Substituted tetrahydrobenzodiazepines as fungicides
By developing new tetrahydrobenzodiazepine compounds and their derivatives, the problem of poor fungicidal activity in existing compounds at low application rates is solved, and a wider activity spectrum and better toxicological and environmental destination characteristics are achieved.
Patent Information
- Application Number
- CN202380079335.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-11-16
- Filing Date
- 2023-11-07
- Publication Date
- 2025-06-24
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Figure CN120202194A_ABST
Abstract
Description
[0001] The present invention relates to novel tetrahydrobenzodiazepines as fungicides The invention also relates to a composition comprising at least one compound I, a method for combating phytopathogenic fungi, and seeds coated with at least one compound of formula I.
[0002] WO 2011037128 discloses some tetrahydrobenzodiazepines Compounds. However, in many cases, especially at low application rates, the fungicidal activity of the known compounds is not satisfactory. Based on this, one object of the present invention is to provide compounds with improved activity and / or a broader spectrum of activity against phytopathogenic fungi. Another object of the present invention is to provide fungicides with improved toxicological properties or with improved environmental fate properties.
[0003] These and further objects are achieved by the tetrahydrobenzodiazepines of formula (I) as defined below Compounds and agriculturally suitable implementations thereof.
[0004] Therefore, the present invention relates to a compound having formula I or an N-oxide, tautomer, stereoisomer or agriculturally acceptable salt thereof
[0005]
[0006] Y is N, CR 1 ;
[0007] R 1 is independently selected at each occurrence from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl;
[0008] R 2 is independently selected at each occurrence from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, O-C1-C6-alkyl, O-C2-C6-alkenyl, O-C2-C6-alkynyl, C3-C6-cycloalkyl, S-C1-C6-alkyl, S-C2-C6-alkenyl, S-C2-C6-alkynyl;
[0009] R 3independently selected, in each case, from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, O-C1-C6-alkyl, O-C2-C6-alkenyl, O-C2-C6-alkynyl, C3-C6-cycloalkyl, S-C1-C6-alkyl, S-C2-C6-alkenyl, S-C2-C6-alkynyl; and
[0010] R 2 and R 3 together with the carbon atom to which they are attached form a phenyl group which is unsubstituted or bears 1, 2 or 3 substituents R 23a ; where
[0011] each R 23a is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl;
[0012] R 4 is independently selected, in each case, from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl;
[0013] R 5 is independently selected, in each case, from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or bear 1, 2 or 3 substituents R 5a ; where
[0014] each R 5a is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl;
[0015] R 6 is independently selected, in each case, from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or bear 1, 2 or 3 substituents R 6a ; where
[0016] each R 6aindependently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl;
[0017] or
[0018] R 5 and R 6 together form an oxo group (=O); or a thio group (=S);
[0019] or
[0020] R 5 and R 6 together with the carbon atom to which they are attached form a 3-, 4-, 5- or 6-membered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1, 2 or 3 heteroatoms selected from O and S as ring members; wherein the carbocyclic or heterocyclic ring is unsubstituted or bears 1, 2 or 3 substituents R 56 ; wherein
[0021] each R 56 independently is halogen, C1-C6-alkyl or C1-C6-haloalkyl;
[0022] R 7 in each case independently is selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein these aliphatic or aromatic groups are unsubstituted or bear 1, 2 or 3 substituents R 7a ; wherein
[0023] each R 7a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl;
[0024] R 8 in each case independently is selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein these aliphatic or aromatic groups are unsubstituted or bear 1, 2 or 3 substituents R 8a ; wherein
[0025] each R 8ais independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl;
[0026] or
[0027] R 7 and R 8 together form an oxo group (=O) or a thio group (=S);
[0028] or
[0029] R 7 and R 8 together with the carbon atom to which they are attached form a 3-, 4-, 5- or 6-membered saturated carbon ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1, 2 or 3 heteroatoms selected from O and S as ring members;
[0030] R 9 is in each case independently selected from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a , a five- or six-membered heteroaryl, aryl or benzyl; wherein the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; wherein the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; wherein the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen;
[0031] wherein
[0032] R 9ais C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, where the benzene ring in the last two mentioned groups is unsubstituted or bears 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl;
[0033] R 9′ is independently selected in each case from H, CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a a five- or six-membered heteroaryl, aryl or benzyl; where the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; where the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; where the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen;
[0034] where
[0035] R 9′a is C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, where the benzene ring in the last two mentioned groups is unsubstituted or bears 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl;
[0036] X is independently selected, in each case, from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, phenyl, benzyl, phenoxy, benzyloxy, C1-C6-thioalkyl;
[0037] N is 0, 1, 2 or 3.
[0038] The N-oxides can be prepared from the compounds of the invention by conventional oxidation methods, for example by treatment of the compound I with an organic peracid such as m-chloroperbenzoic acid (see WO 03 / 64572 or J. Med. Chem. [Journal of Medicinal Chemistry] 38(11), 1892-903, 1995); or with an inorganic oxidant such as hydrogen peroxide (see J. Heterocyc. Chem. [Journal of Heterocyclic Chemistry] 18(7), 1305-8, 1981) or potassium peroxymonosulfate preparation (see J. Am. Chem. Soc. [Journal of the American Chemical Society] 123(25), 5962-5973, 2001). The oxidation can give pure mono-N-oxides or mixtures of different N-oxides, which can be separated by conventional methods such as chromatography.
[0039] The agriculturally acceptable salts of the compounds of formula I particularly encompass salts of cations or acid addition salts of acids, where these cations and anions respectively have no adverse effect on the fungicidal action of the compound I. Suitable cations are in particular alkali metal (preferably sodium and potassium) ions, alkaline earth metal (preferably calcium, magnesium and barium) ions, transition metal (preferably manganese, copper, zinc and iron) ions, and also ammonium ions, which, if desired, can be substituted by 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 tris(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tris(C1-C4-alkyl)sulfoxonium.
[0040] The anions of the acceptable acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compound I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
[0041] Compounds having formula I may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers resulting from restricted rotation about a single bond of an asymmetric group, and geometric isomers. They also form part of the subject matter of the present invention. Those skilled in the art will understand that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. In addition, those skilled in the art know how to separate, enrich, and / or selectively prepare the stereoisomers. The compounds of the present invention may exist as mixtures of stereoisomers (e.g., racemates), individual stereoisomers, or as optically active forms.
[0042] Compounds having formula I may exist in different crystalline modifications, the biological activity of which may differ. They also form part of the subject matter of the present invention.
[0043] With respect to the variables, examples of the intermediates obtained during the preparation of compound I correspond to the examples of the compounds having formula I. The term "compound I" refers to the compounds having formula I.
[0044] Hereinafter, the intermediate compounds are further described. Those skilled in the art will readily understand that the preferred options for the substituents given herein in connection with compound I, and in particular the preferred options given in the following table for the respective substituents, apply correspondingly to the intermediates. Thus, the substituents in each case independently of one another or more preferably in combination have the meanings as defined herein.
[0045] If the synthesis yields a mixture of isomers, separation is generally not necessarily required, since in some cases the individual isomers may interconvert during the work-up for use or during administration (e.g., under the action of light, acids or bases). Such conversions may also occur after use, for example in the treated plant in the case of plant treatment, or in the harmful fungi to be controlled.
[0046] In the definitions of the variables given above, collective terms are used which generally represent the substituents in question. The term "C n -C m " indicates the possible number of carbon atoms in the substituent or substituent part in question in each case.
[0047] The term "halogen" means fluorine, chlorine, bromine and iodine.
[0048] The term "C1-C6-alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 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. Similarly, the term "C2-C4-alkyl" refers to a straight-chain or branched-chain alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (isopropyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl).
[0049] The term "C1-C6-haloalkyl" 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 described above. Examples are "C1-C2-haloalkyl" 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.
[0050] The term "C2-C6-alkenyl" refers to a straight-chain or branched-chain unsaturated hydrocarbon group having 2 to 6 carbon atoms and having a double bond at any position. Examples are "C2-C4-alkenyl" groups such as vinyl, 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.
[0051] The term "C2-C6-haloalkenyl" 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 described above.
[0052] The term "C2-C6-alkynyl" refers to a straight-chain or branched-chain unsaturated hydrocarbon group 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.
[0053] The term "C2-C6-haloalkynyl" 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 described above.
[0054] The term "C3-C6-cycloalkyl" refers to a monocyclic saturated hydrocarbon group having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Thus, saturated three-, four-, five-, six-, seven-, eight-, nine- or ten-membered carbocyclic groups or carbocycles are "C3-C 10 -cycloalkyl".
