Patent Application
20230150989
The present invention relates to malonamide compounds and compositions comprising the same. The invention also relates to the use of the malonamide compounds or the corresponding compositions for controlling unwanted vegetation. Furthermore, the invention relates to methods of applying the malonamide compounds or the corresponding compositions. For the purpose of controlling unwanted vegetation, especially in crops, there is an ongoing need for new herbicides that have high activity and selectivity together with a substantial lack of toxicity for humans and animals.
WO12130798, WO1404882, WO14048882, WO18228985, WO18228986, WO19034602, and WO19145245 describe 3-phenylisoxazoline-5-carboxamides and their use as herbicides.
WO 87/05898 describes the use of malonic acid derivatives for retarding plant growth.
Malonic acid derivatives are also described in U.S. Pat. No. 3,072,473 as plant growth regulants.
The compounds of the prior art often suffer from insufficient herbicidal activity, in particular at low application rates, and/or unsatisfactory selectivity resulting in a low compatibility with crop plants.
Accordingly, it is an object of the present invention to provide further malonamide compounds having a strong herbicidal activity, in particular even at low application rates, a sufficiently low toxicity for humans and animals and/or a high compatibility with crop plants. The malonamide compounds should also show a broad activity spectrum against a large number of different unwanted plants.
These and further objectives are achieved by the compounds of formula (I) defined below including their agriculturally acceptable salts, amides, esters or thioesters.
Accordingly, the present invention provides compounds of formula (I)
wherein the substituents have the following meanings:
including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group.
The present invention also provides formulations comprising at least one compound of formula (I) and auxiliaries customary for formulating crop protection agents.
The present invention also provides combinations comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C).
The present invention also provides the use of compounds of formula (I) as herbicides, i.e. for controlling undesired vegetation.
The present invention furthermore provides a method for controlling undesired vegetation where a herbicidal effective amount of at least one compound of formula (I) is allowed to act on plants, their seeds and/or their habitat.
If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein are capable of forming geometric isomers, for example E/Z isomers, it is possible to use both, the pure isomers and mixtures thereof, according to the invention.
If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein have one or more centres of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, according to the invention.
If the compounds of formula (I), the herbicidal compounds B and/or the safeners C as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.
Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (diolamine salt), tris(2-hydroxyethyl)ammonium (trolamine salt), tris(2-hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N-trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium, and finally the salts of polybasic amines such as N,N-bis-(3-aminopropyl)methylamine and diethylenetriamine.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
Compounds of formula (I), herbicidal compounds B and/or safeners C as described herein having a carboxyl group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-C1-C6-alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, C1-C10-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters and also as thioesters, for example as C1-C10-alkylthio esters. Preferred mono- and di-C1-C6-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2-chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters. Preferred C1-C4-alkoxy-C1-C4-alkyl esters are the straight-chain or branched C1-C4-alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester. An example of a straight-chain or branched C1-C10-alkylthio ester is the ethylthio ester.
The terms used for organic groups in the definition of the variables are, for example the expression “halogen”, collective terms which represent the individual members of these groups of organic units.
The prefix Cx-Cy denotes the number of possible carbon atoms in the particular case. All hydrocarbon chains can be straight-chain or branched.
halogen: fluorine, chlorine, bromine, or iodine, especially fluorine, chlorine or bromine; alkyl and the alkyl moieties of composite groups such as, for example, alkoxy, alkylamino, alkoxycarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, for example C1-C10-akyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-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; heptyl, octyl, 2-ethylhexyl and positional isomers thereof; nonyl, decyl and positional isomers thereof;
haloalkyl: straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. In one embodiment, the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine. In a further embodiment, the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred. Particular preference is given to (C1-C3)-haloalkyl, more preferably (C1-C2)-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-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
alkenyl and also the alkenyl moieties in composite groups, such as alkenyloxy: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one double bond in any position. According to the invention, it may be preferred to use small alkenyl groups, such as (C2-C4)-alkenyl; on the other hand, it may also be preferred to employ larger alkenyl groups, such as (C5-C8)-alkenyl. Examples of alkenyl groups are, for example, C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-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, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
haloalkenyl: alkenyl groups as mentioned above which are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 2-chloroprop-2-en-1-yl, 3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloro-2-en-1-yl, 2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1-yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromo-2-en-1-yl or 2,3-dibromobut-2-en-1-yl; alkynyl and the alkynyl moieties in composite groups, such as alkynyloxy: straight-chain or branched hydrocarbon groups having 2 to 10 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 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; haloalkynyl: alkynyl groups as mentioned above which are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example 1,1-difluoroprop-2-yn-1-yl, 3-chloroprop-2-yn-1-yl, 3-bromoprop-2-yn-1-yl, 3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl;
cycloalkyl and also the cycloalkyl moieties in composite groups: mono- or bicyclic saturated hydrocarbon groups having 3 to 10, in particular 3 to 6, carbon ring members, for example C3-C6-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. In this connection, optionally substituted C3-C8-cycloalkyl means a cycloalkyl radical having from 3 to 8 carbon atoms, in which at least one hydrogen atom, for example 1, 2, 3, 4 or 5 hydrogen atoms, is/are replaced by substituents which are inert under the conditions of the reaction. Examples of inert substituents are CN, C1-C6-alkyl, C1-C4-haloalkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, and C1-C4-alkoxy-C1-C6-alkyl; halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like: monocyclic saturated hydrocarbon groups having 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
cycloalkoxy: cycloalkyl groups as mentioned above which are attached via an oxygen; alkoxy and also the alkoxy moieties in composite groups, such as alkoxyalkyl: an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 10, more preferably 2 to 6, carbon atoms. Examples are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, and also for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy; haloalkoxy: alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular by fluorine, chlorine or bromine. Examples are OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy; and also 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
hydroxyl: OH group which is attached via an O atom;
cyano: CN group which is attached via an C atom;
nitro: NO2 group which is attached via an N atom.
The preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another.
According to particular embodiments of the invention, preference is given to those compounds of formula (I) wherein the variables, either independently of one another or in combination with one another, have the following meanings:
Preferred compounds according to the invention are compounds of formula (I), wherein R1 is selected from the group consisting of hydrogen, (C1-C3)-alkyl, (C3-C4)-cycloalkyl, (C1-C3)-haloalkyl, (C2-C3)-alkenyl, (C2-C3)-alkynyl, (C1-C3)-alkoxy-(C1-C3)-alkyl, (C1-C3)-alkoxy.
Preferred compounds according to the invention are also compounds of formula (I), wherein R1 is selected from the group consisting of hydrogen, (C1-C3)-alkyl, (C3-C4)-cycloalkyl, and (C1-C3)-haloalkyl, in particular hydrogen, methyl, cyclopropyl and 2,2-difluoroethyl.
More preferred compounds according to the invention are compounds of formula (I), wherein R1 is selected from the group consisting of hydrogen, (C1-C3)-alkyl, (C3-C4)-cycloalkyl, and (C1-C3)-alkoxy-(C1-C3)-alkyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R1 is selected from the group consisting of hydrogen, methyl, and methoxymethyl.
In particular, R1 is hydrogen.
Further preferred compounds according to the invention are compounds of formula (I), wherein R2 is selected from the group consisting of hydrogen, halogen and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R2 is selected from the group consisting of hydrogen, halogen and (C1-C3)-alkoxy, in particular, hydrogen, fluorine and methoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R2 is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.
In particular, R2 is hydrogen.
Further preferred compounds according to the invention are compounds of formula (I), wherein R3 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R3 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, (C1-C3)-haloalkoxy.
More preferred compounds according to the invention are compounds of formula (I), wherein R3 is selected from the group consisting of halogen, cyano, and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R3 is selected from the group consisting of halogen, cyano, and (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, (C1-C3)-haloalkoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R3 is selected from the group consisting of hydrogen, halogen, cyano and methyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R3 is selected from the group consisting of hydrogen, halogen, cyano and methyl, (C1-C3)-haloalkoxy, in particular hydrogen, halogen, trifluoromethoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R3 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and methyl.
In particular, R3 is hydrogen or halogen, very particular chlorine or fluorine.
Further preferred compounds according to the invention are compounds of formula (I), wherein R4 is selected from the group consisting of hydrogen, halogen, (C1-C3)-alkyl, (C1-C3)-alkoxy, (C1-C3)-haloalkoxy, (C1-C3)-alkylthio, and (C1-C3)-haloalkylthio.
Further preferred compounds according to the invention are compounds of formula (I), wherein R4 is selected from the group consisting of hydrogen and halogen.
Also preferred compounds according to the invention are compounds of formula (I), wherein R4 is selected from the group consisting of hydrogen, fluorine, chlorine and bromine.
In particular, R4 is hydrogen or hydrogen, fluorine or chlorine, very particular hydrogen.
Further preferred compounds according to the invention are compounds of formula (I), wherein R5 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R5 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, (C1-C3)-haloalkoxy.
More preferred compounds according to the invention are compounds of formula (I), wherein R5 is selected from the group consisting of halogen, cyano, and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R5 is selected from the group consisting of halogen, cyano, and (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, (C1-C3)-haloalkoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R5 is selected from the group consisting of hydrogen, halogen, cyano and methyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R5 is selected from the group consisting of hydrogen, halogen, cyano and methyl, (C1-C3)-haloalkoxy, in particular hydrogen, halogen, trifluoromethoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R5 is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano and methyl.
