3-PHENYLISOXAZOLINE-5-HERBICIDALLY ACTIVE CARBOXAMIDES OF CYCLOPENTENYL CARBOXYLIC ACID DERIVATIVES

专利摘要:
Herbicidally active 3-phenylisoxazoline-5-carboxamides derived from cyclopentenylcarboxylic acid derivatives. the invention relates to 3-phenylisoxazoline-5-carboxamides of cyclopentenylcarboxylic acid derivatives of the general formula (i) and their agrochemically acceptable salts (i) and their use in the plantation protection sector.
公开号:BR112020015096A2
申请号:R112020015096-7
申请日:2019-01-21
公开日:2020-12-08
发明作者:Guido Bojack；Katherine Rose LAW；Andreas van Almsick；Klaus Bernhard Haaf；Hansjörg Dietrich；Elmar GATZWEILER；Anu Bheemaiah MACHETTIRA；Christopher Hugh Rosinger；Elisabeth ASMUS
申请人:Bayer Aktiengesellschaft；
IPC主号:

专利说明:

[001] [001] The invention is related to the technical field of herbicides, especially herbicides for the selective control of weeds and weeds in useful plantations.
[002] [002] Specifically, it is related to 3-phenylisoxazoline-5-carboxamides and -5-thioamides substituted by derivatives of cyclopentenylcarboxylic acid, to processes for their preparation and use as herbicides.
[003] [003] The documents MWO1l995 / 014681 Al, MWO1l995 / 014680 Al, WO 2008/035315 Al, MWO2005 / 051931 Al and WO2005 / 021515 Al each describe, inter alia, 3-phenylisoxazoline-5-carboxamides, which are replaced in the phenyl ring and in positions 3 and 4 by alkoxy radicals. WO1,1998 / 057937 A1 describes, inter alia, compounds that are substituted on the phenyl ring at position 4 by an alkoxy radical. WO2006 / 016237 A1 describes, inter alia, in each case, the compounds that are substituted on the phenyl ring by a starch radical. The compounds described in the documents cited above are disclosed in those documents as being pharmacologically active.
[004] [004] MWO2005 / 021516 A1 discloses 3 - (([3- (3-tert-butylphenyl) -5-ethyl-4,5-dihydro-1,2-oxazol-5-yl] carbonyl) amino ) - 5-fluoro-4-oxopentanoic acid and 3 - (([[(3- (3-tert-butylphenyl) -5-isopropyl-4,5-dihydro-1,2-oxazol-5-yl] carbonyl) amino) -5-fluoro-4-oxopentanoic acid as pharmacologically active compounds.
[005] [005] DE 4026018 A1, EP O 520 371 A2 and DE 4017665 disclose 3-phenylisoxazoline-5-carboxamides carrying a hydrogen atom at position 5 of the isoxazoline ring. These compounds are described as agrochemically active protectors, that is, as compounds that eliminate the action of unwanted herbicides on crop plants. No herbicidal action of these compounds is disclosed. European patent No. 10170238, which has an early priority date, but which will still be published on the priority date of this application, discloses herbicidically and fungically active 3-phenylisoxazoline-5-carboxamides and 3-phenylisoxazoline-5-thioamides carrying a hydrogen atom at position 5 of the isoxazoline ring. Monatshefte Chemie (2010) 141, 461 and Letters in Organic Chemistry (2010), 7, 502 also discloses 3-phenylisoxazoline-5-carboxamides carrying a hydrogen atom at position 5 of the isoxazoline ring. The fungicidal action, and not the herbicidal action, is disclosed for some of the compounds mentioned.
[006] [006] WO 2014/048827 discloses the herbicidal action of 3-phenylisoxazoline-5-carboxylic acids, -5-carboxylic esters, -5-carbaldehydes and -5-nitriles.
[007] [007] WO 2014/048853 discloses isoxazoline-5-carboxamides and -5-thioamides having heterocycles in position 3 (herbicide and fungicide).
[008] [008] The document WO 2014/048940 having quinoline as specific heterocycle in position 3 (fungicide) and the document WO 2014/048882 having alkoxy as specific radical in position 5.
[009] [009] WO 2014/048882 discloses isoxazolinecarboxamides having alkoxy as the specific radical at position 5.
[010] [010] WO 2012/130798 describes herbicidically and fungically active 3-phenylisoxazoline-5-carboxamides and -5-thioamides of substituted heterocycles.
[011] [011] The herbicidal activity of these known compounds, in particular at low rates of application, and / or their compatibility with crop plants remains in need of improvement.
[012] [012] For the reasons presented, there is still a need for potent herbicides and / or plant growth regulators for selective use in cultivation plants or use in non-cultivated land, where these active ingredients should preferably have other advantageous properties in the application , for example, improved compatibility with crop plants.
[013] [013] Consequently, it is the main objective of the present invention to provide compounds that have herbicidal activity (herbicides) that are highly effective against economically important harmful plants even at relatively low application rates and can be used selectively on crop plants, preferably with optimal activity against harmful plants and at the same time, preferably, they have excellent compatibility with crop plants. Preferably, these herbicidal compounds should be particularly effective against a broad spectrum of weeds and should preferably also have excellent activity against a large number of weeds.
[014] [014] In addition to a herbicidal action, several compounds of formula (1) also have a fungicidal action which, however, is not very evident.
[015] [015] Surprisingly, it was found that the 3-phenylisoxazoline-5-carboxamide derivatives of cyclopentenylcarboxylic acid of formula (I) defined below and their salts have excellent herbicidal activity against a wide spectrum of economically important mono and dicotyledonous annual plants.
[016] [016] Therefore, the present invention provides compounds of the general formula (1)
[017] [017] G represents a group of the formula ORº or NRURI ;
[018] [018] Rº and Rº independently of each other represent hydrogen, halogen or cyano, or represent (C1-Cs) -alkyl or (C1-Ca) -alkoxy, each of which is replaced by m radicals of the group consisting of halogen and cyan;
[019] [019] Rº represents cyano or fluorine, or represents (C1-Cs) = alkyl, (C3-Cg) —- cycloalkyl, (C2-Cs) -alkenyl, (C> -Cs) -alkynyl or (C1-Cs) -alkoxy, each of which is replaced by m radicals of the group consisting of halogen, cyano, (C1-Cs) -alkoxy and hydroxy;
[020] [020] Rº represents hydrogen, or represents (C1-C12) -alkyl, (C3-C7) -cycloalkyl, (C3-C7) -cycloalkyl- (C: -Csg) -alkyl, (C2-Cg) - alkenyl, (Cs-Cs) -cycloalkenyl or (C> -Cs) -alkynyl, each of which is replaced by radicals from the group consisting of halogen, cyano, (C1-Cs) -alkoxy, hydroxy and aryl;
[021] [021] Y represents oxygen or sulfur;
[022] [022] W represents oxygen or sulfur;
[023] [023] Z represents a monounsaturated cyclopentane ring that is replaced by k radicals of the group R * º, Rx tr
[024] [024] R * º represents halogen, cyano or CO- & R ', or represents (C1i- C2) -alkyl or (C1i-C)) - alkoxy, each of which is replaced by the m radicals of the group consisting of fluorine and chlorine;
[025] [025] Rº, Rº2 independently of each other, each represents hydrogen, cyan OR ", S (O) n Rº, SO2NRºR ', CO2zRº, CONR“ ºRº6, COR ”, NRºR3, NRºCORº, NRºCONRºRº, NR $ CO> - RÊ, NR $ SO-2Rô, NR $ SO2NR $ Rº, C (R6) = NORº, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or represent (C1i-C12) -alkyl, (C3-Cg) -cycloalkyl , (C3-C7) -cycloalkyl- (C1-C;) - alkyl, (C2-C12) -zalkenyl, (Cs-C7) = cycloalkenyl or (C2-C12) quinyl lime, each of which is replaced by radicals m of the group consisting of halogen, cyan, nitro, OR ', S (O) rRº, SO2NRºR', CO2Rº, CONR “Rº, COR“, NR $ Rº, NRºCORº, NRºCONRºRº, NR6CO.Rº, NRSO02Rº, NRºSO2NRºRº, C (Rº) = NORº, optionally substituted aryl, optionally substituted heteroaryl and optionally substituted heterocyclyl, or
[026] [026] Rº and Rº together with the nitrogen atom to which they are attached form a five, six or seven membered partially or totally unsaturated ring which is optionally mono to hexasubstituted by the radicals of the group consisting of halogen, cyan, nitro, ( C1-Ce) -alkyl, halo- (C1i-Ck) -alkyl, oxo, OR ”, S (0) n Rº, SO2NRºR ', CO2Rº, CONR“ RE, CORS, NRºRº, NR $ CORº, NRºCONRºR6, NR6CO2Rº, NR6SO2Rº, NRͺSO2NRºRº and C (Rº) = NORº and which, in addition to this nitrogen atom, contains carbon atoms or oxygen atoms, sulfur atoms and p elements of the group consisting of NR and NCOR as ring atoms;
[027] [027] Xº, X and XxX independently of each other, each represents hydrogen, halogen or cyano, or represent (C1-C2) - alkyl, in each case replaced by the radicals m of the group consisting of fluorine, chlorine, bromine and ( C1-C2) -alkoxy;
[028] [028] XP and Xº independently of each other each represents hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyan, nitro, S (O) n Rº or COWR ', or represent (C1-C3) -alkyl, ( C1-C3) -alkoxy, (C3-C4) -cycloalkyl, (C2-C3) -alkenyl or (C2-C3) - alkynyl, each of which is replaced by the m radicals of the group consisting of fluorine, chlorine and bromine ;
[029] [029] Rº represents (C1-Csg) -alkyl, (C3-Cs) -cycloalkyl or aryl, each of which is replaced by the m radicals of the group consisting of halogen, cyano and hydroxy;
[030] [030] Rº represents hydrogen or Rº;
[031] [031] R 'represents hydrogen, or represents (C1i-Ck) -alkyl, (C3-C6) -cycloalkyl, (C3-Ca) -alkenyl or (C3-Ca) -alkynyl, each of which is replaced by radicals m of the group consisting of halogen, cyano and (C1-C2) -alkoxy;
[032] [032] Rº represents hydrogen, or represents (C1i-Cs) -alkyl, (C3-C6) -cycloalkyl, (C3-Cs) -alkenyl or (C3-Cg) -alkyl, each of which is replaced by m radicals the group consisting of halogen, cyano and (C1-C2) -alkoxy;
[033] [033] k represents the current number 0, 1 or 2; where for k> 1 Rº independently of the others it can be identical or different;
[034] [034] m represents the current number 0, 1, 2, 3, 4 or 5;
[035] [035] n represents the current number 0, 1 or 2;
[036] [036] o represents the current number 0, 1 or 2;
[037] [037] p represents the current number 0 or 1;
[038] [038] q represents the current number 0 or 1; and
[039] [039] r represents the current number 3, 4, 5 or 6.
[040] [040] Alkyl means saturated straight or branched hydrocarbon radicals having the number of carbon atoms specified in each case, eg, C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, l -methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, l1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,27 dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.
[041] [041] Halogen-substituted alkyl means straight or branched alkyl groups in which some or all of the hydrogen atoms in these groups can be replaced by halogen atoms, for example, Ci-Cr-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl , trichloromethyl, fluoromethyl difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlorofluoroethyl, 2 fluoroethyl, 2-chloro-2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl.
[042] [042] Alkenyl represents branched or straight chain unsaturated hydrocarbon radicals having the number of carbon atoms established in each case and a double bond in any position, for example, C> 2-C-alkenyl as ethylene, 1-propenyl, 2-propenyl, 1-methylethyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2 propenyl, l-pentenyl, 2-pentenyl, 3-7 pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-l-butenyl, 3-methyl-l-butenyl, l-methyl-2-butenyl , 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl , 1,2-dimethyl-1-propenyl, 1,27 dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-
[043] [043] Alquinyl means straight or branched chain hydrocarbon radicals having the number of carbon atoms specified in each case and a triple bond in any position, eg, Ca-Ce-alkynyl, such as ethynyl, l-propynyl, 2 -propynyl (or propargyl), l-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl l1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-l1- butynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1l1-dimethyl-2-propynyl, 1l-ethyl-2-propynyl, 1l-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3- pentinyl, 2-methyl-3-pentynyl, 1-methyl-4-pentinyl, 27 methyl-4-pentynyl, 3-methyl-4-pentinyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3 -butinyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2 -ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.
[044] [044] Cycloalkyl means a saturated carbocyclic ring system preferably having 3-8 ring carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclonexyl. In the case of optionally substituted cycloalkyl, cyclic systems with substituents are included, and also are included —double-substituted substituents on the cycloalkyl radical, for example, an alkylidene group, such as methylidene.
[045] [045] In the case of optionally substituted cycloalkyl, polycyclic aliphatic systems are also included, for example, bicycles [1.1.0] butan-1-yl, bicycles [1.1.0] butan-2-yl, bicycles [2.1.0 ] pentan-1-yl, bicycle [2.1.0] pentan-2-yl, bicycle [2.1.0] pentan-5-yl, bicycle [2.2.1] hept-2-yl (norbornil) adamantan-1-yl and adamantan-2-yl.
[046] [046] In the case of substituted cycloalkyl, spirocyclic aliphatic systems are also included, for example, spiro [2.2] pent-1-yl, spiro [2.3] hex-l1-yl, spiro [2.3] hex-4-yl, 3-spiro [2.3] hex-5-yl.
[047] [047] "Cycloalkenyl" means a non-aromatic, partially unsaturated ring system preferably having 4-8 carbon atoms, eg 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl or 1 - cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl, also including substituents with a double bond in a cycloalkenyl radical, for example, an alkylidene group such as methylidene. optionally substituted, clarifications for substituted cycloalkyl apply accordingly.
[048] [048] Alkoxy means straight or branched saturated alkoxy radicals having the number of carbon atoms specified in each case, for example, C1- C-alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, l -methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-7 methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, l-ethylpropoxy, hexoxy, 1, l-dimethylpropoxy, 1,2- dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2.27 dimethylbutoxy, 2,3-dimethylbutoxy, 3, 3 -dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy. Halogen-substituted alkoxy means straight or branched alkoxy radicals having the number of carbon atoms specified in each case, where some or all of the hydrogen atoms in these groups can be replaced by halogen atoms as specified above, eg Ci-Cao-haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, fluoroethoxy, 2-boro-1 2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 27 chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,11-trifluoropropop -2-oxy.
[049] [049] The term "aryl" represents a mono-, bi- or polycyclic aromatic system preferably having 6 to 14, especially 6 to ring carbon atoms, for example, phenyl, naphthyl, anthryl, phenanthrenyl and the like, preferably phenyl.
[050] [050] The term "optionally substituted aryl" also includes polycyclic systems, such as tetrahydronaphile, indenyl, indanyl fluorenyl, biphenylyl, where the binding site is in the aromatic system. In systematic terms, "aryl" is also usually included by the term "optionally substituted phenyl".
[051] [051] Regardless of each other, the aryls listed above are preferably mono- to pentasubstituted, alkyl, haloalkyl hydroxyl, alkoxy, cycloalkoxy, aryloxy, alkoxyalkylalkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, alkylcarbonyl, alkylcyclyl, alkylcarbonyl, alkylcyclylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl. , heteroarilcarbonil, alkoxycarbonyl, hydroxycarbonyl, cicloalcoxicarbonil, cicloalquilalcoxicarbonil, alkoxycarbonylalkyl, arilalcoxicarbonil, arilalcoxicarbonilalquil, alkynyl, alquinilalquil, alquilalquinil, trisalquilsililalquinil, nitro, amino, cyano, haloalkoxy, haloalkylthio, alkylthio, hidrotio, hydroxyalkyl, heteroarylalkoxy, arylalkoxy, heterocyclylalkoxy, heterociclilalquiltio, heterocyclyloxy , heterocyclylthio, heteroaryloxy, bisalkylamino, alkylamino, cycloalkylamino, hydroxycarbonylalkylamino, alkoxycarbonylalkylamino, arylalkoxycarbonylalkylamino,
[052] [052] A heterocyclic radical (heterocyclyl) contains at least one heterocyclic ring (= carbocyclic ring in which at least one carbon atom needs to be replaced by a hetero atom, preferably by a hetero atom of the group of N, O, S, P) that it is saturated, unsaturated, partially saturated or heteroaromatic and can be unsubstituted or substituted, in which case the binding site is located on a ring atom. If the heterocyclyl radical or the heterocyclic ring is optionally substituted, it can be fused to other carbocyclic or heterocyclic rings. In the case of optionally substituted heterocyclyl, polycyclic systems are also included, for example, 8-azabicyclo [3.2.1] octanyl, 8-azabicyclo [2.2.2] octanyl or l-azabicyclo [2.2.1] heptyl. In the case of optionally substituted heterocyclyl, spirocyclic systems are also included, for example, 1-oxa-5-azaspiro [2.3] hexyl. Unless otherwise defined, the heterocyclic ring preferably contains 3 to 9 ring atoms, especially 3 to 6 ring atoms and one or more, preferably 1 to 4, especially 1, 2 or 3, hetero atoms in the heterocyclic ring, preferably a group of N, O and S, but none of the two oxygen atoms should be directly adjacent, for example, with a hetero atom of the group of N, O and S: 1- or 2- or 3-pyrrolidinyl, 3,4- dihydro-2H-pyrrole-2- or 3-yl, 2,3-dihydro-1H-pyrrole-1- or 2- or 3- or 4- or 5-yl; 2,5-dihydro-1H-pyrrole-1- or 2- or 3-yl, 1- or 2- or 3- or 4-piperidinyl; 2,3,4,5-tetrahydropyridin-2- or 3- or 4- or 5-yl or 6-yl; 1,2,3,6-tetrahydropyridin-l1- or 2- or 3- or 4- or 5- or 6-11; 1,2,3,4-tetrahydropyridin-1- or 2- or 3- or 4- or 5- or 6-yl; 1,4-dihydropyridin-11 or 2- or 3- or 4-yl; 2,3-dihydropyridin-2- or 3- or 4- or 5- or 6-yl; 2,5-dihydropyridin-2- or 3- or 4- or 5- or 6-yl, 1- or 2- or 3- or 4- azepanyl; 2,3,4,5-tetrahydro-1H-azepin-l1- or 2- or 3- or 4- or
[053] [053] Regardless of one another, the heterocycles listed above are preferably mono to hexasubstituted, for example, by hydrogen, halogen, alkyl, haloalkyl, hydroxyl alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxy alkoxy cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroalkyl, aryl, arylalkyl heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarilcarbonil, alkoxycarbonyl, hydroxycarbonyl, cicloalcoxicarbonil, cicloalquilalcoxicarbonil, alkoxycarbonylalkyl, arilalcoxicarbonil, arilalcoxicarbonilalquil, alkynyl, alquinilalquil, alquilalquinil, trisalquilsililalquinil, nitro, amino, cyano, haloalkoxy, haloalkylthio, alkylthio, hidrotio hydroxyalkyl , oOxXo, heteroarylalkoxy, arylalkoxy, heterocyclylalkoxy, heterociclilalquiltio, heterocyclyloxy, heterocyclylthio, heteroaryloxy, bisalquilamino, alkylamino, cycloalkylamino, hidroxicarbonilalquilamino, alkoxycarbonylalkylamino, arilalcoxicarbonilalquilamino, alkoxycarbonylalkyl (alkyl) amino, carbonyl, alkylaminocarbonyl, bisalkylaminocarbonyl, cycloalkylaminocarbonyl, hydroxycarbonylalkylaminocarbonyl, alkoxycarbonylalkylaminocarbonyl, arylalkoxycarbonylalkylaminocarbonyl.
[054] [054] When a base structure is replaced by "one or more radicals" from a list of radicals (= group) or a generically defined group of radicals, this in each case includes simultaneous replacement by several identical and / or structurally different radicals .
[055] [055] In the case of a partially or fully saturated nitrogen heterocycle, it can be joined to the rest of the molecule via carbon or nitrogen.
[056] [056] Suitable substituents for a substituted heterocyclic radical are those specified below and additionally oxo and thioxo. The oxo group as a substituent on a carbon atom is, for example, a carbonyl group on the heterocyclic ring. As a result, lactones and lactams are also preferably included. The oxo group can also occur in ring hetero atoms, which can exist in several different oxidation states, for example, in the case where they form, for example, the divalent groups -N (O0) -, -S (0) - ( also SO in the short form) and -S (0); - (also SO7r in the short form) in the heterocyclic ring. In the case of groups of -N (0) -— and -S (0) -, both enantiomers are included in each case.