[0055] The term "C3-C8-cycloalkyl-C1-C4-alkyl" refers to an alkyl group having 1 to 4 carbon atoms (as defined above), wherein at least one hydrogen atom of the alkyl group is replaced by a cycloalkyl group having 3 to 8 carbon atoms (as defined above).
[0056] The term "saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine- or ten-membered heterocyclic group or heterocycle, wherein the heterocyclic group or heterocycle contains 1, 2, 3 or 4 heteroatoms selected from N, O and S" is to be understood to mean both saturated heterocycles and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include, in addition to carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of O, N and S. For example:
[0057] 3- or 4-membered saturated heterocycles containing 1 or 2 heteroatoms selected from the group consisting of O, N and S as ring members, such as ethylene oxide, aziridine, thiirane, oxetane, azetidine, thietane, [1,2]dioxetane, [1,2]dithietane, [1,2]diazetane; and
[0058] A 5- or 6-membered saturated or partially unsaturated heterocycle containing 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S as ring members, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,4-dihydrofuran-2-yl, 2,4-dihydrofuran-3-yl, 2,3-dihydrothiophen-2-yl, 2,3-dihydrothiophen-3-yl, 2,4-dihydrothiophen-2-yl, 2,4-dihydrothiophen-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydro-1,3,5-triazin-2-yl and 1,2,4-hexahydro-1,2,4-triazin-3-yl, and also the corresponding -ylidene groups; and,
[0059] 7-membered saturated or partially unsaturated heterocycles such as tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1H]azepin- -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin- -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]azepin- -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepin- -1-, -2-, -3- or -4-yl, hexahydroazepin- -1-, -2-, -3- or -4-yl, tetra- and hexahydrooxepinyl, such as 2,3,4,5-tetrahydro[1H]oxepin- -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]oxepin- -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxepin- -2-, -3-, -4-, -5-, -6- or -7-yl, hexahydrooxepin- -1-, -2-, -3- or -4-yl, tetra- and hexahydro-1,3-diazepinyl, tetra- and hexahydro-1,4-diazepinyl, tetra- and hexahydro-1,3-oxazepinyl, tetra- and hexahydro-1,4-oxazepinyl, tetra- and hexahydro-1,3-dioxepinyl, tetra- and hexahydro-1,4-dioxepinyl, and the corresponding -ylidene groups.
[0060] The term "substituted" means substituted by 1, 2, 3 or up to the maximum possible number of substituents.
[0061] The term "5- or 6-membered heteroaryl" or "5- or 6-membered heteroaromatic group" refers to an aromatic ring system that contains 1, 2, 3, or 4 heteroatoms independently selected from the group consisting of N, O, and S in addition to carbon atoms, such as
[0062] 5-membered heteroaryl, such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, thiophen-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-triazol-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
[0063] 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, and 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
[0064] Hereinafter, specific embodiments of the compounds of the present invention are described. Among them, the specific meanings of the corresponding substituents are further detailed, and these meanings are in each case by themselves and in any combination with each other are specific embodiments of the present invention.
[0065] In addition, with respect to the variables, generally, the embodiments of Compound I are equally applicable to the intermediates.
[0066] According to one embodiment of the compound having the formula I, Y is N.
[0067] According to one embodiment of the compound having the formula I, Y is CR 1 .
[0068] According to one embodiment of the compound having the formula I, R 1 is independently selected from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl in each case, preferably R 1 is independently selected from H, C1-C4-alkyl, C1-C4-haloalkyl in each case, more preferably R 1 is independently selected from H, C1-C4-alkyl in each case, most preferably R1 is H in each case.
[0069] According to one embodiment of the compound of formula I, R 2 is independently selected from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, O-C1-C6-alkyl, O-C2-C6-alkenyl, O-C2-C6-alkynyl, C3-C6-cycloalkyl, S-C1-C6-alkyl, S-C2-C6-alkenyl, S-C2-C6-alkynyl.
[0070] According to one embodiment of the compound of formula I, R 2 is independently selected from C1-C4-alkyl and C1-C4-haloalkyl in each case, preferably R 2 is independently selected from H, C1-C4-alkyl, C1-C4-haloalkyl in each case, more preferably R 2 is independently selected from CH3 and CF2H in each case, most preferably R 2 is CH3 in each case.
[0071] According to yet another embodiment of formula I, R 2 is halogen, especially F, Cl, Br or I, more specifically F, Cl or Br, especially F or Cl.
[0072] According to yet another embodiment of formula I, R 2 is F.
[0073] According to yet another embodiment of formula I, R 2 is Cl.
[0074] According to yet another embodiment of formula I, R 2 is Br.
[0075] According to yet another embodiment of formula I, R 2 is CN.
[0076] According to yet another embodiment of formula I, R 2 is C1-C6-alkyl, especially C1-C4-alkyl, such as CH3 or C2H5, especially CH3 or CH2CH3.
[0077] According to yet another embodiment of formula I, R 2 is C1-C6-haloalkyl, especially C1-C4-haloalkyl, such as CF3.
[0078] According to yet another embodiment of formula I, R 2is a C2-C6-alkenyl, especially a C2-C4-alkenyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
[0079] In another specific embodiment according to formula I, R 2 is a C2-C6-haloalkenyl, especially a C2-C4-haloalkenyl, more specifically a C2-C3-haloalkenyl, 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.
[0080] In still another embodiment according to formula I, R 2 is a C2-C6-alkynyl or a C2-C6-haloalkynyl, especially a C2-C4-alkynyl or a C2-C4-haloalkynyl, such as C≡CH, CH2C≡CH, C≡CCl, CH2C≡CCl, or CCl2C≡CCl.
[0081] In another specific embodiment according to formula I, R 2 is O-C1-C6-alkyl, especially C1-C4-alkyl, more specifically C1-C2-alkoxy. R 2 is such as OCH3 or OCH2CH3.
[0082] In another specific embodiment according to formula I, R 2 is O-C1-C6-alkyl.
[0083] In another specific embodiment according to formula I, R 2 is O-C2-C6-alkenyl, especially C2-C4-alkenyl, more specifically C2-C3-alkenyl. R 2 is such as OCH=CH2, OCH2CH=CH2.
[0084] In another specific embodiment according to formula I, R 2 is O-C2-C6-alkynyl, especially C2-C6-alkynyl, especially C2-C4-alkynyl, more specifically C2-C3-alkynyl. R 2 is such as O-CH2-C≡CH.
[0085] In still another embodiment according to formula I, R 2 is a C3-C6-cycloalkyl, especially cyclopropyl or cyclobutyl.
[0086] In another specific embodiment according to formula I, R 2is an S-C1-C6-alkyl, especially a C1-C4-alkyl, more specifically a C1-C2-alkoxy. R 2 is such as SCH3 or SCH2CH3.
[0087] According to another specific embodiment of formula I, R 2 is an S-C1-C6-alkyl.
[0088] According to another specific embodiment of formula I, R 2 is an S-C2-C6-alkenyl, especially a C2-C4-alkenyl, more specifically a C2-C3-alkenyl. R 2 is such as SCH=CH2, SCH2CH=CH2.
[0089] According to another specific embodiment of formula I, R 2 is an S-C2-C6-alkynyl, especially a C2-C6-alkynyl, especially a C2-C4-alkynyl, more specifically a C2-C3-alkynyl. R 2 is such as S-CH2-CΞCH.
[0090] R according to the present invention 2 The particularly preferred embodiments are in Table P2 below, where each row from P2-1 to P2-21 corresponds to a specific embodiment of the present invention, and any combination of P2-1 to P2-21 with each other is a preferred embodiment of the present invention. The connection point of the carbon atom bonded to R 2 is marked with "#" in the figure.
[0091] Table P2:
[0092]
[0093]
[0094] According to one embodiment of formula I, R 3 is selected from the group consisting of: C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, especially CH3, C2H5, CF3, CH2F, CHF2, cyclopropyl, cyclobutyl, more specifically CH3, CH2F, CF2H, CF3, cyclopropyl, cyclobutyl, most preferably CH3, CF2H.
[0095] According to yet another embodiment of formula I, R 3 is a C1-C6-alkyl, especially a C1-C4-alkyl, such as CH3 or C2H5, especially CH3 or CH2CH3.
[0096] According to yet another embodiment of formula I, R 3is a C1-C6-haloalkyl, especially a C1-C4-haloalkyl, such as CF3, FCH2, F2CH, CF3CH2.