In particular, R5 is hydrogen or halogen, very particular chlorine or fluorine.
Further preferred compounds according to the invention are compounds of formula (I), wherein R6 is selected from the group consisting of hydrogen, halogen and (C1-C3)-alkyl.
Preferred compounds according to the invention are also compounds of formula (I), wherein R6 is selected from the group consisting of hydrogen, halogen and (C1-C3)-alkoxy, in particular, hydrogen, fluorine and methoxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R6 is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.
In particular, R6 is hydrogen.
Further preferred compounds according to the invention are compounds of formula (I), wherein R7 is selected from the group consisting of (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-alkenyl, and (C1-C3)-alkoxy-(C1-C3)-alkyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl and cyano.
Also preferred compounds according to the invention are compounds of formula (I), wherein R7 is selected from the group consisting of (C1-C6)-alkyl, (C1-C6)-haloalkyl (C3-C6)-cycloalkyl, and (C3-C6)-alkynyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R7 is selected from the group consisting of (C1-C6)-alkyl, (C3-C6)-cycloalkyl, and (C3-C6)-alkenyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R7 is selected from the group consisting of (C1-C6)-alkyl.
In particular, R7 is methyl or ethyl, very particular methyl.
Further preferred compounds according to the invention are compounds of formula (I), wherein R8 is selected from the group consisting of hydrogen, halogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C6)-haloalkoxy, (C3-C6)-alkenyloxy, and (C3-C6)-alkynyloxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R8 is selected from the group consisting of hydrogen, halogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C6)-haloalkoxy, (C3-C6)-alkenyloxy, and (C3-C6)-alkynyloxy.
Also preferred compounds according to the invention are compounds of formula (I), wherein R8 is selected from the group consisting of hydrogen, halogen, cyano, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, and (C1-C6)-alkoxy.
More preferred compounds according to the invention are compounds of formula (I), wherein R8 is selected from the group consisting of hydrogen and halogen.
In particular, R8 is hydrogen, fluorine, methyl, ethyl, methoxy or ethoxy, very particular hydrogen or fluorine, most particular hydrogen.
Further preferred compounds according to the invention are compounds of formula (I), wherein R9 is selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C3-C6)-cycloalkyl.
Also preferred compounds according to the invention are compounds of formula (I), wherein R9 is selected from the group consisting of hydrogen and (C1-C3)-alkyl.
In particular, R9 is hydrogen, methyl or ethyl, very particular hydrogen.
In the compounds of formula (I), X is selected from the group consisting of a bond (X0) or a divalent unit from the group consisting of (X1), (X2), (X3), (X4), (X5) and (X6), wherein the orientation of (X1), (X2), (X3), (X4), (X5) and (X6) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y.
In a preferred embodiment (compounds of formula (I.X0)), X is a bond (X0):
In another preferred embodiment (compounds of formula (I.X1)), X is (X1), wherein the orientation of (X1) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
In another preferred embodiment (compounds of formula (I.X2)), X is (X2), wherein the orientation of (X2) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
In another preferred embodiment (compounds of formula (I.X3)), X is (X3), wherein the orientation of (X3) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
In another preferred embodiment (compounds of formula (I.X4)), X is (X4), wherein the orientation of (X4) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
In another preferred embodiment (compounds of formula (I.X5)), X is (X5), wherein the orientation of (X5) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
In another preferred embodiment (compounds of formula (I.X6)), X is (X6), wherein the orientation of (X6) within the molecule is as depicted, the left arrow representating the bond to the adjacent nitrogen, the right arrow representating the bond to the adjacent group Y:
Further preferred compounds according to the invention are compounds of formula (I), wherein X is selected from the group consisting of a bond (X0) or a divalent unit from the group consisting of CH2, CH2CH2, CHCH3, CH2CH2CH2, CH(CH2CH3), CH(CH3)CH2, C(CH3)2, C(CH3)2CH2, C(iPr)CH3, CH(CH2iPr)CH2, CH2CH═CH, C(CH3)2C≡C, CH(CF3)CH2, CH(CH3)CH2O, CH2CH2O, CH(cPr)CH2O, CH(CH2OCH3), CH(CH2CH2SCH3), CH(COOH), CH(COOCH3), CH(COOH)CH2, CH(COOCH3)CH2, CH2COH(CF3), CH(CONHCH3), CH(CONHCH3)CH2 and CH2CH2CONHCH2.
Further preferred compounds according to the invention are compounds of formula (I), wherein R10-R15 each independently is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO2Re, CONRbRd, or (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, each substituted by m radicals from the group consisting of fluorine, or (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C3-C6)-alkenyloxy, (C3-C6)-alkynyloxy, (C1-C3)-alkylsulfinyl, (C1-C3)-alkylsulfonyl and (C1-C3)-alkylthio, each substituted by m radicals from the group consisting of fluorine.
Also preferred compounds according to the invention are compounds of formula (I), wherein R10-R15 each independently is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO2Re, CONRbRd, or (C1-C6)-alkyl, (C3-C5)-cycloalkyl, (C2-C6)-alkenyl, each substituted by m radicals from the group consisting of fluorine, or (C1-C6)-alkoxy, (C3-C6)-cycloalkoxy, (C3-C6)-alkenyloxy or (C3-C6)-alkynyloxy, each substituted by m radicals from the group consisting of fluorine.
Also preferred compounds according to the invention are compounds of formula (I), wherein R10-R15 each independently is selected from the group consisting of hydrogen, fluorine, chlorine, CO2Re, CONRbRd, or (C1-C6)-alkyl, substituted by m radicals from the group consisting of fluorine, or (C1-C6)-alkoxy, substituted by m radicals from the group consisting of fluorine. In particular, R10-R15 each independently is selected from the group consisting of halogen, (C1-C6)-alkyl, (C1-C3)-alkoxy, and CO2Re.
Further preferred compounds according to the invention are compounds of formula (I), wherein Y is selected from the group consisting of hydrogen, cyano, hydroxyl, Z, or (C1-C12)-alkyl, (C3-C8)-cycloalkyl, (C2-C12)-alkenyl or (C2-C12)-alkynyl each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxyl, Z, CO2Re, and CONRbRh.
Also preferred compounds according to the invention are compounds of formula (I), wherein Y is selected from the group consisting of hydrogen, cyano, hydroxyl, Z, or (C1-C12)-alkyl, and (C3-C8)-cycloalkyl, each substituted by m radicals from the group consisting of fluorine, CO2Re, and CONRbRh.
Also preferred compounds according to the invention are compounds of formula (I), wherein Y is selected from the group consisting of (C1-C12)-alkyl, (C3-C8)-cycloalkyl, (C2-C12)-alkenyl or (C2-C12)-alkynyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxyl, ORd, Z, OZ, NHZ, S(O)nRa, SO2NRbRd, SO2NRbCORe, CO2Re, CONRbRh, CORb, CONReSO2Ra, NRbRe, NRbCORe, NRbCONReRe, NRbCO2Re, NRbSO2ReNRbSO2NRbRe, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe.
Also preferred compounds according to the invention are compounds of formula (I), wherein Y is selected from the group consisting of (C1-C12)-alkyl, (C3-C8)-cycloalkyl, (C2-C12)-alkenyl or (C2-C12)-alkynyl, each substituted by m radicals from the group consisting of fluorine and CO2Re.
In particular, Y is selected from the group consisting of Z, or (C1-C12)-alkyl, and (C3-C8)-cycloalkyl, each substituted by m radicals from the group consisting of fluorine, (C1-C2)-alkoxy, CO2Re, and CONRbRh.
According to one preferred embodiment, Y is Z.
Preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings, except phenyl, which are formed from r carbon atoms and n oxygen atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, S(O)nRa, SO2NRbRd, SO2NRbCORe, CORb, CONReSO2Ra, NRbRe, NRbCORe, NRbCONReRe, NRbCO2Re, NRbSO2Re, NRbSO2NRbRe, OCONRbRe, OCSNRbRe, PORfRf and C(Rb)═NORe, Rb, Rc, Re and Rf, and where carbon atoms bear n oxo groups.
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings, except phenyl, which are formed from r carbon atoms and n oxygen atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf, and where carbon atoms bear n oxo groups.
Further preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings, except phenyl, which are formed from r carbon atoms, n nitrogen atoms, n sulfur atoms and n oxygen atoms, and which are substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf, and where the sulfur atoms and carbon atoms bear n oxo groups.
Further preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings, except phenyl, which are formed from r carbon atoms, n nitrogen atoms, n sulfur atoms and n oxygen atoms, and which are substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf, and where the sulfur atoms and carbon atoms bear n oxo groups.
Representative examples for the three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings mentioned above, are the following structures:
Representative examples for the four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic rings mentioned above, are the following structures:
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of four- or five-membered saturated or partly unsaturated rings, which are formed from r carbon atoms and n oxygen atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf.
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of four- or five-membered saturated or partly unsaturated rings, which are formed from r carbon atoms and n oxygen atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf.
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of five-membered saturated or partly unsaturated rings, which are formed from 4 carbon atoms and 1 oxygen atom, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf.
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of five-membered saturated or partly unsaturated rings, which are formed from 4 carbon atoms and 1 oxygen atom, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf.
