 H CH3 CH3 s I o~ (racemate) 119 ~ ~ cZHs CHFCH3 H CH3 CH3 (amorphous) s o (racemate) 120 ~ c" CF(CH~)~ H CH3 CH3 w I s~ (racemate) 121 c"3 CF(CH~)~ H CH3 CH3 s (racemate) 122 c"3 CF; H CH3 CH3 s (racemate) 123 c"3 CH~OCH~ H CH3 CH3 s (racemate) 124 c2"5 CH3 H CH3 CH3 m.p.:120°C
F ~ O
(racemate) i 12~ c,'"5 CF(CH~)-, H CH3 CH3 (amorphous) ~o (racemate) i Le A 32 819-Fore~,n countries Table 1 (continued) Ex. R ~ R2 R' R4 RS Physical data and stereochem.
No. specifications 126 ~5 CFA H CH3 CH3 (amorphous) ~o (racemate) i 127 ~5 CHC1CH; H CH3 CH3 (amorphous) ~o (racemate) i 128 ~5 CFA H CH3 CH3 (amorphous) ~o (S enantiomer) i 129 ~5 CF(CH3)2 H CH3 CH3 (amorphous) ~o (S enantiomer) i 130 ~5 CF(CH;)~ H CH3 CH3 (amorphous) o~
(R enantiomer) i 131 ~5 CHFCH; H CH3 CH3 (amorphous) ~o (R enantiomer) i 132 ~5 CHC1CH; H CH3 CH3 (amorphous) ~o (R enantiomer) i 133 ~5 CHC1CH~ H CH3 CH3 (amorphous) (S config.) (racemic) 134 ~"3 C~H~ H CH3 CH3 (amorphous) cz"5 (racemate) ~
w o~
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 135 ~2H5 CFA H CH3 CH3 (amorphous) (racemate) 136 ~2H5 CHFCH3 H CH3 CHI (amorphous) (racemate) i 137 ~ZHS CF(CH3)Z H CH; CH3 (amorphous) (racemate) 138 ~2H5 CHZOCH3 H CH3 CH3 (amorphous) (racemate) i 139 ~ZHS CHC12 H CH3 CH3 ~ (amorphous) (racemate) 140 ~ZHS CH(CH3)~ H CH3 CH3 (amorphous) (racemate) i 141 ~zHS CHCICH3 H CH3 CH3 (amorphous) (racemate) i 142 ~3H~' CF3 H CH3 CH; (amorphous) (racemate) i Le A 32 819-Fore~n countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 143 ~3H~' CHFCH3 H CH3 CH3 (amorphous) (racemate) i 144 ~3H~ ~ CF(CH3)~ H CH3 CH; (amorphous) (racemate) i 145 ~3H~-' CHpOCH3 H CH; CH3 (amorphous) (racemate) 146 ~3H~' CHC12 H CH; CH3 (amorphous) (racemate) i 147 ~3H~' C3H~-n H CHz CH3 (amorphous) (racemate) i 148 ~3H~-~ CH(CH3)2 H CH3 CH3 (amorphous) (racemate) i 149 o2H5 ~ H CH3 CH3 (amorphous) (racemate) i 15C) ~2H5 CH3 H CH3 CH3 (amorphous) (racemate) i H_C
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 R5 Physical data and stereochem.
No. specifications 151 C2H5 CH3 H CH3 CH3 (amorphous) H3C ~ (racemate) HC
152 C2H5 CF(CH3)2 H CH3 CH3 (amorphous) CI ~ S~ (racemate) 153 C2H5 CHC12 H CH3 CH3 loge = 3.74 b~
CI ~ S~ (racemate) , 154 ~ CI CH3 ~ CF(CH3)2 H CH3 CH3 (amorphous) ~ S~ (racemate) 155 CI CZHS CF(CH3)2 H CH3 CH3 (amorphous) (racemate) 156 ~H3 CzHs CF(CH3)~ H CH3 CH3 (amorphous) O ~ S~ (racemate) /
1~7 CH3 CF(CH~)~ H CH3 CHI (amorphous) CI ~ S~ (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R' R4 RS Physical data and stereochem.
specifications 158 CI CzHS CF(CH3)2 H CH3 CH3 (amorphous) CI ~ S~ (racemate) 159 CI CZHs CHFCH3 H CHI CH3 (amorphous) Ct ~ S~ (racemate) 160 C2Hs CHFCH3 H CH3 CH3 (amorphous) F3C ~ S
(racemate) 161 C2H5 CHZOCH3 H CH3 CH3 loge = 2:23 b~
F ~ O~ (racemate) 162 CzHs CZH; H CH3 CH3 (amorphous) (racemate) CsHs 163 CzHs CHFCH; H CH; CH3 (amorphous) (racemate) CsHs Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 164 CZHS CF(CH3)2 H CH3 CH3 (amorphous) (racemate) CsHs 165 CzHS CHC1CH3 H CH3 CH3 (amorphous) (racemate) 166 ~s CHFCH3 H CH3 CH3 log.P = 2.31 a~
O (racemate) CI
CI
167 CH3 CzHs CF(CH3)2 H CH3 CH3 log.P = 2.90 a~
O ~ O~ (racemate) 168 CH3 H H CH; CH; m.p.: 144°C
(racemate) 169 C~ ~ C~H; H CHI CH; (amorphous) (racemate) N
Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R' R' R4 RS Physical data and stereochem.