[0097] In yet another embodiment according to formula I, R 3 is a C2-C6-alkenyl, especially a C2-C4-alkenyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
[0098] In yet another embodiment according to formula I, R 3 is a C2-C6-alkynyl or a C2-C6-haloalkynyl, especially a C2-C4-alkynyl or a C2-C4-haloalkynyl, such as C≡CH, CH2C≡CH, C≡CCl, CH2C≡CCl, or CCl2C≡CCl.
[0099] In another specific embodiment according to formula I, R 3 is O-C1-C6-alkyl, especially C1-C4-alkyl, more specifically C1-C2-alkoxy. R 3 is such as OCH3 or OCH2CH3.
[0100] In another specific embodiment according to formula I, R 3 is O-C2-C6-alkenyl, especially C2-C4-alkenyl, more specifically C2-C3-alkenyl. R 3 is such as OCH=CH2, OCH2CH=CH2.
[0101] In another specific embodiment according to formula I, R 3 is O-C2-C6-alkynyl, especially C2-C6-alkynyl, especially C2-C4-alkynyl, more specifically C2-C3-alkynyl. R 3 is such as O-CH2-C≡CH.
[0102] In another specific embodiment according to formula I, R 3 is O-C1-C6-haloalkyl, especially OCF3, OCCl3, OFCH2, OClCH2, OF2CH, OCl2CH, OCF3CH2, OCCl3CH2 or OCF2CHF2, more specifically OCF3, OF2CH, OFCH2.
[0103] In yet another embodiment according to formula I, R 3 is a C3-C6-cycloalkyl, especially cyclopropyl, cyclobutyl.
[0104] In another specific embodiment according to formula I, R 3 is S-C1-C6-alkyl, especially C1-C4-alkyl, more specifically C1-C2-alkoxy. R 2is such as SCH3 or SCH2CH3.
[0105] According to another specific embodiment of formula I, R 3 is S-C1-C6-alkyl.
[0106] According to another specific embodiment of formula I, R 3 is S-C2-C6-alkenyl, especially C2-C4-alkenyl, more specifically C2-C3-alkenyl. R 2 is such as SCH=CH2, SCH2CH=CH2.
[0107] According to another specific embodiment of formula I, R 3 is S-C2-C6-alkynyl, especially C2-C6-alkynyl, especially C2-C4-alkynyl, more specifically C2-C3-alkynyl. R 2 is such as S-CH2-CΞCH.
[0108] In a particularly preferred embodiment of R according to the present invention 3 is in Table P3 below, where each row from P3-1 to P3-17 corresponds to a specific embodiment of the present invention, and any combination of P3-1 to P3-17 with each other is a preferred embodiment of the present invention. The point of attachment of the carbon atom bonded to R 3 is marked with "#" in the figure.
[0109] Table P3:
[0110]
[0111] In addition, R 2 and R 3 form a benzene ring with the C atom to which they are bonded:
[0112]
[0113] According to an embodiment of the compound having formula I, R 23a is H.
[0114] According to an embodiment (Embodiment Z.1) of the compound having formula I, R 23a is independently selected from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, O-C1-C6-alkyl in each case.
[0115] According to an embodiment (Embodiment Z.2) of the compound having formula I, R 23a is independently selected from halogen in each case.
[0116] According to an embodiment (Embodiment Z.3) of the compound having formula I, R 23aIndependently selected from F and Cl in each case.
[0117] According to one embodiment (Embodiment Z.4) of the compound of formula I, R 23a Is defined in sub-formulas (z.1 to z.22).
[0118]
[0119]
[0120] According to one embodiment of the compound of formula I, R 4 Is independently selected from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl in each case; preferably, R 4 Is independently selected from H, C1-C4-alkyl, C1-C4-haloalkyl in each case; more preferably, R 4 Is independently selected from H, C1-C4-alkyl in each case; most preferably, R 4 Is H in each case.
[0121] According to one embodiment of the compound of formula I, R 5 Is independently selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2-heteroaryl in each case; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 5a ; wherein each R 5a Is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl.
[0122] According to one embodiment of the compound of formula I, R 5 Is independently selected from C1-C6-alkyl (Embodiment 5.1), C1-C6-haloalkyl (Embodiment 5.2), C1-C6-alkyl-O-C1-C6-alkyl (Embodiment 5.3), phenyl, CH2-phenyl (Embodiment 5.4) in each case, wherein phenyl and CH2-phenyl are unsubstituted or substituted by one or two halogens.
[0123] According to a further embodiment of the compound of formula I, R 5 Is CH3 or CF3.
[0124] According to a further embodiment of the compound of formula I, R 5 Is CH3.
[0125] According to a further embodiment of the compound of formula I, R 5 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-O-CH3.
[0126] According to a further embodiment of the compound of formula I, R 5 is CH=CH2, CH2CH=CH2.
[0127] According to a further embodiment of the compound of formula I, R 5 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.
[0128] According to an embodiment of the compound of formula I, R 6 is in each case independently selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 6a ; where each R 6a is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl.
[0129] According to an embodiment of the compound of formula I, R 6 is in each case independently selected from C1-C6-alkyl (Example 6.1), C1-C6-alkyl-O-phenyl (Example 6.2), C1-C6-alkyl-O-C1-C6-alkyl (Example 6.3).
[0130] According to a further embodiment of the compound of formula I, R 6 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, CH=CH2, CH2CH=CH2, CH2-phenyl.
[0131] According to a further embodiment of the compound of formula I, R 5 and R 6 together with the C atom to which they are bonded form a C3-C6-cycloalkyl, or a 3- to 6-membered saturated heterocycle containing 1, 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle may be unsubstituted or substituted by halogen, C1-C6-alkyl, C1-C6-haloalkyl.
[0132] According to a further embodiment of the compound of formula I, R 5 and R 6 form a C3-C6-cycloalkyl (Example 6.4).
[0133] According to a further embodiment of the compound of formula I, R 5 and R 6 form a 3- to 6-membered saturated heterocycle containing 1, 2 or 3 heteroatoms from the group consisting of O and S.
[0134] According to a further embodiment of the compound of formula I, R 5 and R 6 together form a (=O) group (Example 6.5).
[0135] According to a further embodiment of the compound of formula I, R 5 and R 6 together form a (=S) group.
[0136] Preferred embodiments of R 5 and R 6 of the present invention are shown in Table P5 below, where each row from P5-1 to P5-19 corresponds to a specific embodiment of the present invention, and any combination of P5-1 to P5-19 with each other is a preferred embodiment of the present invention. The point of attachment of the carbon atom bonded to R 5 and R 6 is marked with "#" in the figure.
[0137] Table P5,6:
[0138]
[0139]
[0140] According to an embodiment of the compound of formula I, R 7independently selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl in each case; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 7a ; where each R 7a is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl.
[0141] According to one embodiment of the compounds of formula I, R 7 is independently selected from C1-C6-alkyl (Example 7.1), C1-C6-haloalkyl (Example 7.2), C1-C6-alkyl-O-C1-C6-alkyl (Example 7.3), phenyl, CH2-phenyl (Example 7.4), where phenyl and CH2-phenyl are unsubstituted or substituted by one or two halogens.
[0142] According to a further embodiment of the compounds of formula I, R 7 is CH3 or CF3.
[0143] According to a further embodiment of the compounds of formula I, R 7 is CH3.
[0144] According to a further embodiment of the compounds of formula I, R 7 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-O-CH3, CH=CH2, CH2CH=CH2.
[0145] According to a further embodiment of the compounds of formula I, R 7 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.
[0146] According to one embodiment of the compounds of formula I, R 8independently selected from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl in each case; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 8a ; where each R 8a is independently halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl.
[0147] According to one embodiment of the compound of formula I, R 8 is independently selected from C1-C6-alkyl (Example 8.1), C1-C6-alkyl-O-phenyl (Example 8.2), C1-C6-alkyl-O-C1-C6-alkyl (Example 8.3) in each case.
[0148] According to a further embodiment of the compound of formula I, R 8 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, CH=CH2, CH2CH=CH2, CH2-phenyl.
[0149] According to a further embodiment of the compound of formula I, R 7 and R 8 together with the C atom to which they are bonded form a C3-C6-cycloalkyl, or a 3- to 6-membered saturated heterocycle containing 1, 2 or 3 heteroatoms from the group consisting of O and S, where the cycloalkyl or heterocycle can be unsubstituted or substituted by halogen, C1-C6-alkyl, C1-C6-haloalkyl.