[057] [057] According to the invention, the term "heteroaryl" refers to heteroaromatic compounds, that is, fully unsaturated aromatic heterocyclic compounds, preferably 5 to 7 membered rings having 1 to 4, preferably 1 or 2, identical or different heteroatoms preferably O, S or N. The inventive heteroaryls are, for example, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1H-pyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, 1H-imidazol-1-yl; 1H-imidazol-2-yl; 1H-imidazol-4-yl; 1H-imidazol-5-yl; 1H-pyrazol-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1H-pyrazol-5-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H- 1,2,3-triazol-2-yl, 2H-1,2,3-triazol-4-1yl, 1H-1,2,4-triazol-1-yl, 1H-1,2,4- triazol-3-yl, 4H-1,2,4-triazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-0oxadiazol-5-yl, 1,3,4- oxadiazol-2-yl 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl, azepinyl, pyridin-2-yl, pyridin -3-yl, pyridin-4-yl, pyrazin-
[058] [058] Preferred examples are quinolines (eg, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin- 8-il); isoquinolines (e.g., isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl); quinoxaline; quinazoline; kinoline; 1.57 naphthyridine; 1,6-naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine; 2,7-naphthyridine; phthalazine; pyridopyrazines; pyridopyrimidines; pyridopyridazines; pteridines; pyrimidopyrimidines. Examples of heteroaryl are also 5- to 6-membered benzofused rings of the group of 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indol-4-yl, 1H-indole -5-yl, 1H-indol-6-yl, lH-indol-7-yl, l-benzofuran-2-yl, l-benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5 -yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, l-benzothiophen-5-yl , 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1H-indazol-11-yl, 1H-indazol-3-yl, 1H-indazol-4-3i1l, 1H-indazol-5-yl, 1H -indazol-6-1yl, 1H-indazol-7-yl, 2H-indazol-2-yl, 2H-indazol-3-yl, 2H-indazol-4-yl, 2H-indazol-5-yl, 2H-indazole -6-yl, 2H-indazol-7-yl, 2H-isoindol-2-yl, 2H-isoindol-
[059] [059] Regardless of each other, the heteroaryls listed above are preferably mono- to tetra-substituted, for example, by hydrogen, halogen, alkyl, haloalkyl, hydroxyl alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxy alkoxy cycloalkyl, halocycloalkyl, aryl, aryl, alkyl; heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarilcarbonil, alkoxycarbonyl, hydroxycarbonyl, cicloalcoxicarbonil, cicloalquilalcoxicarbonil, alkoxycarbonylalkyl, arilalcoxicarbonil, arilalcoxicarbonilalquil, alkynyl, alquinilalquil, alquilalquinil, trisalquilsililalquinil, nitro, amino, cyano, haloalkoxy, haloalkylthio, alkylthio, hidrotio hydroxyalkyl , oxo, heteroarylalkoxy, arylalkoxy, heterocyclylalkoxy, heterociclilalquiltio, heterocyclyloxy, heterocyclylthio, heteroaryloxy, bisalquilamino, alkylamino, cycloalkylamino, hidroxicarbonilalquilamino, alkoxycarbonylalkylamino, arilalcoxicarbonilalquilamino, alkoxycarbonylalkyl (alkyl) amino, aminoC arbonyl, alkylaminocarbonyl, bisalkylaminocarbonyl, cycloalkylaminocarbonyl, hydroxycarbonylalkylaminocarbonyl, alkoxycarbonylalkylaminocarbonyl, arylalkoxycarbonylalkylaminocarbonyl.
[060] [060] The term "halogen" means fluorine, chlorine, bromine or iodine. If the term is used for a radical, "halogen" means a fluorine, chlorine, bromine or iodine atom.
[061] [061] Depending on the nature of the substituents and the way in which they are attached, the compounds of the general formula (1) can be present as stereoisomers. If, for example, one or more asymmetric carbon atoms and / or sulfoxides are present, enantiomers and diastereomers may occur. Stereoisomers can be obtained from mixtures obtained in the preparation by the usual separation methods, for example, by chromatographic separation processes. Likewise, it is possible to "selectively prepare stereoisomers using stereoselective reactions using optically active and / or auxiliary starting materials.
[062] [062] The invention also relates to all isomers and their mixtures that are included in the general formula (LI), but are not specifically defined. However, the following text will present, for simplicity, the compounds of formula (1), although it means that not only pure compounds, but also, if appropriate, mixtures with various amounts of isometric compounds.
[063] [063] Depending on the nature of the substituents defined above, the compounds of formula (1) have acidic properties and can form salts and, if appropriate, also internal salts or adducts, with inorganic or organic bases or with metal ions. If the compounds of the formula (TI) contain hydroxyl, carboxyl or other groups, which induce acidic properties, these compounds can be reacted with bases to provide salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium and also ammonia, primary, secondary and tertiary amines containing groups (C1-Ca) - (C1i-Ca) -alkanol, alkyl, mono, di and trialcanolamines, choline and chlorocholine, in addition to organic amines, such as trialkylamines, morpholine, piperidine or pyridine. These salts are compounds in which acidic hydrogen is replaced by a suitable agricultural cation, for example, metal salts, especially alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts or ammonium salts, salts with organic amines or quaternary ammonium salts, for example, with cations of the formula [NRR RR], in which R to R '' "'each, independently of each other, represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl, alkylsulfonium and alkylsulfoxonium salts, such as (C1-Ca) - trialkylsulfonium and (C1i-C4s) -trialkylsulfoxonium salts, are also suitable.
[064] [064] The components of formula (I) can form salts by the addition of a suitable inorganic or organic acid, for example, mineral acids, for example, HCl, HBr, H2SOas, H3POs or HNO3 Or organic acids, for example, carboxylic acids , such as formic acid, acetic acid, oxalic acid, lactic acid, salicylic acid or sulfonic acid, for example, pr toluenesulfonic acid, dialkylamino, piperidine, morpholino or pyridine. In this case, these salts comprise the conjugated base of the acid as the anion.
[065] [065] suitable substituents present in the deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups that, in turn, can be protonated, such as amino groups.
[066] [066] If a group is polysubstituted by radicals, it means that this group is replaced by one or more radicals identical or different from those mentioned.
[067] [067] In the formulas specified in this document, the substituents and symbols have the same meaning as described in formula (1), unless defined differently. The arrows in a chemical formula represent the points where it is linked to the rest of the molecule.
[068] [068] Below is a description of preferred, particularly preferred and very particularly preferred definitions for each of the individual substituents. The other substituents of the general formula (1) that are not specified in this document have the definition presented above.
[069] [069] According to a first representation of the present invention,
[070] [070] Rº and Rº preferably and independently of each other each represents hydrogen, fluorine, chlorine or cyano or represent (C1-C3) -alkyl or (C1-C3) -alkoxy which are in each case replaced by the m radicals of the group which consists of fluorine, chlorine, bromine and cyan.
[071] [071] Particularly and preferably, Rº and R independently of each other, they each represent hydrogen, fluorine, chlorine or cyano or represent methyl or methoxy, which are in each case replaced by the radicals m of the group consisting of fluorine and chlorine.
[072] [072] More preferably, R 'and R each represent hydrogen.
[073] [073] According to a second representation of the present invention,
[074] [074] Rº preferably represents cyano or (C! -C4s) -alkyl, (C3-Cs) -cycloalkyl, (C2-Ca) -alkenyl, (C2o-Ca) -alkynyl or (C1i-Ca) - alkoxy, each one of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C1i-C's) -alkoxy and hydroxy.
[075] [075] Particularly and preferably, R represents (C1-C3) - alkyl, (C3-C4a) -cycloalkyl, (C2-C3) zalkenyl or (C1-C3) -alkoxy, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C>) - alkoxy.
[076] [076] According to a third representation of the present invention,
[077] [077] Rº preferably represents hydrogen or represents (C1-C6) -alkyl, (C3-Cg) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-Cs) - alkyl, (C2-Cg) -alkenyl, ( Cs-Cg) -cycloalkenyl or (C2-C6) alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C1i-Ca) -alkoxy, hydroxy and aryl.
[078] [078] According to a fourth representation of the present invention,
[079] [079] Y represents oxygen.
[080] [080] According to a fifth representation of the present invention,
[081] [081] Ww represents oxygen.
[082] [082] According to a sixth representation of the present invention,
[083] [083] Z preferably represents a group Z-1 at 27-22, where Z-1 at 72-22 have the following meaning: F3C Os dO A OE O z1 z2 z3 ZA H3cO CHa z5 z6 z7 z8
[084] [084] Particularly and preferably, Z represents a group Z-1 to 27-12, where Z-1 to Z2-12 have the following meaning: F3C. zZ1 z-2 z3 ZA dO. A z5 z6ô z7 z8 CN CH
[085] [085] More preferably, Z represents Z-l1, Z-4 or 2-6: z1 24 z6 where the arrow in each case denotes a link to the group C = W of the formula (1).
[086] [086] According to a seventh representation of the present invention,
[087] [087] Rº preferably represents fluorine, chlorine, cyano CO> 2H, CO2CH3 or CO: CHxCH3 or represents (C1-C2) -alkyl or (C1-C2) -alkoxy, each of which is replaced by m radicals of the group that consists of fluorine and chlorine.
[088] [088] According to an eighth representation of the present invention,
[089] [089] R4 preferably represents hydrogen or represents (C1-C3) -alkyl or (C3-Ceg) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[090] [090] According to a new representation of the present invention,
[091] [091] R ' preferably represents hydrogen, cyano, OR, S (O) n Rº, SO2NRºR ', COR “, NRºRº, NRºCORº or NRºSO-Rº or represents (C1-C6) -alkyl, (C3-Cg6) -cycloalkyl, (C2-C3 ) -alkenyl or (C2-C3) - alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, OR ', S (O) n Rº, NRºRº and NRºCO-Rº.
[092] [092] According to a tenth representation of the present invention,
[093] [093] R4º and Rº together with the nitrogen atom, to which they are attached, preferably form a five, six or seven membered saturated, partially or totally unsaturated ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, cyano, nitro, (C1-Cs) -alkyl, halo- (Cir Ce) -alkyl, oxo, OR, S (O) n Rº, CO2Rº6, CORó, NRºRº and NRºSO-Rº and that, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o, sulfur atoms p and q elements of the group consisting of NR 'to NCOR like ring atoms.
[094] [094] Particularly and preferably, R! ' and Rº together with the nitrogen atom, to which they are attached, form a five, six or seven-membered saturated, partially or totally unsaturated ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, cyan, nitro, ( C1i-Ce) -alkyl, halo- (C1-Cs) -alkyl, oxo, OR ', CO2Rº and NRSO0.Rº and which, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o, sulfur atoms p and q elements of the group consisting of NR 'a NCOR' as ring atoms.
[095] [095] More preferably, R ** and R * º together with the nitrogen atom, to which they are attached, form a saturated, partially or totally unsaturated five, six or seven membered ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, (C1i-Cs) -alkyl, halo- (Ci-Ce) - alkyl and oxo and which, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o, sulfur atoms and p q of the group consisting of NR ”to NCOR ” like ring atoms.
[096] [096] According to an eleventh representation of the present invention,
[097] [097] Xº, Xº and x preferably and independently of each other each represents hydrogen, fluorine, chlorine, bromine or cyano or represent methyl or methoxy, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[098] [098] Particularly and preferably, x, xi and xs independently of one another represent hydrogen or fluorine. According to a twelfth representation of the present invention,
[099] [099] X and Xº preferably and independently of each other each represents hydrogen, fluorine, chlorine, bromine, hydroxy or cyano or represents (C1-C3) -alkyl, (C1-C3) -alkoxy, (C3-Ca) - cycloalkyl, (C2x -C3) -alkenyl or (C2-C3) -alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and bromine.
[100] [100] Particularly and preferably, x: and xo independently of each other each represents hydrogen, fluorine, chlorine, CF3, CHF; or methyl.
[101] [101] According to a thirteenth representation of the present invention,
[102] [102] Rº preferably represents (C1-C «s) -alkyl or (C3-C6) - cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[103] [103] According to a fourteenth representation of the present invention,
[104] [104] R 'preferably represents hydrogen or represents (C1-C6) -alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) - alkoxy.
[105] [105] According to a fifteenth representation of the present invention,
[106] [106] Rº preferably represents hydrogen or represents (C1-C6g) -alkyl or (C3-Cg) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) -alkoxy .
[107] [107] According to a sixteenth representation of the present invention,
[108] [108] m represents the current number 0, 1, 2 or 3.
[109] [109] In the context of the present invention, the individual preferred, particularly preferred and very preferred meanings of the R! a Rº, R! º to RX, Xº to X6, W, Y and Z and the numbers in force k, m, n, O, p, q and r can be combined together as desired.
[110] [110] This means that the present invention covers the compounds of the general formula (I), in which, for example, the O substituent R! it has a preferred definition and the substituents Rº to R 'have the general definition or the substituent Rº has a preferred definition, the substituent Rº has a particularly preferential or very particularly preferred definition and the remaining substituents have a general definition.
[111] [111] Four of these combinations of the definitions given above for the Rº 'to Rº, Rº to Rº, X substituents to X6, W, Y and Z and for the numbers in force k, m, n, oO, p, q and r are illustrated below by way of example and each of them is disclosed as another representation:
[112] [112] According to a seventeenth representation of the present invention,
[113] [113] G represents a group of the formula ORº;
[114] [114] Re R independently of each other each represents hydrogen, fluorine, chlorine or cyano or represents (C1-C3) -alkyl or (C1-C3) alkoxy which are in each case replaced by the m radicals of the group consisting of fluorine , chlorine, bromine and cyan;
[115] [115] R represents cyano or represents (C1-C3) -alkyl, (C3-Ca) - cycloalkyl, (C2-C3) -alkenyl, (C2o-C3) -alkynyl or (C1-C3) -alkoxy,
[116] [116] Rº represents hydrogen or represents (C1-Cs) -alkyl, (C3-Ce) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-Cs) -alkyl, (C2-Cç6) - alkenyl, (Cs -Ceg) -cycloalkenyl or (C2-Cs) -alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C1-C1a) -alkoxy, hydroxy and aryl.
[117] [117] Y represents oxygen;
[118] [118] W represents oxygen;
[119] [119] z represents a group Z-1l1 to Z2-12, where Z-1 to 27-12 have the following meaning: FC. The DO. AO O. Zz1 Zz2 z3 ZA HkCO, CH z5 z6 z7 z8
[120] [120] Xº, Xº and x is independently of each other each representing hydrogen, fluorine, chlorine, bromine or cyano or representing methyl or methoxy, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[121] [121] XP and Xº independently of each other each represents hydrogen, fluorine, chlorine, bromine, hydroxy or cyano or represents (C1-C3) -alkyl, (C1-C3) -alkoxy, (C3-C4a) -cycloalkyl, (C2-C3) -
[122] [122] m represents the current number 0, 1, 2 or 3.
[123] [123] According to an eighteenth representation of the present invention,
[124] [124] G represents a group of the formula ORº;
[125] [125] Re RQ each represents hydrogen;
[126] [126] Rº represents (C1-C3) -alkyl, (C3-Ca) -cycloalkyl, (C2-C3) - alkenyl or (C1-C3) -alkoxy, each of which is replaced by m radicals of the group consisting of in fluorine, chlorine and (C1-C2) - alkoxy;
[127] [127] Rº represents hydrogen or represents (C1-Cs) -alkyl, (C3-Ce) -cycloalkyl, (C3-C6) -cycloalkyl- (C1-Cs) -alkyl, (C2-Cç6) - alkenyl, (Cs -Ce) -cycloalkenyl or (C2-Cs) -alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C1-Ca) -alkoxy, hydroxy and aryl;
[128] [128] Y represents oxygen;
[129] [129] W represents oxygen;
[130] [130] Z represents a group 2-1, 2-4 or 2-6: z1 ZA z6 where the arrow in each case denotes a link to the group C = W of the formula (1);
[131] [131] Xº, Xº and x independently of each other each represents hydrogen or fluorine;
[132] [132] X and Xº independently of each other each represents hydrogen, fluorine, chlorine, CF3, CHF27 or methyl; and
[133] [133] m represents the current number 0, 1, 2 or 3.
[134] [134] According to a nineteenth representation of the present invention,
[135] [135] G represents a group of the NRURI formula;
[136] [136] Rº and R independently of each other each represents hydrogen, fluorine, chlorine or cyano or represents (C1-C3) -alkyl or
[137] [137] Rº represents cyan or represents (C1-C3) -alkyl, (C3-Ca) - cycloalkyl, (C2-C3) -alkenyl or (C1-C3) -alkoxy, each of which is replaced by m radicals of group consisting of fluorine, chlorine, bromine, cyano, (C1-C2) -alkoxy and hydroxy;
[138] [138] Y represents oxygen;
[139] [139] W represents oxygen;
[140] [140] Z represents a group Z-1 to Z2-12, where Z-11 to 72-12 have the following meaning: F3C. O. dO. TO THE. Zz1 z2 z3 z4 H:; CO CH; z5 Zz6 z7 z8
[141] [141] Xº, Xº and X is independently of each other each representing hydrogen, fluorine, chlorine, bromine or cyano or representing methyl or methoxy, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[142] [142] X and Xº independently of each other each represents hydrogen, fluorine, chlorine, bromine, hydroxy or cyano or represents (C1-C3) -alkyl, (C1-C3) -alkoxy, (C3-C4a) -cycloalkyl, (C2-C3) alkenyl or (C; -C3) -alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and bromine; and
[143] [143] Rº represents (C1i-Cs £) -alkyl or (C3-Cg) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[144] [144] D represents hydrogen or R;
[145] [145] R 'represents hydrogen or represents (C1-Cs) -alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) -alkoxy ;
[146] [146] Rº represents hydrogen or represents (C1-C6) -alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) -alkoxy;
[147] [147] Rº represents hydrogen or represents (C1-C3) -alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[148] [148] Rº preferably represents hydrogen, cyan, OR ', S (0) n Rºà, SO2NRºR', COR “, NRºRº, NR6CORº or NRºSO: Rº or represents (C1-C6) -alkyl, (C3-Cg6g) -cycloalkyl , (C2-C3) -alkenyl or (C2-C3) - alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, OR ', S (O) n Rº, NRºRº and NRºCOXRº; or
[149] [149] R4 and Rº2 together with the nitrogen atom, to which they are attached, form a five, six or seven membered saturated, partially or totally unsaturated ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, cyan , nitro, (C1-C «) - alkyl, halo- (C1i-Cs) - alkyl, oxo, OR, COWRº and NRºSO.Rº and which, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o , sulfur atoms and q elements of the group consisting of NR 'to NCOR as ring atoms;
[150] [150] m represents the current number 0, 1, 2 or 3;
[151] [151] n represents the current number 0, 1 or 2;
[152] [152] o represents the current number 0, 1 or 2;
[153] [153] p represents the current number 0 or 1;
[154] [154] qa represents the current number 0 or 1; and
[155] [155] r represents the current number 3, 4 or 5.
[156] [156] According to a twentieth representation of the present invention,
[157] [157] G represents a group of the NRURIU formula;
[158] [158] R and RQ each represent hydrogen;
[159] [159] Rº represents (C1-C3) -alkyl, (C3-Ca) -cycloalkyl, (C2-C3) - alkenyl or (C1-C3) -alkoxy, each of which is replaced by m radicals of the group consisting of in fluorine, chlorine and (C1-C2) - alkoxy;
[160] [160] Y represents oxygen;
[161] [161] W represents oxygen;
[162] [162] Z represents a group Z-1, Z-4 or 2-6: z1 74 z-6 where the arrow in each case denotes a link to the group C = W of the formula (1);
[163] [163] Xº, Xº and XxX independently of each other each represents hydrogen or fluorine;
[164] [164] X and X ”independently of each other each represents hydrogen, fluorine, chlorine, CF3, CHF> or methyl;
[165] [165] Rº represents (C1-Cs) -alkyl or (C3-Cs) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[166] [166] Rº represents hydrogen or R $;
[167] [167] R 'represents hydrogen or represents (C1i-Cs) -alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) -alkoxy ;
[168] [168] Rº represents hydrogen or represents (C1-C «) - alkyl or (C3-C6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C1-C2) -alkoxy ;
[169] [169] Rº represents hydrogen or represents (C1-C3) -alkyl or (C3-Ce6) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine;
[170] [170] R represents hydrogen, cyan, OR ', S (O) n Rº, SO2NR $ RI, COR “, NRºRº, NRºCORº or NRºSO-Rº or represents (C1-C«) - alkyl, (C3-Ce) -cycloalkyl, (C2x -C3) -alkenyl or (C2-C3) -alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, OR ', S (O) n Rº, NRºRº and NRºCO; R; or
[171] [171] R4 and Rº2 together with the nitrogen atom, to which they are attached, form a five, six or seven membered saturated, partially or totally unsaturated ring which is optionally mono to hexasubstituted by radicals of the group consisting of halogen, ( C1i-C68) -alkyl, halo- (C1-Cs) -alkyl and oxo and which, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o, sulfur atoms p and q elements of the group consisting of NR 'NCOR as ring atoms;
[172] [172] m represents the current number 0, 1, 2 or 3;
[173] [173] n represents the current number 0, 1 or 2;
[174] [174] o represents the current number 0, 1 or 2;
[175] [175] p represents the current number 0 or 1;
[176] [176] q represents the current number 0 or 1; and
[177] [177] r represents the current number 3, 4 or 5.
[178] [178] Examples of the compounds of the general formula (1) are shown below in table form. Table 1 below specifies the substituents defined in the general terms in formula (1).
[179] [179] Table 1.1: Compounds of the general formula (II) where Xº = Xº = Xº = R = R = H, Y = W = 0OeG = OR Example x XxX ”| RZ Rº Comment No. .: (1R, 48S) -cyclopent- 1-001 HF CH3 Z-1 | H 2-en-l-carboxyl (18.4R) -cyclopent- 1-002 HF CH3 Z-1 | H 2-en-1-carboxyl (1R, 48S) -cyclopent- 1-003 HF CH3 Z-1 | CH3 2-en-1-carboxyl (18.4R) -cyclopent- 1-004 HF CH3 Z-1 | CH3 2-en-1-carboxyl (1R, 48S) -cyclopent- 1-005 HF CH3 Z-1 | CHxCH3 2-en-1-carboxyl (18,4R) -cyclopent- 1-006 HF CH3 Z-1 | CHXCH3 2-en-l-carboxyl
[180] [180] Table 1.2: Compounds of the general formula (I) where Xº = Xº = Xº = R | = R = H, Y = W = 0 eG = NRURX Example. A, X3 | X5 [Rô Z NRURI Comment No. .: (1R, 48) - II-Ol H | F | CH3 Z-1 methoxyamino cyclopent-2-en- l1-carboxyl (18.4R) - 11-02 F | F | CH3 2-1 methoxyamino cyclopent -2-en- l1-carboxyl
[181] [181] The compounds, according to the invention, can be prepared by various processes, examples of which are given below: Scheme 1: n ”(9) No. o Ph-Nco or CFCOo-OE O. - o O HnoHHO. Nº UH ”nº 7 Oo H HOH nes / DvF CO B: [a Jo H cr ase DE o Dos oo No o N-O 9 Synthesis of No q c õ * hydrolysis = fl OH starch - (xf! NA - - Rº - RH d
[182] [182] In scheme 1 and the schemes that follow, (X) "represents the substituents Xº, X3, Xi, Xº and Xº. These 1,3-dipolar cycloadloads of nitrile oxides with dipolarophils are described, for example, in Reviews: 1.3 dipolar Cycloaddition Chemistry,
[183] [183] The compounds, according to the invention, substituted at positions 4 and 5 of the isoxazoline ring system can also be prepared by 1,3-dipolar cycloaddition using 1,2-disubstituted olefins as dipolarophils. This reaction generally provides mixtures that can be separated by column chromatography. Optically active isoxazolines can be obtained by chiral HPLC of suitable precursors or end products and also by enantioselective reactions, such as enzyme ester or amide cleavage or using chiral auxiliaries in the dipolarophil, as described by Olssen (J. Org.Chem 1988, 53, 2468).
