Patent Application
20240294544
The present invention relates to new pyridine compounds and the N-oxides and the salts thereof as fungicides as well to their use. The invention also relates to the composition comprising at least one compound I, to the method for combating phytopathogenic fungi and to the seed coated with at least one compound of the formula I.
WO2010125782, WO2009119089, JP2011148714, JP06107647 disclose some pyridine compounds. However, in many cases, in particular at low application rates, the fungicidal activity of known compounds is unsatisfactory. Based on this, it was an objective of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. Another object of the present invention is to provide fungicides with improved toxicological properties or with improved environmental fate properties.
These and further objects are achieved by the pyridine compounds of formula (I), as defined below, and by their agriculturally suitable.
Accordingly, the present invention relates to the compounds of formula I
The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
Agriculturally acceptable salts of the compounds of the formula I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds 1. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may be substituted with one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of acceptable acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Compounds of the formula I can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers arising from restricted rotation about a single bond of asymmetric groups and geometric isomers. They also form part of the subject matter of the present invention. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual stereoisomers, or as an optically active form.
Compounds of the formula I can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention.
In respect of the variables, the embodiments of the intermediates obtained during preparation of compounds I correspond to the embodiments of the compounds of formula I. The term “compounds I” refers to compounds of the formula I.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term “Cn-Cm” indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term “halogen” refers to fluorine, chlorine, bromine and iodine.
The term “C1-C6-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. 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, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 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. Likewise, the term “C2-C4-alkyl” refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec.-butyl), 2-methylpropyl (iso-butyl), 1,1-dimethylethyl (tert.-butyl).
The term “C1-C6-halogenalkyl” refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are “C1-C2-halogenalkyl” groups 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 or pentafluoroethyl.
The term “C1-C6-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group. Examples are “C1-C4-alkoxy” groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methyl, propoxy, 2-methylpropoxy or 1,1-dimethylethoxy.
The term “C1-C6-halogenalkoxy” refers to a C1-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are “C1-C4-halogenalkoxy” groups, such as OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chlorothoxy, 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-difluoro, propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-fluoromethyl-2-fluoroethoxy, 1-chloromethyl-2-chloroethoxy, 1-bromomethyl-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
The term “C2-C6-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position. Examples are “C2-C4-alkenyl” groups, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
The term “C2-C6-halogenalkenyl” refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term “C2-C6-alkenyloxy” refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkenyl group. Examples are “C2-C4-alkenyloxy” groups.
The term “C2-C6-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond. Examples are “C2-C4-alkynyl” groups, such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methyl-prop-2-ynyl.
The term “C2-C6-halogenalkynyl” refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term “C2-C6-alkynyloxy” refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkynyl group. Examples are “C2-C4-alkynyloxy” groups.
The term “C3-C6-cycloalkyl” refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Accordingly, a saturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a “C3-C10-cycloalkyl”.
The term “C3-C6-cycloalkenyl” refers to a monocyclic partially unsaturated 3-, 4-5- or 6-membered carbocycle having 3 to 6 carbon ring members and at least one double bond, such as cyclopentenyl, cyclopentadienyl, cyclohexadienyl. Accordingly, a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a “C3-C10-cycloalkenyl”.
The term “C3-C3-cycloalkyl-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), where According to one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
The term “saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1, 2, 3 or 4 heteroatoms selected from N, O and S” is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms independently selected from the group of O, N and S. For example:
The term “substituted” refers to substituted with 1, 2, 3 or up to the maximum possible number of substituents.
The term “5- or 6-membered heteroaryl” or “5- or 6-membered heteroaromatic” refers to aromatic ring systems including besides carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example, a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,2,4-triazolyl-1-yl, 1,2,4-triazol-3-yl 1,2,4-triazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl; or
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detailed, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates.
According to one embodiment of the compound of formula I, R1 is H.
According to one embodiment of the compound of formula I, R2 is selected from halogen, CN, C1-C6-alkyl, C1-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, O—C1-C6-alkyl, O—C2-C6-alkenyl, O—C2-C6-alkynyl, C3-C6-cycloalkyl.
According to still another embodiment of formula I, R2 is halogen, in particular F, Cl, Br or I, more specifically F, Cl or Br, in particular F or Cl.
According to still another embodiment of formula I, R2 is F.
According to still another embodiment of formula I, R2 is Cl.
According to still another embodiment of formula I, R2 is Br.
According to still another embodiment of formula I, R2 is CN.
According to still another embodiment of formula I, R2 is C1-C6-alkyl, in particular C1-C4-alkyl, such as CH3 or C2H5, in particular CH3 or CH2CH3.
According to still another embodiment of formula I, R2 is C1-C6-halogenalkyl, in particular C1-C4-halogenalkyl, such as CF3.
According to still a further embodiment of formula I, R2 is C2-C6-alkenyl, in particular C2-C4-alkenyl, such as CH═CH2, C(CH3)═CH2, CH2CH═CH2.
According to a further specific embodiment of formula I, R2 is C2-C6-halogenalkenyl, in particular C2-C4-halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH═CHF, CH═CHCl, CH═CF2, CH═CCl2, CH2CH═CHF, CH2CH═CHCl, CH2CH═CF2, CH2CH═CCl2, CF2CH═CF2, CCl2CH═CCl2, CF2CF═CF2, CCl2CCl═CCl2.