Representative examples for the five-membered saturated or partly unsaturated rings, which are formed from 4 carbon atoms and 1 oxygen atom, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents:
Preferred examples for the five-membered saturated or partly unsaturated rings, which are formed from 4 carbon atoms and 1 oxygen atom, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents, preferably to CO2Re:
Preferred examples for the five-membered saturated or partly unsaturated rings, which are formed from 4 carbon atoms and 1 oxygen atom, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents, preferably to CO2Re:
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of five-membered saturated or partly unsaturated rings, which are formed from 5 carbon atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf.
Also preferred compounds according to the invention are compounds of formula (I), wherein Z is selected from the group consisting of five-membered saturated or partly unsaturated rings, which are formed from 5 carbon atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf.
Representative examples for the five-membered saturated or partly unsaturated rings, which are formed from 5 carbon atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents:
Preferred examples for the five-membered saturated or partly unsaturated rings, which are formed from 5 carbon atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents, preferably to CO2Re:
Preferred examples for the five-membered saturated or partly unsaturated rings, which are formed from 5 carbon atoms, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf mentioned above, are the following structures, the arrow indicating the bond to any of the mentioned substituents, preferably to CO2Re:
In particular, Z is selected from the group consisting of cyclobutyl, cyclopentyl, cyclopentenyl, and tetrahydrofuranyl, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf.
Very particular, Z is selected from the group consisting of cyclobutyl, cyclopentyl, cyclopentenyl, and tetrahydrofuranyl, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, Rb, Rc, Re and Rf.
Preferred examples Z.1 to Z.5, each substituted by m radicals from the group consisting of CO2Re, CONRbRh, CONReSO2Ra, Rb, Rc, Re and Rf mentioned above, are the following structures, arrow (1), representing the binding site to X, arrows (2) and (3) indicating the bond to any of the mentioned substituents, in particular to CO2Re, CONRbRh, Rb, Rc, Re and Rf:
Preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred compounds of the present invention are compounds of formula (I), wherein the substituents have the following meanings:
Further preferred embodiments (I.I to I.IV) of compounds of formula (I) are compounds, wherein (I.I): R1, R9 is hydrogen:
(I.II): R1 is hydrogen, R9 is methyl:
(I.III): R1 is methyl, R9 is methyl:
(I.IV): R1 is methyl, R9 is hydrogen:
Compounds of formula (I.I.a,) wherein wherein R1, R2, R6 and R9 are hydrogen are particularly preferred:
Compounds of formula (I.I.b,) wherein wherein R1, R2, R4, R6 and R9 are hydrogen are also particularly preferred:
Compounds of formula (I.I.c,) wherein wherein R1, R2, R6 and R9 are hydrogen, X is a bond (X0) , and Y is Z are particularly preferred:
Compounds of formula (I.I.d,) wherein wherein R1, R2, R4, R6 and R9 are hydrogen, X is a bond (X0), and Y is Z are also particularly preferred:
Compounds of formula (I.II.a,) wherein wherein R1, R2, R6 are hydrogen and R9 is methyl are also particularly preferred:
Compounds of formula (I.II.b,) wherein wherein R1, R2, R4, R6 are hydrogen and R9 is methyl are also particularly preferred: and R9
Compounds of formula (I.III.a,) wherein wherein R2, R6 are hydrogen and R1, R9 are methyl are also particularly preferred:
Compounds of formula (I.III.b,) wherein wherein R2, R4, R6 are hydrogen and R1, R9 are methyl are also particularly preferred:
Compounds of formula (I.IV.a,) wherein wherein R1 is methyl and R2, R6 and R9 are hydrogen are also particularly preferred:
Compounds of formula (I.IV.b,) wherein wherein R1 is methyl and R2, R4, R6 and R9 are hydrogen are also particularly preferred:
In the context of the present invention, compounds wherein R1, R2, R6 and R9 are hydrogen and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 below, are particularly preferred.
Compounds of formula I.1., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.1.1-I.1.1152, are particularly preferred:
Compounds of formula I.2., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.2.1-I.2.1152, are particularly preferred:
Compounds of formula I.3., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.3.1-I.3.1152, are particularly preferred:
Compounds of formula I.4., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.4.1-I.4.1152, are particularly preferred:
Compounds of formula I.5., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.5.1-I.5.1152, are particularly preferred:
Compounds of formula I.6., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.6.1-I.6.1152, are particularly preferred:
Compounds of formula I.7., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.7.1-I.7.1152, are particularly preferred:
Compounds of formula I.8., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.8.1-I.8.1152, are particularly preferred:
Compounds of formula I.9., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.9.1-I.9.1152, are particularly preferred:
Compounds of formula I.10., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.10.1-I.10.1152, are particularly preferred:
Compounds of formula I.11., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.11.1-I.11.1152, are particularly preferred:
Compounds of formula I.12., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.12.1-I.12.1152, are particularly preferred:
Compounds of formula I.13., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.13.1-I.13.1152, are particularly preferred:
Compounds of formula I.14., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.14.1-I.14.1152, are particularly preferred:
Compounds of formula I.15., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.15.1-I.15.1152, are particularly preferred:
Compounds of formula I.16., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.16.1-I.16.1152, are particularly preferred:
Compounds of formula I.17., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.17.1-I.17.1152, are particularly preferred:
Compounds of formula I.18., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.18.1-I.18.1152, are particularly preferred:
Compounds of formula I.19., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.19.1-I.19.1152, are particularly preferred:
Compounds of formula I.20., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.20.1-I.20.1152, are particularly preferred:
Compounds of formula I.21., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.21.1-I.21.1152, are particularly preferred:
Compounds of formula I.22., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.22.1-I.22.1152, are particularly preferred:
Compounds of formula I.23., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.23.1-I.23.1152, are particularly preferred:
Compounds of formula I.24., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.24.1-I.24.1152, are particularly preferred:
Compounds of formula I.25., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.25.1-I.25.1152, are particularly preferred:
Compounds of formula I.26., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.26.1-I.26.1152, are particularly preferred:
Compounds of formula I.27., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.27.1-I.27.1152, are particularly preferred:
Compounds of formula I.28., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.28.1-I.28.1152, are particularly preferred:
Compounds of formula I.29., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.29.1-I.29.1152, are particularly preferred:
Compounds of formula I.30., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.30.1-I.30.1152, are particularly preferred:
Compounds of formula I.31., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.31.1-I.31.1152, are particularly preferred:
Compounds of formula I.32., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.32.1-I.32.1152, are particularly preferred:
Compounds of formula I.33., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.33.1-I.33.1152, are particularly preferred:
Compounds of formula I.34., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.34.1-I.34.1152, are particularly preferred:
Compounds of formula I.35., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.35.1-I.35.1152, are particularly preferred:
Compounds of formula I.36., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.36.1-I.36.1152, are particularly preferred:
Compounds of formula I.37., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.37.1-I.37.1152, are particularly preferred:
Compounds of formula I.38., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.38.1-I.38.1152, are particularly preferred:
Compounds of formula I.39., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.39.1-I.39.1152, are particularly preferred:
Compounds of formula I.40., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.40.1-I.40.1152, are particularly preferred:
Compounds of formula I.41., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.41.1-I.41.1152, are particularly preferred:
Compounds of formula I.42., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.42.1-I.42.1152, are particularly preferred:
Compounds of formula I.43., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.43.1-I.43.1152, are particularly preferred:
Compounds of formula I.44., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.44.1-I.44.1152, are particularly preferred:
Compounds of formula I.45., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.45.1-I.45.1152, are particularly preferred:
Compounds of formula I.46., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.46.1-I.46.1152, are particularly preferred:
Compounds of formula I.47., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.47.1-I.47.1152, are particularly preferred:
Compounds of formula I.48., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.48.1-I.48.1152, are particularly preferred:
Compounds of formula I.49., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.49.1-I.49.1152, are particularly preferred:
Compounds of formula I.50., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.50.1-I.50.1152, are particularly preferred:
Compounds of formula I.51., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.51.1-I.51.1152, are particularly preferred:
Compounds of formula I.52., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.52.1-I.52.1152, are particularly preferred:
Compounds of formula I.53., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.53.1-I.53.1152, are particularly preferred:
Compounds of formula I.54., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.54.1-I.54.1152, are particularly preferred:
Compounds of formula I.55., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.55.1-I.55.1152, are particularly preferred:
Compounds of formula I.56., wherein wherein R1, R2, R6 and R9 are hydrogen, and R3, R4, R5 and R7, R8 have the meanings as defined lines in 1 to 1152 of Table 1 above, i.e. individual compounds I.56.1-I.56.1152, are particularly preferred:
The compounds of formula (I) according to the invention can be prepared by standard processes of organic chemistry, for example by the following processes:
The compounds of formula (I) can be prepared according to methods or in analogy to methods that are described in the prior art. The synthesis takes advantage of starting materials that are commercially available or may be prepared according to conventional procedures starting from readily available compounds.