No. specifications 170 CzHs CHFCH3 H CH3 CH3 (amorphous) S (racemate) 171 CH3 CHFCH3 H CH; CH3 (amorphous) S (racemate) 172 ~H3 CF(CH3)2 H CH3 CH3 (amorphous) (S enantiomer) 173 H3C CHClCH3 H CH3 CH3 m.p.:117°C
(racemate) S
174 CzHs CF(CH3)2 H CH3 CH3 np = 1.4823 \ ~ (racemate) /
F
175 CzHs CHFCH3 H CH3 CH3 n~ = 1.5620 \ w (S enantiomer) F
176 CzHs CHFCH; H CH; CH; log.P = 2.25 '"
\ \ (raccmate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 177 C2He CHFCH3 H CH3 CH3 Iog.P = 1.98 a~
(racemate) i 178 CZHS CF(CHz)~ H CH3 CH3 log.P = 2.91 a~
HjC
( ' (racemate) i 179 CzHS CHC1CH3 H CH; CH3 log.P = 3.05 a~
(racemate) 180 oCH3 CZHS CHFCH3 H CH3 CH3 log.P = 1.41 a~
W w (S enantiomer) i 181 ocH3 cZHs CF(CH3)a H CH3 CH3 Iog.P = 2.72 a~
(S enantiomer) i 182 Hjc / czHS CF(CH3)2 H CH3 CH3 (amorphous) °~ (racemate) 183 CH3 CF(CH3)z H CH3 CH3 np = 1.5713 (racemate) i 184 C2H5 CF(CH3)~ H CH; CH3 (amorphous) F
(racemate) i 18~ ~H3 CF(CH;)~ H CH; CH; (amorphous) (R enantiomer Le A 32 819-Foreign countries The loge values given in Table 1 were determined in accordance with EEC
Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18). Temperature: 43°C.
S (a) Mobile phases for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -corresponding test results are labelled with a) in Table 1.
(b) Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - corresponding test results are labelled with b) in Table 1.
Calibration was earned out using unbranched alkan-2-ones (with from 3 to 16 carbon atoms) with known loge values (the loge values were determined by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
Le A 32 819-Foreign countries ' -75-Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, I part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. 'The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1 000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compound of Preparation Example 2 exhibits strong activity against weeds, combined with good compatibility with crop plants, such as, for example, wheat (c~ Table A; "ai." = active ingredient).
_7E _ > ._ s o J O
O
O
L' O
C
CS
_ c~ o _ 0 N
s y cti c~
o ~
o O
4- v~
U O
O.
a.
Q
U
a~ ~ I
Z-U
°' ~ Z
y li Z
Z
U Z~ N
z L O ~ U
~_' ~ I
O O
v v ~ /
i- ~
Le A 32 819- Foreign countries _77_ Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentrarion.
Test plants having a height of 5 - 15 cm are sprayed with the preparation of active compounds such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1 (100 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction 2~
In this test, for example, the compounds of Preparation Examples l, 2 and 6 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, wheat (cf. Tables B 1 and B2).
~78~
.~ 00 0 o o ~
a ~ "' L
_ ~ o a C~
o p rr C~
W
o V~
a L
o ~ o 0 y o 0 4., o 0 V
fl. 5U
a Z
a~ U
I
p Z-U
t y U
Z Z-ti Z~ U
Z
~Z U
o ~ Z
-/
U Z~ Z
~
~
z ~ U-t Z
-( "- cJ Z= ~ \
~ ~/ I
Z~ U
_. ~ "~
U \I
v p U
J
. U) L
a c /
_79_ U
.O
i, O~
U
O
O O
_cC
O
c3 L
_~ V1 O
U ..~ O
O
Q.
O
O
L
L
O
y U ''-' O
Q..
Q
N
c~ M
s U~ iU
O Z
L
;p ~ U
Z Z
O I
Z \ 'Z
w ~ III/
Z=
U
N
C.O. ~, =~ 2 U > cG
.V V
~~ Q C
[a]p =-109 \ w (S enantiomer) 7 czHS CF(CH~)-, H CH3 CH3 np = 1.5342 s \ ~ (S enantiomer) 8 c2"5 CF; H CH3 CH3 oil v ~ (racemate) s c_HS C-,H~ H CH; CHI oil (racemate) s Le A 32 819-Fore~n countries Table 1 (continued) Ex. R1 R2 R3 R4 RS Physical data No. and stereochem.
specifications 10 ~z"5 CF(CH~)~ H CH3 CH3 n; ° = I .5817 (racemate) s ci 11 ~z"5 CH~OCH~ H CH3 CH3 oil / " ~ (racemate) s 12 ~2"5 CHCI-, H CH3 CH3 oil / " ~ (racemate) s 13 ~5 CHC1CH~ H CH3 CH3 oil / ~ ~ (racemate) J
14 ~2"5 CFA H CH3 CH3 oil s (racemate) 15 ~Z"5 CH3 H CH3 CH3 oil / v ~ (racemate) s 16 ~z"5 CHCI, H CH3 CH3 oil s (racemate) 17 cZ"5 CHFCH~ H CHI CH3 oil /~ " ~ (racemate) s Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R' R3 R4 RS Physical data No. and stereochem.