[184] [184] For the preparation of the compounds according to the invention, it is also possible to use suitable 2-alkoxyacrylamides (scheme 3). This can be obtained from acrylic esters described in scheme 2 after the formation of hydrolysis and amide. Scheme 2: R o nut 7 - Ro sector + ONÇOR = - eo R W RW
[185] [185] One option for activating acrylic acid is carbodiimides, for example, EDCl (Chen, F. M. F .; Benoiton, N. L. Synthesis 1979, 709). For the preparation of acrylamides, see US 2,521,902, JP60112746, J. of Polymer Science 1979, 17 (6),
[186] [186] Transformations of the functional groups R º are possible in the alkene stage or in the isoxazoline stage.
[187] [187] The sets of the compounds of the formula (II) and / or their salts that can be synthesized by the reactions mentioned above can also be prepared in parallel, in which this can be carried out in a manual, automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the preparation or the purification of the products and / or intermediates. In general, this means a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (editor: Gunther Jung), Wiley, 1999, on pages 1 to 34.
[188] [188] The compounds of the formula (TI) according to the invention (and / or its salts), collectively referred to hereinafter as "compounds according to the invention", have excellent herbicidal efficacy against a wide spectrum of harmful monocotyledonous and dicotyledonous plants economically important annual accounts.
[189] [189] Therefore, the present invention also provides a method for controlling unwanted plants or regulating plant growth, preferably in plant crops, in which one or more compounds of the invention are applied to plants (for example, harmful plants, such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), seed (for example, grains, seeds or plant propagules, such as tubers or sprouting parts of germination) or the area in which the plants grow (for example, the area under cultivation ). The compounds of the invention can be implemented, for example, before sowing (if appropriate, also by incorporation into the soil), before or after emergence. Specific examples of some representatives of monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of the invention are as follows, although the enumeration does not indicate the intention to impose restriction on particular species.
[190] [190] Harmful monocotyledonous plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria,
[191] [191] Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, .Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Roripa, Roripa , Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
[192] [192] When the compounds according to the invention are applied to the soil surface before germination, the weed seedlings are completely prevented from emerging or the weeds grow until they reach the cotyledon stage, but then stop growing .
[193] [193] If the active compounds are applied after emergence to the green parts of the plants, growth will stop after treatment, and the harmful plants will either continue in the growth stage at the time of application or die completely after a certain period, so that in this way, the competition between weeds, which is harmful to crop plants, is eliminated very early and in a sustained manner.
[194] [194] According to the invention, compounds can be selective in plantations of useful plants and can also be used as non-selective herbicides.
[195] [195] Due to the herbicidal and growth-regulating properties of the plant, the active compounds can also be used to control harmful plants in harvesting genetically modified plants that are known or still in development. In general, transgenic plants are characterized by advantageous properties in particular, for example, resistance to certain active compounds used in the agribusiness, in particular certain herbicides, resistance to disease in the plant or pathogens of disease in the plant, such as certain insects or micro- organisms such as fungi, bacteria or viruses. Other specific characteristics, for example, are related, for example, to the cultivated material with respect to quantity, quality, storage capacity, composition and specific constituents. For example, there are known transgenic plants with a high starch content or altered starch quality or those with a different fatty acid composition in the cultivated material. Other properties in particular are tolerance or resistance to abiotic stress factors, for example, heat, cold, drought, salinity and ultraviolet radiation.
[196] [196] Preference is given to the use of compounds of formula (I), according to the invention, or to their salts in economically active transgenic plantations of useful or ornamental plants.
[197] [197] The compounds of formula (1) can be used as herbicides in plantations of useful plants that are resistant, or that have become resistant, through genetic engineering, to the phytotoxic effects of herbicides.
[198] [198] Conventional means of producing new plants that have modified properties compared to existing plants consist, for example, of traditional methods of cultivation and mutant generation. Alternatively, new plants with altered properties can be generated with the help of recombinant methods (see, for example, EP 0221044, EP 0131624). What has been described here are, for example, several cases of genetic modifications of crop plants for the purpose of modifying the starch synthesized in plants (eg WO 92/011376 A, WO 92/014827 A, WO 91 / 019806 A), transgenic cultivation plants that are resistant to certain glufosinate type herbicides (cf., for example, EP 0242236 A, EP 0242246 A) or glyphosate type (WO 92 / 000377A) or sulfonylurea type
[199] [199] Several molecular biology techniques that can be used to produce new transgenic plants with modified properties are known in principle; see, eg, I. Potrykus and G. Spangenberg (eds.), Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, "Trends in Plant Science" 1 (1996) 423- 431).
[200] [200] For these genetic manipulations, nucleic acid molecules that allow mutagenesis or sequence change by recombination of DNA sequences can be introduced into plasmids. With the help of standard methods it is possible, for example, to combine base changes, remove parts of strings or add natural or synthetic strings. To join the DNA fragments to each other, adapters or linkers can be placed on the fragments; see, for example, Xambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim 2nd edition, 1996.
[201] [201] For example, the generation of plant cells with reduced activity of a gene product can be achieved by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a co-suppression effect or expression of at least one properly created ribozyme that specifically divides transcripts of the aforementioned gene product. To that end, it is first possible to use DNA molecules that include the entire coding sequence of a gene product including any flanking sequence that may be present and also DNA molecules that only include parts of the coding sequence, in which case these portions must be long enough to have an anti-sense effect on the cells. It is also possible to use DNA sequences that have a high degree of homology for the coding sequences of a gene product, but are not completely identical to them.
[202] [202] When expressing nucleic acid molecules in plants, the synthesized protein can be located in any desired compartment of the plant cell. However, in order to obtain location in a specific compartment, it is possible, for example, to join the coding region in the DNA sequences, which ensures the location in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846- 850; Sonnewald et al., Plant J. 1 (1991), 95-106). Nucleic acid molecules can also be expressed in the organelles of plant cells.
[203] [203] Transgenic plant cells can be regenerated by known techniques to provide growth for whole plants. In principle, transgenic plants can be plants of any desired plant species, that is, not only monocots, but also dicots. In this way, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous genes (= natural) or gene sequences or expression of genes or heterologous gene sequences (= zexterns).
[204] [204] According to the invention, compounds (I) can be used with preference in transgenic crops that are resistant to growth regulators, for example, 2,4-D, dicamba or herbicides that inhibit essential plant enzymes, for example, acetolact synthase (ALS), EPSP synthase, glutamine synthase (GS) or hydroxyphenylpyruvate dioxigenase (HPPD) or sulfonylurea group herbicides, glyphosates, glufosinates or benzoloxazoles and analogous active compounds or any desired combinations of these active compounds.
[205] [205] The compounds of the invention can be used with particular preference in transgenic crop plants that are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. More preferably, the compounds according to the invention can be used in transgenic crop plants, such as corn or soybeans with the trade name or designation OptimumTM GATTM (glyphosate ALS tolerant), for example.
[206] [206] When the active compounds of the invention are used in transgenic plantations, not only do the effects on the harmful plants observed in other plantations occur, but also frequently the effects that are specific to the application in the transgenic crop in particular, for example, a spectrum of modified or specifically comprehensive weeds that can be controlled, changed application rates that can be used for application, preferably a good combination with the herbicides to which the transgenic plantation is resistant and influenced by the growth and production of transgenic crop plants.
[207] [207] Therefore, the invention is also related to the use of the compounds according to the invention of formula (1), as herbicides to control harmful plants in transgenic crop plants.
[208] [208] The compounds of the invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, powder products or granules in the usual formulations. Therefore, the invention also provides herbicide and plant growth regulation compositions that comprise the compounds of the invention.
[209] [209] The compounds of the invention can be formulated in several ways, according to the necessary biological and / or physicochemical parameters. Possible formulations include, for example, wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, solutions sprayable, suspension concentrates (SC) dispersions based on oil or water, oil miscible solutions, capsule suspensions (CS), powder products (DP), dressings, granules for distribution and application in the soil, granules (GR) in the form microgranules, spray granules, absorption and adsorption granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes. These types of individual formulation are known in principle and are described, for example, in: Winnacker-Kúchler, "Chemische Technologie [Chemical Technology]", Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, " Pesticide Formulations ", Marcel Dekker, NY, 1973, K. Martens," Spray Drying "Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
[210] [210] The required formulation aids, such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2a. ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide", 2a. ed., Interscience, N.Y. 1963; McCutcheon's
[211] [211] Based on these formulations, it is also possible to produce combinations with other active compounds, for example, insecticides, acaricides, herbicides, fungicides and also with protectors, fertilizers and / or growth regulators, for example, in the form of finished formulation or like a tank mix.
[212] [212] Active compounds that can be used in combination with the compounds according to the invention in mixed formulations or in the tank mixture are, for example, active compounds that are based on the inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvilshikimate- 3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxigenase, phytene desaturase, photosystem I, photosystem II or protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or The Pesticide Manual ", 16th edition, The British Crop Protection Council and the Royal Soc. Of Chemistry, 2006 and cited literature. Known herbicides or plant growth regulators that can be combined with the compounds according to the invention are, for example, the following, in which said active compounds are designated with their "common name" according to the International Organization for Standardization (ISO) or with the chemical name or code number. They always cover all forms of application, such as, for example, acids, salts, esters and also all isomeric forms, such as stereoisomers and optical isomers, even if they are not explicitly mentioned.
[213] [213] Examples of such herbicidal blending elements are: acetochlor, acifluorfen, acifluorfen sodium, aclonifen, alachlor, alidochlor, alloxidim, alloxidim sodium, ametrin, amicarbazone,
[2114] [2114] Examples of plant growth regulators as possible mixing elements are: acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancimidol, 6-benzylaminopurine, brassinolid, catechol, chlormequat chloride, cloprop, cyclanilide, acid 3 - (cycloprop-l-enyl) propionic, daminozide, dazomet, n-decanol, dikegulac, sodium dikegulac, endotal, endotypotassium, -disodium and mono (N, N-
[215] [215] Protectors can be used in combination with the compounds of formula (1), according to the invention, and optionally in combination with other active compounds, such as insecticides, acaricides, herbicides, fungicides, as listed above are preferably selected in group consisting of: S1) Compounds of the formula (S1) 'O (Ra') ra Uh 7 (S1) Wa Ra where the symbols and indices have the meanings below:
[216] [216] No. represents a natural number from 0 to 5, preferably from 0 to 3;
[217] [217] RJ represents halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, nitro or (C1-C4s) -haloalkyl;
[218] [218] W. represents a divalent unsubstituted or substituted heterocyclic radical from the group of partially unsaturated five-membered heterocycles having 1 to 3 ring heteroatoms of group N and group O, where at least one atom of ST SA NS Fis NX AS * R $ Re RÁ Ra
[219] [219] m, represents O or 1;
[220] [220] RV represents ORxº , SR or NRVSR or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is joined to the carbonyl group at (S1) via the atom of nitrogen and is unsubstituted or substituted by radicals in the group consisting of (C1i-Ca) - alkyl, (C1-Ca) -alkoxy or optionally substituted phenyl, preferably a radical of the formula OR. , NHRAº or N (CH3)> , especially the ORº formula ;
[221] [221] R represents hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms;
[222] [222] Rº represents hydrogen, (C1i-Ck) -alkyl, (Ci-Ceg) -alkoxy or substituted or unsubstituted phenyl;
[223] [223] D represents H, (Ci-Cs) -alkyl, (C1i-Cs) -haloalkyl, (Ci- Ca) -salcoxi- (C1-Cs) -alkyl, cyano or COOR-.º, where R. º represents hydrogen, (C1i-Cs) -alkyl, (C1i-Cs) -haloalkyl, (C1i-Ca) -alkoxy- (Ci- Ca) -alkyl, (C1i-C6) -hydroxyalkyl, (C3-Ci2) - cycloalkyl or tri- (Ci- Ca) -alkylsilyl;
[224] [224] Ra, RW, RV. are identical or different and represent hydrogen, (C1-Cg) -alkyl, (C1-Cg) -haloalkyl, (C3-C12) = substituted or unsubstituted cycloalkyl or phenyl; preferably: a) dichlorophenylpyrazoline-3-carboxylic acid (S1 ) type compounds, preferably compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid , ethyl 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpir-diethyl"), and related compounds as described in WO -A- 91/07874; b) dichlorophenylpyrazole carboxylic acid (S1P) derivatives, preferably compounds such as ethyl 1- (2,4-dichlorophenyl) -5-methylpyrazol-3-carboxylate (S1-2), ethyl 1- (2,4-dichlorophenyl) -5 -
[225] [225] Rs) represents halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, nitro or (C1-Ca) -haloalkyl;
[226] [226] No. represents a natural number from 0 to 5, preferably 0 to 3;
[227] [227] Rs represents ORs , SRs or NR = sºRgº or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the O and S group, which is joined via the nitrogen atom to the carbonyl group (S2) and is unsubstituted or substituted by the radicals of the (C1-C4s) -alkyl, (C1i-Ca) -alkoxy or optionally substituted phenyl group, preferably a radical of the formula ORs , NHRsº or N (CH3)., especially of the formula ORs ;
[228] [228] Rs represents hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms;
[229] [229] Reº represents hydrogen, (C1i-Cs) -alkyl, (Ci-Cs) -alkoxy or substituted or unsubstituted phenyl;
[230] [230] Tr represents a (C; or C2) -alkodiyl chain that is unsubstituted or substituted by one or two (C1-Ca) -alkyl radicals or by [(C1-C3) -alkoxy] carbonyl; preferably: a) compounds of the type 8-quinolinoxyacetic acid (82º), preferably 1-methyl hexyl (5-chloro-8-quinolinoxy) acetate ("cloquintocet-mexil") (S2-1), (1, 3-dimethylbut -1-yl) (5-chloro-8-quinolinoxy) acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate (S2-3), 1-allyloxyprop-2-yl (5- chloro-8-quinolinoxy) acetate (S2-4), ethyl (5-chloro-8-quinolinoxy) acetate (S2-5), methyl (5-chloro-8-quinolinoxy) acetate (S2-6), ally (5 -chloro-8-quinolinoxy) acetate (S2-7), 2- (2-propylideneiminoxy) -l-ethyl (S-chloro-8-quinolinoxy) acetate (S2-8), 2-oxoprop-l-yl (5 -chloro-8-quinolinoxy) acetate (S2-9) and related compounds, as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-AO 492 366 and also ( 5-chloro-8-quinolinoxy) acetic acid (S2-10), hydrates and their salts, for example, lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002/34048; b) compounds of the type ((5-chloro-8-quinolinoxy) malonic acid (S2P), preferably compounds such as diethyl (5-chloro-8-
[231] [231] Re represents (C1i-C1a) -alkyl, (C1i-Ca) -haloalkyl, (Co-Ca) - alkenyl, (C2-Ca) -haloalkenyl, (C3-C7) -cycloalkyl, preferably dichloromethyl;
[232] [232] Re , Rc are identical or different and represent hydrogen, (C1-Ca) -alkyl, (C2-C4a) -alkenyl, (C2-Ca) -alkynyl, (C1-Ca) -haloalkyl, (Co-Ca) -haloalkenyl, (C1i -Ca) -alkylcarbamoyl- (C1-Ca) -alkyl, (C2-Ca) - = alkenylcarbamoyl- (C1-C4a) -alkyl, (C1-Ca) - alkoxy- (C1-Ca) -alkyl, dioxolanyl- (C1-C1a) -alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl or Rê and Rô together they form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably: active compounds of the dichloroacetamide type, which are often used as pre-emergence protectors (protectors that act on the soil), for example, "diclormid" (N, N-diallyl-2,2-dichloroacetamide) (S3-1 ), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl- Stauffer's 1,3-oxazolidine (S3-3), "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG -1292 "(N-allyl-N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide) from PPG Industries (S3-5)," DKA-24 "(N-allyl-N - [(allylaminocarbonyl ) methyl] dichloroacetamide) from Sagro-Chem (S3-6),
[233] [233] An represents SOx-NR5º-CO or CO-NRr3-SOz
[234] [234] Xp represents CH or N;
[235] [235] Ro) represents CO-NRrºRvé or NHCO-Rvy ';
[236] [236] Rº represents halogen, (C1-C4a) -haloalkyl, (C1-Ca) - haloalkoxy, nitro, (C1-Ca) -alkyl, (C1i-Ca) -alkoxy, (C1-Ca) - alkylsulfonyl, ( C1i-Cs) -alkoxycarbonyl or (C1i-C4a) -alkylcarbonyl;
[237] [237] Ro represents hydrogen, (C1-C4sa) -alkyl, (C2-Ca) -alkenyl or (C2-Ca) -alkynyl;
[238] [238] Ro! represents halogen, nitro, (C1-Ca) -alkyl, (C1-Ca) - haloalkyl, (C1i-Cs) -haloalkoxy, (C3-Cg) -cycloalkyl, phenyl, (Cir Ca) -alkoxy, cyan, (C1i -Ca) -alkylthio, (C1-Ca) -alkylsulfinyl, (Cir Ca) -alkylsulfonyl, (C1-Ca) coxycarbonyl salt or (C1 = -Ca) - alkylcarbonyl;
[239] [239] Ro represents hydrogen, (C1-C6) -alkyl, (C3-C6) cycloalkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (Cs-Ce) - cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing vp heteroatoms of the group consisting of nitrogen, oxygen and sulfur, where the last seven radicals are replaced by vp substituents of the group consisting of halogen, (C1-C6) - alkoxy, (C1-C6) -haloalkoxy, (C1- C2) kylsulfinyl salt, (C1-C2) = alkylsulfonyl, (C3-Ce6) -cycloalkyl, (C1i-C4s) -alkoxycarbonyl, (Cir
[240] [240] D represents hydrogen, (C1i-Csk) -alkyl, (C2o-Cs) -alkenyl or (C2-Cg) -alkynyl, where the last three radicals are replaced by the vp radicals of the group consisting of halogen, hydroxyl, (C1-C4s) -alkyl, (C1i-Ca) -alkoxy and (C1-Cs) -alkylthio or
[241] [241] Rô and Roé together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical;
[242] [242] RW 'represents hydrogen, (C1-Ca) -alkylamino, di- (Ci-Ca) - alkylamino, (C1-C6) -alkyl, (C3-Ce) -cycloalkyl, where the last two radicals are replaced by vp substituents of the group consisting of halogen, (C1i-Ca) -alkoxy, (Ci-Ce) -haloalkoxy and (C1-Ca) -alkylthio and, in the case of cyclic radicals, also (C1-Ca) - alkyl and ( C1i-C4a) -haloalkyl;
[243] [243] does not represent O, 1 or 2;
[244] [244] my represents 1 or 2;
[245] [245] vp represents O, 1, 2 or 3; among these, preference is given to compounds of the N-acylsulfonamide type, for example, of the formula (S4º) below, which are known, for example, in WO-A-97/45016 L LT (Roo ADDED in DH o H in what
[246] [246] R 'represents (C1i-Cs) -alkyl, (C3-Ce £) -cycloalkyl, where the last 2 radicals are replaced by the vp substituents from the group consisting of halogen, (C1i-C4a) -alkoxy , (C1-C6) - haloalkoxy and (C1-Cs) -alkylthio and, in the case of cyclic radicals, also (C1-Ca) -alkyl and (C1-Ca) -haloalkyl;
[247] [247] Roº represents halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, CF3;
[248] [248] my represents 1 or 2;
[249] [249] vp represents 0, 1, 2 or 3; and also acylsulfamoylbenzamides, for example, of the formula (S4 ”) below, which are known, for example, in WO-A-99/16744,
[250] [250] Ro = cyclopropyl and (RV) = 2-OMe ("cyprosulfamide", S4-1),
[251] [251] Roó = cyclopropyl and (R5º) = 5-Cl-2-OMe (S4-2)
[252] [252] Ro = ethyl and (Ro) = 2-OMe (S4-3)
[253] [253] Roº = isopropyl e (R67º) = 5-Cl-2-OMe (S4-4) e
[254] [254] Ro = isopropyl and (R5º) = 2-OMe (S4-5) and also compounds of the type N-acylsulfamoylphenylurea, of the formula (S4º), which are known, for example, in EP-A-365484, R5A Oo Oo o 4 Ne des NA S ho (S4º)
[255] [255] Roº and Roº independently of each other represents hydrogen, (C1i-Cg) -alkyl, (C3-Cg) -cycloalkyl, (C3-Ck) -alkenyl, (C3-C6) -alkynyl,
[256] [256] Roº represents halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, CF3,
[257] [257] my represents 1 or 2; for example, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea ("metcamifen", S4-6), 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3- dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, and also N-phenylsulfonyltereftalamides of the formula (S49), which are known, for example, in CN 101838227, Ro ”A í 3 fq (R5dmo H and (S4º)
[258] [258] Roº represents halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, CF3;
[259] [259] my represents 1 or 2;
[260] [260] Ro represents hydrogen, (C1-C6) -alkyl, (C3-C6) - cycloalkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (Cs-C6) - cycloalkenyl. S5) Active compounds of the class of hydroxy aromatics and derivatives of aromatic-aliphatic carboxylic acid (S5), for example, ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic, 3,5-di-acid hydroxybenzoic acid, 4-hydroxy salicylic acid, 4-fluoro salicylic acid, 2-hydroxy cinnamic acid, 2,4-dichloro cinnamic acid, as described in WO-A-2004/084631, WO-A- 2005/015994, WO-A -2005/016001. S6) Active compounds of the 1,2-dihydroquinoxalin-2-one (S6) class, for example, l1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, l1 -methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl) -3- (2-thienyl) -l1,2-dihydroquinoxalin-2-one hydrochloride, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630. S7) Compounds of the formula (S7), as described in MWO-A-HÇo (Qre C. RIAÁCTS Bo Sn nes 1998/38856, in which symbols and indices are defined as follows:
[261] [261] Re, Rê independently of one another are halogen, (C1-Ca) -alkyl, (C1-Ca) -alkoxy, (C1-C4a) -haloalkyl, (C1-Ca) - alkylamino, di- (C1-C4a) -alkylamino, nitro ;
[262] [262] Air represents COORr or COSReºé
[263] [263] Re , Re independently of one another are hydrogen, (C1-Ca) -alkyl, (C2o-C6) -alkenyl, (C2-Ca) -alkynyl, cyanoalkyl, (Cir
[264] [264] nx! represents 0 or 1
[265] [265] neº, ne independently of one another they are 0, 1 or 2, preferably: diphenylmethoxyacetic acid, ethyl diphenylmethoxyacetate, methyl diphenylmethoxyacetate (CAS reg. no. 41858-19-9) (S7-1). sS8) Compounds of the formula (S8), as described in MWO-A- 98 / 27,049, Rs O
[266] [266] X- represents CH or N,
[267] [267] No. in the case where Xr = N represents an integer from 0 to 4 and in the case where X -; = CH represents an integer from 0 to 5,
[268] [268] Rrº 'represents halogen, (C1-C4a) -alkyl, (C1-C4a) -haloalkyl, (C1-Ca) -alkoxy, (C1-C4s) -haloalkoxy, nitro, (C1i-Ca) -alkylthio, (Ci Ca) -alkylsulfonyl, (C1-C4) zalcoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy,
[269] [269] Rsº represents hydrogen or (C1-C1) -alkyl,
[270] [270] Rr represents hydrogen, (C1i-Cs) -alkyl, (C2o-Ca) -alkenyl, (C2-Ca) -alkynyl or aryl, in which each of the aforementioned carbon radicals is substituted or not substituted by one or more, preferably up to three radicals identical or different from the group consisting of halogen and alkoxy; or their salts, preferably compounds in which
[271] [271] Xr stands for CH,
[272] [272] No. represents an integer from 0 to 2,
[273] [273] Rrº represents halogen, (C1-C4a) -alkyl, (C1-C4a) -haloalkyl, (C1-Ca) -alkoxy, (C1-C4s) -haloalkoxy,
[274] [274] Rs represents hydrogen or (C1-C1) -alkyl,
[275] [275] Rr represents hydrogen, (C1i-Csg) -alkyl, (C2> -C4) -alkenyl,
[276] [276] Re represents halogen, (C1-Ca) -alkyl, methoxy, nitro, cyan, CF3, OCF3,
[277] [277] Yc, Ze independently of each other represents O or S,
[278] [278] ne represents an integer from 0 to 4,
[279] [279] Rs represents (C1-C16) -alkyl, (C2-C6) -alkenyl, (C3-C6) cycloalkyl, aryl; benzyl, halobenzyl,
[280] [280] Re represents hydrogen or (C1-Cs) -alkyl. S11) Active compounds of the oxyimino (S11) type of compounds, which are known as seed coating agents, for example, "oxabetrinyl" ((2) -1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is well known as a millet / sorghum seed coat protector against metolachlor damage, "fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-l- ethanone O- (1,3-dioxolan-2-ylmethyl) oxime) (S11-2), which is known as a seed coating protector for millet / sorghum against damage from metolachlor and "ciometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile) (S11-3), which is well known as a seed coating protector for millet / sorghum against damage from metolachlor.