According to still a further embodiment of formula I, R2 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C≡CH, CH2C≡CH, C≡CCl, CH2C≡CCl, or CCl2C≡CCl.
According to a further specific embodiment of formula I, R2 is O—C1-C6-alkyl, in particular C1-C4-alkyl, more specifically C1-C2-alkoxy. R2 is such as OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R2 is O—C1-C6-alkyl, According to a further specific embodiment of formula I, R2 is O—C2-C6-alkenyl in particular C2-C4-alkenyl, more specifically C2-C3-alkenyl. R2 is such as OCH═CH2, OCH2CH═CH2.
According to a further specific embodiment of formula I, R2 is O—C2-C6-alkynyl, in particular C2-C6-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R2 is such as O—CH2—C≡CH.
According to still another embodiment of formula I, R2 is C3-C6-cycloalkyl, in particular cyclopropyl or cyclobutyl.
Particularly preferred embodiments of R2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-21 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-21 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R2 is bound is marked with “#” in the drawings.
According to one embodiment of formula I, R3 is selected from the group consisting of C1-C6-alkyl, C1-C6-halogenalkyl, C3-C6-cycloalkyl, in particular CH3, C2H5, CF3, CH2F, CHF2, cyclopropyl, cyclobutyl, more specifically CH3, CH2F, CF2H, CF3, cyclopropyl, cyclobutyl most preferred CH3, CF3, CF2H.
According to still another embodiment of formula I, R3 is C1-C6-alkyl, in particular C1-C4-alkyl, such as CH3 or C2H5, in particular CH3 or CH2CH3.
According to still another embodiment of formula I, R3 is C1-C6-halogenalkyl, in particular C1-C4-halogenalkyl, such as CF3, FCH2, F2CH, CF3CH2.
According to still a further embodiment of formula I, R3 is C2-C6-alkenyl, in particular C2-C4-alkenyl, such as CH═CH2, C(CH3)═CH2, CH2CH═CH2.
According to still a further embodiment of formula I, R3 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C≡CH, CH2C≡CH, C≡CCl, CH2C≡CCl, or CCl2C≡CCl.
According to a further specific embodiment of formula I, R3 is O—C1-C6-alkyl, in particular C1-C4-alkyl, more specifically C1-C2-alkoxy. R3 is such as OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R3 is O—C2-C6-alkenyl in particular C2-C4-alkenyl, more specifically C2-C3-alkenyl. R3 is such as OCH═CH2, OCH2CH═CH2.
According to a further specific embodiment of formula I, R3 is O—C2-C6-alkynyl, in particular C2-C6-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R3 is such as O—CH2—C≡CH.
According to a further specific embodiment of formula I, R3 is O—C1-C6-halogenalkyl, in particular OCF3, OCCl3, OFCH2, OClCH2, OF2CH, OCl2CH, OCF3CH2, OCCl3CH2 or OCF2CHF2, more specifically OCF3, OF2CH, OFCH2.
According to still another embodiment of formula I, R3 is C3-C6-cycloalkyl, in particular cyclopropyl, cyclobutyl.
Particularly preferred embodiments of R3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-17 corresponds to one particular embodiment of the invention, wherein P3-1 to P3-17 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R3 is bound is marked with “#” in the drawings.
According to one embodiment of the compound of formula I, R4 is H.
According to one embodiment of the compound of formula I,
According to one embodiment of the compound of formula I, R5 is in each case independently selected from C1-C6-alkyl (embodiment 5.1), C1-C6-halogenalkyl (embodiment 5.2), C1-C6-alkyl-O—C1-C6-alkyl (embodiment 5.3), phenyl, CH2-phenyl (embodiment 5.4), wherein phenyl and CH2-phenyl is unsubstituted or substituted by one or two halogen.
According to one further embodiment of the compound of formula I, R5 is CH3 or CF3.
According to one further embodiment of the compound of formula I, R5 is CH3.
According to one further embodiment of the compound of formula I, R5 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2—CH(CH3)2, CH2—C(CH3)3, CH2—O—CH3.
According to one further embodiment of the compound of formula I, R5 is phenyl, 2-F-phenyl, 4-F-phenyl, 2,4-F2-phenyl, 2-Cl-phenyl, 4-Cl-phenyl, CH2-phenyl, CH2-2-F-phenyl, CH2-4-F-phenyl.
According to one embodiment of the compound of formula I, R6 is in each case independently selected from are in each case independently selected from F, CN, C1-C6-alkyl, C1-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, C1-C6-alkyl-O—C1-C6-alkyl, phenyl, benzyl, C1-C6-alkyl-O-phenyl,
According to one embodiment of the compound of formula I, R6 is in each case independently selected from C1-C6-alkyl (embodiment 6.1), C1-C6-alkyl-O-phenyl (embodiment 6.2), C1-C6-alkyl-O—C1-C6-alkyl (embodiment 6.3).
According to one further embodiment of the compound of formula I, R6 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2—CH(CH3)2, CH2—C(CH3)3, CH2—CH(CH3)—C(CH3)3, CH2—CH2—C(CH3)3, CH2—O—CH3, CH2—O—(CH3)3, CH2—O-phenyl.
According to one further embodiment of the compound of formula I, R5 and R6 form together with the C atoms to which they are bound a C3-C6-cycloalkyl or a 3- to 6-membered saturated heterocycle which contains 1, 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubstituted or substituted by halogen, C1-C6-alkyl, C1-C6-halogenalkyl According to one further embodiment of the compound of formula I, R5 and R6 form C3-C6-cycloalkyl (embodiment 6.4).