[0150] According to a further embodiment of the compound of formula I, R 7 and R 8 form a C3-C6-cycloalkyl (Example 8.4).
[0151] According to a further embodiment of the compound of formula I, R 7 and R 8 form a 3- to 6-membered saturated heterocycle containing 1, 2 or 3 heteroatoms from the group consisting of O and S.
[0152] According to a further embodiment of the compound of formula I, R 7 and R 8 together form a (=O) group (Example 8.5).
[0153] Preferred embodiments of R 7 and R 8 of the present invention are shown in Table P78 below, where each row from P7-1 to P7-19 corresponds to a specific embodiment of the present invention, and any combination of P7-1 to P7-19 with each other is a preferred embodiment of the present invention. The point of attachment of the carbon atom bonded to R 7 and R 8 is marked with "#" in the figure.
[0154] Table P7,8:
[0155]
[0156]
[0157] According to a further embodiment of the compound of formula I,
[0158] R 9 is independently selected in each case from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a , a five- or six-membered heteroaryl, aryl or benzyl; wherein the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; wherein the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; wherein the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen;
[0159] wherein
[0160] R 9ais C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, where the benzene ring in the last two mentioned groups is unsubstituted or carries 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl.
[0161] In yet another embodiment according to formula I, R 9 is Cl, F.
[0162] In yet another embodiment according to formula I, R 9 is CN, CH2CN or CH(CH3)CN.
[0163] In another specific embodiment according to formula I, R 9 is CH(=O).
[0164] In another specific embodiment according to formula I, R 9 is OCH3 or OCH2CH3.
[0165] In another specific embodiment according to formula I, R 9 is C(=O)C1-C6-alkyl, where the alkyl is CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or isopentyl.
[0166] In another specific embodiment according to formula I, R 9 is C(=O)C2-C6-alkenyl, where the alkenyl is CH=CH2, CH2CH=CH2.
[0167] In another specific embodiment according to formula I, R 9 is C(=O)C2-C6-alkynyl, where the alkynyl is CΞCH, CH2CΞCH.
[0168] In another specific embodiment according to formula I, R 9 is C(=O)C3-C6-cycloalkyl, where the cycloalkyl is cyclopropyl (C3H7) or cyclobutyl (C4H9).
[0169] In another specific embodiment according to formula I, R 9 is C(=O)NH-C1-C4-alkyl or C(=O)N-(C1-C4-alkyl)2, where the alkyl is CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
[0170] In yet another embodiment according to formula I, R 9is a C1-C6-alkyl group such as CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or isopentyl.
[0171] In yet another embodiment according to formula I, R 9 is a C1-C6-alkyl group, especially a C1-C4-alkyl group such as CH3, C2H5, n-propyl, isopropyl.
[0172] In yet another embodiment according to formula I, R 9 is a C1-C6-haloalkyl group, especially a C1-C4-haloalkyl group such as CF3, CCl3, FCH2, ClCH2, F2CH, Cl2CH, CF3CH2, CCl3CH2 or CF2CHF2.
[0173] In yet another embodiment according to formula I, R 9 is a C3-C6-cycloalkyl group, especially cyclopropyl.
[0174] In yet another embodiment according to formula I, R 9 is a C3-C6-halocycloalkyl group. In a specific embodiment, R 9b is a fully or partially halogenated cyclopropyl group such as 1-F-cyclopropyl, 1-Cl-cyclopropyl, 1,1-F2-cyclopropyl, 1,1-Cl2-cyclopropyl.
[0175] In yet another embodiment according to formula I, R 9 is a C2-C6-alkenyl group, especially a C2-C4-alkenyl group such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
[0176] In another specific embodiment according to formula I, R 9 is a C2-C6-haloalkenyl group, especially a C2-C4-haloalkenyl group, more specifically a C2-C3-haloalkenyl group 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.
[0177] In yet another embodiment according to formula I, R 9 is a C2-C6-alkynyl group or a C2-C6-haloalkynyl group, especially a C2-C4-alkynyl group or a C2-C4-haloalkynyl group such as C≡CH, CH2C≡CH.
[0178] In yet another embodiment according to formula I, R 9 is -S(=O)2-R 9a wherein R9a Preferably a C1-C6-alkyl group, especially a C1-C4-alkyl group, such as CH3, C2H5, n-propyl, isopropyl.
[0179] In yet another embodiment according to formula I, R 9 is an aryl group, especially a phenyl group, where the aryl or phenyl moiety is in each case unsubstituted or substituted by the same or different groups R which are independently selected from the following 9b substituents: halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl and C1-C2-haloalkoxy, especially F, Cl, Br, CH3, OCH3, CF3 and OCF3. According to one embodiment, R 9 is an unsubstituted phenyl group. According to another embodiment, R 9 is a phenyl group substituted by one, two or three (especially one) halogens especially selected from F, Cl and Br, more specifically selected from F and Cl.
[0180] In yet another embodiment according to formula I, R 9 is a 5-membered heteroaryl group, such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, thiophen-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-triazol-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.
[0181] In yet another embodiment according to formula I, R 9 is a 6-membered heteroaryl group, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
[0182] In yet another embodiment according to formula I, R 9independently selected from H, halogen, OH, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy and C3-C6-cycloalkyl in each case, where R 9 the acyclic part of is unsubstituted or substituted by the same or different groups R as defined and preferably as defined herein 9a and where R 9 the carbocyclic, phenyl and heteroaryl parts of are unsubstituted or substituted by the same or different groups R as defined and preferably as defined herein 9b substituted.
[0183] Particularly preferred embodiments of R according to the invention are in Table P9 below, where each row from P9-1 to P9-31 corresponds to a specific embodiment of the invention, and where P9-1 to P9-31 in any combination with each other are preferred embodiments of the invention. The point of attachment of the carbon atom bonded to R 9 is marked with "#" in the figure. 9
[0184] Table P9:
[0185]
[0186]
[0187] R 9 ′ is independently selected from H, CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a , a five- or six-membered heteroaryl, aryl or benzyl; wherein the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; wherein the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; wherein the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen;
[0188] wherein
[0189] R 9a is C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, wherein the benzene ring in the last two mentioned groups is unsubstituted or bears 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl.
[0190] In yet another embodiment according to formula I, R 9 ′ is H.
[0191] In yet another embodiment according to formula I, R 9 ′ is Cl, F.
[0192] In yet another embodiment according to formula I, R 9 ′ is CN, CH2CN or CH(CH3)CN.
[0193] In another specific embodiment according to formula I, R 9 ′ is CH(=O).
[0194] In another specific embodiment according to formula I, R 9 ′ is OCH3 or OCH2CH3.
[0195] In another specific embodiment according to formula I, R 9 ′ is C(=O)C1-C6-alkyl, wherein the alkyl is CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or isopentyl.
[0196] In another specific embodiment according to formula I, R 9 ′ is C(=O)C2-C6-alkenyl, wherein the alkenyl is CH=CH2, CH2CH=CH2.
[0197] In another specific embodiment according to formula I, R9 ' is C(=O)C2-C6-alkynyl, wherein the alkynyl is C≡CH, CH2C≡CH.
[0198] In another specific embodiment according to formula I, R 9 ' is C(=O)C3-C6-cycloalkyl, wherein the cycloalkyl is cyclopropyl (C3H7) or cyclobutyl (C4H9).
[0199] In another specific embodiment according to formula I, R 9 ' is C(=O)NH-C1-C4-alkyl or C(=O)N-(C1-C4-alkyl)2, wherein the alkyl is CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
[0200] In yet another embodiment according to formula I, R 9 ' is C1-C6-alkyl, such as CH3, C2H5, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or isopentyl.
[0201] In yet another embodiment according to formula I, R 9 ' is C1-C6-alkyl, especially C1-C4-alkyl, such as CH3, C2H5, n-propyl, isopropyl.
[0202] In yet another embodiment according to formula I, R 9 ' is C1-C6-haloalkyl, especially C1-C4-haloalkyl, such as CF3, CCl3, FCH2, ClCH2, F2CH, Cl2CH, CF3CH2, CCl3CH2 or CF2CHF2.
[0203] In yet another embodiment according to formula I, R 9 ' is C3-C6-cycloalkyl, especially cyclopropyl.
[0204] In yet another embodiment according to formula I, R 9 ' is C3-C6-halocycloalkyl. In a particular embodiment, R 9′b is a fully or partially halogenated cyclopropyl, such as 1-F-cyclopropyl, 1-Cl-cyclopropyl, 1,1-F2-cyclopropyl, 1,1-Cl2-cyclopropyl.