[281] [281] RW represents a radical of (C1-C «) - haloalkyl and
[282] [282] RW represents hydrogen or halogen and
[283] [283] Rô, Rnº independently of each other represent hydrogen, (C1-C16) -alkyl, (C2-C16) Fal kenyl or (C2-C16) - alkynyl, where each of the last three radicals is unsubstituted or replaced by one or more radicals in the halogen group, hydroxyl, cyano, (C1-C4a) -alkoxy, (C1-C4a) -haloalkoxy, (C1-Ca) -alkylthio, (C1-Ca) -alkylamino, di [(C1- Ca) -alkyl] amino, [(C1-Ca) -alkoxy] carbonyl, [(C1-Ca) -haloalkoxy] carbonyl, (C3-C6) - cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted and heterocyclyl that is unsubstituted or substituted, or (C3-C6) -cycloalkyl, (Ca-Cg6) - cycloalkenyl, (C3-Cs) -cycloalkyl fused on one side of the ring in a 4 to 6 saturated or unsaturated carboxylic ring members or (Ca-Cg) -cycloalkenyl fused on one side of the ring in a 4- to 6-membered saturated or unsaturated carboxylic ring, where each of the last 4 radicals is unsubstituted or replaced by one or more radicals in the group consisting of halogen, hydroxyl, cyano, (C1-C4s) -alkyl, (C1i-C4s) -haloalkyl, (C1i-Ca) -alkoxy, (C1-Ca) - haloalkoxy, (C1-Ca) -alkylthio, (C1-Ca) - alkylamino, di [(C1-Ca) - alkyl] amino, [(C1-C4) -alkoxy] carbonyl, [(C1i-Ca) - haloalkoxy] carbonyl, (C3-Cg) -cycloalkyl that is unsubstituted or substituted, phenyl which is unsubstituted or substituted and heterocyclyl which is unsubstituted or substituted, or
[284] [284] Laugh represents (C1-C4a) -alkoxy, (C2o-Ca) -alkenyloxy, (Co-Ce6) - alkynyloxy or (C2> -C4s) -haloalkoxy and
[285] [285] RW represents hydrogen or (C1-C1a) -alkyl or
[286] [286] Rs and RWº together with the directly attached nitrogen atom represent a four to eight membered heterocyclic ring, like the nitrogen atom, can also contain ring heteroatoms, preferably up to two additional ring heteroatoms in the N, O group and S e which is substituted or unsubstituted by one or more radicals of the halogen group, cyano, nitro, (C1-Cs) -alkyl, (C1i-C4s) -haloalkyl, (C1-Ca) -alkoxy, (C1- Ca) - haloalkoxy and (C1-Cs) -alkylthio. S16) Active compounds that are used mainly as herbicides, but also have a protective action on cultivated plants, for example, (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, (R , S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acid acetic (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (A4-chlorophenoxy) butyric acid 3,6-dichloro-2-methoxy benzoic acid (dicamba),
[287] [287] Particularly preferred protectors are mefenpirediethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexil, benoxacor, diclormid and metcamifene.
[288] [288] wettable powders are preparations uniformly dispersible in water which, in addition to the active compound and except for a diluent or inert substance, also comprise surfactants of ionic or non-ionic type (wetting agent, dispersant), eg, polyethoxylated alkylphenols, alcohols polyethoxylated fatty acids, polyethoxylated fatty amines, polyglycolether fatty alcohol sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonate, sodium 2,2'-dinaftylmethane-6,6'-disulphonate, sodium dibutylnaphthalenesulfonate or sodium oylmethyl. To produce wettable powders, the active herbicidal compounds are finely ground in standard devices, such as hammer mills, blower mills and air jet mills, and mixed simultaneously or subsequently with the formulation aids.
[289] [289] Emulsifiable concentrates are produced by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or relatively high boiling aromatics or hydrocarbons or mixtures of organic solvents, with the addition of one or more ionic surfactants and / or non-ionic (emulsifiers). Examples of emulsifiers that can be used are: calcium alkylarylsulfonates, such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers, such as polyglycol esters, alkylaryl polyglycol ethers, fatty acids, polyglycol ethers, ethylene oxide / ethylene oxide condensation products alkyl polyethers, sorbitan esters, for example, sorbitan fatty acid esters or polyoxyethylene sorbitan esters, for example, polyoxyethylene sorbitan fatty esters.
[290] [290] Dust removal products are obtained by grinding the active compound with finely distributed solids, for example,
[291] [291] Suspension concentrates can be water or oil based. They can be prepared, for example, by wet grinding by means of commercial ball mills and optional addition of surfactants which, for example, have already been listed above for the other types of formulation.
[292] [292] Emulsions, for example, oil in water (EW) emulsions, can be produced, for example, by means of agitators, colloid mills and / or static mixers that use aqueous organic solvents and, optionally, surfactants such as those already listed above, for example, for other types of formulations.
[293] [293] Granules can be prepared by spraying the active compound on the granular inert material capable of adsorption or by applying concentrates of the active compound to the surface of carrier substances, such as sand, kaolinite or granular inert material by means of adhesives, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the usual way for the production of fertilizer granules - if desired as a mixture with fertilizers.
[294] [294] Water dispersible granules are usually produced by the usual processes, such as spray drying, fluid bed granulation, container granulation, mixing with high speed mixers and extrusion without solid inert material.
[295] [295] For the production of container, fluidized bed, extruder and spray granules, see, for example, the processes in "Spray - Drying Handbook" 3a. Ed. 1979, G. Goodwin Ltd., London, OJ.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff .; "" "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
[296] [296] For further details regarding the formulation of crop protection compositions, see, for example, GC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans,
[297] [297] Agrochemical preparations generally contain 0.1 to 99% by weight, especially 0.1 to 95% by weight of the compounds of the invention. In wettable powders, the concentration of the active compound is, for example, approximately 10 to 90% by weight; the rest at 100% by weight consists of the constituents of the usual formulation. In emulsifiable concentrates, the concentration of the active compound can be approximately 1% to 90% and preferably 5 to 80% by weight. Formulations in powder form comprise 1 to 30% by weight of active compound, preferably normally from 5 to 20% by weight of active compound; sprayable solutions contain approximately 0.05% to 80% by weight, preferably 2% to 50% by weight of active compound. In the case of water-dispersible granules, the content of the active compound depends partially on whether the compound is in liquid or solid form and in which granulation aids, fillers, etc. are used. In water-dispersible granules, the content of the active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
[298] [298] Furthermore, the aforementioned active compound formulations "optionally comprise the respective wetting, dispersing, emulsifying, penetrating preservatives, antifreeze and solvents, fillers, carriers and tinctures, foam deformers, evaporation inhibitors and usual agents that influence pH and viscosity.
[299] [299] Based on these formulations, it is also possible to produce combinations with other active pesticidal substances, for example, insecticides, acaricides, herbicides, fungicides and also with protectors, fertilizers and / or growth regulators, for example, in the form of finished formulation or as a tank mix.
[300] [300] For application, formulations in commercial form are, if appropriate, diluted in the usual way, for example, in the case of dusts that can be moistened, emulsifiable concentrates, dispersions and granules dispersible in water with water. Powder type preparations, granules for application to the soil or granules for spreading and sprayable solutions are usually not diluted with other inert substances before application.
[301] [301] The required application rate of the compounds of formula (1) and their salts varies according to external conditions, such as, inter alia, temperature, humidity and the type of herbicide used. It can vary within wide limits, for example, between 0.001 and 10.0 kg / ha or more of the active substance, but is preferably between 0.005 and 5 kg / ha, more preferably in the range of 0.01 to 1.5 kg / ha ha, particularly preferably in the range of 0.05 to 1 kg / ha 9g / ha. This applies to the pre-emergence and post-emergence application.
[302] [302] A carrier is a natural or synthetic substance, organic or inorganic with which combinations of active compounds are mixed or combined for better applicability, in particular for application to plants or parts of the plant or seed. The carrier, which can be solid or liquid, is generally inert and should be suitable for use in agriculture.
[303] [303] Useful solid or liquid carriers include: for example, ammonium salts and natural rock powders, such as kaolin, clays, talc, chalk, quartz, atapulgite, montmorillonite or diatomaceous earth, and synthetic rock powders, such as silica finely divided, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and related derivatives. Likewise, it is possible to use mixtures of these carriers. Solid carriers useful for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, as well as granules of organic material, such as sawdust, coconut shells, corn cobs and smoke stalks.
[304] [304] Liquified gaseous extenders or carriers are liquids that are gaseous at standard temperature and under atmospheric pressure, for example, aerosol propellants, such as halogenated hydrocarbons or butane, propane, nitrogen and carbon dioxide.
[305] [305] In the formulations it is possible to use adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate or also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Extra additives can be mineral and vegetable oils.
[306] [306] When the extender used is water, it will also be possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example, mineral oil fractions, mineral oils and vegetables, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide and also water.
[307] [307] The compositions according to the invention can also comprise other components, for example, surfactants. Useful surfactants are emulsifiers and / or foams, dispersants or wetting agents that have ionic or non-ionic properties or mixtures of these surfactants. Some examples are salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates, ethylene dioxide with fatty alcohols or with fatty acids or with fatty amino acids, substituted phenols (preferably alkylphenols or arylphenols), ester salts sulfosuccinic, derivatives of taurine (preferably alkyl taurates), phosphoric esters of alcohols or polyethoxylated phenols, fatty acid esters of polyols and derivatives of compounds containing sulphates, sulphonates and phosphates, for example, alkyl alkyl polyglycol ethers, alkyl sulphates, alkyl sulphates, arylsulfonates, protein hydrolysates, lignin sulphite and methylcellulose residue liquors. The presence of a surfactant will be necessary if one of the active compounds and / or one of the inert carriers is insoluble in water and when the application is carried out in water. The proportion of surfactants is between 5 and 40 percent by weight of the inventive composition. It is possible to use dyes, such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, in addition to organic dyes, such as alizarin dyes, azo dyes and phthalocyanine metal dyes and trace nutrients, such as iron salts , manganese, boron, copper, cobalt, molybdenum and zinc.
[308] [308] If appropriate, it is also possible that other additional components are present, for example, protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestering complexing agents. In general, the active compounds can be combined with any solid or liquid additive commonly used for formulation purposes. In general, the compositions and formulations according to the invention contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0, 1 and 95% by weight, more preferably between 0.5 and 90 % of the active compound, more preferably between 10 and 70 percent by weight. The active compounds or compositions according to the invention can be used in this way or, depending on their respective particular physical and / or chemical properties, in the form of their formulations or in the forms of use prepared therefrom, such as aerosols, suspensions capsule, cold mist concentrates, hot mist concentrate, encapsulated granules, fine granules, fluidizable concentrates for seed treatment, ready-to-use solutions, powders, emulsifying concentrates, water emulsion oils, oil emulsion water, macrogranules , microgranules, oil dispersible powders, oil miscible fluidizable concentrates, oil miscible liquids, foams, pastes, pesticide-coated seed, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, powders and granules , water-soluble and dispersible granules or tablets, water-soluble powders for seed treatment, wettable powders , natural products and synthetic substances impregnated with active ingredient, as well as microencapsulations in polymeric substances and in seed coating materials, as well as formulations of cold mist and ULV hot mist.
[309] [309] The mentioned formulations can be produced in a manner known to you, for example, by mixing the active compounds with at least one usual extender, solvent or diluent, emulsifier, dispersant and / or binder or fixative, wetting agent, water repellent , optionally desiccants and UV stabilizers and optionally dyes and pigments, defoamers, preservatives, secondary thickeners, tacifiers, gibberellins and also other processing aids.
[310] [310] The compositions according to the invention include not only formulations that are already ready for use and can be applied with an instrument appropriate to the plant or seed, but also commercial concentrates that need to be diluted with water before use.
[311] [311] According to the invention, the active compounds can be present in this way or in their formulations (commercial standard) or in the forms of use prepared from these formulations as a mixture with other active compounds (known), as insecticides, attractive , sterilizers, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, protectors, fertilizers or semi-chemicals.
[312] [312] According to the invention, the treatment of plants and plant parts with active compounds or compositions is carried out directly or by action around them, habitat or storage space using the usual treatment methods, for example, through immersion, spraying,
[313] [313] One of the advantages of the present invention is that the particular systemic properties of the active ingredients and inventive compositions mean that treating the seed with these active ingredients and these compositions protects not only the seed itself, but also the resulting plants after emergence against phytopathogenic fungi. Thus, immediate treatment of the plantation at the moment of sowing or shortly thereafter can be dispensed with.
[314] [314] It is also considered advantageous that the active ingredients or inventive compositions can also be specially used for transgenic seed, in which case the plant that grows from that seed is capable of expressing a protein, which acts against pests . The treatment of this seed with the active ingredients or inventive compositions, simply by expressing the protein, for example, an insecticidal protein, can result in the control of certain pests. Surprisingly, an additional synergistic effect can be seen in this case, which additionally increases the effectiveness of protection against pest attack.
[315] [315] According to the invention, the compositions are suitable for protecting seed from any variety of plant that is used in agriculture, greenhouses, forests or horticulture and viticulture. In particular, this is the seed of cereals (such as wheat, barley, rye, triticale, sorghum / millet and oats), corn, cotton, soy, rice, potatoes, sunflower, beans, coffee, beets (for example, sugar beet and fodder beet), peanuts, rapeseed, poppy, olive, coconut, cocoa, sugar cane, tobacco, vegetables and legumes (such as tomatoes, cucumbers, onions and lettuce), grass and ornamental plants (see also below). The treatment of cereal seed (such as wheat, barley, rye, triticale and oats), corn and rice is of particular importance.
[316] [316] As also described below, the treatment of transgenic seed with the active compounds according to the invention or compositions is of particular importance. This is related to the plant seed that contains a heterologous gene that allows the expression of a polypeptide or protein with insecticidal properties. the heterologous gene in the transgenic seed may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. This heterologous gene originates preferentially from Bacillus sp., In which case the gene product is effective against the European corn borer and / or the western corn rootworm. The heterologous gene originates most preferably from Bacillus thuringiensis.
[317] [317] In the context of the present invention, the inventive composition is applied to the seed alone or in an appropriate formulation. Preferably, the seed is treated in a state in which it is stable enough so that no damage occurs during the treatment. In general, the seed can be treated at any time between harvest and sowing. It is customary to use the seed that has been separated from the plant and released from the ears, peels, stems, layers, branches or fruit pulp. For example, it is possible to use the seed that has been harvested, cleaned and dried to a moisture content of less than 15% by weight. As an alternative, it is also possible to use seed, which, after drying, for example, was treated with water and dried again.
[318] [318] In general, in seed treatment it must be ensured that the amount of the composition, according to the invention, and / or additional additives applied to the seed is chosen so that the germination of the seed is not impaired, and the plant that germinates of it is not damaged. This must be ensured, in particular in the case of active compounds, which can have phytotoxic effects at certain rates of application.
[319] [319] The compositions, according to the invention, can be applied directly, that is, without containing any other components and without having been diluted. In general, it is preferable to apply the compositions to the seed in the form of an appropriate formulation. Formulations and methods suitable for Seed Treatment are known to those skilled in the art and described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 Al, WO 2002 / 080675 A1, WO 2002/028186 A2.
[320] [320] The active compounds that can be used according to the invention can be converted into the usual seed coating formulations, such as solutions, emulsions, suspensions, foaming powders, pastes or other seed coating compositions and also ULV formulations.
[321] [321] These formulations are produced in a known way, by mixing active compounds with usual additives, for example, extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
[322] [322] The dyes that may be present in usable seed coating formulations, according to the invention, are all the usual dyes for these purposes. It is possible to use pigments, which are moderately soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
[323] [323] Useful wetting agents that may be present in seed coating formulations usable according to the invention are all substances that promote wetting and that are common in the formulation of agrochemical active compounds. Alkyl naphthalenesulfonates, such as diisopropyl or diisobutyl naphthalenesulfonates, can be used with preference.
[324] [324] Suitable dispersants and / or emulsifiers that may be present in usable seed coating formulations, according to the invention, are all the nonionic, anionic and cationic dispersants common in the formulation of agrochemically active compounds. Preference is given to the use of non-ionic or anionic dispersants or mixtures of non-ionic or anionic dispersants. Suitable non-ionic dispersants include especially block polymers of ethylene oxide / propylene oxide, alkylphenol polyglycol ether and triestrirylphenol polyglycol ethers and their phosphate or sulfate derivatives. suitable anionic dispersants are especially lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
[325] [325] defoamers which may be present in usable seed coating formulations according to the invention are all the usual foam inhibiting substances for the formulation of agrochemically active compounds. Silicone defoamers and magnesium stearate can be used with preference.
[326] [326] The preservatives that can be present in usable seed coating formulations, according to the invention, are all substances usable for these purposes in agrochemical compositions. Examples include dichlorophen and benzyl hemiformal alcohol.
[327] [327] The thickeners that may be present in usable seed coating formulations according to the invention are all substances usable for these purposes in agrochemical compositions. [6] preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clay and finely divided silica.
[328] [328] Useful adhesives that may be present in usable seed coating formulations according to the invention are all the usual binders usable in seed coating products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
[329] [329] Seed coating formulations usable according to the invention can be used, directly or after having been previously diluted with water, for the treatment of a wide range of different seeds, including the seed of transgenic plants. In this case, additional synergistic effects can also occur in the interaction with the substances formed by expression.
[330] [330] For the treatment of the seed with seed coating formulations that can be used according to the invention or with preparations prepared from them with the addition of water, the useful equipment are all the mixing units usually used to coat the seed. seed. Specifically, the seed coating procedure is to place the seed in a mixer, add a particular desired amount of seed coating formulations, in this way or after the previous dilution with water, and mix everything until the formulation is homogeneously distributed in the seed . If appropriate, this will be followed by a drying operation.
[331] [331] According to the invention, the active compounds, given the excellent compatibility of the plant, the favorable homeotherm toxicity and the excellent environmental compatibility, are suitable for the protection of plants and plant organs, to increase the yields of crops and to improve the quality of the harvest. They can preferably be used as plant protection agents. They are active against resistant and normally sensitive species and also against all or specific stages of development.