According to one further embodiment of the compound of formula I, R5 and R6 form 3- to 6-membered saturated heterocycle which contains 1, 2 or 3 heteroatoms from the group consisting of 0 and S.
According to one further embodiment of the compound of formula I, R5 and R6 form 3- to 6-membered saturated heterocycle which contains one 0 (embodiment 6.5).
Preferred embodiments of R5, R6 according to the invention are in Table P5 below, wherein each line of lines P5-1 to P5-18 corresponds to one particular embodiment of the invention, wherein P5-1 to P5-18 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R5 and R6 is bound is marked with “#” in the drawings.
According to one embodiment of the compound of formula I, X is in each case independently selected from halogen (embodiment X.1), CN, C1-C6-alkyl (embodiment X.2), C1-C6-halogenalkyl (embodiment X.3), O—C1-C6-alkyl (embodiment X.4), O—C1-C6-halogenalkyl (embodiment X.5).
According to one embodiment of the compound of formula I, X is in each case independently selected from halogen, O—C1-C6-alkyl.
According to one embodiment of the compound of formula I, X is in each case independently selected from F or Cl.
According to one embodiment of the compound of formula I, X is C3-C6-cycloalkyl.
According to one embodiment of the compound of formula I, n is 0.
According to one embodiment of the compound of formula I, n is 1.
According to one embodiment of the compound of formula I, n is 2.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is F.
According to one embodiment Xn is as defined below:
and X is selected from F, Cl, I, CH3, cyclopropyl, CH═CH2, C≡CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
and X is F.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, which represent preferred combinations of embodiments that are defined above for each of the variables R2, R3 and X (represented by embodiments X.1 to X.6), n in compounds of formula I as defined below.
Preferred embodiments of the present invention are the following compounds I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6. In these formulae, the substituents R5, R6 and Xn are independently as defined above or preferably defined herein:
In particular with a view to their use, according to one embodiment, preference is given to the compounds of the compounds I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; that are compiled in the Tables 1a to 7a. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6 in which Xn is H and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.1a.B-1 to I.A-1.1a.B-180, I.A-2.1a.B-1 to I.A-2.1a.B-180, I.A-3.1a.B-1 to I.A-3.1a.B-180, I.A-4.1a.B-1 to I.A-4.1a.B-180, I.A-5.1a.B-1 to I.A-5.1a.B-180, I.A-6.1a.B-1 to I.A-6.1a.B-180).
Table 2a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 8-F and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.2a.B-1 to I.A-1.2a.B-180, I.A-2.2a.B-1 to I.A-2.2a.B-180, I.A-3.2a.B-1 to I.A-3.2a.B-180, I.A-4.2a.B-1 to I.A-4.2a.B-180, I.A-5.2a.B-1 to I.A-5.2a.B-180, I.A-6.2a.B-1 to I.A-6.2a.B-180).
Table 3a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 8-Cl and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.3a.B-1 to I.A-1.3a.B-180, I.A-2.3a.B-1 to I.A-2.3a.B-180, I.A-3.3a.B-1 to I.A-3.3a.B-180, I.A-4.3a.B-1 to I.A-4.3a.B-180, I.A-5.3a.B-1 to I.A-5.3a.B-180, I.A-6.3a.B-1 to I.A-6.3a.B-180) Table 4a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 7,8-F2 and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.4a.B-1 to I.A-1.4a.B-180, I.A-2.4a.B-1 to I.A-2.4a.B-180, I.A-3.4a.B-1 to I.A-3.4a.B-180, I.A-4.4a.B-1 to I.A-4.4a.B-180, I.A-5.4a.B-1 to I.A-5.4a.B-180, I.A-6.4a.B-1 to I.A-6.4a.B-180).
Table 5a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 5,8-F2 and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.5a.B-1 to I.A-1.5a.B-180, I.A-2.5a.B-1 to I.A-2.5a.B-180, I.A-3.5a.B-1 to I.A-3.5a.B-180, I.A-4.5a.B-1 to I.A-4.5a.B-180, I.A-5.5a.B-1 to I.A-5.5a.B-180, I.A-6.5a.B-1 to I.A-6.5a.B-180) Table 6a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 7-OCH3 and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.6a.B-1 to I.A-1.6a.B-180, I.A-2.6a.B-1 to I.A-2.6a.B-180, I.A-3.6a.B-1 to I.A-3.6a.B-180, I.A-4.6a.B-1 to I.A-4.6a.B-180, I.A-5.6a.B-1 to I.A-5.6a.B-180, I.A-6.6a.B-1 to I.A-6.6a.B-180) Table 7a Compounds of the formula I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6; in which Xn is 6,8-F2 and the meaning for the combination of R5 and R6 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.7a.B-1 to I.A-1.7a.B-180, I.A-2.7a.B-1 to I.A-2.7a.B-180, I.A-3.7a.B-1 to I.A-3.7a.B-180, I.A-4.7a.B-1 to I.A-5.7a.B-180, I.A-5.7a.B-1 to I.A-5.7a.B-180, I.A-6.7a.B-1 to I.A-6.7a.B-180)
Compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula I. The compounds of the 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.
For example, compounds I can be prepared by a by palladium catalyzed Suzuki coupling reaction between a boronic acid derivative represented by formula 3 and a triflate derivative represented by formula 2 using a palladium complex in an organic solvent. It is preferred to conduct the reaction at elevated temperature, preferably between 60 and 160° C., and using 1-3 equivalents of boronic acid derivative represented by formula 3 per 1 equivalent triflate 2, as described in WO2009119089A1.