specifications 18 cZHs CF(CH3)-, H CH3 CH3 oil v ~ (racemate) s 19 CH3 CHCICH~ H CH3 CH3 nD - 1.5961 (S enantiomer) /
[a]p -_128.35°
20 ~ CzHs CHC1CH~ H CH3 CH3 20 [a]p - -102.5 (S enantiomer) 21 CzHs CHBrCH~ H CH3 CH3 (amorphous) \ (racemate) /
CI
22 CzHs CHBrCH~ H CH3 CH3 n~~ = 1.5932 (racemate) /
23 CH3 CH(CH~)~ H CH3 CH3 nD = 1.6123 (racemate) /
~4 CH3 CF~CF~ H CH3 CH3 n~~~ = 1.5373 (racemate) /
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data No. and stereochem.
specifications 25 CH3 CHFCH3 H CH3 CH3 np = 1.5930 (racemate) /
26 CzHS CHFCH; H CH3 CH3 np = 1.5709 (S enantiomer) /
27 CzHs CF(CH3)? H CH3 CH3 (S enantiomer) /
28 CzHs CHFCH~ H CH3 CH3 np = 1.5932 (R enantiomer) /
29 CzHS CF(CH~)~ H CH3 CH3 np = 1.5820 (R enantiomer) /
30 CzHs CHC1CH~ H CH3 CH3 n~ = 1.5975 (R enantiomer) /
31 CzHs CHCI~ H CH3 CH3 n~~' = I
.6053 I ~ ~ ~ (R enantiomer) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data No. and stereochem.
specifications 32 CH3 CHCl2 H CH3 CH3 \ (racemate) CI
33 CH3 CH~OCH3 H CH3 CH3 \ \ (racemate) CI
34 CHs CHC1CH; H CH3 CH3 \ \ (racemate) /
CI
35 CH3 CHFCH~ H CH3 CH3 nD = 1.5999 \ ~ (S enantiomer) /
CI
36 CH3 CFA H CH3 CH3 n~ = 1.5871 \ ~ (S enantiomer) /
CI
37 CH3 CF~CF~ H CH3 CH3 \ \ (S enantiomer) /
CI
38 CH3 CHFCH~ H CH3 CH3 \ \ (R enantiomer) /
CI
Le A 32 819-Foreign countries Table 1 (continued) Ex.. R~ R2 R3 R4 RS Physical data and No.
stereochem.
specifications 39 CzHs CFA H CHI CHI (S enantiomer) \ w CI
40 CH3 CHFCH; H CH3 CH3 \ (S enantiomer) /
41 CH3 CF(CH~), H CH3 CH3 \ (S enantiomer) \ (S enantiomer) /
43 CH3 CHC1CH~ H CH3 CH3 \ (racemate) \ (S enantiomer) 4~ CH3 C-,H~ H CHI CH3 \ (S enantiomer) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R' R3 R4 R5 Physical data and stereochem.
specifications \ (S enantiomer) / /
47 CH3 CHFCH; H CH3 CH3 \ (S enantiomer) / /
48 CH3 CF(CH~)2 H CH3 CH3 \ (S enantiomer) / /
49 CH3 CF(CH3)2 H CH3 CH3 H3C ~ (racemate) /
50 CH3 CHFCH; H CH3 CH3 H3C ~ (racemate) ~ 1 CH3 CFA H CH3 CH3 H3C ~ (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 52 ~H3 CF3 H CH3 CH3 F
\ \ (racemate) F
53 ~H3 CHFCH~ H CH3 CH3 F \ (racemate) F
54 ~H3 CF(CH~)2 H CH3 CH3 F \ (racemate) /
F
55 ~H3 CF(CH3)~ H CH3 CH3 (racemate) 56 ~H3 CHFCH~ H CH3 CH3 (racemate) 57 ~zHs CHCI-, H CH3 CH3 (amorphous) \ \ (S enantiomer) I
I, ~8 CzHs CF; H CH3 CH3 (amorphous) \ (S enantiomer) I
I, /
I
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R' R4 RS Physical data and stereochem.
No. specifications 59 ~ZHS CF(CH3)2 H CH3 CH3 (amorphous) s (racemate) Br 60 ~ZHS C2H5 H CH3 CH3 nip' = 1.583?
H3~ ~ (racemate) s 61 CzHS CHFCH~ H CH3 CH3 np = 1.5745 H3~ ~ (racemate) s 62 ~H3 CF(CH~)~ H CH3 CH3 O (racemate) 63 CzHs CF(CH~)~ H CH3 CH3 S (racemate) 64 CzHs CHFCH~ H CH3 CH3 np = 1.5093 S (racemate) 6~ CzHs C~H~ H CH3 CH3 n« = 1.498?