Compounds of the formula (I) can be prepared from the carboxylic acids (III) and commercially available amines (II) using an organic base and a coupling reagent. Thus, compounds of formula (I) can be synthesized from the corresponding carboxylic acids (1 eq.) using a coupling reagent (1-2 eq.), for example T3P (propanephosphonic acid anhydride) or HATU (O-(7-azabenzotriazole-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluorphosphate), an organic base (1-3 eq.) and the amines (II) (1-3 eq.). The reaction is typically carried out in an organic solvent. Preferably an aprotic organic solvent is used. Most preferably tetrahydrofuran (THF), N,N-dimethylformamide (DMF) or acetonitrile (ACN) are used. The reaction is carried out at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Preferably the organic base is triethylamine or N,N-diisopropylethylamine.
The carboxylic acids (III) are commercially available or can be prepared from the corresponding esters (IV) (wherein RP is alkyl or benzyl). If RP is alkyl, esters (IV) may be cleaved using aqueous alkali metal hydroxides. Preferably lithium hydroxide, sodium hydroxide or potassium hydroxide (1-2 eq.) are employed. The reaction is typically carried out in mixtures of water and an organic solvent. Preferably the organic solvent is THF, methanol or acetonitrile. The reaction is carried out at temperatures between 0° C. and 100° C. Preferably the reaction is carried at room temperature. If RP is benzyl in (IV), then the ester may be cleaved using palladium on charcoal (0.001-1 eq.) as catalyst and hydrogen gas at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Typically, an organic solvent is employed. Preferably THF, methanol or ethanol are employed.
Compounds of the formula (IV) can be prepared from the carboxylic acids (VI) and commercially available amines (V) using a base and a coupling reagent. Thus, compounds of formula (IV) can be synthesized from the corresponding carboxylic acids (1 eq.) using a coupling reagent (1-2 eq.), for example T3P (propanephosphonic acid anhydride) or HATU (O-(7-azabenzotriazole-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluorphosphate), an organic base (1-3 eq.) and the amines (V) (1-3 eq.). The reaction is typically carried out in an organic solvent. Preferably an aprotic organic solvent is used. Most preferably tetrahydrofuran (THF), N,N-dimethylformamide (DMF) or acetonitrile (ACN) are used. The reaction is carried out at temperatures between 0° C. to refluxing temperatures. Preferably the reaction is carried out at room temperature. Preferably the organic base is triethylamine or N,N-diisopropylethylamine.
Carboxylic acid (VI) may be prepared from the corresponding diester by selective cleavage of one ester group. If Rq is an alkyl ester, selective ester cleavage may be achieved using an aqueous base. Preferably an alkali metal hydroxide is used. Most preferably lithium hydroxide, sodium hydroxide or potassium hydroxide are used. The reaction is typically carried out in mixtures of water and an organic solvent. Preferably THF, methanol or acetonitrile are employed. The reaction is carried out at temperatures between 0° C. and 100° C., preferably at room temperature.
Alternatively, trimethyltin hydroxide (e.g. 1 eq.) in 1,2-dichlorethane at room temperature to reflux may be used (as described in Angew. Chem. Int. Ed, 2005, 44: 1378-1382), preferably at reflux. If Rq is benzyl in (VII), then the ester may be cleaved using palladium on charcoal (0.001-1eq.) as catalyst and hydrogen gas at temperatures between 0° C. and reflux. Preferably the reaction is carried out at room temperature. Typically, an organic solvent is employed. Preferably THF, methanol or ethanol are employed.
The diesters (VII) are either commercially available or may be prepared from the corresponding diazo-compounds (VIII) using dirhodiumtetraacetat ([Rh(OAc)2]2) (0.001-0.1 eq.) and the alcohol HO—R7, yielding alkoxy malonates (VII) (R8═H). The reaction is typically carried out in an organic solvent, preferably in toluene at temperatures between 0° to 100° C. Preferably the reaction is done at 60° C. as described in Angew. Chem. Int. Ed. 2014, 53, 14230-14234. Diazo compounds (VIII), if not commercially available, may be prepared as described in Angew. Chem. Int. Ed. 2014, 53, 14230-14234.
Alternatively, diesters (VII), may be synthesized from a commercially available monoester (XI), a base and a chloroformate (XII) (1-3 eq.) as described in Bioorganic & Medicinal Chemistry Letters, 12(11), 1501-1505; 2002. The reaction is typically carried out in an organic solvent, preferably in tetrahydrofuran. Suitable temperatures range between −78° C. and 25° C. Preferably the reaction is allowed to warm from −78° C. to 25° C. over a period of 16 h. Preferably lithiumdiisopropylamide (1 eq.) is used as a base.
Alternatively diesters (VII), wherein R8 is fluorine, can be prepared from the corresponding non-fluorinated malonates using 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) (Selectfluor) as described in WO12/129384. Water and/or an organic solvent are used. Preferably the reaction is carried out in acetonitrile. The reaction is carried out at a temperature between 0° C. and reflux temperature, preferably at 60° C. using 1 to 4 equivalents of 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) (Selectfluor). Alternatively, N-Fluorobenzenesulfonimide (CAS 133745-75-2) may be employed (see for example Differding, E., & Ofner, H. (1991). N-Fluorobenzenesulfonimide: A practical reagent for electrophilic fluorinations. Synlett, 1991(03)) 187-189).
Amines of the formula (XIII) can be prepared from the lactames (XIV), which are either commercially available or may be prepared by alkylation as described in Org. Process Res. Dev. 2018, 22, 337-343, and commercially available alcohols (XV) using thionyl chloride (2eq.) as described in Tetrahedron Lett. 2001, 42, 1347-1350. The reaction is typically carried out in the coupling alcohols (XV) as the solvent. The reaction is carried out at temperatures between 0° C. to refluxing temperatures. Preferably the reaction is carried out at room temperature.
To widen the spectrum of action, the compounds of formula (I) may be mixed with many representatives of other herbicidal or growth-regulating active ingredient groups and then applied concomitantly. Suitable components for combinations are, for example, herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.
It may furthermore be beneficial to apply the compounds of formula (I) alone or in combination with other herbicides, or else in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Other additives such as non-phytotoxic oils and oil concentrates may also be added.
In one embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) (compound A or component A) and at least one further active compound selected from herbicides B (compound B), preferably herbicides B of class b1) to b15), and safeners C (compound C).
In another embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) and at least one further active compound B (herbicide B).
Examples of herbicides B which can be used in combination with the compounds A of formula (I) according to the present invention are:
b1) From the Group of the Lipid Biosynthesis Inhibitors:
ACC-herbicides such as alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-72-6); 4-(2′,4′-Dichloro-4-cyclopropyl[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312337-51-1); 4-(2′,4′-Dichloro -4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester; 4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1312340-83-2); 4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-ylcarbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicides such as benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
b2) From the Group of the ALS Inhibitors:
sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron,
imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam,
pyrimidinylbenzoates such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1-methylethyl ester (CAS 420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01-8),
sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; and triafamone;
among these, a preferred embodiment of the invention relates to those compositions comprising at least one imidazolinone herbicide;
b3) From the Group of the Photosynthesis Inhibitors:
amicarbazone, inhibitors of the photosystem II, e.g. 1-(6-tert-butylpyrimidin-4-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1654744-66-7), 1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1637455-12-9), 1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (CAS 1637453-94-1), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (CAS 1654057-29-0), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one (CAS 1654747-80-4), 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; (CAS 2023785-78-4), 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 2023785-79-5), 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1701416-69-4), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1708087-22-2), 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one (CAS 2023785-80-8), 1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one (CAS 1844836-64-1), triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate. Among these, a preferred embodiment of the invention relates to those compositions comprising at least one aryl urea herbicide. Among these, likewise a preferred embodiment of the invention relates to those compositions comprising at least one triazine herbicide. Among these, likewise a preferred embodiment of the invention relates to those compositions comprising at least one nitrile herbicide;
b4) From the Group of the Protoporphyrinogen-IX Oxidase Inhibitors:
acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (CAS 1300118-96-0), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione (CAS 1304113-05-0), methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate (CAS 948893-00-3), and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754-02-4), 2-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-fluorophenoxy]-2-methoxy-acetic acid methyl ester (CAS 1970221-16-9), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester (CAS 2158274-96-3), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]acetic acid ethyl ester (CAS 158274-50-9), methyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2271389-22-9), ethyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2230679-62-4), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester (CAS 2158275-73-9), 2-[[3[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy] acetic acid ethyl ester (CAS 2158274-56-5), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide (CAS 2158274-53-2), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide (CAS 2158276-22-1);
b5) From the Group of the Bleacher Herbicides:
PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione (CAS 1486617-21-3), pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bleacher, unknown target: aclonifen, amitrole flumeturon 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifl uoromethyl)benzamide (CAS 1361139-71-0), bixlozone and 2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS 81778-66-7);
b6) From the Group of the EPSP Synthase Inhibitors:
glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);
b7) From the Group of the Glutamine Synthase Inhibitors:
bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;
b8) From the Group of the DHP Synthase Inhibitors:
asulam;
b9) From the Group of the Mitosis Inhibitors:
compounds of group K1: dinitroanilines such as benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin, phosphoramidates such as amiprophos, amiprophos-methyl, and butamiphos, benzoic acid herbicides such as chlorthal, chlorthal-dimethyl, pyridines such as dithiopyr and thiazopyr, benzamides such as propyzamide and tebutam; compounds of group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham; among these, compounds of group K1, in particular dinitroanilines are preferred;
b10) From the Group of the VLCFA Inhibitors:
chloroacetamides such as acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetanilides such as flufenacet and mefenacet, acetanilides such as diphenamid, naproanilide, napropamide and napropamide-M, tetrazolinones such fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone and isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
b11) From the Group of the Cellulose Biosynthesis Inhibitors:
chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and 1-cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine (CAS 175899-01-1);
b12) From the Group of the Decoupler Herbicides:
dinoseb, dinoterb and DNOC and its salts;
b13) From the Group of the Auxinic Herbicides:
2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters (CAS 943832-60-8); MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9) and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid (CAS 1629965-65-6);
b14) From the Group of the Auxin Transport Inhibitors: Diflufenzopyr, Diflufenzopyr-Sodium, Naptalam and Naptalam-Sodium;
b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine tetflupyrolimet, and tridiphane.