Compounds of the formula 2 can be prepared from cyclic amide compound 4 by treatment with triflic anhydride and in the presence of a base such as pyridine, 2,6-lutidine, 2,3,5-colidine, triethylamine, tributylamine and diisopropylethylamine etc.; or a tertiary cyclic amine such as 1.4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,8-diazabicyclo[5.4.0]undeca-7-ene or an aromatic amine such as N,N-dimethylaniline, N,N-diethylaniline, 4-dimethylaminopyridine in an organic halogenated aliphatic hydrocarbons solvent such as chloroform, dichloromethane, dichloroethane, as described in WO2009119089A1 and EP2179994B1.
The cyclic amide compounds of the formula 4 are commercially available or can be accessed from the respective salicylic amide 5 by acetal formation with dimethoxy alkane or dimethoxy cycloalkane in an organic solvent and in the presence of an acid like p-toluenesulfonic acid (p-TsOH), pyridinium p-toluenesulfonate, sulfuric acid or acetic acid (for precedents see for example Tetrahedron (2015), 71(34), 5554-5561, Journal of Organic Chemistry (1981), 46(16), 3340-2, Bioorganic & Medicinal Chemistry (2006), 14(6), 1978-1992).
The compounds of the formula 4 can also be prepared via condensation between salicylic amide 5 and ketones 7, catalyzed by secondary amines such as pyrrolidine, morpholine, etc.
The reactions are best carried out in refluxing benzene or toluene with 10% amine catalyst (for precedents see for example J. Org. Chem. 1981, 46, 3340-3342, Synthesis 1978, 886).
The compounds I and the compositions thereof, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.
The compounds I and the compositions thereof are preferably useful in the control of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats, or rice; beet, e. g. sugar beet or fodder beet; fruits, e. g. pomes (apples, pears, etc.), stone fruits (e.g. plums, peaches, almonds, cherries), or soft fruits, also called berries (strawberries, raspberries, blackberries, gooseberries, etc.); leguminous plants, e. g. lentils, peas, alfalfa, or soybeans; oil plants, e. g. oilseed rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e. g. squashes, cucumber, or melons; fiber plants, e. g. cotton, flax, hemp, or jute; citrus fruits, e. g. oranges, lemons, grapefruits, or mandarins; vegetables, e. g. spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits, or paprika; lauraceous plants, e. g. avocados, cinnamon, or camphor; energy and raw material plants, e. g. corn, soybean, oilseed rape, sugar cane, or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants; or ornamental and forestry plants, e. g. flowers, shrubs, broad-leaved trees, or evergreens (conifers, eucalypts, etc.); on the plant propagation material, such as seeds; and on the crop material of these plants.
More preferably, compounds I and compositions thereof, respectively are used for controlling fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term “plant propagation material” is to be understood to denote all the generative parts of the plant, such as seeds; and vegetative plant materials, such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants; including seedlings and young plants to be transplanted after germination or after emergence from soil.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
According to the invention all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
Most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (MG 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
The term “cultivated plants” is to be understood as including plants which have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to create mutations at a specific locus of a plant genome. Targeted mutagenesis frequently uses oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases. 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 to add a trait or improve or modify a trait. These integrated genes are also referred to as transgenes, 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 herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis and genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are e.g. available under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione, has been created via the use of transgenes.
Transgenes to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621, goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1, 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 inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.
Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-01981-5, 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 include, but are not limited to, 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, SYHTOH2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 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.
Transgenes to provide insect resistance preferably are toxin genes of Bacillus spp. 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. In addition, transgenes of plant origin, such as genes coding for protease inhibitors, like CpTI and pinII, can be used. A further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, 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 include, but are not limited to, MON87701, MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, 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.
Cultivated plants with increased yield have been created by using the transgene athb17 (e.g. corn event MON87403), or bbx32 (e.g. soybean event MON87712).
Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A (e.g. soybean events 260-05, MON87705 and MON87769).
Tolerance to abiotic conditions, such as drought, has been created by using the transgene cspB (corn event MON87460) and Hahb-4 (soybean event IND-00410-5).
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process resulting in a cultivated plant with stacked traits. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations 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). Further information on specific events and methods to detect them can be found for canola events MS1, MS8, RF3, GT73, MON88302, KK179 in WO01/031042, WO01/041558, WO01/041558, WO02/036831, WO11/153186, WO13/003558; for cotton events MON1445, MON15985, MON531 (MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701, 81910 in WO02/034946, WO02/100163, WO02/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, WO07/017186, WO08/122406, WO08/151780, WO12/134808, WO13/112527; for corn events GA21, MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MON87403, MON87419 in WO98/044140, US02/102582, U.S. Ser. No. 03/126,634, WO04/099447, WO04/011601, WO05/103301, WO05/061720, WO05/059103, WO06/098952, WO06/039376, US2007/292854, WO07/142840, WO07/140256, WO08/112019, WO09/103049, WO09/111263, WO10/077816, WO11/084621, WO11/062904, WO11/022469, WO13/169923, WO14/116854, WO15/053998, WO15/142571; for potato events E12, F10, J3, J55, V11, X17, Y9 in WO14/178910, WO14/178913, WO14/178941, WO14/179276, WO16/183445, WO17/062831, WO17/062825; for rice events LLRICE06, LLRICE601, LLRICE62 in WO00/026345, WO00/026356, WO00/026345; and for soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHTOH2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04/074492, WO06/130436, WO06/108674, WO06/108675, WO08/054747, WO08/002872, WO09/064652, WO09/102873, WO10/080829, WO10/037016, WO11/066384, WO11/034704, WO12/051199, WO12/082548, WO13/016527, WO13/016516, WO14/201235.