[332] [332] The plants that can be treated according to the invention include the following main cultivation plants: corn, soybeans, cotton, Brassica oil seeds, such as Brassica napus (eg Canola), Brassica rapa, B. juncea (eg, mustard (field) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, grapes and various fruits and vegetables of various botanical taxa, eg Rosaceae sp. (eg soft fruits such as apples and pears, but also hard-shelled fruits such as apricots, cherries, almonds and peaches and fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae Sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp., (Eg, banana and plantations), Rubiaceae sp. ( eg coffee), Theaceae sp. Sterculiceae sp., Rutaceae sp. (eg lemons, oranges and grapefruit); Solanaceae sp. (eg tomatoes, potatoes, peppers, aubergine as), Liliaceae sp., Compositae sp. (eg, lettuce, artichoke and chicory - including chicory root, endive or common chicory), Umbelliferae sp. (eg, carrot, parsley, celery and celeriac), Cucurbitaceae sp. (eg, cucumber - including cucumber used in preserves, pumpkin, watermelon, gourd and melon), Alliaceae sp. (eg, leeks and onions), Cruciferae sp. (eg, white cabbage, red cabbage, broccoli, cauliflower, brussels sprouts, chinese cabbage, kohlrabi, radish, wild horseradish, watercress and chard), Leguminosae sp. (eg, peanuts, peas and beans - eg, Spanish beans and fava beans), Chenopodiaceae sp. (eg Swiss chard, mangold, spinach, beet) Malvaceae sp. (eg, okra), Asparagaceae (eg, asparagus); useful plants and ornamental plants in the garden and in the forest; and in each case, genetically modified types of these plants.
[333] [333] As mentioned earlier, it is possible to treat all plants and their parts according to the invention. In a preferential representation, species of wild plants and plant cultivars or those obtained by conventional techniques of biological generation, such as crossing or protoplastic fusion and related parts, are treated. In another preferred representation, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in conjunction with traditional methods (“genetically modified organisms”) and their parts, will be treated. The terms "parts" or "parts of plants" or "parts of the plant" have been explained previously. Particular preference is given in accordance with the invention to the treatment of plants of the respective commercial plant cultivars or those in use. Plant cultivars must be understood as plants that have new properties ("characteristics") that have grown through conventional production, mutagenesis or recombinant DNA techniques. They can be cultivars, varieties, biotypes and genotypes.
[334] [334] According to the invention, the treatment method can be used in the treatment of genetically modified organisms (GMOs), for example, plants or seeds. Genetically modified plants (or transgenic plants) are those in which the heterologous genes have been stably integrated into the genome. The term "heterologous gene" essentially means a gene that is supplied or obtained outside the plant and which, after introduction into the nuclear genome, the chloroplast genome or the mitochondrial genome, gives the transformed plant new or improved agronomic characteristics, because it expresses a protein or polypeptide of interest or another gene present in the plant or other genes present in the plant are regulated or deactivated (for example, by means of antisense technology, cosuppression technologies or RNAi [RNA interference] J technologies). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its specific presence in the plant's genome is called a transformation or transgenic event.
[335] [335] Depending on the species of the plant or its cultivar, its location and growing conditions (soil, climate, vegetation period, diet), the treatment of the invention can also result in superadditive (“synergistic”) effects. For example, the following effects are possible that exceed the effects actually expected: reduced application rates and / or increased activity spectrum and / or more efficacy of the active ingredients and compositions that can be used according to the invention, better plant growth , more tolerance to high or low temperatures, more tolerance to drought or salinity of water or soil, increased flowering performance, easier harvesting, accelerated ripening, more harvest yield, larger fruits, greater plant height, green color leaves, early flowering, higher quality and / or higher nutritional value of harvested products, higher concentration of sugar in fruits, better storage stability and / or processability of harvested products.
[336] [336] At certain application rates, combinations of the active ingredient of the invention can also have a strengthening effect on plants. Consequently, they are suitable for mobilizing the plant's defense system against attack by unwanted phytopathogenic fungi and / or microorganisms and / or viruses. This could possibly be one of the reasons for the improved activity of the combinations of the invention, for example, against fungi. Plant strengthening substances (resistance induction) should be understood as, in the present context, those substances or combinations of substances that are capable of stimulating the defensive system of plants so that, when subsequently inoculated with unwanted phytopathogenic fungi, the plants treated have a high degree of resistance to these unwanted phytopathogenic fungi. The substances of the invention can therefore be used to protect plants against attack by the pathogens mentioned in a certain period after treatment. The period in which protection is achieved usually extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active ingredients.
[337] [337] The plants and their cultivars that are preferably treated according to the invention include all plants that have genetic material that transmit useful characteristics particularly advantageous to those plants (obtained by means of generation or biotechnology).
[338] [338] Plants and their cultivars, which are equally and preferably treated according to the invention, are resistant to one or more factors of biotic stress, that is, these plants show a better defense against animal and microbial pests, such as nematodes, insects, small arachnids, phytopathogenic fungi, bacteria, viruses and / or viroids.
[339] [339] Examples of nematode-resistant plants are described, for example, in the following U.S. patent applications: 11 / 765,491, 11 / 765,494, 10 / 926,819, 10 / 782,020, 12 / 032,479 10 / 783,417, 10 / 782,096, 11 / 657,964, 12 / 192,904, 11 / 396,808, 12 / 166,253, 12 / 166,239, 12 / 166,124, 12 / 166,209, 11 / 762,886 12 / 364,335, 11 / 763,947, 12 / 252,453, 12 / 209,354, 12 / 209,354, 12 / 491,396 and 12 / 497,221.
[340] [340] The plants and their cultivars that can also be treated according to the invention are those plants that are resistant to one or more abiotic stress factors. Abiotic stress conditions can include, for example, dryness, exposure to low temperatures, exposure to heat, osmotic stress, waterlogging, increased soil salinity, elevated exposure to minerals, exposure to ozone, exposure to strong light, limited availability of nutrients nitrogen, limited availability of phosphorus nutrients or lack of shade.
[341] [341] The plants and their varieties that can also be treated according to the invention are those plants characterized by the improvement of production characteristics. The improved production in these plants may be the result of, for example, better plant physiology, growth and development, water use efficiency, water retention efficiency, improved nitrogen use, improved carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can also be affected by the best plant architecture (conditions under stress and without stress), including, without limitation, early flowering and flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pericarp size, number of pericarp or ear, seed mass, improved seed filling, reduced seed dispersion, reduced pericarp dehiscence and resistance to tipping. In addition, production characteristics include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processing capacity and better storage stability.
[342] [342] The plants that can be treated according to the invention are hybrid plants that already express the characteristics of heterosis or hybrid effect that results in generally higher production, vigor, better health and resistance to biotic and abiotic stress factors. Generally these plants are produced by crossing a natural sterile male parent line (female type crossing parent) with another natural fertile male parent line (male type crossing parent). Hybrid seed is usually grown from sterile male plants and sold to growers. Sterile plants can sometimes (eg, in maize) be produced by stripping (ie, the mechanical removal of male reproductive organs or male flowers), but male sterility is generally the result of genetic determinants in the genome of the plant. In this case, and especially when the seed is the desired product to be grown from hybrid plants, it is generally beneficial to ensure that male fertility in hybrid plants, which contain the genetic determinants responsible for male sterility, is fully restored. This can be accomplished by ensuring that male-type breeding parents have appropriate fertility restoring genes that are capable of restoring male fertility in hybrid plants that contain the genetic determinants responsible for male sterility. The genetic determinants for male sterility can be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) have been described, for example, for Brassica species. However, the genetic determinants for male sterility can also be located in the nuclear genome. Sterile male plants can also be obtained by methods of botanical biotechnology, such as genetic engineering. A particularly useful means of obtaining sterile male plants is described in WO 89/10396 in which, for example, a ribonuclease, such as a barnase, is selectively expressed in the tapetum cells in the stamens. Fertility can be restored by the expression in tapetum cells of a ribonuclease inhibitor, such as barstar.
[343] [343] The plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can be treated according to the invention are herbicide-tolerant plants, that is, plants that have become tolerant to one or more herbicides . Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits this tolerance to the herbicide.
[344] [344] Those herbicide-tolerant plants are, for example, glyphosate-tolerant plants, that is, plants that have become tolerant to the herbicide glyphosate or its salts. Plants can become tolerant to glyphosate by several methods. Thus, for example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene that encodes the enzyme S5-enolpiruvilshikimate-3-phosphate synthase (EPSPS). Examples of the EPSPS genes are the AroA gene (CT7 mutant) from the bacterium Salmonella typhimurium (Comai et al., 1983, Science, 221, 370-371), the CP4 gene from the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding an EPSPS petunia (Shah et al., 1986, Science 233, 478-481), an EPSPS tomato (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or an Eleusine EPSPS (WO 01/66704). It may also be a mutated EPSPS. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxide reductase enzyme. Glyphosate tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants that contain naturally occurring mutations from the genes mentioned above. Plants that express EPSPS genes that transmit glyphosate tolerance have been described. Plants that express other genes that transmit glyphosate tolerance, for example, decarboxylase genes, have been described.
[345] [345] Other herbicide-resistant plants are, for example, plants that have become tolerant to herbicides by inhibiting the enzyme's glutamine synthase, such as bialafos, phosphinothricin or glufosinate. These plants can be obtained by expressing a herbicide detoxifying enzyme or a mutant glutamine synthase enzyme that is resistant to inhibition. An example of an effective detoxifying enzyme is an enzyme that encodes a phosphinothricin acetyltransferase (such as the bar or pat protein of Streptomyces species). Plants that express an exogenous phosphinothricin acetyltransferase have been described.
[346] [346] In addition, herbicide-tolerant plants are also plants that have been made tolerant to herbicides by inhibiting the enzyme hydroxyphenylpyruvate dioxigenase (HPPD). Hydroxyphenylpyruvate dioxigenases are enzymes that catalyze the reaction in which parahydroxyphenylpyruvate (HPP) is converted to homogentisate. Plants tolerant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutated or chimeric HPPD enzyme as described in Wo 96/38567, WO 99/24585, WO 99 / 24586, WO 2009/144079, WO 2002/046387 or US 6,768,044. Tolerance to HPPD inhibitors can also be obtained by transforming plants with genes that encode certain enzymes allowing the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787. Plant tolerance to HPPD inhibitors can also be improved by transforming plants with a gene encoding a prefenate dehydrogenase enzyme in addition to a gene encoding an HPPD tolerant enzyme, as described in WO 2004/024928. In addition, plants can become more tolerant of HPPD inhibitors by inserting in their genome a gene that encodes an enzyme that metabolizes or degrades HPPD inhibitors, for example, CYP450 enzymes (see WO 2007/103567 and WO 2008/150473) .
[347] [347] Other herbicide-resistant plants are those that have become tolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulfonylurea herbicides, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or sulfonylaminocarbonyltriazolinone. It is known that different mutations in the enzyme ALS (also known as acetohydroxy synthase, AHAS), are also known to confer tolerance to different herbicides and groups of herbicides, as described, for example, in Tranel and Wright, (Weed Science 2002, 50 , 700-712). The production of plants tolerant to sulfonylurea and plants tolerant to imidazolinone has been described. In addition, sulfonylurea and imidazolinone tolerant plants have also been described.
[348] [348] Other plants tolerant to imidazolinone and / or sulfoniurea can be obtained by induced mutagenesis, by selection in cell cultures in the presence of the herbicide or by generating a mutation as, for example, for soy in US 5,084,082, for rice in WO 97/41218, for sugar beet in US 5,773,702 and WO 99/057965, for lettuce in US 5,198,599 or for sunflower in WO 01/065922).
[349] [349] The plants or plant varieties (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention are insect resistant transgenic plants, that is, plants that have become resistant to attack by certain insects. Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits this resistance to insects.
[350] [350] In the present context, the term "insect resistant transgenic plant" includes any plant that contains at least one transgene that consists of a coding sequence that encodes the following:
[351] [351] Of course transgenic insect-resistant plants, as used here, also include any plant that consists of a combination of genes that encodes the proteins of any of the classes 1 to 10 mentioned above. In one representation, an insect resistant plant contains more than one transgene that encodes a protein from any of classes 1 to 10 above to expand the range of affected target insect species or to prevent the development of insect resistance to plants with the use of different proteins with insecticidal action for the same target insect species, but with a different mode of action, such as binding to different receptor binding sites in the insect.
[352] [352] In the present context, an "insect resistant transgenic plant" additionally includes any plant that contains at least one transgene that comprises a sequence for producing double-stranded RNA that, after consumption of food by an insect pest, prevents the growth of this plague.
[353] [353] Plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention are tolerant to abiotic stress factors. Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits this resistance to stress. Useful plants particularly tolerant of stress include the following: a. plants containing a transgene capable of reducing the expression and / or activity of the poly (ADP-ribose) polymerase (PARP) gene in plant cells or plants; B. plants that contain a stress tolerance enhancing transgene capable of reducing the expression and / or activity of the PARG coding genes of plants or plant cells;
[354] [354] Plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention show the altered quantity, quality and / or storage stability of the cultivated product and / or properties alterations of specific components of the cultivated product, such as: 1) Transgenic plants that synthesize a modified starch, which in its physical and chemical characteristics, in particular amylose content or amylose / amylopectin ratio, the degree of branching, the length medium chain, side chain distribution, viscosity behavior, frost resistance, starch granule size and / or starch granule morphology, is changed compared to the starch synthesized in plants or plant cells of the wild type so that this modified starch is better suited for specific applications. 2) Transgenic plants that synthesize non-starch carbohydrate polymers or that synthesize non-starch carbohydrate polymers with altered properties compared to wild type plants without generic modification. Examples are plants that produce polyfructose, especially of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4, glucans and plants that produce alternan. 3) Transgenic plants that produce hyaluronan. 4) Transgenic plants or hybrid plants, such as onions with specific properties, such as "content of highly soluble solids", "low acidity" (LP) and / or "long storage" (LS).
[355] [355] The plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention are cotton plants with altered fibrous characteristics. Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits these altered fibrous characteristics and include: a) plants, such as cotton plants, containing an altered form of cellulose synthase genes; b) plants, such as cotton plants, that contain an altered form of nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase; Cc) plants, such as cotton plants, with high expression of sucrose synthase; d) plants, such as cotton plants, in which the plasmododematal obstruction time at the base of the fiber cell is altered, for example, by down-regulation of (6 -1,3-fibroselective glucanase; e) plants, such as cotton plants, with fibers with altered reactivity, for example, through the expression of the N-acetylglucosamine transferase gene, which includes nodC and chitinsintase genes.
[356] [356] The plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention are plants, such as rapeseed or Brassica plants with altered oil profile characteristics. Such plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits these altered oily characteristics and include: a) plants, such as rapeseed plants, that produce oil having a high oleic acid content; b) plants, such as rapeseed plants, that produce oil having a low linoleic acid content; Cc) plants, such as rapeseed plants, that produce oil having a low level of saturated fatty acids.
[357] [357] Plants or plant cultivars (obtainable by plant biotechnology methods, such as genetic engineering)
[358] [358] The plants or plant cultivars (obtained by methods of botanical biotechnology, such as genetic engineering) that can also be treated according to the invention are plants, such as rapeseed or Brassica plants with altered seed dissemination characteristics. These plants can be obtained by genetic transformation or by selecting plants that contain a mutation that transmits these altered characteristics and include plants, such as rapeseed with delayed or reduced seed spread.
[359] [359] Particularly useful transgenic plants that can be treated according to the invention are plants with transformation events or combinations of transformation events that are the subject of petitions granted or pending unregulated status in the USA at the Animal and Plant Health Inspection Service ( APHIS) of the United States Department of Agriculture (USDA). Information related to this is available at any time at APHIS (4700 River Road Riverdale, MD 20737, USA), for example, via the website http://www.aphis.usda.gov/brs/not reg.html. On the filing date of this request, petitions with the following information were granted or pending in APHIS: - Petition: Petition identification number. The technical description of the transformation event can be found in the specific petition document available from APHIS on the website via the petition number. These descriptions are disclosed in this document for reference purposes. - Extension of a petition: Reference to a previous petition for which an extension of scope or term is being requested.
[360] [360] Particularly useful transgenic plants that can be treated according to the invention are those that comprise one or more genes that encode one or more toxins, for example, transgenic plants sold under the following trade names: YIELD GARDO (eg maize, cotton, soybeans), KnockOut & O (eg maize), BiteGardO (eg maize), BT-XtraGO (eg maize), StarLink8 (eg maize), BollgardO (cotton), NucotnO ( cotton), Nucotn 33BO (cotton), NatureGardO (eg maize), Protecta8 and NewLeafO (potato). Examples of herbicide-tolerant plants include maize varieties, cotton varieties and soy varieties that are available under the following trade names: Roundup ReadyO (glyphosate tolerance, eg maize, cotton, soybean), Liberty Link8 & (tolerance phosphinothricin, for example, rapeseed oil) IMIGO (imidazolinone tolerance) and SCSQO (sulfonylurea tolerance), for example, corn. The herbicide-resistant plants (plants grown conventionally for herbicide tolerance) that can be cited include varieties sold under the name ClearfieldO (for example, maize).
[361] [361] Particularly useful transgenic plants that can be treated according to the invention are those that contain transformation events or a combination of transformation events and are listed, for example, in the databases of various national or regional regulatory agencies ( see, for example, http://gmoinfo.jrc.it/gmp browse.aspx and http: // ceraggmce.org / index.php evidcode = & hst IDKXCode = & gType = & AbbrCode = & atCode = & stCode = & coIDCode = & action = gm crop database & mode = Submit).
[362] [362] The active compounds or compositions, according to the invention, can also be used in the protection of materials, for protection of industrial materials against attack and destruction by unwanted microorganisms, for example, fungi and insects.
[363] [363] In addition, the compounds according to the invention can be used as anti-blocking compositions, alone or in combinations with other active compounds.
[364] [364] Industrial materials in the present context are understood to mean non-living materials that have been prepared for use in industry. For example, the industrial materials that must be protected by the active compounds, according to the invention, against microbial alteration or destruction can be adhesives, gums, paper, wallpaper and cardboard, fabrics, carpets, leather, wood, paints and articles plastic, cooling lubricants and other materials that can be infected or destroyed by microorganisms. The variety of materials to be protected also includes parts of plants and production buildings, for example, water circuits for cooling, cooling and heating systems and ventilation and air conditioning systems, which can be affected by the proliferation of micro- organisms. Industrial materials within the scope of the present invention preferably include adhesives, glues, paper and cardboard, leather, wood, paints, cooling lubricants and heat transfer fluids, particularly and preferably wood. The active compounds or compositions, according to the invention, can prevent adverse effects, such as decay, deterioration, discoloration or mold formation. In addition, the compounds, according to the invention, can be used to protect objects that come in contact with salt water or brackish water, especially hulls, screens, nets, buildings, moorings and signaling systems, against obstruction.
[365] [365] The method according to the invention for controlling unwanted fungi can also be employed to protect stored goods. Here, stored goods are natural substances of plant or animal origin or the processing of their products of natural origin for which long-term protection is desired. Stored goods of plant origin, for example, stems, leaves, tubers, seeds, fruits, grains, can be protected as soon as harvested or after processing by (pre) drying, humidification, comminution, crushing, pressure or roasting. The stored goods also include wood, both unprocessed, as construction timber, barriers and electricity poles, and in the form of finished products, such as furniture. Stored goods of animal origin are, for example, fur, leather, fur and animal hair. The active compounds, according to the invention, can prevent adverse effects, such as rotting, deterioration, discoloration or mold formation.
[366] [366] Examples without limitation of pathogens of fungal diseases, which can be treated according to the invention, include: Diseases caused by pathogens of downy mildew, for example, species of Blumeria, for example, Blumeria graminis; Podosphaera species, for example, Podosphaera leucotricha; Sphaerotheca species, for example, Sphaerotheca fuliginea; species of Uncinula, for example, Uncinula necator; diseases caused by pathogens of rust disease, for example, Gymnosporangium species, for example, Gymnosporangium sabinae; Hemileia species, for example, Hemileia vastatrix; Phakopsora species, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, for example, Puccinia recondita or Puccinia triticina; VUromyces species, for example, Uromyces appendiculatus; diseases caused by pathogens in the Oomycetes group, for example, Bremia species, for example, Bremia lactucae; Peronospora species, for example, Peronospora pisi or P. brassicae; Phytophthora species, for example, Phytophthora infestans; Plasmopara species, for example, Plasmopara viticola; species of Pseudoperonospora, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, for example, Pythium ultimum; leaf spot diseases and leaf wilt diseases caused, for example, by Alternaria species, for example, Alternaria solani; species of Cercospora, for example, Cercospora beticola; Cladiosporium species, for example, Cladiosporium cucumerinum; species of Cochliobolus, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); Colletotrichum species, for example, Colletotrichum lindemuthanium; Cycloconium species, for example, Cycloconium oleaginum; Diaporthe species, for example, Diaporthe citri; Elsinoe species, for example, Elsinoe fawcettii; Gloeosporium species, for example, Gloeosporium laeticolor; Glomerella species, for example, Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example, Leptosphaeria maculans; Magnaporthe species, for example, Magnaporthe grisea; Microdochium species, for example, Microdochium nivale; Mycosphaerella species, for example, Mycosphaerelle graminicola and M. fijiensis; species of Phaeosphaeria, for example, Phaeosphaeria nodorum; Pyrenophora species, for example, Pyrenophora teres; Ramularia species, for example, Ramularia collo-cygni; Rhynchosporium species, for example, Rhynchosporium secalis; Septoria species, for example, Septoria apii; Typhula species, W W for example, Typhula incarnata; Venturia species, for example, Venturia inaequalis; root and stem diseases caused, for example, by species of Corticiumy for example, Corticium graminearum; Fusarium species, for example, Fusarium oxysporum; Gaeumannomyces species, for example, Gaeumannomyces graminis; Rhizoctoniay species, for example, Rhizoctonia solani; Tapesia species, for example, Tapesia acuformis; Thielaviopsis species, for example, Thielaviopsis basicola; ear and panicle diseases (including maize crops) caused, for example, by Alternaria species, for example, Alternaria Spp .; Aspergillus species, for example, Aspergillus flavus;
[367] [367] The following soybean diseases can be controlled with preference:
[368] [368] Fungal diseases on leaves, stems, pods and seeds caused, for example, by spotting on the alternaria leaf (species Alternaria atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), brown spot (Septoria glycines), spot on leaf by cercospora and pest (Cercospora kikuchii), canephora leaf pest (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy downy mildew (Peronospora manshurica), drechslera leaf, glycerin (drechslera) frogeye (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictaoyaecola), pericarp pest and stem (Phomopsis soye), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf, pyrenochaeta pyrenochaeta, pyrenochaeta pyrenochaeta aerial rhizoctonia, foliage and network pest (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), mange (Sphaceloma glycines), leaf pest stemphylium (Stemphylium botryosum), localized leaf spot (Corynespora cassiicola).