Moreover, it may be useful to apply the compounds of formula (I) in combination with safeners. Safeners are chemical compounds which prevent or reduce damage on useful plants without having a major impact on the herbicidal action of the compounds of the formula (I) towards undesired vegetation. They can be applied either before sowings (e.g. on seed treatments, shoots or seedlings) or in the pre-emergence application or post-emergence application of the useful plant. The safeners and the compounds of formula (I) and optionally the herbicides B can be applied simultaneously or in succession.
In another embodiment of the present invention the combinations according to the present invention comprise at least one compound of formula (I) and at least one safener C (component C).
Examples of safeners are e.g. (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acids, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.
Examples of safener compounds C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4), metcamifen and BPCMS (CAS 54091-06-4).
The active compounds B of groups b1) to b15) and the active compounds C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); Farm Chemicals Handbook 2000 volume 86, Meister Publishing Company, 2000; B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart 1995; W. H. Ahrens, Herbicide Handbook, 7th edition, Weed Science Society of America, 1994; and K. K. Hatzios, Herbicide Handbook, Supplement for the 7th edition, Weed Science Society of America, 1998. 2,2,5-Trimethyl-3-(dichloroacetyl)-1,3-oxazolidine [CAS No. 52836-31-4] is also referred to as R-29148. 4-(Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane [CAS No. 71526-07-3] is also referred to as AD-67 and MON 4660.
The assignment of the active compounds to the respective mechanisms of action is based on current knowledge. If several mechanisms of action apply to one active compound, this substance was only assigned to one mechanism of action.
The invention also relates to formulations comprising at least an auxiliary and at least one compound of formula (I) according to the invention.
A formulation comprises a pesticidally effective amount of a compound of formula (I). The term “effective amount” denotes an amount of the combination or of the compound of formula (I), which is sufficient for controlling undesired vegetation, especially for controlling undesired vegetation in crops (i.e. cultivated plants) and which does not result in a substantial damage to the treated crop plants. Such an amount can vary in a broad range and is dependent on various factors, such as the undesired vegetation to be controlled, the treated crop plants or material, the climatic conditions and the specific compound of formula (I) used.
The compounds of formula (I), their salts, amides, esters or thioesters can be converted into customary types of formulations, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further formulation types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for formulation types and their preparation are:
i) Water-Soluble Concentrates (SL, LS)
10-60 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention and 5-15 wt % wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upon dilution with water.
ii) Dispersible Concentrates (DC)
5-25 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention and 1-10 wt % dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.
iii) Emulsifiable Concentrates (EC)
15-70 wt % of compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention and 5-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt % of compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention and 1-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt % by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type formulation up to 40 wt % binder (e.g. polyvinylalcohol) is added.
vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)
50-80 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C)according to the invention are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)
50-80 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are ground in a rotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are comminuted with addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) and water ad 100 wt % to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
iv) Microemulsion (ME)
5-20 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are added to 5-30 wt % organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
iv) Microcapsules (CS)
An oil phase comprising 5-50 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt % of a compound of formula (I) according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt %. The wt % relate to the total CS formulation.
ix) Dustable Powders (DP, DS)
1-10 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt %.
x) Granules (GR, FG)
0.5-30 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xi) Ultra-Low Volume Liquids (UL)
1-50 wt % of a compound of formula (I) or a combination comprising at least one compound of formula (I) (component A) and at least one further compound selected from the herbicidal compounds B (component B) and safeners C (component C) according to the invention are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.
The formulation types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.
The formulations and/or combinations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of the compounds of formula (I).
The compounds of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The formulations in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. (nach unten verschoben)
Methods for applying compounds of formula (I), formulations and/or combinations thereof, on to plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compounds of formula (I), formulations and/or combinations thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
Various types of oils, wetting agents, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the compounds of formula (I), the formulations and/or the combinations comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
The user applies the compounds of formula (I) according to the invention, the formulations and/or the combinations comprising them usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the formulation is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the formulation according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and optionally active substances from the groups B and/or C), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, individual components of the formulation according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the formulation according to the invention or partially premixed components, e. g components comprising compounds of formula (I) and optionally active substances from the groups B and/or C), can be applied jointly (e.g. after tank mix) or consecutively.
The compounds of formula (I), are suitable as herbicides. They are suitable as such, as an appropriate formulation or in combination with at least one further compound selected from the herbicidal active compounds B (component B) and safeners C (component C).
The compounds of formula (I), or the formulations and/or combinations comprising the compounds of formula (I), control undesired vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
The compounds of formula (I), or the formulations and/or the combinations comprising them, are applied to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha). The compounds of formula (I), or the formulations and/or the combinations comprising them, may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.
Application of the compounds of formula (I), or the formulations and/or the combinations comprising them, can be done before, during and/or after, preferably during and/or after, the emergence of the undesired vegetation.
Application of the compounds of formula (I), or the formulations and/or the combinations can be carried out before or during sowing.
The compounds of formula (I), or the formulations and/or the combinations comprising them, can be applied pre-, post-emergence or pre-plant, or together with the seed of a crop plant. It is also possible to apply the compounds of formula (I), or the formulations and/or the combinations comprising them, by applying seed, pretreated with the compounds of formula (I), or the formulations and/or the combinations comprising them, of a crop plant. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the combinations are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesired vegetation growing underneath, or the bare soil surface (post-directed, lay-by).
In a further embodiment, the compounds of formula (I), or the formulations and/or the combinations comprising them, can be applied by treating seed. The treatment of seeds comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of formula (I), or the formulations and/or the combinations prepared therefrom. Here, the combinations can be applied diluted or undiluted.
The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the crop plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
When employed in plant protection, the amounts of active substances applied, i.e. the compounds of formula (I), component B and, if appropriate, component C without formulation auxiliaries, are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha and in particular from 0.1 to 0.75 kg per ha.
In another embodiment of the invention, the application rate of the compounds of formula (I), component B and, if appropriate, component C, is from 0.001 to 3 kg/ha, preferably from 0.005 to 2.5 kg/ha and in particular from 0.01 to 2 kg/ha of active substance (a.s.).
In another preferred embodiment of the invention, the rates of application of the compounds of formula (I) according to the present invention (total amount of compounds of formula (I)) are from 0.1 g/ha to 3000 g/ha, preferably 10 g/ha to 1000 g/ha, depending on the control target, the season, the target plants and the growth stage.
In another preferred embodiment of the invention, the application rates of the compounds of formula (I) are in the range from 0.1 g/ha to 5000 g/ha and preferably in the range from 1 g/ha to 2500 g/ha or from 5 g/ha to 2000 g/ha.
In another preferred embodiment of the invention, the application rate of the compounds of formula (I) is 0.1 to 1000 g/ha, preferably 1 to 750 g/ha, more preferably 5 to 500 g/ha.
The required application rates of herbicidal compounds B are generally in the range of from 0.0005 kg/ha to 2.5 kg/ha and preferably in the range of from 0.005 kg/ha to 2 kg/ha or 0.01 kg/ha to 1.5 kg/h of a.s.
The required application rates of safeners C are generally in the range of from 0.0005 kg/ha to 2.5 kg/ha and preferably in the range of from 0.005 kg/ha to 2 kg/ha or 0.01 kg/ha to 1.5 kg/h of a.s.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
In another embodiment of the invention, to treat the seed, the amounts of active substances applied, i.e. the compounds of formula (I), component B and, if appropriate, component C are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
In case of combinations according to the present invention it is immaterial whether the compounds of formula (I), and the further component B and/or the component C are formulated and applied jointly or separately.
In the case of separate application, it is of minor importance, in which order the application takes place. It is only necessary, that the compounds of formula (I), and the further component B and/or the component C are applied in a time frame that allows simultaneous action of the active ingredients on the plants, preferably within a time-frame of at most 14 days, in particular at most 7 days.
Depending on the application method in question, the compounds of formula (I), or the formulations and/or combinations comprising them, can additionally be employed in a further number of crop plants for eliminating undesired vegetation. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Preferred crops are Arachis hypogaea, Beta vulgaris spec. altissima, Brassica napus var. napus, Brassica oleracea, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Medicago sativa, Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus dulcis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Especially preferred crops are crops of cereals, corn, soybeans, rice, oilseed rape, cotton, potatoes, peanuts or permanent crops.
The compounds of formula (I) according to the invention, or the formulations and/or combinations comprising them, can also be used in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
The term “crops” as used herein includes also (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.
Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-Ø1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTØH2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinII. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
Crops comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-ØØ41Ø-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and WO2017/011288.
The use of the compounds of formula (I) or formulations or combinations comprising them according to the invention on crops may result in effects which are specific to a crop comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigor, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of ingredients or new ingredients, specifically to improve raw material production, e.g., potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
Furthermore, it has been found that the compounds of formula (I) according to the invention, or the formulations and/or combinations comprising them, are also suitable for the defoliation and/or desiccation of plant parts of crops such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton. In this regard, formulations and/or combinations for the desiccation and/or defoliation of crops, processes for preparing these formulations and/or combinations and methods for desiccating and/or defoliating plants using the compounds of formula (I) have been found.
As desiccants, the compounds of formula (I) are particularly suitable for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.
Also of economic interest is to facilitate harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pernicious fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the controlled defoliation of useful plants, in particular cotton.
Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.
Chemical bonds, drawn as bars in chemical formulae (see e.g. Cpds I40, I60 below), indicate the relative stereochemistry on the ring system.
Triethylamine (24.24 g, 240 mmol) was added dropwise to a solution of O1-benzyl O3-tert-butyl propanedioate (1) (30 g, 120 mmol) and tosyl azide (26 g, 132 mmol) in acetonitrile (300 mL) at 10° C. The mixture was stirred at 20° C. for 48 h. The mixture was concentrated and purified with silica gel chromatography (petroleum ether:ethyl acetate=5:1) to give O1-benzyl O3-tert-butyl-2-diazo propanedioate (2) (25 g, 75% yield) as yellow oil. 1H NMR: (400 MHz, CDCl3) δ 7.40-7.34 (m, 5H), 5.27 (s, 2H), 1.52 (s, 9H).
Dirhodiumtetraacetat ([Rh(OAc)2]2) (143 mg) was added to a solution of O1-benzyl O3-tert-butyl-2-diazo propanedioate (2) (20 g, 72.46 mmol), methanol (14 mL) in toluene (300 mL) at 15° C. The mixture was stirred for 16 h at 60° C. The mixture was filtered and the filtrate was concentrated, purified by silica gel chromatography eluted with (petroleum ether:tert-butyl methyl ether=5:1) to give O1-benzyl O3-tert-butyl 2-methoxypropanedioate (3) (19 g, 93% yield) as yellow oil. 1H NMR: (400 MHz, CDCl3) δ=7.43-7.30 (m, 5H), 5.32-5.20 (m, 2H), 4.33 (s, 1H), 3.55-3.46 (m, 3H), 1.39 (s, 9H).
To a solution of O1-benzyl O3-tert-butyl 2-methoxypropanedioate (3) (19 g, 67.85 mmol) in dichloromethane (150 mL) was added trifluoroacetic acid (TFA), (30 mL). The mixture was stirred for 6 h at 20° C. The mixture was added to water and extracted with dichloromethane, the organic layers were washed with water, brine, dried, concentrated to give compound 3-benzyloxy-2-methoxy-3-oxo-propanoic acid (4) (11.5 g, 75% yield) as yellow oil. 1H NMR: (400 MHz, CDCl3) δ=10.40 (br s, 1H), 7.43-7.30 (m, 5H), 5.28 (s, 2H), 4.51 (s, 1H), 3.53 (s, 3H).
1-Propanephosphonic anhydride solution (T3P) (22.7 g, 35.71 mmol, 50% in ethyl acetate) was added to a solution of 3-benzyloxy-2-methoxy-3-oxo-propanoic acid (4) (4 g, 17.86 mmol) and 3,5-dichloro aniline (5) (3.45 g, 21.4 mmol) in acetonitrile (100 mL). The mixture was stirred at 70° C. for 16 h. The mixture was poured into ice water and extracted with ethyl acetate. The organic layers were washed with brine, dried, concentrated, purified by column chromatograph on silica gel eluted with (petroleum ether:tert-butyl methyl ether=5:1) to give benzyl 3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoate 6 (5.5 g, 81% yield) as yellow oil. 1H NMR: (400 MHz, CDCl3) δ 8.33 (br s, 1H), 7.53 (d, J=1.8 Hz, 2H), 7.42-7.34 (m, 5H), 7.14 (t, J=1.8 Hz, 1H), 5.29 (s, 2H), 4.47 (s, 1H), 3.54 (s, 3H).
Palladium on Carbon (Pd/C) (1 g, 10%) was added to a solution of benzyl 3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoate (6) (5.5 g, 14.98 mmol) in tetrahydrofuran (100 mL). The mixture was stirred for 2 h at 10° C. under hydrogen gas H2 (15 psi). The mixture was filtered over Celite pad; the filtrate was concentrated to give 3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoic acid (Inter A) (3.5 g, 84% yield) as a yellow solid. 1H NMR: (400 MHz, CD3OD) δ 7.69 (d, J=1.9 Hz, 2H), 7.18 (t, J=1.8 Hz, 1H), 4.48 (s, 1H), 3.53 (s, 3H).
Synthesis was carried out in analogy to Walker, Daniel P. et al Synthesis, (7), 1113-1119, 2011.
To a solution of methyl 4-bromofuran-2-carboxylate (1) CAS 58235-80-6 (6 g, 29.27 mmol) in toluene (60 mL) was added tert-butyl carbamate (BocNH2) (4.1 g, 35.12 mmol), potassium carbonate (10.1 g, 73.14 mmol), Cul (1.67 g, 8.78 mmol) and (CH3NHCH2)2 (1.54 g, 17.56 mmol) at 15° C. Then, the mixture was stirred at 130° C. under N2 for 16 h. The mixture was diluted with water (150 mL), filtered and extracted with ethyl acetate (100 mL), the organic layers were washed with brine, dried, concentrated and purified by silica gel chromatography (petroleum ether:ethyl acetate=10:1) to give methyl 4-(tert-butoxycarbonylamino)furan-2-carboxylate (1.75 g) as white solid.
To a solution of dry Rhodium on Carbon (Rh/C) (2.5 g, cat.) in methanol (500 mL) was added methyl 4-(tert-butoxycarbonylamino)furan-2-carboxylate (2) (5 g, 20.66 mmol) at 15° C. Then the mixture was stirred at 30° C. under hydrogen gas (H2) (50 psi) for 16 h. The mixture was filtered and concentrated to give cis-4-(tert-butoxycarbonylamino)tetrahydrofuran-2-carboxylate (3) (3 g, 60% yield) as white solid which was used without further purification in the next step.
To a mixture cis-4-(tert-butoxycarbonylamino)tetrahydrofuran-2-carboxylate (3) (4.2 g, 17.15 mmol) in dichloromethane (140 mL) was added HCl in ethylacetate (140 ml, 1M) at 15° C. and stirred at 25° C. for 4 h. The mixture was concentrated to give methyl cis-4-aminotetrahydrofuran-2-carboxylate Inter B (3 g, crude) as white solid (HCl-salt). 1H NMR: (400 MHz, D2O) δ 4.62 (dd, J=8.9, 6.9 Hz, 1H), 4.15-4.00 (m, 3H), 3.79 (s, 3H), 2.88-2.78 (m, 1H), 2.19-2.11 (m,1H).
To a mixture of Inter A (718 mg, 2.09 mmol) in acetotnitrile (15 mL) was added Inter B (467 mg, 2.59 mmol), 1-propanephosphonic anhydride solution (T3P) (2.47 g, 3.885 mmol) in ethyl acetate and diisopropylethylamine (1.85 mL, 17.36 mmol) at 25° C. and stirred at 75° C. for 2 h under N2. The mixture was poured into water, extracted with ethyl acetate, washed with brine, dried over by sodium sulfate, concentrated and purified by prep-H PLC (acetonitrile/water with trifluoroacetic acid) to give the desired methyl cis-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]tetrahydrofuran-2-carboxylate (Cpd. I.40) (170 mg, 16.% yield) as a white solid. 1H NMR: (400 MHz, CDCl3) δ 8.86-8.95 (m, 1H) 7.49-7.60 (m, 3H) 7.13 (d, J=1.76 Hz, 1H), 4.52-4.73 (m, 2H), 4.26 (d, J=3.51 Hz, 1H), 3.94-4.08 (m, 2H) 3.80 (d, J=17.82 Hz, 3H), 3.67 (d, J=3.01 Hz, 3H), 2.50-2.61 (m, 1H), 2.09 (dt, J=7.09, 3.73 Hz, 1H).
To a mixture of methyl cis-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]tetrahydrofuran-2-carboxylate (2.7 g, 6.9 mmol) in tetrahydrofuran (32.4 mL) was added LiOH (1.16 g, 27.7 mmol) in water (10.8 mL) at 25° C. and stirred at 25° C. for 2 h. The mixture was poured into water, extracted with ethyl acetate, washed with brine, dried over sodium sulfate, concentrated and purified by prep-HPLC (trifluoroacetic acid 0.1%, acetonitrile-water) to give cis-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]tetrahydrofuran-2-carboxylate (Cpd. I.60) (1.3 g, 48.3% yield) as white solid. 1H NMR: (400 MHz, DMSO-d6) δ 10.34 (d, J=5.26 Hz, 1H), 8.30 (dd, J=16.22, 7.02 Hz, 1H), 7.78 (t, J=1.75 Hz, 2H), 7.32 (t, J=1.75 Hz, 1H), 4.27-4.41 (m, 3H) 3.90 (ddd, J=8.55, 6.36, 1.75 Hz, 1H), 3.64 (dt, J=8.66, 5.54 Hz, 1H), 3.37 (s, 3H), 1.93 (dtd, J=12.77, 6.22, 6.22, 2.85 Hz, 1H).