The use of compounds I and compositions thereof, respectively, on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain transgene 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 vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases:
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).
According to one embodiment compounds I.A-1.1a.B-1 to I.A-1.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.1a.B-1 to I.A-2.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.1a.B-1 to I.A-3.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.1a.B-1 to I.A-4.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.1a.B-1 to I.A-5.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.1a.B-1 to I.A-6.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.2a.B-1 to I.A-1.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.2a.B-1 to I.A-2.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.2a.B-1 to I.A-3.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.2a.B-1 to I.A-4.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.2a.B-1 to I.A-5.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.2a.B-1 to I.A-6.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.3a.B-1 to I.A-1.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.3a.B-1 to I.A-2.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.3a.B-1 to I.A-3.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.3a.B-1 to I.A-4.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.3a.B-1 to I.A-5.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.3a.B-1 to I.A-6.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.4a.B-1 to I.A-1.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.4a.B-1 to I.A-2.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.4a.B-1 to I.A-3.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.4a.B-1 to I.A-4.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.4a.B-1 to I.A-5.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.4a.B-1 to I.A-6.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.5a.B-1 to I.A-1.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.5a.B-1 to I.A-2.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.5a.B-1 to I.A-3.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.5a.B-1 to I.A-4.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.5a.B-1 to I.A-5.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.5a.B-1 to I.A-6.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.6a.B-1 to I.A-1.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.6a.B-1 to I.A-2.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.6a.B-1 to I.A-3.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.6a.B-1 to I.A-4.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.6a.B-1 to I.A-5.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.6a.B-1 to I.A-6.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.7a.B-1 to I.A-1.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.7a.B-1 to I.A-2.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.7a.B-1 to I.A-3.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.7a.B-1 to I.A-4.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.7a.B-1 to I.A-5.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.7a.B-1 to I.A-6.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds Ex-1 to Ex-92 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
The compounds I and compositions thereof, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvest, and in the protection of materials.
The term “stored products or harvest” is understood to denote natural substances of plant or animal origin and their processed forms for which long-term protection is desired. Stored products of plant origin, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and alike. Preferably, “stored products” is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms, where application of compounds I and compositions thereof can also prevent disadvantageous effects such as decay, discoloration or mold.
The term “protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper, paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber, or fabrics against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
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.
The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material, and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
The term “plant health” is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other, such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients), and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds I are employed as such or in form of compositions by treating the fungi, the plants, plant propagation materials, such as seeds; soil, surfaces, materials, or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds; soil, surfaces, materials or rooms by the fungi.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term “fungicidally effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of stored products or harvest or of materials and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material, the climatic conditions and the specific compound I used.
Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
When employed in plant protection, the amounts of active substances applied 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 treatment of plant propagation materials, such as seeds, e. g. by dusting, coating, or drenching, amounts of active substance of generally 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 kg of plant propagation material (preferably seeds) are required.
The user applies the agrochemical composition usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition 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.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types (see also “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International) 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). The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or by Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, 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, and alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, 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-methyl pyrrolidone, fatty acid dimethyl amides; 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 alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin 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 of alkyl naphthalenes, sulfosuccinates, or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids, of 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 vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
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 polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound 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, carboxymethyl cellulose), 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 polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substances (e.g. at least one compound I). The agrochemical compositions generally comprise between 5 and 99.9%, preferably between 10 and 99.9%, more preferably between 30 and 99%, and in particular between 40 and 90%, by weight of at least one auxiliary. The active substances (e.g. compounds 1) are employed in a purity of from 90% to 100%, preferably from 95-% to 100% (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, 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. The compositions 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%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking, as well as in-furrow application methods. Preferably, compound I or the compositions 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, wetters, adjuvants, fertilizers, or micronutrients, and further pesticides (e. g. fungicides, growth regulators, herbicides, insecticides, safeners) may be added to the compounds I or the compositions thereof as premix, or, not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained (synergistic mixtures).
The following list of pesticides 1l, in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; U.S. Pat. Nos. 3,296,272; 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441, WO 16/156241, WO 16/162265). Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil) are considered as active components (e. g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides). The weight ratios and percentages used for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1×1010 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells. In addition, CFU may also be understood as the number of (juvenile) individual nematodes in case of nematode biopesticides, such as Steinemema feltiae.
In the binary mixtures the weight ratio of the component 1) and the component 2) generally depends from the properties of the components used, usually it is in the range of from 1:10,000 to 10,000:1, often from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1, even more preferably from 1:4 to 4:1 and in particular from 1:2 to 2:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often from 100:1 to 1:1, regularly from 50:1 to 1:1, preferably from 20:1 to 1:1, more preferably from 10:1 to 1:1, even more preferably from 4:1 to 1:1 and in particular from 2:1 to 1:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1:10, often from 10,000:1 to 1:1, regularly from 5,000:1 to 5:1, preferably from 5,000:1 to 10:1, more preferably from 2,000:1 to 30:1, even more preferably from 2,000:1 to 100:1 and in particular from 1,000:1 to 100:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often from 1:1 to 1:100, regularly from 1:1 to 1:50, preferably from 1:1 to 1:20, more preferably from 1:1 to 1:10, even more preferably from 1:1 to 1:4 and in particular from 1:1 to 1:2. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1:20,000, often from 1:1 to 1:10,000, regularly from 1:5 to 1:5,000, preferably from 1:10 to 1:5,000, more preferably from 1:30 to 1:2,000, even more preferably from 1:100 to 1:2,000 to and in particular from 1:100 to 1:1,000.