S (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
N' specifications 66 CH3 CF(CH~)2 H CH3 CH3 S (racemate) 67 CH3 CHFCH~ H CH3 CH3 (racemate) 68 CH3 C2H~ H CH3 CH3 S (racemate) HsC
69 CH3 CF(CH~), H CH3 CH3 p = 1.5956 n H3C ~ ~ (racemate) S
70 CH3 CHFCH~ H CH3 CH3 np = 1.6049 H3C ~ ~ (racemate) S
71 CH3 C~H~ H CH3 CH3 (racemate) H3C / ~
S \
7? CH3 H H CH3 CH3 S (racemate) CI
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
No. specifications 73 CH3 CF(CH3)2 H CH3 CH3 (amorphous) S (racemate) CI
74 CH3 C~HS H CH3 CH3 (amorphous) S (racemate) CI
75 CH3 CHFCH~ H CH3 CH3 (amorphous) S (racemate) CI
76 CzHs CHC1CH~ H CH3 CH3 \ (racemate) 77 CZHS CHFCH~ H CH3 CH3 (racemate) CI
S
CI
78 c"3 CFA H CH3 CH3 (S enantiomer) i 79 ~z"5 CF(CH~)-, H CH3 CH3 (racemate) i 80 ~ ~" CF(CH~)-, H CH3 CHI
(racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 81 ~ I cH CHFCH3 H CH3 CH3 w (racemate) 82 ~ CF3 H CH3 CH3 (S enantiomer) i 83 ~ CHFCH; H CH3 CH3 (R enantiomer) i 84 ~5 CHFCH~ H CH3 CH3 (amorphous) ~o (racemate) i 85 ~5 C~H~ H CH3 CH3 ~o (racemate) i 86 cZHS CH(CH;)~ H CH3 CH3 F3C ~ O
(racemate) 87 cZ"5 CHFCH~ H CH3 CH3 F3C ~ O
(racemate) i 88 c2H5 CF(CH~)-, H CH3 CH3 F3C ~ O
(racemate) i 89 ~ CF(CH;)~ H CH3 CH3 (racemate) H,C
Le A 32 819-Foreign countries Table 1 (continued) Ex. R 1 R2 R3 R4 RS Physical data and stereochem.
No. specifications 90 ~H3 CF(CH3)~ H CH3 CH3 log.P=3.33b>
H3C ~ O
(racemate) /
91 ~H3 CHFCH~ H CH3 CH3 H3C ~ O
( (racemate) /
92 ~H3 C~HS H CH3 CH3 H3C ~ O
(racemate) /
93 ~2H5 C2H~ H CH3 ~ CH3 H3C ~ O
(racemate) /
94 ~zHS CHC1CH; H CH3 CH3 H3C ~ O
(racemate) /
95 ~zHS CHFCH; H CH3 CH3 H3C ~ O
(racemate) /
96 ~2H5 CH(CH~)-, H CH3 CH3 H,C ~ O
( raCenlate Le A 32 819-Forei~ countries Table 1 (continued) Ex. R ~ R2 R3 R4 R5 Physical data and stereochem.
No. specifications 97 c2"5 CF(CH3)2 H CH3 CH3 ",c ~ o~
(racemate) /
CH, 98 cz"5 CF(CH3)-_, H CH3 CH3 log.P=3.09b>
F ~ O
(racemate) /
99 cz"5 CHFCH; H CH3 CH3 (amorphous) F \ O
(racemate) /
100 cz"5 CFA H CH3 CH3 F ~ O
(racemate) /
101 ~z"5 C,HS H CH3 CH3 F ~ O
(racemate) /
102 ~ CF(CH3)-, H CH3 CH3 s (racemate) 103 c,2H5 CF(CH~)~ H CH3 CH3 ~s (racemate) /
104 c"3 CF(CH~)~ H CH3 CH3 (amorphous) ci ~ s~
(racemate) / ci Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 105 ~ZHS CF(CH3)2 H CH3 CH3 H3C ~ S
(racemate) 106 , cH3 CF(CH3)~ H CH3 CH3 (amorphous) (racemate 107 , I cZHS CF(CH3)~ H CH3 CH3 (amorphous) racemate ( ) 108 ' c~ CHFCH~ H CH3 CH3 (amorphous) (racemate) 109 ~ c~ c H CHFCH~ H CH3 CH3 (amorphous) z 5 (racemate) 110 ~ ~~ c H CF(CH3)~ H CH3 CH3 (racemate 111 , c H CHFCH; H CH3 CH3 (amorphous) (racemate) 112 cH3 CF(CH~)~ H CH3 CH3 (amorphous) (racemate) 113 cH3 CH(CH~)-, H CH3 CH3 (racemate) 114 cH3 CHFCH~ H CH3 CH3 (amorphous) !, i cz"5 (racemate) I w ~ o~
Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R'- R3 R4 RS Physical data and stereochem.
No. specifications 115 c"3 CHC1CH~ H CH3 CH3 (racemate) ~o 116 , c"3 c " CHFCH~ H CH3 CH3 (amorphous) (racemate) 117 , c"3 c " CF(CH;)~ H CH3 CH3 (amorphous) w I o~ (racemate) 118 cz"5 CF(CH3)2 H CH3 CH3 s I o~ (racemate) 119 ~ ~ cZHs CHFCH3 H CH3 CH3 (amorphous) s o (racemate) 120 ~ c" CF(CH~)~ H CH3 CH3 w I s~ (racemate) 121 c"3 CF(CH~)~ H CH3 CH3 s (racemate) 122 c"3 CF; H CH3 CH3 s (racemate) 123 c"3 CH~OCH~ H CH3 CH3 s (racemate) 124 c2"5 CH3 H CH3 CH3 m.p.:120°C
F ~ O
(racemate) i 12~ c,'"5 CF(CH~)-, H CH3 CH3 (amorphous) ~o (racemate) i Le A 32 819-Fore~,n countries Table 1 (continued) Ex. R ~ R2 R' R4 RS Physical data and stereochem.