[0205] In yet another embodiment according to formula I, R 9′ is C2-C6-alkenyl, especially C2-C4-alkenyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
[0206] In another specific embodiment according to formula I, R 9′is a C2-C6-haloalkenyl, in particular a C2-C4-haloalkenyl, more specifically a C2-C3-haloalkenyl, 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.
[0207] In yet another embodiment according to formula I, R 9′ is a C2-C6-alkynyl or a C2-C6-haloalkynyl, in particular a C2-C4-alkynyl or a C2-C4-haloalkynyl, such as C≡CH, CH2C≡CH.
[0208] In yet another embodiment according to formula I, R 9′ is -S(=O)2-R 9′a wherein R 9′a is preferably a C1-C6-alkyl, in particular a C1-C4-alkyl, such as CH3, C2H5, n-propyl, isopropyl.
[0209] In yet another embodiment according to formula I, R 9′ is an aryl, in particular a phenyl, wherein the aryl or phenyl moiety is in each case unsubstituted or substituted by the same or different groups R 9′b independently of one another selected from the following: halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl and C1-C2-haloalkoxy, in particular F, Cl, Br, CH3, OCH3, CF3 and OCF3. According to one embodiment, R 9′ is an unsubstituted phenyl. According to another embodiment, R 9′ is a phenyl substituted by one, two or three (in particular one) halogen(s) especially selected from F, Cl and Br, more specifically selected from F and Cl.
[0210] In yet another embodiment according to formula I, R 9′is a 5-membered heteroaryl, such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, thiophen-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-triazol-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.
[0211] According to yet another embodiment of formula I, R 9′ is a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
[0212] According to yet another embodiment of formula I, R 9′ is independently selected in each case from H, halogen, OH, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy and C3-C6-cycloalkyl, where the acyclic part of R 9′ is unsubstituted or substituted by the same or different groups R as defined and preferably as defined herein 9′a and where the carbocyclic, phenyl and heteroaryl parts of R 9′ are unsubstituted or substituted by the same or different groups R as defined and preferably as defined herein 9′b substituted.
[0213] Particularly preferred embodiments of R according to the invention 9″ are in Table P9' below, where each row from P9'-1 to P9'-32 corresponds to a specific embodiment of the invention, where P9'-1 to P9'-32 can also be arbitrarily combined with each other as preferred embodiments of the invention. The point of attachment of the carbon atom bonded to R 9′ is marked with "#" in the figure.
[0214] Table P9':
[0215]
[0216]
[0217] According to one embodiment of the compound of formula I, X is independently selected in each case from halogen (Embodiment X.1), CN, C1-C6-alkyl (Embodiment X.2), C1-C6-haloalkyl (Embodiment X.3), O-C1-C6-alkyl (Embodiment X.4), O-C1-C6-haloalkyl (Embodiment X.5).
[0218] According to one embodiment of the compound of formula I, X is independently selected in each case from halogen, O-C1-C6-alkyl.
[0219] According to one embodiment of the compound of formula I, X is independently selected in each case from F or Cl.
[0220] According to one embodiment of the compound of formula I, X is C3-C6-cycloalkyl.
[0221] According to one embodiment of the compound of formula I, n is 0.
[0222] According to one embodiment of the compound of formula I, n is 1.
[0223] According to one embodiment of the compound of formula I, n is 2.
[0224] According to one embodiment, Xn is defined as follows:
[0225]
[0226] and X is selected from F, Cl, I, CH3, cyclopropyl, CH=CH2, CΞCH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
[0227] According to one embodiment, Xn is defined as follows:
[0228]
[0229] and X is F.
[0230] According to one embodiment, Xn is defined as follows:
[0231]
[0232] and X is selected from F, Cl, I, CH3, cyclopropyl, CH=CH2, CΞCH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
[0233] According to one embodiment, Xn is defined as follows:
[0234]
[0235] And X is F.
[0236] According to one embodiment, n is 0.
[0237] In a further aspect, the present invention relates to embodiments E.1 to E.275 listed in Table E, which represent preferred combinations of the embodiments defined above for each of the variables R 2 、R 3 and X (represented by embodiments X.1 to X.6), and n in the compound of formula I is defined as follows.
[0238]
[0239] Table E:
[0240]
[0241]
[0242]
[0243]
[0244]
[0245]
[0246]
[0247]
[0248] In a further aspect, the present invention relates to embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.1, and R 6 is represented by embodiment 6.1.
[0249] In a further aspect, the present invention relates to embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.2, and R 6 is represented by embodiment 6.1.
[0250] In a further aspect, the present invention relates to embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.3, and R 6 is represented by embodiment 6.1.
[0251] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.4, and R 6 is represented by Example 6.1.
[0252] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.1, and R 6 is represented by Example 6.2.
[0253] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.2, and R 6 is represented by Example 6.2.
[0254] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.3, and R 6 is represented by Example 6.2.
[0255] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.4, and R 6 is represented by Example 6.2.
[0256] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.1, and R 6 is represented by Example 6.3.
[0257] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.2, and R 6 is represented by Example 6.3.
[0258] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.3, and R 6 is represented by Example 6.3.
[0259] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 5 is represented by Example 5.4, and R 6 is represented by Example 6.3.
[0260] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 5 and R 6 are represented by Example 6.4.
[0261] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 5 and R 6 are represented by Example 6.5.
[0262] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.1, and R 8 is represented by Example 8.1.
[0263] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.2, and R 8 is represented by Example 8.1.
[0264] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.3, and R 8 is represented by Example 8.1.
[0265] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.4, and R 8 is represented by Example 8.1.
[0266] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.1, and R 8 is represented by Example 8.2.
[0267] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.2, and R 8 is represented by Example 8.2.
[0268] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R 7 is represented by Example 7.3, and R 8 is represented by Example 8.2.
[0269] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, where R7 represented by Example 7.4, and R 8 represented by Example 8.2.
[0270] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 is represented by Example 7.1, and R 8 is represented by Example 8.3.
[0271] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 is represented by Example 7.2, and R 8 is represented by Example 8.3.
[0272] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 is represented by Example 7.3, and R 8 is represented by Example 8.3.
[0273] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 is represented by Example 7.4, and R 8 is represented by Example 8.3.
[0274] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 and R 8 are represented by Example 8.4.
[0275] In another aspect, the present invention relates to Examples E.1 to E.275 listed in Table E, wherein R 7 and R 8 are represented by Example 8.7.
[0276] In particular, considering their use, according to one embodiment, it is preferred to assemble the following compounds in Tables 1a to 12a: Compound I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6. Additionally, each group mentioned for the substituents in the tables by itself (independent of the combinations mentioned) is a particularly preferred aspect of the substituents.
[0277] In particular, considering their use, according to one embodiment, it is preferred to assemble the following compounds in Tables 1a to 12a: Compound I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6. In addition, each group mentioned for the substituents in the table itself (independent of the combinations mentioned) is a particularly preferred aspect of the substituents.