In the ternary mixtures, i.e. compositions comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1. Any further active components are, if desired, added in a ratio of from 20:1 to 1:20 to the component 1). These ratios are also suitable for mixtures applied by seed treatment.
When mixtures comprising microbial pesticides are employed in crop protection, the application rates range from 1×106 to 5×1016 (or more) CFU/ha, preferably from 1×108 to 1×1013 CFU/ha, and even more preferably from 1×109 to 5×1015 CFU/ha and in particular from 1×1012 to 5×1014 CFU/ha. In the case of nematodes as microbial pesticides (e. g. Steinemema feltiae), the application rates regularly range from 1×105 to 1×1012 (or more), preferably from 1×108 to 1×1011, more preferably from 5×108 to 1×1010 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infective juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment, the application rates generally range from 1×106 to 1×1012 (or more) CFU/seed, preferably from 1×106 to 1×109 CFU/seed. Furthermore, the application rates with respect to seed treatment generally range from 1×107 to 1×1014 (or more) CFU per 100 kg of seed, preferably from 1×109 to 1×1012 CFU per 100 kg of seed.
Preference is given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Qo site in group A), more preferably selected from compounds (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34) and (A.1.35); particularly selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.25), (A.1.34) and (A.1.35).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Qi site in group A), more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); particularly selected from (A.2.3), (A.2.4) and (A.2.6).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.11), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.28), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23), (A.3.24), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other respiration inhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.11); in particular (A.4.11).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from C14 demethylase inhibitors in group B), more preferably selected from compounds (B.1.4), (B.1.5), (B.1.8), (B.1.10), (B.1.11), (B.1.12), (B.1.13), (B.1.17), (B.1.18), (B.1.21), (B.1.22), (B.1.23), (B.1.25), (B.1.26), (B.1.29), (B.1.34), (B.1.37), (B.1.38), (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); particularly selected from (B.1.5), (B.1.8), (B.1.10), (B.1.17), (B.1.22), (B.1.23), (B.1.25), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43) and (B.1.46).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from Delta14-reductase inhibitors in group B), more preferably selected from compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from phenylamides and acyl amino acid fungicides in group C), more preferably selected from compounds (C.1.1), (C.1.2), (C.1.4) and (C.1.5); particularly selected from (C.1.1) and (C.1.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6), (C.2.7) and (C.2.8).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1.2), (D.1.5) and (D.2.6).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group G), more preferably selected from compounds (G.3.1), (G.3.3), (G.3.6), (G.5.1), (G.5.3), (G.5.4), (G.5.5), G.5.6), G.5.7), (G.5.8), (G.5.9), (G.5.10) and (G.5.11);
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from compounds (H.2.2), (H.2.3), (H.2.5), (H.2.7), (H.2.8), (H.3.2), (H.3.4), (H.3.5), (H.4.9) and (H.4.10); particularly selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group 1), more preferably selected from compounds (1.2.2) and (1.2.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); in particular (J.1.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); particularly selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59).
The biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
The microbial pesticides, in particular those from groups L1), L3) and L5), embrace not only the isolated, pure cultures of the respective microorganism as defined herein, but also its cell-free extract, its suspension in a whole broth culture and a metabolite-containing culture medium or a purified metabolite obtained from a whole broth culture of the microorganism.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www.wfcc.info/ccinfo/collection/by acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pullulans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in BlossomProtect® from bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 originally isolated in wheat reagion of South Brazil (Passo Fundo) at least prior to 1980 (BR 11005; e. g. GELFIX® Gramineas from BASF Agricultural Specialties Ltd., Brazil), A. brasilense strains Ab-V5 and Ab-V6 (e. g. in AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quattro Barras, Brazil or Simbiose-Maiz® from Simbiose-Agro, Brazil; Plant Soil 331, 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331; U.S. Pat. No. 8,445,255); B. amyloliquefaciens ssp. plantarum strains formerly also sometimes referred to as B. subtilis, recently together with B. methylotrophicus, and B. velezensis classified as B. velezensis (Int. J. Syst. Evol. Microbiol. 66, 1212-1217, 2016): B. a. ssp. plantarum or B. velezensis D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. a. ssp. plantarum or B. velezensis FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. a. ssp. plantarum or B. velezensis FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. a. ssp. plantarum or B. velezensis MB1600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1; e. g. Integral® from BASF Corp., USA), B. a. ssp. plantarum or B. velezensis QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. a. ssp. plantarum or B. velezensis TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1BE; ATCC BAA-390; CA 2471555 A1; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA); B. firmus CNCM 1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, U.S. Pat. No. 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01; e. g. PROMIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; U.S. Pat. No. 8,445,255), B. pumilus KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; U.S. Pat. No. 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, MQnsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from E. saccharina larval cadavers (NRRL B-50753; e. g. Beta Pro® from BASF Agricultural Specialties (Pty) Ltd., South Africa), B. t. ssp. tenebrionis NB-176-1, a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 B1; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.I., Italy), B. bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhizobium elkanii strains SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with a North American isolate, and used in commercial inoculants since 1968 (Appl. Environ. Microbiol. 73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited at SEMIA known from Appl. Environ. Microbiol. 73(8), 2635, 2007: SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab conditions by Embrapa-Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium minitans CON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care plc, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112-126, 2011; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABANPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol. 22(7), 747-761, 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var. anisopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (U.S. Pat. No. 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; WO1991/02051; Crop Protection 27, 352-361, 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371; DSM 26969), P. p. ssp. plantarum strain Lu17007 (WO 2016/020371; DSM 26970); Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, Feb. 2, 2011; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (=ATCC 74319), ATCC 20851 and/or ATCC 22348 (=ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1), 91-102, 1998; U.S. Pat. No. 5,026,417, WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 1; e. g. Regalia® SC from Marrone Biolnnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), Trichoderma asperelloides JM41R isolated in South Africa (NRRL 50759; also referred to as T. fertile; e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa), T. harzianum T-22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
According to another embodiment of the mixtures, the at least one pesticide II is selected from the groups L1) to L5):
The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L1) and L2), as described above, and if desired at least one suitable auxiliary.