No. specifications 126 ~5 CFA H CH3 CH3 (amorphous) ~o (racemate) i 127 ~5 CHC1CH; H CH3 CH3 (amorphous) ~o (racemate) i 128 ~5 CFA H CH3 CH3 (amorphous) ~o (S enantiomer) i 129 ~5 CF(CH3)2 H CH3 CH3 (amorphous) ~o (S enantiomer) i 130 ~5 CF(CH;)~ H CH3 CH3 (amorphous) o~
(R enantiomer) i 131 ~5 CHFCH; H CH3 CH3 (amorphous) ~o (R enantiomer) i 132 ~5 CHC1CH; H CH3 CH3 (amorphous) ~o (R enantiomer) i 133 ~5 CHC1CH~ H CH3 CH3 (amorphous) (S config.) (racemic) 134 ~"3 C~H~ H CH3 CH3 (amorphous) cz"5 (racemate) ~
w o~
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 135 ~2H5 CFA H CH3 CH3 (amorphous) (racemate) 136 ~2H5 CHFCH3 H CH3 CHI (amorphous) (racemate) i 137 ~ZHS CF(CH3)Z H CH; CH3 (amorphous) (racemate) 138 ~2H5 CHZOCH3 H CH3 CH3 (amorphous) (racemate) i 139 ~ZHS CHC12 H CH3 CH3 ~ (amorphous) (racemate) 140 ~ZHS CH(CH3)~ H CH3 CH3 (amorphous) (racemate) i 141 ~zHS CHCICH3 H CH3 CH3 (amorphous) (racemate) i 142 ~3H~' CF3 H CH3 CH; (amorphous) (racemate) i Le A 32 819-Fore~n countries Table 1 (continued) Ex. R~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 143 ~3H~' CHFCH3 H CH3 CH3 (amorphous) (racemate) i 144 ~3H~ ~ CF(CH3)~ H CH3 CH; (amorphous) (racemate) i 145 ~3H~-' CHpOCH3 H CH; CH3 (amorphous) (racemate) 146 ~3H~' CHC12 H CH; CH3 (amorphous) (racemate) i 147 ~3H~' C3H~-n H CHz CH3 (amorphous) (racemate) i 148 ~3H~-~ CH(CH3)2 H CH3 CH3 (amorphous) (racemate) i 149 o2H5 ~ H CH3 CH3 (amorphous) (racemate) i 15C) ~2H5 CH3 H CH3 CH3 (amorphous) (racemate) i H_C
Le A 32 819-Foreign countries Table 1 (continued) Ex. R~ R2 R3 R4 R5 Physical data and stereochem.
No. specifications 151 C2H5 CH3 H CH3 CH3 (amorphous) H3C ~ (racemate) HC
152 C2H5 CF(CH3)2 H CH3 CH3 (amorphous) CI ~ S~ (racemate) 153 C2H5 CHC12 H CH3 CH3 loge = 3.74 b~
CI ~ S~ (racemate) , 154 ~ CI CH3 ~ CF(CH3)2 H CH3 CH3 (amorphous) ~ S~ (racemate) 155 CI CZHS CF(CH3)2 H CH3 CH3 (amorphous) (racemate) 156 ~H3 CzHs CF(CH3)~ H CH3 CH3 (amorphous) O ~ S~ (racemate) /
1~7 CH3 CF(CH~)~ H CH3 CHI (amorphous) CI ~ S~ (racemate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R' R4 RS Physical data and stereochem.
specifications 158 CI CzHS CF(CH3)2 H CH3 CH3 (amorphous) CI ~ S~ (racemate) 159 CI CZHs CHFCH3 H CHI CH3 (amorphous) Ct ~ S~ (racemate) 160 C2Hs CHFCH3 H CH3 CH3 (amorphous) F3C ~ S
(racemate) 161 C2H5 CHZOCH3 H CH3 CH3 loge = 2:23 b~
F ~ O~ (racemate) 162 CzHs CZH; H CH3 CH3 (amorphous) (racemate) CsHs 163 CzHs CHFCH; H CH; CH3 (amorphous) (racemate) CsHs Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 164 CZHS CF(CH3)2 H CH3 CH3 (amorphous) (racemate) CsHs 165 CzHS CHC1CH3 H CH3 CH3 (amorphous) (racemate) 166 ~s CHFCH3 H CH3 CH3 log.P = 2.31 a~
O (racemate) CI
CI
167 CH3 CzHs CF(CH3)2 H CH3 CH3 log.P = 2.90 a~
O ~ O~ (racemate) 168 CH3 H H CH; CH; m.p.: 144°C
(racemate) 169 C~ ~ C~H; H CHI CH; (amorphous) (racemate) N
Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R' R' R4 RS Physical data and stereochem.