To a solution of dimethylmethoxy malonate (CAS 5018-30-4) (1) (7.6 g, 47 mmol) in dimethylformamide (50 mL) under argon was added sodium hydride (60%, 2.2 g) at 50° C. The resulting mixture was stirred at 50° C. for further 30 min until no more hydrogen gas evolved. After cooling down to room temperature, 1-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (selectfluor, CAS 140681-55-6) (25 g) was added. The resulting mixture was stirred over night at room temperature. The reaction was quenched with saturated aqueous ammonium chloride solution and extracted with ethyl acetate (3×100 mL). The organic phase was dried over sodium sulfate. The dried organic phase was filtered and concentrated under reduced pressure to afford the crude product dimethyl 2-fluoro-2-methoxy-propanedioate (2) (7.9 g, 93% yield). 1H NMR: (400 MHz, CDCl3) δ 3.89 (s, 6H), 3.58 (s, 3H).
To dimethyl 2-fluoro-2-methoxy-propanedioate (2) (7.9 g, 44 mmol) in tetrahydrofuran/water (1:1) was added lithium hydroxide (LiOH) (1.05 g, 44 mmol). The reaction mixture was stirred at room temperature overnight. Tetrahydrofuran was removed under reduced pressure. The resulting aqueous solution was extracted with tert-butyl methyl ether (2×100 mL) and the organic phases discarded. The aqueous layer was adjusted to pH 1 using concentrated hydrochloric acid, extracted with ethyl acetate (3×100 mL). The organic phases were dried over sodium sulfate. The dried organic phase was filtered and concentrated under reduced pressure to afford the crude product 2-fluoro-2,3-dimethoxy-3-oxo-propanoic acid (3) (5.3 g, 73% yield). 1H NMR: (400 MHz, CDCl3) δ 3.92 (s, 3H), 3.61 (s, 3H).
Amide bond formation was carried out as described above (example 1, compound 6). Yield 56% for methyl 3-(3,5-dichloroanilino)-2-fluoro-2-methoxy-3-oxo-propanoate (4). 1H NMR: (400 MHz, CDCl3) δ 8.26 (s,1H), 7.57 (s, 2H), 7.18 (s, 1H), 3.92 (s, 3H), 3.63 (s, 3H).
To methyl 3-(3,5-dichloroanilino)-2-fluoro-2-methoxy-3-oxo-propanoate (4) (3.8 g, 12 mmol) in 1,2-dichloroethane (100 mL) was added trimethyltin hydroxide (Me3SnOH) (4.4 g, 25 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 h, then the reaction mixture was extracted with saturated sodium bicarbonate solution in water (3×100 mL). The combined organic phases were adjusted to pH 1 using concentrated hydrogen chloride solution in water. The resulting mixture was extracted with ethyl acetate (3×100 mL). The organic phases were dried over sodium sulfate. The dried organic phase was filtered and concentrated under reduced pressure to afford the crude 3-(3,5-dichloroanilino)-2-fluoro-2-methoxy-3-oxo-propanoate (5) (1.2 g, 33% yield). LC-MS (M+H)+:295.8.
To a solution of the carboxylic acid (0.3 g) in dimethylformamide (DMF, 10 mL) the amine 6 (CAS 229613-83-6) was added. To the resulting solution was added HATU (0.42 g) and then diisopropylethylamine (0.53 mL). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (10 mL) and sat. aqueous bicarbonate solution (10 mL) The resulting mixture was extracted with ethyl acetate (3×50 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding methyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-fluoro-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene-1-carboxylate (0.2 g, 47%, 1.144) as a mixture of diastereoisomers (1:1). 1H NMR (500 MHz, Chloroform-d) δ 8.65 (s, 1H), 7.57 (d, J=1.8 Hz, 2H), 7.43-7.33 (m, 1H), 7.19-7.13 (m, 1H), 6.03-5.98 (m, 1H), 5.95-5.89 (m, 1H), 5.11-5.04 (m, 1H), 3.81-3.73 (m, 3H), 3.65-3.53 (m, 4H), 2.54-2.45 (m, 1H), 2.06-1.98 (m, 1H).
To a solution of (1R,4S)-2-azabicyclo[2.2.1]hept-5-en-3-one (CAS 79200-56-9) (20.0 g, 183 mmol) in tetrahydrofuran (50 mL) sodium hydride (8.8 g, 0.22 mol) was added at 0° C. After stirring for 30 minutes iodomethane (52 g, 0.37 mmol) was added at 0° C. and the mixture stirred overnight. After quenching with sat. ammonium chloride solution (50 mL), the aqueous phase was separated and extracted with ethyl acetate (3×50 mL). The combined extracts were washed with brine, dried over sodium sulfate and concentrated to give (1R,4S)-2-methyl-2-azabicyclo[2.2.1]hept-5-en-3-one (5.6 g, 25%) as a colorless oil.
To a solution of (1R,4S)-2-methyl-2-azabicyclo[2.2.1]hept-5-en-3-one (3.0 g, 24 mmol) in methanol (30 mL) thionyl chloride (3.5 mL, 49 mmol) were added at 0° C. After stirring for 3 h at room temperature, the mixture was concentrated to afford Inter C (2.6 g, 56%) as a colorless salt. 1H NMR (400 MHz, D2O) δ 6.29 (ddd, J=5.7, 2.5, 1.6 Hz, 1H), 6.03 (dt, J=5.7, 2.3 Hz, 1H), 4.37 (m, 1H), 3.81 (m, 1H), 3.75 (s, 3H), 2.70 (m, 4H), 2.16 (dt, J=14.7, 5.0 Hz, 1H).
To a solution of the carboxylic acid (1.0 g, 3.6 mmol) in dimethylformamide (DMF,10 mL) the amine Inter C (0.79 g, 4.1 mmol) was added. To the resulting solution was added HATU (1.57 g, 4.13 mmol) and then diisopropylethylamine (1.8 mL, 11 mmol). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (30 mL) and sat. aqueous bicarbonate solution (30 mL) The resulting mixture was extracted with ethyl acetate (3×50 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding methyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]-methyl-amino]cyclopent-2-ene-1-carboxylate (700 mg, 47%, 1.155) as a mixture of diastereoisomers (1:1). 1H NMR (400 MHz, Chloroform-d) δ 8.45 (m, 2H), 7.54 (m, 4H), 7.12 (m, 2H), 6.01 (m, 2H), 5.81 (m, 2H), 5.70 (m, 2H), 5.01 (m, 2H), 4.82 (d, J=7.6 Hz, 1H), 4.75 (d, J=5.7 Hz, 1H), 3.51 (m, 8H), 3.03 (d, J=4.8 Hz, 3H), 2.83 (d, J=3.4 Hz, 3H), 2.55 (m, 2H), 2.36 (m, 4H), 2.07 (m, 4H), 1.87 (m, 4H), 1.60 (m, 4H).
To a solution of the carboxylic acid (120 g) in dimethylformamide (DMF, 500 mL) the hydrochloride salt of methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate (88.1 g, 496 mmol) (CAS 229613-83-6) was added. To the resulting solution was added HATU (189 g, 496 mmol) and then diisopropylethylamine (220 mL). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (50 mL) and sat. aqueous bicarbonate solution (50 mL) The resulting mixture was extracted with ethyl acetate (3×100 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding methyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene-1-carboxylate (105 g, 60%, I.123) as a mixture of diastereoisomers (1:1). 1H NMR (500 MHz, Chloroform-d) δ 9.14 (s, 1H), 9.08 (s, 1H), 7.53 (dd, J=5.8, 1.8 Hz, 4H), 7.27 (m, 2H), 7.09 (m, 2H), 5.92 (m, 4H), 5.06 (q, J=9.0 Hz, 2H), 4.27 (d, J=5.1 Hz, 2H), 3.73 (s, 6H), 3.66 (s, 3H), 3.64 (s, 3H), 3.54 (m, 2H), 2.49 (tt, J=13.8, 8.4 Hz, 2H), 1.95 (ddt, J=14.1, 10.6, 3.5 Hz, 2H).
To methyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene-1-carboxylate (Cpd. I.123) (6.0 g, 15 mmol) in 1,2-dichloroethane (100 mL) was added trimethyltin hydroxide (Me3SnOH) (5.4 g, 30 mmol) at room temperature. The reaction mixture was stirred at room temperature for 16 h, then the reaction mixture was extracted with saturated sodium bicarbonate solution in water (3×100 mL). The combined organic phases were adjusted to pH 1 using concentrated hydrogen chloride solution in water. The resulting mixture was extracted with ethyl acetate (3×100 mL). The organic phases were dried over sodium sulfate. The dried organic phase was filtered and concentrated under reduced pressure to afford the crude (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene carboxylic acid (5.0 g, 86% yield, 1.136) as a mixture of diastereoisomers (1:1). 1H NMR (500 MHz, Chloroform-d) δ 9.18 (s, 1H), 9.13 (s, 1H), 7.53 (m, 4H), 7.38 (m, 2H), 7.10 (m, 2H), 5.97 (m, 4H), 5.07 (s, 2H), 4.29 (m, 2H), 3.61 (m, 8H), 2.53 (m, 2H), 1.99 (m, 2H).