[0278]
[0279]
[0280]
[0281]
[0282]
[0283]
[0284]
[0285]
[0286]
[0287] Table 1a Compounds having the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, wherein R 9 is CH3 and X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds to a row in Table B in each case (compounds I.A-1.1a.B-1 to I.A-1.1a.B-784, I.A-2.1a.B-1 to I.A-2.1a.B-784, I.A-3.1a.B-1 to I.A-3.1a.B-784, I.A-4.1a.B-1 to I.A-4.1a.B-784, I.A-5.1a.B-1 to I.A-5.1a.B-784, I.A-6.1a.B-1 to I.A-6.1a.B-784, I.A-7.1a.B-1 to I.A-7.1a.B-784, I.A-8.1a.B-1 to I.A-8.1a.B-784, I.A-9.1a.B-1 to I.A-9.1a.B-784; compounds I.B-1.1a.B-1 to I.B-1.1a.B-784, I.B-2.1a.B-1 to I.B-2.1a.B-784, I.B-3.1a.B-1 to I.B-3.1a.B-784, I.B-4.1a.B-1 to I.B-4.1a.B-784, I.B-5.1a.B-1 to I.B-5.1a.B-784, I.B-6.1a.B-1 to I.B-6.1a.B-784, I.B-7.1a.B-1 to I.B-7.1a.B-784, I.B-8.1a.B-1 to I.B-8.1a.B-784, I.B-9.1a.B-1 to I.B-9.1a.B-784; compounds I.C-1.1a.B-1 to I.C-1.1a.B-784, I.C-2.1a.B-1 to I.C-2.1a.B-784, I.C-3.1a.B-1 to I.C-3.1a.B-784, I.C-4.1a.B-1 to I.C-4.1a.B-784, I.C-5.1a.B-1 to I.C-5.1a.B-784, I.C-6.1a.B-1 to I.C-6.1a.B-784, I.C-7.1a.B-1 to I.C-7.1a.B-784, I.C-8.1a.B-1 to I.C-8.1a.B-784, I.C-9.1a.B-1 to I.C-9.1a.B-784; compounds I.D-1.1a.B-1 to I.D-1.1a.B-784, I.D-2.1a.B-1 to I.D-2.1a.B-784, I.D-3.1a.B-1 to I.D-3.1a.B-784, I.D-4.1a.B-1 to I.D-4.1a.B-784, I.D-5.1a.B-1 to I.D-5.1a.B-784, I.D-6.1a.B-1 to I.D-6.1a.B-784, I.D-7.1a.B-1 to I.D-7.1a.B-784, I.D-8.1a.B-1 to I.D - 8.1a.B - 784, I.D - 9.1a.B - 1 to I.D - 9.1a.B - 784; Compounds I.E - 1.1a.B - 1 to I.E - 1.1a.B - 784, I.E - 2.1a.B - 1 to I.E - 2.1a.B - 784, I.E - 3.1a.B - 1 to I.E - 3.1a.B - 784, I.E - 4.1a.B - 1 to I.E - 4.1a.B - 784, I.E - 5.1a.B - 1 to I.E - 5.1a.B - 784, I.E - 6.1a.B - 1 to I.E - 6.1a.B - 784, I.E - 7.1a.B - 1 to I.E - 7.1a.B - 784, I.E - 8.1a.B - 1 to I.E - 8.1a.B - 784, I.E - 9.1a.B - 1 to I.E - 9.1a.B - 784; Compounds I.F - 1.1a.B - 1 to I.F - 1.1a.B - 784, I.F - 2.1a.B - 1 to I.F - 2.1a.B - 784, I.F - 3.1a.B - 1 to I.F - 3.1a.B - 784, I.F - 4.1a.B - 1 to I.F - 4.1a.B - 784, I.F - 5.1a.B - 1 to I.F - 5.1a.B - 784, I.F - 6.1a.B - 1 to I.F - 6.1a.B - 784, I.F - 7.1a.B - 1 to I.F - 7.1a.B - 784, I.F - 8.1a.B - 1 to I.F - 8.1a.B - 784, I.F - 9.1a.B - 1 to I.F - 9.1a.B - 784; Compounds I.G - 1.1a.B - 1 to I.G - 1.1a.B - 784, I.G - 2.1a.B - 1 to I.G - 2.1a.B - 784, I.G - 3.1a.B - 1 to I.G - 3.1a.B - 784, I.G - 4.1a.B - 1 to I.G - 4.1a.B - 784, I.G - 5.1a.B - 1 to I.G - 5.1a.B - 784, I.G - 6.1a.B - 1 to I.G - 6.1a.B - 784; Compounds I.H - 1.1a.B - 1 to I.H - 1.1a.B - 784, I.H - 2.1a.B - 1 to I.H - 2.1a.B - 784, I.H - 3.1a.B - 1 to I.H - 3.1a.B - 784, I.H - 4.1a.B - 1 to I.H - 4.1a.B - 784, I.H - 5.1a.B - 1 to I.H - 5.1a.B - 784, I.H - 6.1a.B - 1 to I.H - 6.1a.B - 784; Compounds I.I - 1.1a.B - 1 to I.I - 1.1a.B - 784, I.I - 2.1a.B - 1 to I.I - 2.1a.B - 784, I.I - 3.1a.B - 1 to I.I - 3.1a.B - 784, I.I - 4.1a.B - 1 to I.I - 4.1a.B-784, I.I-5.1a.B-1 to I.I-5.1a.B-784, I.I-6.1a.B-1 to I.I-6.1a.B-784; compound I.J-1.1a.B-1 to I.J-1.1a.B-784, I.J-2.1a.B-1 to I.J-2.1a.B-784, I.J-3.1a.B-1 to I.J-3.1a.B-784, I.J-4.1a.B-1 to I.J-4.1a.B-784, I.J-5.1a.B-1 to I.J-5.1a.B-784, I.J-6.1a.B-1 to I.J-6.1a.B-784; compound I.K-1.1a.B-1 to I.K-1.1a.B-784, I.K-2.1a.B-1 to I.K-2.1a.B-784, I.K-3.1a.B-1 to I.K-3.1a.B-784, I.K-4.1a.B-1 to I.K-4.1a.B-784, I.K-5.1a.B-1 to I.K-5.1a.B-784, I.K-6.1a.B-1 to I.K-6.1a.B-784; compound I.L-1.1a.B-1 to I.L-1.1a.B-784, I.L-2.1a.B-1 to I.L-2.1a.B-784, I.L-3.1a.B-1 to I.L-3.1a.B-784, I.L-4.1a.B-1 to I.L-4.1a.B-784, I.L-5.1a.B-1 to I.L-5.1a.B-784, I.L-6.1a.B-1 to I.L-6.1a.B-784).
[0288] Table 2a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2CH3 and the X of each individual compound 1 , X 2 , R 5 , R 6 , R 7 and R 8The meaning of the combinations corresponds to a row in Table B in each case (compounds I.A-1.2a.B-1 to I.A-1.2a.B-784, I.A-2.2a.B-1 to I.A-2.2a.B-784, I.A-3.2a.B-1 to I.A-3.2a.B-784, I.A-4.2a.B-1 to I.A-4.2a.B-784, I.A-5.2a.B-1 to I.A-5.2a.B-784, I.A-6.2a.B-1 to I.A-6.2a.B-784, I.A-7.2a.B-1 to I.A-7.2a.B-784, I.A-8.2a.B-1 to I.A-8.2a.B-784, I.A-9.2a.B-1 to I.A-9.2a.B-784; compounds I.B-1.2a.B-1 to I.B-1.2a.B-784, I.B-2.2a.B-1 to I.B-2.2a.B-784, I.B-3.2a.B-1 to I.B-3.2a.B-784, I.B-4.2a.B-1 to I.B-4.2a.B-784, I.B-5.2a.B-1 to I.B-5.2a.B-784, I.B-6.2a.B-1 to I.B-6.2a.B-784, I.B-7.2a.B-1 to I.B-7.2a.B-784, I.B-8.2a.B-1 to I.B-8.2a.B-784, I.B-9.2a.B-1 to I.B-9.2a.B-784; compounds I.C-1.2a.B-1 to I.C-1.2a.B-784, I.C-2.2a.B-1 to I.C-2.2a.B-784, I.C-3.2a.B-1 to I.C-3.2a.B-784, I.C-4.2a.B-1 to I.C-4.2a.B-784, I.C-5.2a.B-1 to I.C-5.2a.B-784, I.C-6.2a.B-1 to I.C-6.2a.B-784, I.C-7.2a.B-1 to I.C-7.2a.B-784, I.C-8.2a.B-1 to I.C-8.2a.B-784, I.C-9.2a.B-1 to I.C-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-784, I.D-8.2a.B-1 to I.D-8.2a.B-784, I.D-9.2a.B-1 to I.D-9.2a.B-784; compounds I.D-1.2a.B-1 to I.D-1.2a.B-784, I.D-2.2a.B-1 to I.D-2.2a.B-784, I.D-3.2a.B-1 to I.D-3.2a.B-784, I.D-4.2a.B-1 to I.D-4.2a.B-784, I.D-5.2a.B-1 to I.D-5.2a.B-784, I.D-6.2a.B-1 to I.D-6.2a.B-784, I.D-7.2a.B-1 to I.D-7.2a.B-7D - 8.2a.B - 784, I.D - 9.2a.B - 1 to I.D - 9.2a.B - 784; Compounds I.E - 1.2a.B - 1 to I.E - 1.2a.B - 784, I.E - 2.2a.B - 1 to I.E - 2.2a.B - 784, I.E - 3.2a.B - 1 to I.E - 3.2a.B - 784, I.E - 4.2a.B - 1 to I.E - 4.2a.B - 784, I.E - 5.2a.B - 1 to I.E - 5.2a.B - 784, I.E - 6.2a.B - 1 to I.E - 6.2a.B - 784, I.E - 7.2a.B - 1 to I.E - 7.2a.B - 784, I.E - 8.2a.B - 1 to I.E - 8.2a.B - 784, I.E - 9.2a.B - 1 to I.E - 9.2a.B - 784; Compounds I.F - 1.2a.B - 1 to I.F - 1.2a.B - 784, I.F - 2.2a.B - 1 to I.F - 2.2a.B - 784, I.F - 3.2a.B - 1 to I.F - 3.2a.B - 784, I.F - 4.2a.B - 1 to I.F - 4.2a.B - 784, I.F - 5.2a.B - 1 to I.F - 5.2a.B - 784, I.F - 6.2a.B - 1 to I.F - 6.2a.B - 784, I.F - 7.2a.B - 1 to I.F - 7.2a.B - 784, I.F - 8.2a.B - 1 to I.F - 8.2a.B - 784, I.F - 9.2a.B - 1 to I.F - 9.2a.B - 784; Compounds I.G - 1.2a.B - 1 to I.G - 1.2a.B - 784, I.G - 2.2a.B - 1 to I.G - 2.2a.B - 784, I.G - 3.2a.B - 1 to I.G - 3.2a.B - 784, I.G - 4.2a.B - 1 to I.G - 4.2a.B - 784, I.G - 5.2a.B - 1 to I.G - 5.2a.B - 784, I.G - 6.2a.B - 1 to I.G - 6.2a.B - 784; Compounds I.H - 1.2a.B - 1 to I.H - 1.2a.B - 784, I.H - 2.2a.B - 1 to I.H - 2.2a.B - 784, I.H - 3.2a.B - 1 to I.H - 3.2a.B - 784, I.H - 4.2a.B - 1 to I.H - 4.2a.B - 784, I.H - 5.2a.B - 1 to I.H - 5.2a.B - 784, I.H - 6.2a.B - 1 to I.H - 6.2a.B - 784; Compounds I.I - 1.2a.B - 1 to I.I - 1.2a.B - 784, I.I - 2.2a.B - 1 to I.I - 2.2a.B - 784, I.I - 3.2a.B - 1 to I.I - 3.2a.B - 784, I.I - 4.2a.B - 1 to I.I - 4.2a.B - 784, I.I - 5.2a.B - 1 to I.I - 5.2a.B - 784, I.I - 6.2a.B - 1 to I.I - 6.2a.B - 784; Compound I.J - 1.2a.B - 1 to I.J - 1.2a.B - 784, I.J - 2.2a.B - 1 to I.J - 2.2a.B - 784, I.J - 3.2a.B - 1 to I.J - 3.2a.B - 784, I.J - 4.2a.B - 1 to I.J - 4.2a.B - 784, I.J - 5.2a.B - 1 to I.J - 5.2a.B - 784, I.J - 6.2a.B - 1 to I.J - 6.2a.B - 784; Compound I.K - 1.2a.B - 1 to I.K - 1.2a.B - 784, I.K - 2.2a.B - 1 to I.K - 2.2a.B - 784, I.K - 3.2a.B - 1 to I.K - 3.2a.B - 784, I.K - 4.2a.B - 1 to I.K - 4.2a.B - 784, I.K - 5.2a.B - 1 to I.K - 5.2a.B - 784, I.K - 6.2a.B - 1 to I.K - 6.2a.B - 784; Compound I.L - 1.2a.B - 1 to I.L - 1.2a.B - 784, I.L - 2.2a.B - 1 to I.L - 2.2a.B - 784, I.L - 3.2a.B - 1 to I.L - 3.2a.B - 784, I.L - 4.2a.B - 1 to I.L - 4.2a.B - 784, I.L - 5.2a.B - 1 to I.L - 5.2a.B - 784, I.L - 6.2a.B - 1 to I.L - 6.2a.B - 784).
[0289] Table 3a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2CH2CH3 and the X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds to a row in Table B in each case (compounds I.A-1.3a.B-1 to I.A-1.3a.B-784, I.A-2.3a.B-1 to I.A-2.3a.B-784, I.A-3.3a.B-1 to I.A-3.3a.B-784, I.A-4.3a.B-1 to I.A-4.3a.B-784, I.A-5.3a.B-1 to I.A-5.3a.B-784, I.A-6.3a.B-1 to I.A-6.3a.B-784, I.A-7.3a.B-1 to I.A-7.3a.B-784, I.A-8.3a.B-1 to I.A-8.3a.B-784, I.A-9.3a.B-1 to I.A-9.3a.B-784; compounds I.B-1.3a.B-1 to I.B-1.3a.B-784, I.B-2.3a.B-1 to I.B-2.3a.B-784, I.B-3.3a.B-1 to I.B-3.3a.B-784, I.B-4.3a.B-1 to I.B-4.3a.B-784, I.B-5.3a.B-1 to I.B-5.3a.B-784, I.B-6.3a.B-1 to I.B-6.3a.B-784, I.B-7.3a.B-1 to I.B-7.3a.B-784, I.B-8.3a.B-1 to I.B-8.3a.B-784, I.B-9.3a.B-1 to I.B-9.3a.B-784; compounds I.C-1.3a.B-1 to I.C-1.3a.B-784, I.C-2.3a.B-1 to I.C-2.3a.B-784, I.C-3.3a.B-1 to I.C-3.3a.B-784, I.C-4.3a.B-1 to I.C-4.3a.B-784, I.C-5.3a.B-1 to I.C-5.3a.B-784, I.C-6.3a.B-1 to I.C-6.3a.B-784, I.C-7.3a.B-1 to I.C-7.3a.B-784, I.C-8.3a.B-1 to I.C-8.3a.B-784, I.C-9.3a.B-1 to I.C-9.3a.B-784; compounds I.D-1.3a.B-1 to I.D-1.3a.B-784, I.D-2.3a.B-1 to I.D-2.3a.B-784, I.D-3.3a.B-1 to I.D-3.3a.B-784, I.D-4.3a.B-1 to I.D-4.3a.B-784, I.D-5.3a.B-1 to I.D-5.3a.B-784, I.D-6.3a.B-1 to I.D-6.3a.B-784, I.D-7.3a.B-1 to I.D-7.3a.B-784, I.D-8.3a.B-1 to I.D - 8.3a.B - 784, I.D - 9.3a.B - 1 to I.D - 9.3a.B - 784; Compounds I.E - 1.3a.B - 1 to I.E - 1.3a.B - 784, I.E - 2.3a.B - 1 to I.E - 2.3a.B - 784, I.E - 3.3a.B - 1 to I.E - 3.3a.B - 784, I.E - 4.3a.B - 1 to I.E - 4.3a.B - 784, I.E - 5.3a.B - 1 to I.E - 5.3a.B - 784, I.E - 6.3a.B - 1 to I.E - 6.3a.B - 784, I.E - 7.3a.B - 1 to I.E - 7.3a.B - 784, I.E - 8.3a.B - 1 to I.E - 8.3a.B - 784, I.E - 9.3a.B - 1 to I.E - 9.3a.B - 784; Compounds I.F - 1.3a.B - 1 to I.F - 1.3a.B - 784, I.F - 2.3a.B - 1 to I.F - 2.3a.B - 784, I.F - 3.3a.B - 1 to I.F - 3.3a.B - 784, I.F - 4.3a.B - 1 to I.F - 4.3a.B - 784, I.F - 5.3a.B - 1 to I.F - 5.3a.B - 784, I.F - 6.3a.B - 1 to I.F - 6.3a.B - 784, I.F - 7.3a.B - 1 to I.F - 7.3a.B - 784, I.F - 8.3a.B - 1 to I.F - 8.3a.B - 784, I.F - 9.3a.B - 1 to I.F - 9.3a.B - 784; Compounds I.G - 1.3a.B - 1 to I.G - 1.3a.B - 784, I.G - 2.3a.B - 1 to I.G - 2.3a.B - 784, I.G - 3.3a.B - 1 to I.G - 3.3a.B - 784, I.G - 4.3a.B - 1 to I.G - 4.3a.B - 784, I.G - 5.3a.B - 1 to I.G - 5.3a.B - 784, I.G - 6.3a.B - 1 to I.G - 6.3a.B - 784; Compounds I.H - 1.3a.B - 1 to I.H - 1.3a.B - 784, I.H - 2.3a.B - 1 to I.H - 2.3a.B - 784, I.H - 3.3a.B - 1 to I.H - 3.3a.B - 784, I.H - 4.3a.B - 1 to I.H - 4.3a.B - 784, I.H - 5.3a.B - 1 to I.H - 5.3a.B - 784, I.H - 6.3a.B - 1 to I.H - 6.3a.B - 784; Compounds I.I - 1.3a.B - 1 to I.I - 1.3a.B - 784, I.I - 2.3a.B - 1 to I.I - 2.3a.B - 784, I.I - 3.3a.B - 1 to I.I - 3.3a.B - 784, I.I - 4.3a.B - 1 to I.I - 4.3a.B-784, I.I-5.3a.B-1 to I.I-5.3a.B-784, I.I-6.3a.B-1 to I.I-6.3a.B-784; compound I.J-1.3a.B-1 to I.J-1.3a.B-784, I.J-2.3a.B-1 to I.J-2.3a.B-784, I.J-3.3a.B-1 to I.J-3.3a.B-784, I.J-4.3a.B-1 to I.J-4.3a.B-784, I.J-5.3a.B-1 to I.J-5.3a.B-784, I.J-6.3a.B-1 to I.J-6.3a.B-784; compound I.K-1.3a.B-1 to I.K-1.3a.B-784, I.K-2.3a.B-1 to I.K-2.3a.B-784, I.K-3.3a.B-1 to I.K-3.3a.B-784, I.K-4.3a.B-1 to I.K-4.3a.B-784, I.K-5.3a.B-1 to I.K-5.3a.B-784, I.K-6.3a.B-1 to I.K-6.3a.B-784; compound I.L-1.3a.B-1 to I.L-1.3a.B-784, I.L-2.3a.B-1 to I.L-2.3a.B-784, I.L-3.3a.B-1 to I.L-3.3a.B-784, I.L-4.3a.B-1 to I.L-4.3a.B-784, I.L-5.3a.B-1 to I.L-5.3a.B-784, I.L-6.3a.B-1 to I.L-6.3a.B-784).