The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L3) and L4), as described above, and if desired at least one suitable auxiliary.
Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.1.25), (L.1.26), (L.1.27), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2), and (L.4.1); even more preferably selected from (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.5), (L.5.6); (L.4.2), and (L.4.1). These mixtures are particularly suitable for treatment of propagation materials, i. e. seed treatment purposes and likewise for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, corn and leguminous plants such as soybean.
Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L.1.17), (L.1.18), (L.1.22), (L.1.23), (L.1.24), (L.1.25), (L.1.26), (L.1.27), (L.2.2); (L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably selected from (L.1.2), (L.1.7), (L.1.11), (L.1.13), (L.1.14), (L.1.15), (L.1.18), (L.1.23), (L.3.3), (L.3.4), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.15), and (L.4.2). These mixtures are particularly suitable for foliar treatment of cultivated plants, preferably of vegetables, fruits, vines, cereals, corn, and leguminous crops such as soybeans.
The compositions comprising mixtures of active ingredients can be prepared by usual means, e. g. by the means given for the compositions of compounds 1.
When living microorganisms, such as pesticides II from groups L1), L3) and L5), form part of the compositions, such compositions can be prepared by usual means (e. g. H. D. Burges: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008/002371, U.S. Pat. Nos. 6,955,912, 5,422,107).
p-TsOH (98 mg, 0.2 eq) was added to a suspension of 3-fluoro-2-hydroxy-benzamide (400 mg, 1 eq) and cyclobutanone (542 mg, 3 eq) in toluene (30 ml), and the mixture was heated at reflux with azeotropic removal of water for 12 h. The reaction solution was cooled and concentrated in vacuo, and the resultant residue was diluted with ethyl acetate, washed successively with 2 N HCl, water and brine, and dried over anhydrous magnesium sulfate. Removal of solvent in vacuo afforded the titled compound (526 mg) as a brown powder.
1H NMR (400 MHz, CDCl3): μ [ppm]: 8.02-7.86 (m, 1H), 7.47 (ddd, J=8.3, 7.3, 1.7 Hz, 1H), 7.10 (td, J=7.5, 1.1 Hz, 1H), 7.01 (ddd, J=8.3, 1.1, 0.5 Hz, 1H), 6.62 (s, 1H), 2.65-2.50 (m, 2H), 2.34 (ddtt, J=12.5, 6.4, 3.1, 1.5 Hz, 2H), 2.07-1.91 (m, 1H), 1.84 (dtt, J=11.6, 9.3, 6.4 Hz, 1H).
Trifluoromethanesulfonic anhydride (7.8 g, 2.5 eq) and 2,6-lutidine (2.38 g, 2 eq) were added dropwise to a suspension of spiro[3H-1,3-benzoxazine-2,1′-cyclobutane]-4-one (2.1 g, 1 eq) in dichloromethane (120 mL) under cooling at −78° C., and the mixture was stirred at the same temperature for 1.0 hour. The reaction mixture stirred for 20 min at 0° C., poured into ice water, and the solution was extracted with dichloromethane. The organic layer was washed successively with a saturated aqueous solution of sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give the titled compound (1.8 g) as a brown oil. The title compound was used directly without further purification.
[6-(difluoromethyl)-5-methyl-3-pyridyl]boronic acid (572 mg, 1.1 eq), potassium carbonate (1.54 g, 4 eq), water (2 ml) and dichlorobis(triphenylphosphine)palladium(II) (391 mg, 0.2 eq) were added to a solution of spiro[1,3-benzoxazine-2,1′-cyclobutane]-4-yl trifluoromethanesulfonate (900 mg, 1 eq) in dimethoxyethane (10 mL), and the mixture was stirred under argon atmosphere at 80° C. for 2.5 hours. After cooling, the reaction solution was diluted with ethyl acetate, and the solution was washed successively with water and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The crude product was purified by High Performance Liquid Chromatography on silica gel (HPLC-column Kinetex XB C18 1.7μ (50×2.1 mm); eluent: acetonitrile/water (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) to give the titled compound (97 mg) as a yellow-brown oil.