To a solution of the carboxylic acid (Cpd. I.136) (500 mg, 1.29 mmol) in dimethylformamide (DMF, 10 mL) 2-chloroethanol (0.26 mL, 3.9 mmol) was added. To the resulting solution was added HATU (540 mg, 1.42 mmol) and then triethylamine (0.68 mL, 3.9 mmol). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (10 mL) and sat. aqueous bicarbonate solution (10 mL) The resulting mixture was extracted with ethyl acetate (3×20 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding 2-chloroethyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene-1-carboxylate (260 mg, 45%, I.142) as a mixture of diastereoisomers (2:1). 1H NMR (500 MHz, Chloroform-d) δ 9.08 (m, 2H), 7.52 (m, 4H), 7.20 (s, 1H), 7.10 (m, 2H), 5.94 (m, 4H), 5.11 (m, 2H), 4.37 (m, 4H), 4.27 (m, 2H), 3.69 (m, 13H), 2.57 (m, 2H), 1.96 (m, 2H).
To a solution of carboxylic acid (Cpd. I.136) (200 mg, 0.517 mmol) in tetrahydrofuran (5 mL) dimethylformamide (DMF, 0.1 mL, 0.5 mmol) and oxalyl chloride (0.09 mL, 1.0 mmol) were added. After stirring for 1 h, sodium benzylate (CAS 20194-18-7) (60 mg, 0.45 mmol) was added to the mixture and stirring was continued for 3 h. After quenching the reaction with water (5 mL), the aqueous layer was separated and extracted with ethyl acetate (3×5 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding benzyl (1S,4R)-4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]cyclopent-2-ene-1-carboxylate (24 mg, 10%, I.175) as a mixture of diastereoisomers (1:1). LC-MS (M+H)+:477.1.
To a solution of the carboxylic acid (Cpd. I.136) (300 mg, 0.775 mmol) in dimethylformamide (DMF, 5 mL) propargylamine (CAS 2450-71-7) (51 mg, 0.93 mmol) was added. To the resulting solution was added HATU (95%, 372 mg, 0.93 mmol) and then diisopropylethylamine (0.40 mL, 2.3 mmol). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (5 mL) and sat. aqueous bicarbonate solution (5 mL) The resulting mixture was extracted with ethyl acetate (3×10 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding N-(3,5-dichlorophenyl)-2-methoxy-N′-[(1R,4S)-4-(prop-2-ynylcarbamoyl)cyclopent-2-en-1-yl]propanediamide (47 mg, 14%, I.201) as a mixture of diastereoisomers (1:1). 1H NMR (500 MHz, Chloroform-d) δ 8.98 (m, 2H), 7.66 (s, 2H), 7.55 (m, 4H), 7.10 (s, 2H), 5.92 (m, 6H), 5.05 (d, J=7.9 Hz, 2H), 4.25 (s, 2H), 4.08 (m, 4H), 3.66 (s, 3H), 3.64 (s, 3H), 3.33 (s, 2H), 2.42 (m, 2H), 2.27 (m, 2H), 1.93 (t, J=14.7 Hz, 2H).
To a solution of the carboxylic acid (Inter A) (10 g, 36 mmol) in dimethylformamide (DMF, 100 mL) methyl 4-aminobutyrate hydrochloride (CAS 13031-60-2) (5.5 g, 36 mmol) was added. To the resulting solution was added HATU (15 g, 40 mol) and then triethylamine (15 mL, 108 mmol). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (50 mL) and sat. aqueous bicarbonate solution (50 mL) The resulting mixture was extracted with ethyl acetate (3×100 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding methyl 4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]butanoate (10.6 g, 78%, Cpd. I.26). 1H NMR (500 MHz, Chloroform-d) δ 9.29 (s, 1H), 7.51 (d, J=1.9 Hz, 2H), 7.08 (m, 2H), 4.31 (s, 1H), 3.68 (s, 3H), 3.64 (s, 3H), 3.37 (q, J=6.7 Hz, 2H), 2.38 (t, J=7.2 Hz, 2H), 1.89 (p, J=7.1 Hz, 2H).
To a solution of methyl 4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]butanoate (Cpd. I.26) (700 mg, 1.86 mmol) in 1:1 mixture of water (20 mL) and THF (20 mL) lithium hydroxide (102 mg, 4.24 mmol) was added. After stirring overnight, the reaction was quenched with aqueous hydrochloride (1 nn, 10 mL) and extracted with ethyl acetate (3×10 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure yielding 4-[[3-(3,5-dichloroanilino)-2-methoxy-3-oxo-propanoyl]amino]butanoic acid (550 mg, 82%) as a colorless oil. 1H NMR (500 MHz, Chloroform-d) δ 8.22 (s, 1H), 7.53 (d, J=1.8 Hz, 2H), 7.11 (s, 1H), 3.75 (d, J=5.9 Hz, 1H), 3.67 (s, 3H), 3.29 (td, J=7.0, 2.7 Hz, 2H), 3.22 (d, J=5.9 Hz, 1H), 2.37 (t, J=7.2 Hz, 2H), 1.90 (p, J=7.1 Hz, 2H).
To a solution of the carboxylic acid (Cpd. I.116) (200 mg, 0.551 mmol) in dichloromethane (30 mL) methanesulfonamide (157 mg, 1.65 mmol), 4-dimethylaminopyridine (DMAP, 20 mg, 0.17 mmol) and N,N′-dicyclohexylmethanediimine (DCC, 114 mg, 0.551 mmol) were added. After stirring overnight, the reaction was quenched with water (20 mL) and extracted with ethyl acetate (3×20 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding N-(3,5-dichlorophenyl)-N′-[4-(methanesulfonamido)-4-oxo-butyl]-2-methoxy-propanediamide (25 mg, 10%, Cpd. I.202-A). LC-MS (M+H)+:439.9.
To a solution of the carboxylic acid Cpd. I.116 (200 mg, 0.551 mmol) in dimethylformamide (DMF, 10 mL) methoxy(methyl)ammoniumchloride (80.6 mg, 0.826 mmol) was added. To the resulting solution was added HATU (314 mg, 0.826 mol) and then triethylamine (0.23 mL, 1.62 mmol). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture was added water (10 mL) and sat. aqueous bicarbonate solution (10 mL) The resulting mixture was extracted with ethyl acetate (3×10 mL). The combined organic phases were dried (sodium sulfate), filtered and evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding N-(3,5-dichlorophenyI)-2-methoxy-N′-[4-[methoxy(methyl)amino]-4-oxo-butyl]propanediamide (180 mg, 81%, Cpd. I.203). 1H NMR (500 MHz, Chloroform-d) δ 9.12 (s, 1H), 7.53 (d, J=1.8 Hz, 2H), 7.21 (s, 1H), 7.10 (t, J=1.8 Hz, 1H), 4.26 (s, 1H), 3.66 (s, 3H), 3.65 (s, 3H), 3.37 (qd, J=6.6, 3.9 Hz, 2H), 3.17 (s, 3H), 2.50 (m, 2H), 1.90 (m, 2H).
High Performance Liquid Chromatography: HPLC-column Kinetex XB C18 1.7μ (50×2.1 mm); eluent:acetonitrile/water+0.1% trifluoroacetic acid (gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min).
In analogy to the examples described above, the following compounds of formula (I), wherein R1 and R9 are hydrogen, were prepared, starting from commercially available diesters and using commercially available amines:
In analogy to the examples described above, the following compounds of formula (I), wherein R2, R6, R8 and R9 are hydrogen, were prepared, starting from commercially available diesters and using commercially available amines:
In analogy to the examples described above, the following compounds of formula (I), wherein R6 and R8 are hydrogen, were prepared, starting from commercially available diesters and using commercially available amines:
In analogy to the examples described above, the following compounds of formula (I), wherein R1, R6 and R9 are hydrogen, were prepared, starting from commercially available diesters and using commercially available amines:
The herbicidal activity of the compounds of formula (I) was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the test plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
Depending on the species, the test plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the test plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of 70 to 90 and a very good herbicidal activity is given at values of 90 to 100.
The test plants used in the greenhouse experiments were of the following species:
Abutilon theophrasti
Alopercurus myosuroides
Amaranthus retroflexus
Apera spica-venti
Avena fatua
Echinocloa crus-galli
Lolium multiflorum
Polygonum convolvulus
Setaria faberi
Setaria viridis
At an application rate of 0.125 kg/ha, applied by the pre-emergence method:
At an application rate of 0.250 kg/ha, applied by the pre-emergence method:
At an application rate of 0.500 kg/ha, applied by the pre-emergence method:
At an application rate of 1,000 kg/ha, applied by the pre-emergence method:
At an application rate of 0.125 kg/ha, applied by the post-emergence method:
At an application rate of 0.250 kg/ha, applied by the post-emergence method:
At an application rate of 0.500 kg/ha, applied by the post-emergence method:
| Number | Date | Country | Kind |
|---|---|---|---|
| 20160157.2 | Feb 2020 | WO | international |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/053846 | 2/17/2021 | WO |