No. specifications 170 CzHs CHFCH3 H CH3 CH3 (amorphous) S (racemate) 171 CH3 CHFCH3 H CH; CH3 (amorphous) S (racemate) 172 ~H3 CF(CH3)2 H CH3 CH3 (amorphous) (S enantiomer) 173 H3C CHClCH3 H CH3 CH3 m.p.:117°C
(racemate) S
174 CzHs CF(CH3)2 H CH3 CH3 np = 1.4823 \ ~ (racemate) /
F
175 CzHs CHFCH3 H CH3 CH3 n~ = 1.5620 \ w (S enantiomer) F
176 CzHs CHFCH; H CH; CH; log.P = 2.25 '"
\ \ (raccmate) Le A 32 819-Foreign countries Table 1 (continued) Ex. R ~ R2 R3 R4 RS Physical data and stereochem.
No. specifications 177 C2He CHFCH3 H CH3 CH3 Iog.P = 1.98 a~
(racemate) i 178 CZHS CF(CHz)~ H CH3 CH3 log.P = 2.91 a~
HjC
( ' (racemate) i 179 CzHS CHC1CH3 H CH; CH3 log.P = 3.05 a~
(racemate) 180 oCH3 CZHS CHFCH3 H CH3 CH3 log.P = 1.41 a~
W w (S enantiomer) i 181 ocH3 cZHs CF(CH3)a H CH3 CH3 Iog.P = 2.72 a~
(S enantiomer) i 182 Hjc / czHS CF(CH3)2 H CH3 CH3 (amorphous) °~ (racemate) 183 CH3 CF(CH3)z H CH3 CH3 np = 1.5713 (racemate) i 184 C2H5 CF(CH3)~ H CH; CH3 (amorphous) F
(racemate) i 18~ ~H3 CF(CH;)~ H CH; CH; (amorphous) (R enantiomer Le A 32 819-Foreign countries The loge values given in Table 1 were determined in accordance with EEC
Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18). Temperature: 43°C.
S (a) Mobile phases for the determination in the acidic range: 0.1 % aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile -corresponding test results are labelled with a) in Table 1.
(b) Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - corresponding test results are labelled with b) in Table 1.
Calibration was earned out using unbranched alkan-2-ones (with from 3 to 16 carbon atoms) with known loge values (the loge values were determined by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
Le A 32 819-Foreign countries ' -75-Use Examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, I part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. 'The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1 000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compound of Preparation Example 2 exhibits strong activity against weeds, combined with good compatibility with crop plants, such as, for example, wheat (c~ Table A; "ai." = active ingredient).
_7E _ > ._ s o J O
O
O
L' O
C
CS
_ c~ o _ 0 N
s y cti c~
o ~
o O
4- v~
U O
O.
a.
Q
U
a~ ~ I
Z-U
°' ~ Z
y li Z
Z
U Z~ N
z L O ~ U
~_' ~ I
O O
v v ~ /
i- ~
Le A 32 819- Foreign countries _77_ Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentrarion.
Test plants having a height of 5 - 15 cm are sprayed with the preparation of active compounds such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1 (100 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction 2~
In this test, for example, the compounds of Preparation Examples l, 2 and 6 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, wheat (cf. Tables B 1 and B2).
~78~
.~ 00 0 o o ~
a ~ "' L
_ ~ o a C~
o p rr C~
W
o V~
a L
o ~ o 0 y o 0 4., o 0 V
fl. 5U
a Z
a~ U
I
p Z-U
t y U
Z Z-ti Z~ U
Z
~Z U
o ~ Z
-/
U Z~ Z
~
~
z ~ U-t Z
-( "- cJ Z= ~ \
~ ~/ I
Z~ U
_. ~ "~
U \I
v p U
J
. U) L
a c /
_79_ U
.O
i, O~
U
O
O O
_cC
O
c3 L
_~ V1 O
U ..~ O
O
Q.
O
O
L
L
O
y U ''-' O
Q..
Q
N
c~ M
s U~ iU
O Z
L
;p ~ U
Z Z
O I
Z \ 'Z
w ~ III/
Z=
U
N
C.O. ~, =~ 2 U > cG
.V V
~~ Q C
Claims (10)
1. Substituted aminoalkylideneaminotriazines of the general formula (I), in which R1 represents the grouping -A-Z, in which A represents optionally substituted straight-chain or branched alkanediyl which optionally contains at the beginning or at the end or within the alkanediyl chain an oxygen atom, a sulphur atom, an imino (NH) or an alkylimino (N-alkyl) group, and Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, R2 represents hydrogen, cyano, halogen, or represents in each case optionally substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkenyl, alkinyl or cycloalkyl, R3 represents hydrogen or alkyl, R4 represents hydrogen or alkyl, and R5 represents alkyl.