[369] [369] Fungal diseases in roots and at the base of the stem caused, for example, by black root rot (Calonectria crotalariae), coal rot (Macrophomina phaseolina), fusarium pest or deterioration, root rot, and pericarp rot and paste (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), root rot mycoleptodiscus (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pericarp and stem pest (Diaporthe phaseolorum), stem cancer (Diaporthe phaseolorum), stem cancer (Diaporthe phaseolorum) stem cancer (Diaporthe phaseolorum) stem cancer (Diaporthe phaseolorum) stem cancer (Diaporthe phaseolorum) stem cancer (Diaporthe phaseolorum). , rotting of phytophthora (Phytophthora megasperma), rotting of brown stem (Phialophora gregata), rotting of pythium (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum, root decay, rotting fungi (Rhizoctonia solani), sclerotinia stem deterioration (Sclerotinia sclerotiorum), pest of southern sclerotinia (Sclerotinia rolfsii), root rot of thielaviopsis (Thielaviopsis basicola).
[370] [370] Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and sludge organisms. According to the invention, the active compounds preferentially act against fungi, especially molds, discoloration of wood and wood-destroying fungi (Basidiomycetes), and against sludge and algae organisms. Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, like Aspergillus niger; Chaetomium, like Chaetomium globosum; Coniophora, like Coniophora puetana; Lentinus, like Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, like Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerofoma, such as Sclerophoma pityophila; Trichoderma such as Trichoderma viride; Escherichia, like Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, like Staphylococcus aureus.
[371] [371] In addition, the active compounds according to the invention also have very good antimycotic activity. They have a very broad spectrum of antimycotic activity, in particular, against dermatophytes and yeasts, molds and diphasic fungi, (for example, against the Candida species, such as Candida albicans, Candida glabrata) and the species Epidermophyton floccosum, Aspergillus, as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, as Trichophyton mentagrophytes, Microsporon species, as Microsporon canis and audouinii. The list of these fungi in no way constitutes a restriction of the mycotic spectrum that can be controlled and is for illustrative purposes only.
[372] [372] The active compounds, according to the invention, can therefore be used in medical and non-medical applications.
[373] [373] If appropriate, the compounds according to the invention can, at certain concentrations or particular application rates, also be used as herbicides, protectors, growth regulators or agents to improve plant properties, or as microbicides, for example. example, as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). They can, depending on the case, also be used as intermediates or precursors for the synthesis of other active compounds. A. Chemical products
[374] [374] NMR data from selected examples are listed in the conventional form (values 5, multiplet division, number of hydrogen atoms) or as lists of NMR peaks. In the NMR peak list method, the NMR data of the selected examples are recorded as NMR peak lists, where for each signal peak the value of 5 in ppm is first and then separated by a space, the signal strength is listed. The value of 3 / signal strength number pairs for different signal peaks are listed with a semicolon separating each other.
[375] [375] Therefore, the peak list for an example has the following format: ô1 (intensity :;); 52 (intensity> 2); .....; di (intensityi); ...; On (intensity)
[376] [376] The intensity of the sharp signals is related to the height of the signals in a printed example of an NMR spectrum in cm and shows the actual ratios of the signal intensities. In the case of broad signals, several peaks or the center of the signal and its relative strength can be shown compared to the most intense signal in the spectrum.
[377] [377] To calibrate the chemical shift of the 'H NMR spectrum, we use tetramethylsilane and / or the chemical shift of the solvent, particularly in the case of spectra that are measured in DMSO. Therefore, the tetramethylsilane peak can, but need not, occur in the NMR peak lists.
[378] [378] 'H NMR peak lists are similar to conventional' H NMR impressions and therefore generally contain all of the peaks listed in a conventional NMR interpretation.
[379] [379] Furthermore, like conventional! H NMR prints, they can show solvent signals, stereoisomeric signals from the target compounds, which are also provided by the invention and / or impurity peaks.
[380] [380] In the compound signal report in the solvent and / or water delta range, our 'H NMR peak lists show the standard solvent peaks, for example, DMSO peaks in DMSO-Ds and the water peak, which usually has a high intensity on average.
[381] [381] The stereoisomers peaks of the target compounds and / or impurity peaks generally have a lower intensity on average than the peaks of the target compounds (for example, with a purity> 90%).
[382] [382] These stereoisomers and / or impurities may be common for the particular preparation process. Their spikes can therefore help to identify the reproduction of our preparation process with reference to "fingerprints of by-products".
[383] [383] An expert, who calculates the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with expected values evaluated empirically), can, if necessary, isolate the peaks of the target compounds, using the filters as an option additional intensity. This isolation would be similar to the selection of the relevant peak in the interpretation of conventional 1H NMR.
[384] [384] Further details of the * H NMR peak lists can be found in the Research Disclosure Database #
[385] [385] The following examples illustrate the invention in detail. Intermediate 1 Preparation of 3,5-difluoro-N-hydroxybenzenecarboxyidoyl chloride
[386] [386] Similar to the procedure in WO2012 / 130798 for 3, -dichloro-N-hydroxybenzenecarboxyidoyl chloride, 3,5-difluoro-N-hydroxybenzenecarboxyidoyl chloride was prepared from 3,5-difluorobenzaldehyde in two steps. Intermediate 2 Preparation of methyl 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-carboxylate
[387] [387] Similar to the procedure in WO2012 / 130798 for methyl 3- (3,5-dichlorophenyl) -5-methyl-4H-isoxazol-5-carboxylate, methyl 3- (3,5-difluorophenyl) -5- methyl-4H-isoxazole-5-carboxylate was prepared from 3,5-difluorobenzaldehyde in three stages. Intermediate 3 Preparation of 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-carboxylic acid
[388] [388] Similar to the procedure in WO2012 / 130798 for 3- (3,5-dichlorophenyl) -5-methyl-4H-isoxazol-5-carboxylic acid, 3- (3,5-difluorophenyl) -5-methyl -4H-isoxazol-5-carboxylic acid was prepared by hydrolysis of methyl 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-carboxylate. Intermediate 4 Preparation of 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-carbonyl chloride
[389] [389] Similar to the procedure in WO2012 / 130798 for N-tert-butyl-3- (3,5-dichlorophenyl) -5-methyl-4,5-dihydro-1,2-oxazol-5- carboxamide, 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-carbonyl chloride was prepared from 3- (3,5-difluorophenyl) -5-methyl-4H-isoxazol-5-acid carboxylic acid by reaction with oxalyl chloride and used as a raw product without further purification. Intermediate 5 Preparation of methyl 3- (3,5-difluorophenyl) -5- (1-hydroxyethyl) -4H-isoxazol-5-carboxylate
[390] [390] 19.9 g (104 mmol) of 3,5-difluoro-N-hydroxybenzimidoyl chloride (see Intermediate 1) were dissolved in 330 ml of 2-propanol and 15.0 g (104 mmol) of methyl 3- hydroxy-2-methylenebutanoate were added. After the addition of 43.8 9g (522 mmol) of sodium bicarbonate, the suspension was heated to 50ºC and the room temperature was maintained for 2 hours until the complete conversion of the initial material. The suspension was filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was mixed in dichloromethane and then washed with saturated sodium chloride solution, and the organic phase was dried over sodium sulfate and, after filtration, concentrated under reduced pressure. The crude product thus obtained was mixed in toluene and, by the addition of n-heptane, was crystallized. This produced 25.5 g (86%) of methyl 3- (3,5-difluorophenyl) -5- (11-hydroxyethyl) -4H-isoxazol-5-carboxylate as colorless crystals.
[391] [391] Diastereomer 1: 'H NMR (CDCl3): 5 = 1.20 (d, 3H), 2.36 (d, 1H), 3.52 (dy, 1H), 3.72 (dy, 1H), 3.83 (s, 3H), 4.34 (m, 1H),
[392] [392] Diastereomer 2:! H NMR (CDCl13): à = 1.29 (d, 3H), 2.12 (d, 1H), 3.58 (dy, 1H), 3.68 (d, 1H), 3.83 (s, 3H), 4.23 (m, 1H),
[393] [393] 29.9 (105 mmol) of methyl 3- (3,5-difluorophenyl) -5- (1-hydroxyethyl) -4H-isoxazol-5-carboxylate in 660 ml of dichloromethane were cooled to 0 ° C and 16.3 g (210 mmol) of pyridine were added. A solution of 38.6 g (137 mmol) of trifluoromethane sulfonic anhydride in 80 ml of dichloromethane was added slowly. After 30 minutes at 0ºC, 300 ml of dichloromethane were added, and the organic phase was washed three times in each case with 200 ml of a saturated solution of sodium chloride and 1 N hydrochloric acid (3: 1). The organic phase was then washed with saturated sodium chloride solution and dried over sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was used in the next step without further purification.
[394] [394] Diastereomer 1:! H NMR (CDCl13): à = 1.54 (d, 3H), 3.44 (d, 1H), 3.89 (s, 3H), 3.94 (d, 1H), 5.49 (q, 1H), 6.91 (m, 1H),
[395] [395] Diastereomer 2:! H NMR (CDCl3): 5 = 1.59 (d, 3H), 3.53 (d, 1H), 3.89 (s, 3H), 3.90 (d, 1H), 5.57 (q, 1H), 6.91 (m, 1H),
[396] [396] 43.0 g (103 mmol) of the crude product from the previous step (methyl 3- (3,5-difluorophenyl) -5- [1- (trifluoromethylsulfonyloxy) ethyl] -4H-isoxazol-5-carboxylate) were dissolved in 500 ml of dimethylacetamide, and a solution of 18.8 g (124 mmol) of DBU in 50 ml of dimethylacetamide was added in drops for 20 minutes. The reaction mixture was stirred at room temperature for 2 hours and then poured into ice cold 1 N hydrochloric acid and extracted twice with 500 ml of diethyl ether each time. The combined organic phases were dried over sodium sulfate, filtered and concentrated under reduced pressure. After chromatographic purification on silica gel using mobile phase dichloromethane, the crude product was crystallized from cyclohexane. This produced 23.4 g (85%) of colorless crystals. 'H NMR (CDCl3): 5 = 3.34 (d, 1H), 3.84 (s, 3H), 3.93 (d, 1H), 5.38 (dy, 1H), 5.55 (df, 1H), 6.14 (dd, 1H) , 6.88 (my, 1H), 7.19 (m, 2H). Intermediate 8 Preparation of 3- (3,5-difluorophenyl) -5-vinyl-4H-isoxazol-5-carboxylic acid
[397] [397] 21 ml of 2N aqueous sodium hydroxide solution was added to 7.5 g (28.0 mmol) of methyl 3- (3,5-difluorophenyl) - 5-vinyl-4H-isoxazol-5-carboxylate and the mixture was heated to reflux for 8 h. After cooling, the reaction mixture was washed with ethyl acetate, the aqueous phase was acidified to pH
[398] [398] 2.70 g (10.6 mmol) of 3- (3,5-difluorophenyl) -5-vinyl-4H-isoxazole-5-carboxylic acid were added to 45 ml of dichloromethane and three drops of dimethylformamide (DMF ) followed by 2.03 9 (15.9 mmol) of oxalyl chloride were then added. A vigorous evolution of gas was observed. The mixture was stirred at room temperature for 6 hours, and the solvent and excess oxalyl chloride were evaporated under reduced pressure. The resulting crude product was used in the next step without further purification. Intermediate 10 Preparation of 3-fluoro-N-hydroxybenzenecarboximidoyl chloride
[399] [399] In a manner analogous to the procedure in WO2012 / 130798 for 3,5-dichloro-N-hydroxybenzenecarboximidoyl chloride, 3-fluoro-N-hydroxybenzenecarboximidoyl chloride was prepared in two steps from 3-fluorobenzaldehyde. Intermediate 11 Preparation of methyl 3- (3-fluorophenyl) -5-methyl-4H-isoxazol-5-carboxylate
[400] [400] Similar to the procedure in WO2012 / 130798 for methyl 3- (3,5-dichlorophenyl) -5-methyl-4H-isoxazol-5-carboxylate, methyl 3- (3-fluorophenyl) -5-methyl- 4H-isoxazol-5-carboxylate was prepared from 3-fluorobenzaldehyde in three steps. Intermediate 12 Preparation of 3- (3-fluorophenyl) -5-methyl-4H-isoxazol-5-carboxylic acid
[401] [401] Similar to the procedure in WO2012 / 130798 for 3- (3,5-dichlorophenyl) -5-methyl-4H-isoxazol-5-
[402] [402] Methyl (1R, 48S) -4-aminocyclopent-2-ene-1-carboxylate hydrochloride can be prepared from the commercially available “Vince lactam” (1S, 4R) -2-azabicycle [2.2.1] hept- 5-en- 3-one in a manner similar to the method described by Marco D. Migliore et al .: J. Med. Chem. 2007, 50, 6485-6492. Intermediate 14 Preparation of methyl 1 (18.4R) -4-aminocyclopent-2-ene-1-carboxylate hydrochloride
[403] [403] Methyl (18.4R) -4-aminocyclopent-2-ene-1-carboxylate hydrochloride can be prepared from the commercially available “Vince lactam” (1R, 4S) -2-azabicyclo [2.2.1] hept- 5-en- 3-one by the method described by Marco D. Migliore et al .: J. Med. Chem. 2007, 50, 6485-6492. Intermediate 15 Preparation of methyl (4R) -4-aminocyclopent-l-ene-l-carboxylate hydrochloride
[404] [404] Methyl (4R) -4-aminocyclopent-l-ene-1-carboxylate hydrochloride can be prepared from Intermediate 13 in a manner analogous to the method described by MEB Smith et al .: Tetrahedron Letters 42 (2001) 1347-1350 . Intermediate 16 Preparation of methyl (48) -4-aminocyclopent-l-ene-l-carboxylate hydrochloride
[405] [405] Methyl (48) -4-aminocyclopent-1-ene-1-carboxylate hydrochloride can be prepared from Intermediate 14 by the method described by M. E. B. Smith et al .: Tetrahedron Letters 42 (2001) 1347-1350. Example 1-003 Preparation of methyl (1R, 4S8) -4- [[[3- (3-fluorophenyl) -5-methyl-4H- 1,2-0oxazol-5-yl] carbonyl] amino] cyclopent-2- eno-l-carboxylate
[406] [406] 200 mg (0.90 mmol) of 3- (3-fluorophenyl) -5-methyl-4H-isoxazole-5-carboxylic acid and 154 mg (0.99 mmol) of 86% of 1-hydroxybenzotriazole (HOBt ) were stirred together in 10 ml of dichloromethane at room temperature for 30 min. 175 mg (0.99 mmol) of methyl (1R, 48S) -4-aminocyclopent-2-ene-1-carboxylate hydrochloride, 343 ma (1.79 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDAC) and 347 mg (2.69 mmol) of N, N-diisopropylethylamine (DIPEA, "Húnig's Base") were then added in succession, and the mixture was stirred at room temperature for 16 hours.
[407] [407] The reaction mixture was then washed with 0.5 M hydrochloric acid, and the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was chromatographed on silica gel (mobile phase: ethyl acetate / n-heptane). This produced 290 mg (91%) of the title compound. Example 1-001 Preparation of (1R, 48) -4- [[[3- (3-fluorophenyl) -5-methyl-4H-1,2-oxazol-5-yl] carbonyl] amino] cyclopent-2-ene -l-carboxylate acid
[408] [408] 270 milliliters (0.78 mmol) of methyl (1R, 48) -4 - [[[3- (3-fluorophenyl) -5-methyl-4H-1,2-oxazol-5-yl] carbonyl] amino] cyclopent-2-ene-1-carboxylate were dissolved in 4 ml of tetrahydrofuran and cooled to 0 ° C. A solution of 156 mg (3.90 mmol) of sodium hydroxide in 4 ml of water was added dropwise to this solution, which was then left to warm to room temperature. After three hours, the mixture was diluted with water and acidified with 2M hydrochloric acid.
[409] [409] The mixture was then extracted with ethyl acetate, and the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was chromatographed on silica gel (mobile phase: ethyl acetate / n-heptane). This produced 190 mg (72%) of the title compound.
[410] [410] 31 mg (0.09 mmol) of (1R, 48) -4 - [[[3- (3-fluorophenyl) -5-methyl-4H-1,2-oxazol-5-yl] carbonyl] amino ] cyclopent-2-ene-1-carboxylic acid and 16 mg (0.10 mmol) of pure 86% 1-hydroxybenzotriazole (HOBt) were mixed together in 2 ml of dichloromethane, and the mixture was stirred at room temperature for 20 min . 9 mg (0.11 mmol) of methoxyamine hydrochloride, 36 mg (0.19 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDAC) and 37 mg (0.28 mmol) of N, N- diisopropylethylamine (DIPEA, "Huúnig's base") were then added in succession, and the mixture was stirred at room temperature for 16 hours.
[411] [411] The reaction mixture was then washed with 0.5 M hydrochloric acid, and the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was chromatographed on silica gel (mobile phase: ethyl acetate / n-heptane). This produced 26 mg (72%) of the title compound. Example II1I-03 Preparation of methyl (4R) -4- [[[(SSR) -3- (3-fluorophenyl) -5-methyl-4H-1,2-0xazol-5-yl] carbonyl] amino] cyclopentene- l-carboxylate
[412] [412] 501 mg (2.25 mmol) of 3- (3-fluorophenyl) -5-methyl-4H-isoxazol-5-carboxylic acid and 439 mg (2.47 mmol) of methyl (4R) - 4-aminocyclopent -l-ene-1-carboxylate were dissolved in 20 ml of dichloromethane, 4.29 g (6.74 mmol) of 50% concentration propylphosphonic anhydride solution (T3P) and the mixture was allowed to stir at temperature room for 4 hours.
[413] [413] The reaction mixture was then washed with saturated sodium bicarbonate solution, and the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was chromatographed on silica gel (mobile phase: ethyl acetate / n-heptane). This produced 720 mg (90%) of the title compound.
[414] [414] 620 mg (1.79 mmol) of methyl (4R) -4- [[[(5SR) -3- (3-fluorophenyl) -5-methyl-4H-1,2-oxazol-5-yl] carbonyl] amino] cyclopentene-1-carboxylate were dissolved in 6 ml of tetrahydrofuran and cooled to 0ºC. A solution of 129 mg (5.37 mmol) of lithium hydroxide in 6 ml of water was added dropwise to this solution, which was then left to warm to room temperature. After 30 minutes, due to poor solubility of the starting materials, an additional 1 ml of tetrahydrofuran and 1 ml of water were added. After four hours, the mixture was diluted with water and acidified with 2M hydrochloric acid. After extraction with ethyl acetate, the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was used raw. This produced 610 mg (100%) of the title compound. Example IV-03 (5SR) -3- (3-Fluorophenyl) -N - [(1R) -3- [(methoxyamino) carbonyl] cyclopent-3-en-l1-yl] -5-methyl-4H-1, 2-oxazole-5-carboxamide
[415] [415] 121 mg (0.36 mmol) of (4R) -4 - [[[(5SR) -3- (3-fluorophenyl) -5-methyl-4H-1,2-oxazol-5-yl] carbonyl ] amino] cyclopentene-1-carboxylic acid and 36 mg (0.44 mmol) of methoxylamine hydrochloride, 36 mg (0.19 mmol) were dissolved in 5 ml of dichloromethane, 347 mg (0.55 mmol) of anhydride solution propylphosphonic in 50% concentration (T3P) and 92 mg (0.91 mmol) of triethylamine were added, and the mixture was left stirring at room temperature for 2 hours.
[416] [416] The reaction mixture was then washed with saturated sodium bicarbonate solution, and the organic phase was separated, dried with sodium sulfate and concentrated under reduced pressure. The evaporation residue was chromatographed on silica gel (mobile phase: ethyl acetate / n-heptane). This produced 86 mg (65%) of the title compound.
[417] [417] In analogy to the preparation examples cited above and at the appropriate point and taking into account the general details regarding the preparation of isoxazoline carboxamides, the following compounds are obtained:
[418] [418] Table 2.1: Compounds 2.1-1 to 2.1-240 according to the invention of the general formula (I.l1), where Z- (C = W) -O-Rº is as defined below.