1H NMR (400 MHz, CDCl3): μ [ppm]: 8.67-8.60 (m, 1H), 7.90-7.84 (m, 1H), 7.42 (td, J=7.8, 1.6 Hz, 1H), 7.12 (dd, J=7.7, 1.6 Hz, 1H), 7.02 (d, J=8.2 Hz, 1H), 6.98-6.93 (m, 1H), 6.75 (t, J=54.5 Hz, 1H), 2.59 (s, 3H), 2.57-2.46 (m, 4H), 1.99 (dddd, J=25.7, 15.6, 7.8, 4.1 Hz, 2H).
The compounds listed in Table I were prepared in an analogous manner.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-2, Ex-3, Ex-4, Ex-5 and Ex-6 respectively, showed 0% growth of the pathogen.
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4 and Ex-6 respectively, showed 1% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-2, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-10, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-28, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70*, Ex-71, Ex-72, Ex-73, Ex-74, Ex-76, Ex-77, Ex-79, Ex-87, Ex-88, Ex-89 respectively, showed unto 11% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-6, Ex-8, Ex-9, Ex-13, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-26, Ex-27, Ex-28, Ex-29, Ex-32, Ex-33, Ex-35, Ex-36, Ex-38, Ex-39, Ex-42, Ex-44, Ex-51, Ex-63, Ex-64, Ex-65, Ex-67, Ex-73, Ex-74, Ex-76, Ex-77 respectively, showed unto 19% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septorion tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-8, Ex-14, Ex-15, Ex-18, Ex-21, Ex-22, Ex-23, Ex-26, Ex-29, Ex-30, Ex-33, Ex-42, Ex-46, Ex-49, Ex-50, Ex-66, Ex-68, Ex-70*, Ex-72, Ex-73, Ex-74, Ex-76, Ex-77, Ex-79 respectively, showed unto 20% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Microdochium nivale isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-19, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70 respectively, showed unto 18% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Colletotrichum orbiculare isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-60, Ex-62, Ex-63, Ex-65, Ex-69 respectively, showed unto 17% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Leptosphaeria nodorum isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70 respectively, showed unto 19% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Fusarium gramminearis isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-6, Ex-8, Ex-9, Ex-13, Ex-17, Ex-20, Ex-21, Ex-22, Ex-26, Ex-29, Ex-33, Ex-35, Ex-36, Ex-38, Ex-44, Ex-65, Ex-66, Ex-67 respectively, showed unto 17% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Monilinia laxa isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-5, Ex-6, Ex-7, Ex-11, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-44, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-62, Ex-63, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 16% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Ustilago maydis isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-4, Ex-5, Ex-7, Ex-8, Ex-11, Ex-12, Ex-13, Ex-15, Ex-18, Ex-20, Ex-21, Ex-33, Ex-36, Ex-40, Ex-42, Ex-44, Ex-67 respectively, showed unto 19% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Pyrenophora teres Qoi (FL129) resistant isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-23, Ex-24, Ex-25, Ex-27, Ex-29, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-36, Ex-38, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-62, Ex-63, Ex-69 respectively, showed unto 16% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Leptosphaeria maculans isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-30, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-40, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 10% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Corynespora cassiicola isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-17, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-27, Ex-29, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 19% growth of the pathogen.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Corynespora cassiicola (CORYCA-G) G413A mutant isolates in a DOB media (ph 7) was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1, Ex-4, Ex-5, Ex-6, Ex-7, Ex-8, Ex-9, Ex-11, Ex-12, Ex-13, Ex-14, Ex-15, Ex-16, Ex-17, Ex-18, Ex-19, Ex-20, Ex-21, Ex-22, Ex-23, Ex-24, Ex-25, Ex-26, Ex-27, Ex-29, Ex-31, Ex-32, Ex-33, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-39, Ex-41, Ex-42, Ex-44, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-70* respectively, showed unto 19% growth of the pathogen.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
The compound was dissolved in a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solventemulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml.
This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 2411C and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-13, Ex-14, Ex-17, Ex-20, Ex-30, Ex-31, Ex-34, Ex-36 and Ex-38 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 90% infected.
Oilseed rapes were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to runoff with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the applicated rape petals were fixed with 25 μl of 2.5% methylcellulose on leaf 1 and 2. 25 μl of a spore suspension of Sclerotinia sclerotiorum was pipetted on each fixed rape petal. After 14 days at 20° C. and a relative humidity of 60% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-1, Ex-25, Ex-33, Ex-42, Ex-46, Ex-47, Ex-49, Ex-50, Ex-54, Ex-55 and Ex-63 respectively, showed up to at most 10% growth of the pathogen whereas the untreated plants were 100% infected.
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24° C. and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-13, Ex-14, Ex-17, Ex-20, Ex-31, Ex-34, Ex-35, Ex-36, Ex-37, Ex-38, Ex-42, Ex-45, Ex-46, Ex-47, Ex-48, Ex-49, Ex-50, Ex-51, Ex-52, Ex-56, Ex-57, Ex-58, Ex-60, Ex-62, Ex-64, Ex-70* and Ex-73 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 100% infected.
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The plants were then cultivated in the greenhouse for 7 days and then inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24° C. and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-1, Ex-2, Ex-35, Ex-37, Ex-49 and Ex-63 respectively, showed up to at most 15% growth of the pathogen whereas the untreated plants were 90% infected.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOE solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Colletotrichum orbiculare in an aqueous bio malt solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21174263.0 | May 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/062598 | 5/10/2022 | WO |