2. Compounds of the formula (I) according to Claim 1, characterized in that R1 represents the grouping -A-Z, in which A represents optionally cyano- or halogen-substituted straight-chain or branched alkanediyl having 1 to 6 carbon atoms, which optionally contains at the beginning or at the end or within the alkanediyl chain oxygen, sulphur, imino (NH) or C1-C4-alkylimino, and Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthal-azinyl, where the possible substituents of these radicals are in each case preferably selected from the following group:
hydroxyl, cyano, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkyl-carbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, Cl-C4-alkyl-; C1-C4-halogenoalkyl-, Cl-C4-alkoxy- or Cl-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, R'- represents hydrogen, cyano, halogen, represents in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C I -C4-alkoxy-, C 1-C4-alkylthio-, C 1-C4-alkylsulphinyl- or C 1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halo~~en-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or CI-C,~-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms., R3 represents hydrogen or alkyl having 1 to 6 carbon atoms, R4 represents hydrogen or alkyl having 1 to 6 carbon atoms, and R5 represents alkyl having 1 to 6 carbon atoms.
hydroxyl, cyano, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkyl-carbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, Cl-C4-alkyl-; C1-C4-halogenoalkyl-, Cl-C4-alkoxy- or Cl-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, R'- represents hydrogen, cyano, halogen, represents in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C I -C4-alkoxy-, C 1-C4-alkylthio-, C 1-C4-alkylsulphinyl- or C 1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally cyano- or halo~~en-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or CI-C,~-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms., R3 represents hydrogen or alkyl having 1 to 6 carbon atoms, R4 represents hydrogen or alkyl having 1 to 6 carbon atoms, and R5 represents alkyl having 1 to 6 carbon atoms.
3. Compounds of the formula (I) according to Claim 1, characterized in that A, R2, R3, R4 and R5 are as defined in Claim 2 and Z represents in each case substituted or unsubstituted phenyl or naphthyl, where the possible substituents are as defined in Claim 2.
4. Compounds of the formula (I) according to Claim l, characterized in that A, R2, R3, R4 and R5 are as defined in Claim 2 and Z represents in each case substituted or unsubstituted heterocyclyl, where the possible heterocyclyl groupings and the possible substituents are as defined in Claim 2.
5. Compounds of the formula (I) according to Claim 1, characterized in that R1 represents the grouping -A-Z, in which A represents in each case optionally cyano-, fluorine- or chlorine-substituted methylene (-CH2-), dimethylene (ethane-1,2-diyl, -CH2CH2-), ethylidene (ethane-1,1-diyl, -CH(CH3)-), tri-methylene (propane-1,3-diyl, -CH2CH2CH2), propylidene (propane-1,1-diyl, -CH(C2,H5)-), propane-2,3-diyl (-CH(CH3)CH2-), 2-methyl-propane-1,3-diyl (-CH2CH(CH3)CH2-), 3-oxa-propane-1,3-diyl (-CH2CH2O-), 2-oxa-propane-1,3-diyl (-CH2OCH2-), tetramethylene (butane-1,4-diyl -CH2CH2CH2CH2-), butane-2,4-diyl (-CH(CH3)CH2CH2-), butane-2,3-diyl (-CH(CH3)CH(CH3)-), 3-methyl-butane-2,4-diyl (-CH(CH3)CH(CH3)CH2-), 4-oxa-butane-2,4-diyl (-CH(CH3)CH2O-), pentane-3,5-diyl (-CH(C2H5)CH2CH2-), 5-oxa-pentane-3,5-diyl (-CH(C2H5)CH2O-), 4-oxa-pentane-2,5-diyl (-CH(CH3)CH2OCH2-) or 5-oxa-hexane-3,6-diyl (-CH(C2H5)CH2OCH2-), and Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the series consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl, where the possible substituents of these radicals are in each case preferably selected from the group below:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i- propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- and/or chlorine-substituted methylcarbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- or t-butoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoro-, methyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or trifluoromethoxy-substiuted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, R2 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propyl-sulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R3 represents hydrogen, methyl or ethyl, R4 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, and R5 represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl.
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i- propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- and/or chlorine-substituted methylcarbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s- or t-butoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoro-, methyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or trifluoromethoxy-substiuted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy, R2 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propyl-sulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, represents in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R3 represents hydrogen, methyl or ethyl, R4 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, and R5 represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl.
6. Process for preparing compounds of the formula (I) according to Claim 1, characterized in that substituted aminotriazines of the general formula (II) in which R1 and R2 are as defined in Claim 1, are reacted with substituted amino compounds of the general formula (III) in which R3, R4 and R5 are as defined in Claim 1 and R represents alkyl, if appropriate in the presence of a diluent.