[419] [419] Table 2.2: Compounds 2.2-1 to 2.2-240 according to the invention of the general formula (1.2), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NO ZOO A
[420] [420] Table 2.3: Compounds 2.3-1 to 2.3-240 according to the invention of the general formula (1.3), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NO ZOO A
[421] [421] Table 2.4: Compounds 2.4-l1 to 2.4-240 according to the invention of the general formula (I.4), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[422] [422] Table 2.5: Compounds 2.5-1 to 2.5-240 according to the invention of the general formula (1.5), where Z- (C = W) -O-Rº is as defined in Table 2.1. Oo nO Z. O 4
[423] [423] Table 2.6: Compounds 2.6-1 to 2.6-240 according to the invention of the general formula (1.6), where 2Z- (C = W) -O-Rº is as defined in Table 2.1. O NO ZE OA
[424] [424] Table 2.7: Compounds 2.7-1 to 2.7-240 according to the invention of the general formula (1.7), where 2Z- (C = W) -O-Rº is as defined in Table 2.1. O
[425] [425] Table 2.8: Compounds 2.8-1 to 2.8-240 according to the invention of the general formula (1.8), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[426] [426] Table 2.9: Compounds 2.9-l1 to 2.9-240 according to the invention of the general formula (1.9), where Z- (C = W) -O-Rº is as defined in Table 2.1. [o NO 2 O A Nº> “R and DONA er (1.9),
[427] [427] Table 2.10: Compounds 2.10-1 to 2.10-240 according to the invention of the general formula (1.10), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[428] [428] Table 2.11: Compounds 2.11-1 to 2.11-240 according to the invention of the general formula (I.11), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[429] [429] Table 2.12: Compounds 2.12-1 to 2.12-240 according to the invention of the general formula (1.12), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[430] [430] Table 2.13: Compounds 2.13-1 to 2.13-240 according to the invention of the general formula (1.13), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[431] [431] Table 2.14: Compounds 2.14-1 to 2.14-240 according to the invention of the general formula (I.l14), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[432] [432] Table 2.15: Compounds 2.15-1 to 2.15-240 according to the invention of the general formula (1.15), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[433] [433] Table 2.16: Compounds 2.16-1 to 2.16-240 according to the invention of the general formula (1.16), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[434] [434] Table 2.17: Compounds 2.17-1 to 2.17-240 according to the invention of the general formula (1.17), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[435] [435] Table 2.18: Compounds 2.18-1 to 2.18-240 according to the invention of the general formula (1.18), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[436] [436] Table 2.19: Compounds 2.19-1 to 2.19-240 according to the invention of the general formula (1.19), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[437] [437] Table 2.20: Compounds 2.20-1 to 2.20-240 according to the invention of the general formula (1.20), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[438] [438] Table 2.21: Compounds 2.21-1 to 2.21-240 according to the invention of the general formula (1.21), where Z- (C = W) -O-Rº is as defined in Table 2.1. NO 22 O to CI! N v R
[439] [439] Table 2.22: Compounds 2.22-1 to 2.22-240 according to the invention of the general formula (1.22), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[440] [440] Table 2.23: Compounds 2.23-l1 to 2.23-240 according to the invention of the general formula (1.23), where Z- (C = W) -O-Rº is as defined in Table 2.1. [and]
[441] [441] Table 2.24: Compounds 2.24-1 to 2.24-240 according to the invention of the general formula (1.24), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[442] [442] Table 2.25: Compounds 2.25-1 to 2.25-240 according to the invention of the general formula (1.25), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NO ZE OA DOOR
[443] [443] Table 2.26: Compounds 2.26-1 to 2.26-240 according to the invention of the general formula (1.26), where 2Z- (C = W) -O-Rº is as defined in Table 2.1. o NO Z Ox A Nº “R o PAIN F Ww H3C E F (1.26),
[444] [444] Table 2.27: Compounds 2.27-1 to 2.27-240 according to the invention of the general formula (1.27), where Z- (C = W) -O-Rº is as defined in Table 2.1. the NO ZOO. A Nº Di and OX Z w
[445] [445] Table 2.28: Compounds 2.28-1 to 2.28-240 according to the invention of the general formula (1.28), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[446] [446] Table 2.29: Compounds 2.29-1l1 to 2.29-240 according to the invention of the general formula (1.29), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[447] [447] Table 2.30: Compounds 2.30-1 to 2.30-240 according to the invention of the general formula (1.30), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[448] [448] Table 2.31: Compounds 2.31-1 to 2.31-240 according to the invention of the general formula (1.31), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[449] [449] Table 2.32: Compounds 2.32-1 to 2.32-240 according to the invention of the general formula (1.32), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[450] [450] Table 2.33: Compounds 2.33-1 to 2.33-240 according to the invention of the general formula (1.33), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NO ZOO A DOES F
[451] [451] Table 2.34: Compounds 2.34-1 to 2.34-240 according to the invention of the general formula (1.34), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[452] [452] Table 2.35: Compounds 2.35-1 to 2.35-240 according to the invention of the general formula (1.35), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[453] [453] Table 2.36: Compounds 2.36-1 to 2.36-240 according to the invention of the general formula (1.36), where Z- (C = W) -O-Rº is as defined in Table 2.1. Oo
[454] [454] Table 2.37: Compounds 2.37-1l1 to 2.37-240 according to the invention of the general formula (1.37), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[455] [455] Table 2.38: Compounds 2.38-1 to 2.38-240 according to the invention of the general formula (1.38), where Z- (C = W) -O-Rº is as defined in Table 2.1. [and]
[456] [456] Table 2.39: Compounds 2.39-1 to 2.39-240 according to the invention of the general formula (1.39), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[457] [457] Table 2.40: Compounds 2.40-1 to 2.40-240 according to the invention of the general formula (1.40), where Z- (C = W) -O-Rº is as defined in Table 2.1. [NO ZOO No “R - | Ex F Ww H3C E CHz3 (1.40),
[458] [458] Table 2.41: Compounds 2.41-1 to 2.41-240 according to the invention of the general formula (1.41), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[459] [459] Table 2.42: Compounds 2.42-1 to 2.42-240 according to the invention of the general formula (1.42), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[460] [460] Table 2.43: Compounds 2.43-1 to 2.43-240 according to the invention of the general formula (1.43), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[461] [461] Table 2.44: Compounds 2.44-1 to 2.44-240 according to the invention of the general formula (1.44), where Z- (C = W) -O-Rº is as defined in Table 2.1. NO ZOO to No “R Cl. 1 H v CF3 e (1.44),
[462] [462] Table 2.45: Compounds 2.45-1 to 2.45-240 according to the invention of the general formula (1.45), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[463] [463] Table 2.46: Compounds 2.46-1l to 2.46-240 according to the invention of the general formula (1.46), where Z- (C = W) -O-Rº is as defined in Table 2.1. NO 22 O A
[464] [464] Table 2.47: Compounds 2.47 to 2.47-240 according to the invention of the general formula (1.47), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[465] [465] Table 2.48: Compounds 2.48-1 to 2.48-240 according to the invention of the general formula (1.48), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[466] [466] Table 2.49: Compounds 2.49-1 to 2.49-240 according to the invention of the general formula (1.49), where Z- (C = W) -O-Rº is as defined in Table 2.1. O IN THE DUCHY
[467] [467] Table 2.50: Compounds 2.50-1 to 2.50-240 according to the invention of the general formula (1.50), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NO Z O DONE F. H The W
[468] [468] Table 2.51: Compounds 2.51-1 to 2.51-240 according to the invention of the general formula (1.51), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[469] [469] Table 2.52: Compounds 2.52-1 to 2.52-240 according to the invention of the general formula (1.52), where Z- (C = W) -O-Rº is as defined in Table 2.1.
[470] [470] Table 2.53: Compounds 2.53-1 to 2.53-240 according to the invention of the general formula (1.53), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[471] [471] Table 2.54: Compounds 2.54-1 to 2.54-240 according to the invention of the general formula (1.54), where Z- (C = W) -O-Rº is as defined in Table 2.1. o NO DANONE! F DX NS
[472] [472] Table 2.55: Compounds 2.55-1 to 2.55-240 according to the invention of the general formula (1.55), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[473] [473] Table 2.56: Compounds 2.56-1 to 2.56-240 according to the invention of the general formula (1.56), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[474] [474] Table 2.57: Compounds 2.56-l1 to 2.56-240 according to the invention of the general formula (1.57), where Z- (C = W) -O-Rº is as defined in Table 2.1. O
[475] [475] Table 2.58: Compounds 2.56-1 to 2.56-240 according to the invention of the general formula (1.58), where Z- (C = W) -O-Rº is as defined in Table 2.1. O NA NOR
[476] [476] Table 3.1: Compounds 3.1-1 to 3.1-390 according to the invention of the general formula (IIT.1), where Z- (C = W) -N (R4) -R is as defined below. the R | NO 22 No 12
[477] [477] Table 3.1 No. Z. ç No. Z ú e e
[478] [478] Table 3.2: Compounds 3.2-1 to 3.2-390 according to the invention of the general formula (II.2), where Z- (C = W) -N (R4!) - R is as defined in Table 3.1.
[479] [479] Table 3.3: Compounds 3.3-1 to 3.3-390 according to the invention of the general formula (II.3), where Z- (C = W) -N (R4) -R is as defined in Table 3.1. AND IS
[480] [480] Table 3.4: Compounds 3.4-l1 to 3.4-390 according to the invention of the general formula (II.4), in which Z- (C = W) -N (R4) -R ” is as defined in Table 3.1. the Ro 1 Z N E XCNÓER
[481] [481] Table 3.5: Compounds 3.5-1 to 3.5-390 according to the invention of the general formula (II.5), in which Z- (C = W) -N (R4) -R ” is as defined in Table 3.1. 1
[482] [482] Table 3.6: Compounds 3.6-1 to 3.6-390 according to the invention of the general formula (II.6), in which Z- (C = W) -N (R4) -R ” is as defined in Table 3.1. o RÚ 1 nO - E. No 12 R
[483] [483] Table 3.7: Compounds 3.7-l1 to 3.7-390 according to the invention of the general formula (II.7), where Z- (C = W) -N (Rt!) - R is as defined in Table 3.1. n
[484] [484] Table 3.8: Compounds 3.8-1 to 3.8-390 according to the invention of the general formula (II.8), where Z- (C = W) -N (R *!) - R is as defined in Table 3.1. RR nO will No12 CcHz3 (11.8),
[485] [485] Table 3.9: Compounds 3.9-1 to 3.9-390 according to the invention of the general formula (II.9), where Z- (C = W) -N (RX!) - R is as defined in Table 3.1.
[486] [486] Table 3.10: Compounds 3.10-1 to 3.10-390 according to the invention of the general formula (II.10), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . Rº 1 and W H3C (IT.10),
[487] [487] Table 3.11: Compounds 3.11-1 to 3.11-390 according to the invention of the general formula (II.11), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . the Rº N2 nºeÊ Ni H3C (IT.11),
[488] [488] Table 3.12: Compounds 3.12-1 to 3.12-390 according to the invention of the general formula (II.12), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . RR 1 H3C E F (IT.12),
[489] [489] Table 3.13: Compounds 3.13-1 to 3.13-390 according to the invention of the general formula (I1.13), where Z- (C = W) -N (RU) -RVº is as defined in Table 3.1 .
[490] [490] Table 3.14: Compounds 3.14-1 to 3.14-390 according to the invention of the general formula (II.14), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o Rº 1 NO ZE AN 12 R
[491] [491] Table 3.15: Compounds 3.15-1 to 3.15-390 according to the invention of the general formula (II.15), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . the RR
[492] [492] Table 3.16: Compounds 3.16-1 to 3.16-390 according to the invention of the general formula (II.16), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . AND IS
[493] [493] Table 3.17: Compounds 3.17-1 to 3.17-390 according to the invention of the general formula (II1.17), where Z- (C = W) -N (RU) -RVº is as defined in Table 3.1 .
[494] [494] Table 3.18: Compounds 3.18-1 to 3.18-390 according to the invention of the general formula (II.18), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R NO E AN 12
[495] [495] Table 3.19: Compounds 3.19-1 to 3.19-390 according to the invention of the general formula (II.19), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R - O N Z N 512 Nº DR Cc | Ex
[496] [496] Table 3.20: Compounds 3.20-1 to 3.20-390 according to the invention of the general formula (I1.20), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R O Z —N XX so [0 H
[497] [497] Table 3.21: Compounds 3.21-1 to 3.21-390 according to the invention of the general formula (I1.21), where Z- (C = W) -N (RU) -RVº is as defined in Table 3.1 .
[498] [498] Table 3.22: Compounds 3.22-1 to 3.22-390 according to the invention of the general formula (II.22), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . RR NO Z AN 12 DR CHa F No. (11.22),
[499] [499] Table 3.23: Compounds 3.23-1 to 3.23-390 according to the invention of the general formula (II.23), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R NO 2 AN 12 No. DR CF3 F (11.23),
[500] [500] Table 3.24: Compounds 3.24-1 to 3.24-390 of the general formula (I1.24) where Z- (C = W) -N (R !!) -R ' is as defined in Table 3.1. o R N2 Z AN 12 No DR F. | H PA Oo W H3CÍ F (11.24),
[501] [501] Table 3.25: Compounds 3.25-1 to 3.25-390 according to the invention of the general formula (II.25), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 .
[502] [502] Table 3.26: Compounds 3.26-1 to 3.26-390 according to the invention of the general formula (II.26), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . the RÚ | NO 2Z Ny 12
[503] [503] Table 3.27: Compounds 3.27-1 to 3.27-390 according to the invention of the general formula (II.27), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . the RÚ | NO ZON 12 and DDS ”W H2JC F (11.27),
[504] [504] Table 3.28: Compounds 3.28-1 to 3.28-390 according to the invention of the general formula (I1.28), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . nu N2 À Z À - Nº SR
[505] [505] Table 3.29: Compounds 3.29-1 to 3.29-390 according to the invention of the general formula (II1.29), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 .
[506] [506] Table 3.30: Compounds 3.30-1 to 3.30-390 according to the invention of the general formula (II.30), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . the UK | NO 2Z AN 12 - EXORÔESR er o (11.30),
[507] [507] Table 3.31: Compounds 3.31-1 to 3.31-390 according to the invention of the general formula (II.31), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . kJ N2 À Z & o 2 SR F DX ET The W
[508] [508] Table 3.32: Compounds 3.32-1 to 3.32-390 according to the invention of the general formula (II.32), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . n
[509] [509] Table 3.33: Compounds 3.33-1 to 3.33-390 according to the invention of the general formula (II.33), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 .
[510] [510] Table 3.34: Compounds 3.34-1 to 3.34-390 according to the invention of the general formula (II.34), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . LE
[511] [511] Table 3.35: Compounds 3.35-1 to 3.35-390 according to the invention of the general formula (II.35), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o RU 1 N2 ZON 12 Nº “DR
[512] [512] Table 3.36: Compounds 3.36-1 to 3.36-390 according to the invention of the general formula (II1.36), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . 1
[513] [513] Table 3.37: Compounds 3.37-1 to 3.37-390 according to the invention of the general formula (I1.37), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . nn
[514] [514] Table 3.38: Compounds 3.38-1 to 3.38-390 according to the invention of the general formula (I1.38), where Z- (C = W) -N (RU) -RVº is as defined in Table 3.1 . the EU | N2 ZON 12 Nº “DR and DOR
[515] [515] Table 3.39: Compounds 3.39-1 to 3.39-390 according to the invention of the general formula (II.39), where Z- (C = W) -N (RU) -RVE is as defined in Table 3.1 . the RR | N = 2 Z AN 12 Nº Y DR F. | H Ww H3C cr 3 (11.39),
[516] [516] Table 3.40: Compounds 3.40-1 to 3.40-390 according to the invention of the general formula (I1I.40), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 .
[517] [517] Table 3.41: Compounds 3.41-1 to 3.41-390 according to the invention of the general formula (II.41), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . nn
[518] [518] Table 3.42: Compounds 3.42-1 to 3.42-390 according to the invention of the general formula (I1.42), where Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . the Rº | N2 2 Z N 12 DOER F. E W
[519] [519] Table 3.43: Compounds 3.43-1 to 3.43-390 according to the invention of the general formula (I1.43), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R nO ZQ AN 12
[520] [520] Table 3.44: Compounds 3.44-1 to 3.44-390 according to the invention of the general formula (I1.44), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . O Rº NO ZON 12 No “R [6 | H x CF3 a (11.44),
[521] [521] Table 3.45: Compounds 3.45-1 to 3.45-390 according to the invention of the general formula (I1.45), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o R - O Z N "No. Y No CI. H O Ww H3C e (11.45),
[522] [522] Table 3.46: Compounds 3.46-1 to 3.46-390 according to the invention of the general formula (I1.46), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o Rº NO Z AN 12
[523] [523] Table 3.47: Compounds 3.47 to 3.47-390 according to the invention of the general formula (I1I.47), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1. o Rn nO ZON 12 SR No. [o | H v
[524] [524] Table 3.48: Compounds 3.48-1 to 3.48-390 according to the invention of the general formula (I1.48), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . o RÚ 1 NO 2Z AN 12 o DX NES Z W
[525] [525] Table 3.49: Compounds 3.49-1 to 3.49-390 according to the invention of the general formula (I1.49), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . n
[526] [526] Table 3.50: Compounds 3.50-1 to 3.50-390 according to the invention of the general formula (II.50), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . n R
[527] [527] Table 3.51: Compounds 3.51-1 to 3.51-390 according to the invention of the general formula (II.51), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . RR NO ZON 12
[528] [528] Table 3.52: Compounds 3.52-1 to 3.52-390 according to the invention of the general formula (II.52), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . the RO | NO ZON 2
[529] [529] Table 3.53: Compounds 3.53-1 to 3.53-390 according to the invention of the general formula (II.53), where Z- (C = W) -N (RU) -RVE is as defined in Table 3.1 . n
[530] [530] Table 3.54: Compounds 3.54-1 to 3.54-390 according to the invention of the general formula (II.54), where 2Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . n
[531] [531] Table 3.55: Compounds 3.55-1 to 3.55-390 according to the invention of the general formula (II.55), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . No. NO ZON 12 No. PR
[532] [532] Table 3.56: Compounds 3.56-1 to 3.56-390 according to the invention of the general formula (II.56), where Z- (C = W) -N (RU) -RV2 is as defined in Table 3.1 . n
[533] [533] Table 3.57: Compounds 3.56-1 to 3.56-390 according to the invention of the general formula (II.57), where 2Z- (C = W) -N (RU) -RVE is as defined in Table 3.1 . the RÚ!
[534] [534] Table 3.58: Compounds 3.56-1 to 3.56-390 according to the invention of the general formula (II.58), where 2Z- (C = W) -N (RU) -RV is as defined in Table 3.1 . the UK! NO Z — N e | No. Y "Ri
[535] [535] A powder product is obtained by mixing 10 parts by weight of a compound of formula (1) and 90 parts by weight of talc as an inert substance and spraying the mixture in a hammer mill.
[536] [536] A wettable water-dispersible powder is readily obtained by mixing 25 parts by weight of a compound of the formula
[537] [537] A water-dispersible dispersion concentrate is readily obtained by mixing 20 parts by weight of a compound of the formula (I), 6 parts by weight of alkylphenol polyglycol ether (G & Triton XxX 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, from about 255 to over 277ºC) and grinding the mixture in a friction ball mill to a thickness of less than 5 microns.
[538] [538] An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (1), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier.
[539] [539] Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of the formula (1), 10 ”of calcium lignosulfonate,” of sodium lauryl sulfate, 3 ”of polyvinyl alcohol and 7” of kaolin , grinding the mixture in a fixed disc mill and granulating the powder in a fluidized bed by spraying water as a granulation liquid.
[540] [540] Water-dispersible granules are also obtained by homogenizing and pre-spraying in a colloid mill, parts by weight of a compound of the formula (1), 5 ”sodium 2,2'-dinaftymethane-6,6'- disulfonate, 2 ”sodium oleoylmethyltaurinate,
[541] [541] Seeds of monocotyledonous and dicotyledonous weeds and cultivation plants are arranged in plastic and wooden fiber containers and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the cover soil surface as an aqueous suspension or emulsion with the addition of 0.5% additive at an application rate of water of 600 1 / ha (converted). After treatment, the containers are placed in a greenhouse and kept under ideal growing conditions for the test plants. After 3 weeks, the effect of the preparations is recorded visually compared to the untranslated controls as percentages. For example, 100% activity = plants have died, 0% activity = as control plants.
[542] [542] In the tables below, the following abbreviations are used: Unwanted plants / weeds ABUTH: Abutilon theophrasti ALOMY: Alopecurus myosuroides AMARE: Amaranthus retroflexus AVEFA: Avena fatua ECHCG: Echinochloa crus-galli HORMU: Hordeum murinum LOLRI: LUMRI: Odorless grasshopper PHBPU: Pharbitis purpurea POLCO: Polygonum convolvulus SETVI: Setaria viridis STEME: Stellaria media VERPE: Veronica persica VIOTR: Viola tricolor Table 4.1: Pre-emergence herbicidal action against ALOMY in%
[543] [543] Table 4.2: Pre-emergence herbicidal action against AVEFA in herbicidal action against [%]
[544] [544] Table 4.3: Pre-emergence herbicidal action against CYPRES in Herbicidal action against [3%] Number | Application rate vn example | [9 / ha] & pe e 1-006 80 100 EE e
[545] [545] Table 4.4: Pre-emergence herbicidal action against ECHCG in
[546] [546] Table 4.5: Pre-emergence herbicidal action against LOLRI in herbicidal action against [%] Number | Esse Rate! x | example | [9 / ha] s [the ee and mr e FE E EEE FAITH FP
[547] [547] Table 4.6: Pre-emergence herbicidal action against SETVI in Herbicidal action against [%] Number | Et ro example rate | [9 / ha] E per E
[548] [548] Table 4.7: Pre-emergence herbicidal action against ABUTH in Herbicidal action against [%] Number | Application rate x example | [9 / ha] 3 me e e
[549] [549] Table 4.8: Pre-emergence herbicidal action against AMARE in Herbicidal action against [3%] Number | Engl a rate | example | [9 / ha] s
[550] [550] Table 4.9: Pre-emergence herbicidal action against MATIN in Herbicidal action against [3%] Number | Application rate z example | [9 / ha] & ros fee fg pp Es ir FAITH PE
[551] [551] Table 4.10: Pre-emergence herbicidal action against PHBPU in ACTION herbicide against [3%] Number | Application rate 2 example | [9 / ha] E and e
[552] [552] Table 4.11: Pre-emergence herbicidal action against POLCO in Herbicidal action against [3%] Number | Application rate O the example | [9 / ha] 3 ee e
[553] [553] Table 4.12: Pre-emergence herbicidal action against STEME in Herbicidal action against [%] Number | Eng a Rate | example | [9 / ha] E pm e e FER PE PE EEE E EE TE PE EE E FP
[554] [554] Table 4.13: Pre-emergence herbicidal action against VIOTR in Herbicidal action against [%] Number | Application rate - “example | [9 / ha] S e o AND IS FAITH
[555] [555] Table 4.14: Pre-emergence herbicidal action against VERPE in Action herbicide against [%] Number | Application rate by example | [9 / ha] ú pp Pr e e 11-06 80 90 PE E AND IS
[556] [556] Table 4.15: Pre-emergence herbicidal action against HORMU in ACTION herbicide against [3%] Number | Rate of Estes! x | example | [9 / ha] Ss pp and pr fe e
[557] [557] As shown by the results, compounds according to the invention, such as, for example, compounds No. 1-002 and other compounds in the tables (1I-004, 1-006, 1I-012, 1-013, 11- 02, II-04, II-06, II-0O7, II-l2, II-l6, III-O2, III-O04, III-O06, IV-Ol, I1V-02, IV-02, IV-04, IV-06, IV -07), when used in pre-emergence treatment, have very good activity (80% to 100% herbicidal action) against harmful plants, such as Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Echinochloa crus-galli, Hordeum murinum, Lolium rigidum, Matricaria inodora, Pharbitis purpurea, Polygonum convolvulus, Setaria viridis, Stellaria media, Veronica persica and Viola tricolor at an application rate of 0.08 kg of active substance or less per hectare.
[558] [558] Seeds of monocotyledonous and dicotyledonous weeds and cultivation plants are placed in sandy clay in plastic or wooden fiber containers, covered with soil and grown in a greenhouse under controlled growing conditions. 2 to 3 weeks after sowing, the test plants are treated at the stage of a leaf. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plants as an aqueous suspension or emulsion with the addition of 0.5% additive at an application rate of water of 600 1 / ha (converted). After the test plants have been kept in the greenhouse under ideal growing conditions for approximately 3 weeks, the activity of the preparations is evaluated visually in comparison to untreated controls. For example, 100% activity = plants have died, 0% activity = as control plants.
[559] [559] Table 5.1: Post-emergence herbicidal action against ALOMY in Herbicidal action against [%] Number | Application rate = example | [9 / ha] ã Fm and 1-004 80 80 Fm fo e
[560] [560] Table 5.2: Post-emergence herbicidal action against AVEFA in Herbicidal action against [%] Number | Application rate 4 example | [9 / ha] 8 and the e
[561] [561] Table 5.3: Post-emergence herbicidal action against ECHCG in Herbicidal action against [3%] Number | Application rate D example | [9 / ha] É ee e pp Es fr e pre
[562] [562] Table 5.4: Post-emergence herbicidal action against LOLRI in Herbicidal action against [3%]
[563] [563] Table 5.5: Post-emergence herbicidal action against SETVI in Herbicidal action against [%] Number | Example rate | [9 / ha] E PET Te
[564] [564] Table 5.6: Post-emergence herbicidal action against ABUTH in Herbicidal action against [3%] Number | Application rate = example | [9 / ha] 3 Fm e 1-008 80 90
[565] [565] Table 5.7: Post-emergence herbicidal action against AMARE in Herbicidal action against [%] Number | Rate of These! air | example | [9 / ha] s fe fe
[566] [566] Table 5.8: Post-emergence herbicidal action against MATIN in Herbicidal action against [3%] Number | Application rate z example | [9 / ha] & e e 1-008 80 90
[567] [567] Table 5.9: Post-emergence herbicidal action against PHBPU in Herbicidal action against [%] Number | Application rate 2 example | [9 / ha] 8 ese e e PRE EE E
[568] [568] Table 5.10: Post-emergence herbicidal action against POLCO in Herbicidal action against [%] Number | Application rate example | [9 / ha] 3 es e and pref pref
[569] [569] Table 5.11: Post-emergence herbicidal action against STEME in Herbicidal action against [3%] Number | Engl a rate | example | [9 / ha] FA mm fe we pm e e
[570] [570] Table 5.12: Post-emergence herbicidal action against VIOTR in
[571] [571] Table 5.13: Post-emergence herbicidal action against VERPE in herbicidal action against [3%] Number | Application rate AND example | [9 / ha] Is
[572] [572] Table 5.14: Post-emergence herbicidal action against HORMU in Herbicidal action against [%] Number | Example Eder rate | [9 / ha] õ [os ee if AND IS FREE ET E EEE EEE EEE E AND IS EEE EEE E EEE
[573] [573] As shown by the results, the compounds according to the invention, such as compounds No. 1I-002 and other compounds in the tables (I-004, 1-006, 1-007, 1-008, I- 009, 1I-010, I-011, I-012, 1I-013, I-014, 1I-015, I-016, 1-017, I- 018, 1-019, 1-020, 1- 021, 1-022, 1I-023, 1-024, 1-025, 1-026, I- 027, 1I-028, 1I-029, 1I-030, 1I-031, 1I-032, 1-033, 1I-034, 1-035, I-036, 1-037, 1I-038, 1I-039, 1-040, 1-041, 1-042, 1-043, 1-044, I- 045, I- 046, I-047, I-048, I-049, I-050, I-051, 1I-052, 1-053, I-054, 1I-055, 1I-056, 1I-057, 1I-058, 1I-059, 1-060, 1-061, 1-062, I-063, I-064, I-065, I-066, I-067, I-068, I-069, I-070, 1- 071, I-072, 1I-073, I-074, 1I-075, 1I-076, 1I-077, 1-078, 1-079, 1-080, I- 081, 1I-082, 1I-083, I-0O84, 1I-085, I-086, 1I-087, 1I-088, 1-089, I- 090, 1I-091, I-092, I-093, I-094, I-095, I- 096, I-097, 1-098, I-099, I-100, I-104 TII-02, II-O04, II-O06, II-O7, II-O8, II-09, II-10, II -11, II-12, II-14, II-15, II-16, II-18, 11-22, 11-25, II-26, I1-27 , II-28, II-29, II-30, II-31, II-32, II-33, II-34, II-35, II-36, II-37, 11-39, III-02, III -06, III-07, III-08, III-09, III-10, III-12, III-13, III-16, III-17, IV-02, IV-04, IV-06, IV-07 , IV-10, V-0l, V-04) when used for post-emergency treatment, have very good activity (80% to 100% herbicidal action) against harmful plants, such as Abutilon theophrasti, Alopecurus myosuroides, Avena fatua, Echinochloa crus-galli, Hordeum murinum, Lolium rigidum, Pharbitis purpurea, Polygonum convolvulus, Setaria viridis, Stellaria media, Veronica persica and Viola tricolor at an application rate of 0.08 kg of active substance or less per hectare.

权利要求:
Claims (28)
[1]
1. 3-Phenylisoxazoline-5-carboxamides and -5-thioamides of the general formula (1)
Y x nad z e
E RP AEE w
R R XÊ x x O, or its agrochemically acceptable salts, characterized by the fact that G represents a group of the formula OR “or NRUR! ; R 'and Rº independently of each other represent hydrogen, halogen or cyano, or represent (C; -C'4) -alkyl or (C1-Ca) - alkoxy, each of which is replaced by m radicals of the group consisting of halogen and cyan; Rº represents cyano or fluorine, or represents (C1, -Cs) -alkyl, (C3-CgÉ) -cycloalkyl, (C>; - Cs) -alkenyl, (C2; -Cs) -alkynyl or (C1; -Cs) - alkoxy, each of which is replaced by m radicals of the group consisting of halogen, cyano, (C1-Cs) -alkoxy and hydroxy; Rº represents hydrogen, or represents (C;, - C2) -alkyl, (C3-C7;) -cycloalkyl, (C3-C7) -cycloalkyl- (C;, - Csg) -alkyl, (C2-Cg) - alkenyl , (Cs-Cg) -cycloalkenyl or (C3; -Cg) -alkynyl, each of which is replaced by radicals but from the group consisting of halogen, cyano, (C1-C «g) -alkoxy, hydroxy and aryl ; Y represents oxygen or sulfur; W represents oxygen or sulfur; Z represents a monounsaturated cyclopentane ring that is replaced by k radicals of the group Rºº,
RX jo
Z where the arrow in each case denotes a link to the group C = W of the formula (1); RX represents halogen, cyano or CO; R ', or represents (C;, - C;) - alkyl or (C;, - C,)) - alkoxy, each of which is replaced by the radicals m of the group consisting of fluorine and chlorine; R !!, RM independently of each other, each one represents hydrogen, cyan OR ', S (O) n Ri, SOJXNRºR', COXRº, CONRºRº, COR ”, NR $ Rº, NRºCORº, NRºCONRºRº, NR $ CO-Rê, NR $ SO-2Rº , NR $ SOsNRºRº, C (Ró) = NORº, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or represent (C; -C; i)) - alkyl, (C3-Cg) -cycloalkyl, (C3-C7 ) -cycloalkyl- (C, -C;) - alkyl, (C7-C12) kenyl salt, (C5-C7) = cycloalkenyl or (C2-C12) -alkynyl, each of which is replaced by m radicals of the group that consists of halogen, cyan, nitro, OR ', S (O) í, Rº, SO2WNRºR', COs; Rº, CONR “ºRº, COR“, NRºRº, NRºCORº, NRºCONRºRº, NRºCO, sRº, NR $ SO, -Rº, NRºSO, NRºRº, C (Rº) = NOR , optionally substituted aryl, optionally substituted heteroaryl and optionally substituted heterocyclyl, or R4º and R * together with the nitrogen atom to which they are attached form a five, six or seven membered partially or totally unsaturated ring which is optionally mono to hexasubstituted by the radicals of the group consisting of halogen, cyan, nitro, (C1-C6) -alkyl , halo- (Ci-Ck) -alkyl, oxo, OR, S (O) n Rº, SOJNRºRI, CO2Rº, CONRºRº, COR ”, NRºRº, NRºCORº, NRºCONRºRº, NRºCO; Rº, NR $ SO-Rº, NRºSO, NRºRº and C (Rº) = NORº and which, in addition to this nitrogen atom, contains carbon atoms or oxygen atoms, sulfur atoms p and q elements of the group consisting of NR and NCOR 'as ring atoms; xº, Xº and Xº independently of each other, each representing hydrogen, halogen or cyano, or represent (C;, - C;) - alkyl, in each case replaced by the radicals m of the group consisting of fluorine, chlorine, bromine and ( C ;, - C> -) - alkoxy; x and x independently of each other each represents hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyan, nitro, S (0) n Rº or COR, or represent (C;, - C; 3) -alkyl, (C1 -C3) -alkoxy, (C3-Ca) -cycloalkyl, (C7; -C3) -alkenyl or (C; -C3;) - alkynyl, each of which is replaced by the m radicals of the group consisting of fluorine, chlorine and bromine; Rº represents (C, -Cg) -alkyl, (C3-Cg) -cycloalkyl or aryl, each of which is replaced by the radicals m of the group consisting of halogen, cyano and hydroxy; R $ represents hydrogen or Rº; R 'represents hydrogen, or represents (C;, - Cg;) -> - alkyl, (C3-Ce) -cycloalkyl, (C3-Ca) -alkenyl or (C3-Ca]) - alkynyl, each of which is replaced by the radicals m of the group consisting of halogen, cyano and (C;, - C;) - alkoxy; R8 represents hydrogen, or represents (C; i-Cg) -alkyl, (Can Cs) -cycloalkyl, (C3; -Cg) -alkenyl or (C3; -Csg) -alkynyl, each of which is replaced by m radicals the group consisting of halogen, cyano and (C, -C;) - alkoxy; k represents the current number 0, 1 or 2; where for k> 1 R * º independently of the others it can be identical or different; m represents the current number O, 1, 2, 3, 4 or 5; n represents the current number 0, 1 or 2; o represent the current number 0, 1 or 2; Pp represents the current number O or 1; q represent the current number 0 or 1; and r represents the current number 3, 4, 5 or 6.
[2]
Compounds of the general formula (I) according to claim 1, characterized by R 'and R independently of each other each represents hydrogen, fluorine, chlorine or cyano or represent (C1-C3) -alkyl or (C1-C; 3) -alkoxy which are in each case replaced by the m radicals of the group consisting of fluorine, chlorine , bromine and cyan.
[3]
Compounds of the general formula (I) according to claim 1 or 2, characterized in that R ° represents (C1-C'4.) - alkyl, (C3-Cs) - cycloalkyl, (C3; -C1) -alkenyl, (C7; -C'4) -alkynyl or (C, -C1]) - alkoxy, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C1; -Ca) - alkoxy and hydroxy;
[4]
Compounds of the general formula (II) according to any one of claims 1 to 3, characterized in that Rº represents hydrogen or represents (C1-CÉ) -alkyl, (C3-Cg6) -cycloalkyl,
(C3-Cg) -cycloalkyl- (C, -Cs) -alkyl, (C7-Cg) -alkenyl, (Cs-Cg6) cycloalkenyl or (C2-Cg6) -alkynyl, each of which is replaced by m radicals group consisting of fluorine, chlorine, bromine, cyano, (C1, -C's) -alkoxy, hydroxy and aryl.
[5]
Compounds of the general formula (II) according to any one of claims 1 to 4, characterized in that Y represents oxygen.
[6]
Compounds of the general formula (I) according to any one of claims 1 to 5, characterized in that W represents oxygen.
[7]
Compounds of the general formula (I) according to any one of claims 1 to 6, characterized in that Z represents a group Z-1 at 2-22, 2-1 at 72-22 having the following meaning:
F3C Z1 z2 Zz3 ZA H3; CO CHs Zz5 Zz6 Zz7 z8
CN CH; 3 Fer FS R zo Zz10 Zn z12 CH; Ç 2 o Ç 2 "É Z-13 Z14 Z-15 Zz16 H; CO CH NC CH3 Z1A7 Zz-18 Zz19 Z-20 Z21 Zz-22 where the arrow in each case denotes a link to the group C = W of formula (1).
[8]
Compounds of the general formula (I) according to any one of claims 1 to 7, characterized in that R "º represents fluorine, chlorine, cyano COzH, CO; CH; or CO, CH,; CH; or represent (C ; 1- C2) -alkyl or (C1-C>) - alkoxy, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[9]
Compounds of the general formula (II) according to any one of Claims 1 to 8, characterized in that R * represents hydrogen or represents (C1, -C;) - alkyl or (C3-Cg) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[10]
Compounds of the general formula (1) according to any one of claims 1 to 9, characterized by R represent hydrogen, cyano or hydroxy or represent OR ', S (O) rn Rº, NRºRº, NRͺCO2RE, (Ci-Cg) -alkyl, (C3-Cg) -cycloalkyl, (C; -C3) -alkenyl or (C2- C3) salquinyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano and hydroxy.
[11]
Compounds of the general formula (1) according to any one of claims 1 to 10, characterized by RU! and R ' º together with the nitrogen atom, to which they are attached, form a five, six or seven membered saturated, partially or totally unsaturated ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, cyan, nitro, (C1-Cg) -alkyl, halo- (C, -Csk) -alkyl, oxo, OR ', CO, Rº and NRºSO0: Rº and which, in addition to this nitrogen atom, contains carbon atoms r, carbon atoms oxygen o, sulfur atoms p and q elements of the group consisting of NR 'to NCOR' as ring atoms.
[12]
12. Compounds of the general formula (1) according to any one of claims 1 to 11, characterized by Xº, Xº and Xº independently of each other, each representing hydrogen, fluorine, chlorine, bromine or cyano or representing methyl or methoxy, each of which is replaced by m radicals of the group consisting of fluorine and chlorine.
[13]
13. Compounds of the general formula (TI) according to any one of claims 1 to 12, characterized by XX and XxX independently of each other represent hydrogen, fluorine, chlorine, bromine, hydroxy or cyano or represent (C; -C3) -alkyl, (C1-C3) -saloxy, (C3-Cs) -cycloalkyl, (C7-C; ) -alkenyl or (C3; -C3) - alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and bromine.
[14]
14. Compounds of the general formula (II) according to any one of claims 1 to 13, characterized in that Rº represents (C; - Ce) -alkyl or (C3-CgÉg) -cycloalkyl, each of which is replaced by radicals m of the group consisting of fluorine and chlorine.
[15]
Compounds of the general formula (1) according to any one of claims 1 to 14, characterized in that R 'represents hydrogen or represents (C; -Ck) -alkyl or (C3-Cg) -cycloalkyl, each of which is replaced by radicals m of the group consisting of fluorine, chlorine and (C; iC;) - alkoxy.
[16]
16. Compounds of the general formula (I) according to any one of claims 1 to 15, characterized in that Rº represents hydrogen or represents (C1; -Ck;) - alkyl or (C3-Cg) -cycloalkyl, each of which it is replaced by radicals m of the group consisting of fluorine, chlorine and (C; 1-C7;) - alkoxy.
[17]
17. Compounds of the general formula (II) according to any one of claims 1 to 16, characterized by the number in force m being 0, 1, 2 or 3.
[18]
18. Compounds of the general formula (1) according to claim 1, characterized in that G represents a group of the formula OR; R 'and R each represents hydrogen; R3 represents (C1-C3) -alkyl, (C3-C4) -cycloalkyl, (C2-C3) - alkenyl or (C;, - C; 3) -alkoxy, each of which is replaced by m radicals of the group that consists of fluorine, chlorine and (C, -C;) - alkoxy; Rº represents hydrogen or represents (C, -C «;) - alkyl, (C3-C6) - cycloalkyl, (C3-Cg) -cycloalkyl- (C;, - Ck) -alkyl, (C3; -Cs) -alkenyl , (Cs-Cg) -cycloalkenyl or (C7; -Csg) 7-alkynyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine, bromine, cyano, (C; iC,]) - alkoxy , hydroxy and aryl; Y represents oxygen; W represents oxygen; Z represents a group Z-l1, 2-4 or 2-6:
z1 z4 z-6 where the arrow in each case denotes a link to the group C = W of the formula (1); xº, Xº and x independently of each other each represents hydrogen or fluorine; XxX and Xº ”independently of each other, each representing hydrogen, fluorine, chlorine, CF3, CHF; or methyl; and m represents the current number 0, 1, 2 or 3.
[19]
19. Compounds of the general formula (1) according to claim 1, characterized in that G represents a group of the formula NRUÚRI ; R 'and Rº each represent hydrogen; R3º represents (C1-C3) -alkyl, (C3-Ca) -cycloalkyl, (C2-C3) - alkenyl or (C; -C;) - alkoxy, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C; 1-C2) - alkoxy; Y represents oxygen; W represents oxygen; Z represents a group Z-l1, 2-4 or 2-6: z1 ZA z-6 where the arrow in each case denotes a link to the group C = W of the formula (1); x , Xº and xo independently of each other each represents hydrogen or fluorine; XxX and X ”independently of each other, each representing hydrogen, fluorine, chlorine, CF ;, CHF; or methyl; Rº represents (C; -Cg) -alkyl or (C3-Cg) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine and chlorine; Rº represents hydrogen or Rº;
R 'represents hydrogen or represents (C;, - C;) - alkyl or (C3; - Cs) -cycloalkyl, each of which is replaced by radicals m of the group consisting of fluorine, chlorine and (C; -C; ) -alkoxy; Rô represents hydrogen or represents (C;, - Cs;) - alkyl or (C3-Cs) -cycloalkyl, each of which is replaced by m radicals of the group consisting of fluorine, chlorine and (C;, - C2;) -alkoxy; RU represents hydrogen or represents (C;, - C;) - alkyl or (C3-Cs) -cycloalkyl, each of which is replaced by radicals m of the group consisting of fluorine and chlorine; R$ represent hydrogen, cyan, OR, S (O) n Rº, SO2NRºR ', COR ”, NRºRº, NRºCORº or NRºSO, Rº or represents (C; i-Ck;) - alkyl, (C3-Cg6) - cycloalkyl, (C ); - C;) - alkenyl or (C; -C;) - alkynyl, each of which is replaced by radicals m of the group consisting of fluorine, chlorine, bromine, cyano, OR ', S (O) rn Rº , NRºRº and NRºCO; Rº; or R and R2 together with the nitrogen atom, to which they are attached, they form a five, six or seven membered saturated, partially or totally unsaturated ring that is optionally mono to hexasubstituted by radicals of the group consisting of halogen, (C1-Cg) 7- alkyl, halo- (C;, - Cg) -alkyl and oxo and which, in addition to this nitrogen atom, contains carbon atoms r, oxygen atoms o, sulfur atoms p and q elements of the group consisting of NR ”to NCOR as ring atoms; m represents the current number 0, 1, 2 or 3; n represents the current number 0, 1 or 2; o represent the current number 0, 1 or 2; Pp represents the current number O or 1; q represent the current number 0 or 1; and r represents the current number 3, 4 or 5.
[20]
20. Herbicidal composition or plant growth regulation composition, characterized in that it comprises one or more compounds of the general formula (I) or their salts according to any one of claims 1 to 19.
[21]
21. Herbicidal composition according to claim 20, characterized in that it comprises a formulation aid.
[22]
22. Herbicidal composition according to claim 20 or 21, characterized in that it comprises at least one active compound from the group of insecticides, acaricides, herbicides, fungicides, protectors and / or growth regulators.
[23]
23. Herbicidal composition according to claim 20 or 21, characterized in that it comprises a protector.
[24]
24. Herbicidal composition according to claim 23, characterized in that the protector is selected from the group consisting of mefenpir-diethyl, cyprosulfamide, isozadifen-ethyl, cloquintocet-mexil, benoxacor and diclormid.
[25]
25. Method of controlling unwanted plants, characterized by an effective amount of at least one compound of the formula (1) according to any one of claims 1 to 19 or a herbicidal composition according to any one of claims 20 to 24 applied to plants or the location of unwanted vegetation.
[26]
26. Use of the compounds of the formula (LI) according to any one of claims 1 to 19 or of herbicidal compositions according to any one of claims 20 to 24, characterized in that it is for controlling unwanted plants.
[27]
27. Use according to claim 26, characterized in that the compounds of formula (I) are used to control unwanted plants in useful plantations.
[28]
28. Use according to claim 27, characterized in that the useful plants are transgenic plants.

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法律状态:
2021-12-07| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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EP18153354|2018-01-25|

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EP18153354.8|2018-01-25|

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PCT/EP2019/051333|WO2019145245A1|2018-01-25|2019-01-21|Herbicidally active 3-phenylisoxazoline-5-carboxamides of cyclopentenyl carboxylic acid derivatives|

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