7. Herbicidal compositions, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.
8. Use of compounds of the formula (I) according to Claim 1 for controlling undesirable vegetation.
9. Method for controlling weeds, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on the weeds or their habitat.
10. Process for preparing herbicidal compositions, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19802236.0 | 1998-01-22 | ||
| DE19802236A DE19802236A1 (en) | 1998-01-22 | 1998-01-22 | New amino alkylidene-substituted triazines, useful as herbicides |
| PCT/EP1999/000095 WO1999037627A1 (en) | 1998-01-22 | 1999-01-09 | Substituted aminoalkylidenamino triazines as herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2318096A1 true CA2318096A1 (en) | 1999-07-29 |
Family
ID=7855289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002318096A Abandoned CA2318096A1 (en) | 1998-01-22 | 1999-01-09 | Substituted aminoalkylidenamino triazines as herbicides |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1049680A1 (en) |
| JP (1) | JP2002501058A (en) |
| KR (1) | KR20010015897A (en) |
| CN (1) | CN1294584A (en) |
| AU (1) | AU2278699A (en) |
| BR (1) | BR9907212A (en) |
| CA (1) | CA2318096A1 (en) |
| DE (1) | DE19802236A1 (en) |
| WO (1) | WO1999037627A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19825379A1 (en) * | 1998-06-06 | 1999-12-09 | Bayer Ag | Use of substituted 2,4-diamino-1,3,5-triazines for controlling animal pests |
| DE19842894A1 (en) * | 1998-09-18 | 2000-03-23 | Hoechst Schering Agrevo Gmbh | Synergistic herbicidal combination useful for selective weed control in crops, especially cereals, comprising amino-triazine herbicide and another herbicide |
| DE19933937A1 (en) * | 1999-07-20 | 2001-01-25 | Bayer Ag | Optically active thienylalkylamino-1,3,5-triazines |
| DE19962931A1 (en) * | 1999-12-24 | 2001-06-28 | Bayer Ag | New thienylalkylamino-1,3,5-triazine derivatives are herbicides useful as defoliants, desiccants and especially weedkillers |
| DE10035038A1 (en) * | 2000-07-19 | 2002-01-31 | Aventis Cropscience Gmbh | Substituted 2-amino-1,3,5-triazines, process for their preparation and use as herbicides and plant growth regulators |
| DE10123845A1 (en) * | 2001-05-16 | 2003-02-13 | Bayer Cropscience Gmbh | 2,4-diamino-1,3,5-triazines, process for their preparation and use as herbicides and plant growth regulators |
| EP1836894A1 (en) | 2006-03-25 | 2007-09-26 | Bayer CropScience GmbH | Novel sulfonamide-containing solid formulations |
| EP1790227A1 (en) | 2005-11-25 | 2007-05-30 | Bayer CropScience AG | Aqueous suspension-concentrates of 2,4-diamino-s-triazine herbicides |
| DE102007013362A1 (en) | 2007-03-16 | 2008-09-18 | Bayer Cropscience Ag | Use of polyalkylene oxide for enhancing penetration of herbicidal agents into plants, for preparing plant protection agents and to combat pests and weeds |
| EP1844654A1 (en) | 2006-03-29 | 2007-10-17 | Bayer CropScience GmbH | Penetration enhancer for agrochemicals |
| DE102006016884A1 (en) * | 2006-04-11 | 2007-10-25 | Bayer Cropscience Ag | Substituted diamino-1,3,5-triazines, process for their preparation and their use as herbicides and plant growth regulators |
| WO2011076731A1 (en) | 2009-12-23 | 2011-06-30 | Bayer Cropscience Ag | Liquid formulation of 2-iodo-n-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoyl]benzolsulfonamide |
| US9375002B2 (en) * | 2012-03-29 | 2016-06-28 | Bayer Intellectual Property Gmbh | 5-aminopyrimidine derivatives and use thereof for combating undesired plant growth |
| KR102139101B1 (en) | 2019-05-27 | 2020-07-30 | 주식회사 뉴들 | Adult authentication system |
| KR102324779B1 (en) | 2021-06-17 | 2021-11-11 | 주식회사 큐버모티브 | User authentication system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH601999A5 (en) * | 1974-05-29 | 1978-07-14 | Ciba Geigy Ag | Herbicidal compsn. contg. a triazinyl-amidine |
| JPH0753719B2 (en) * | 1986-08-22 | 1995-06-07 | 出光興産株式会社 | Triazine derivative, production method thereof and herbicide containing the same as active ingredient |
| DE19531084A1 (en) * | 1995-08-24 | 1997-02-27 | Hoechst Schering Agrevo Gmbh | 2,4-diamino-1,3,5-triazines, process for their preparation and their use as herbicides and plant growth regulators |
-
1998
- 1998-01-22 DE DE19802236A patent/DE19802236A1/en not_active Withdrawn
-
1999
- 1999-01-09 JP JP2000528551A patent/JP2002501058A/en active Pending
- 1999-01-09 CA CA002318096A patent/CA2318096A1/en not_active Abandoned
- 1999-01-09 WO PCT/EP1999/000095 patent/WO1999037627A1/en not_active Application Discontinuation
- 1999-01-09 AU AU22786/99A patent/AU2278699A/en not_active Abandoned
- 1999-01-09 CN CN99804348A patent/CN1294584A/en active Pending
- 1999-01-09 EP EP99902527A patent/EP1049680A1/en not_active Withdrawn
- 1999-01-09 BR BR9907212-2A patent/BR9907212A/en not_active Application Discontinuation
- 1999-01-09 KR KR1020007007330A patent/KR20010015897A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010015897A (en) | 2001-02-26 |
| BR9907212A (en) | 2000-10-24 |
| EP1049680A1 (en) | 2000-11-08 |
| JP2002501058A (en) | 2002-01-15 |
| DE19802236A1 (en) | 1999-07-29 |
| AU2278699A (en) | 1999-08-09 |
| CN1294584A (en) | 2001-05-09 |
| WO1999037627A1 (en) | 1999-07-29 |
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