[0290] Table 4a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CN and the X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds to a row in Table B in each case (compounds I.A-1.4a.B-1 to I.A-1.4a.B-784, I.A-2.4a.B-1 to I.A-2.4a.B-784, I.A-3.4a.B-1 to I.A-3.4a.B-784, I.A-4.4a.B-1 to I.A-4.4a.B-784, I.A-5.4a.B-1 to I.A-5.4a.B-784, I.A-6.4a.B-1 to I.A-6.4a.B-784, I.A-7.4a.B-1 to I.A-7.4a.B-784, I.A-8.4a.B-1 to I.A-8.4a.B-784, I.A-9.4a.B-1 to I.A-9.4a.B-784; compounds I.B-1.4a.B-1 to I.B-1.4a.B-784, I.B-2.4a.B-1 to I.B-2.4a.B-784, I.B-3.4a.B-1 to I.B-3.4a.B-784, I.B-4.4a.B-1 to I.B-4.4a.B-784, I.B-5.4a.B-1 to I.B-5.4a.B-784, I.B-6.4a.B-1 to I.B-6.4a.B-784, I.B-7.4a.B-1 to I.B-7.4a.B-784, I.B-8.4a.B-1 to I.B-8.4a.B-784, I.B-9.4a.B-1 to I.B-9.4a.B-784; compounds I.C-1.4a.B-1 to I.C-1.4a.B-784, I.C-2.4a.B-1 to I.C-2.4a.B-784, I.C-3.4a.B-1 to I.C-3.4a.B-784, I.C-4.4a.B-1 to I.C-4.4a.B-784, I.C-5.4a.B-1 to I.C-5.4a.B-784, I.C-6.4a.B-1 to I.C-6.4a.B-784, I.C-7.4a.B-1 to I.C-7.4a.B-784, I.C-8.4a.B-1 to I.C-8.4a.B-784, I.C-9.4a.B-1 to I.C-9.4a.B-784; compounds I.D-1.4a.B-1 to I.D-1.4a.B-784, I.D-2.4a.B-1 to I.D-2.4a.B-784, I.D-3.4a.B-1 to I.D-3.4a.B-784, I.D-4.4a.B-1 to I.D-4.4a.B-784, I.D-5.4a.B-1 to I.D-5.4a.B-784, I.D-6.4a.B-1 to I.D-6.4a.B-784, I.D-7.4a.B-1 to I.D-7.4a.B-784, I.D-8.4a.B-1 to I.D-8.4a.B-784, I.D-9.4a.B-1 to I.D-9.4a.B-784; Compounds I.E-1.4a.B-1 to I.E-1.4a.B-784, I.E-2.4a.B-1 to I.E-2.4a.B-784, I.E-3.4a.B-1 to I.E-3.4a.B-784, I.E-4.4a.B-1 to I.E-4.4a.B-784, I.E-5.4a.B-1 to I.E-5.4a.B-784, I.E-6.4a.B-1 to I.E-6.4a.B-784, I.E-7.4a.B-1 to I.E-7.4a.B-784, I.E-8.4a.B-1 to I.E-8.4a.B-784, I.E-9.4a.B-1 to I.E-9.4a.B-784; Compounds I.F-1.4a.B-1 to I.F-1.4a.B-784, I.F-2.4a.B-1 to I.F-2.4a.B-784, I.F-3.4a.B-1 to I.F-3.4a.B-784, I.F-4.4a.B-1 to I.F-4.4a.B-784, I.F-5.4a.B-1 to I.F-5.4a.B-784, I.F-6.4a.B-1 to I.F-6.4a.B-784, I.F-7.4a.B-1 to I.F-7.4a.B-784, I.F-8.4a.B-1 to I.F-8.4a.B-784, I.F-9.4a.B-1 to I.F-9.4a.B-784; Compounds I.G-1.4a.B-1 to I.G-1.4a.B-784, I.G-2.4a.B-1 to I.G-2.4a.B-784, I.G-3.4a.B-1 to I.G-3.4a.B-784, I.G-4.4a.B-1 to I.G-4.4a.B-784, I.G-5.4a.B-1 to I.G-5.4a.B-784, I.G-6.4a.B-1 to I.G-6.4a.B-784; Compounds I.H-1.4a.B-1 to I.H-1.4a.B-784, I.H-2.4a.B-1 to I.H-2.4a.B-784, I.H-3.4a.B-1 to I.H-3.4a.B-784, I.H-4.4a.B-1 to I.H-4.4a.B-784, I.H-5.4a.B-1 to I.H-5.4a.B-784, I.H-6.4a.B-1 to I.H-6.4a.B-784; Compounds I.I-1.4a.B-1 to I.I-1.4a.B-784, I.I-2.4a.B-1 to I.I-2.4a.B-784, I.I-3.4a.B-1 to I.I-3.4a.B-784, I.I-4.4a.B-1 to I.I-4.4a.B-784, I.I-5.4a.B-1 to I.I-5.4a.B-784, I.I-6.4a.B-1 to I.I-6.4a.B-784; compounds I.J-1.4a.B-1 to I.J-1.4a.B-784, I.J-2.4a.B-1 to I.J-2.4a.B-784, I.J-3.4a.B-1 to I.J-3.4a.B-784, I.J-4.4a.B-1 to I.J-4.4a.B-784, I.J-5.4a.B-1 to I.J-5.4a.B-784, I.J-6.4a.B-1 to I.J-6.4a.B-784; compounds I.K-1.4a.B-1 to I.K-1.4a.B-784, I.K-2.4a.B-1 to I.K-2.4a.B-784, I.K-3.4a.B-1 to I.K-3.4a.B-784, I.K-4.4a.B-1 to I.K-4.4a.B-784, I.K-5.4a.B-1 to I.K-5.4a.B-784, I.K-6.4a.B-1 to I.K-6.4a.B-784; compounds I.L-1.4a.B-1 to I.L-1.4a.B-784, I.L-2.4a.B-1 to I.L-2.4a.B-784, I.L-3.4a.B-1 to I.L-3.4a.B-784, I.L-4.4a.B-1 to I.L-4.4a.B-784, I.L-5.4a.B-1 to I.L-5.4a.B-784, I.L-6.4a.B-1 to I.L-6.4a.B-784).
[0291] Table 5a Compounds having the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, wherein R 9 is CH2CN and X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds in each case to a row of Table B (compounds I.A-1.5a.B-1 to I.A-1.5a.B-784, I.A-2.5a.B-1 to I.A-2.5a.B-784, I.A-3.5a.B-1 to I.A-3.5a.B-784, I.A-4.5a.B-1 to I.A-4.5a.B-784, I.A-5.5a.B-1 to I.A-5.5a.B-784, I.A-6.5a.B-1 to I.A-6.5a.B-784, I.A-7.5a.B-1 to I.A-7.5a.B-784, I.A-8.5a.B-1 to I.A-8.5a.B-784, I.A-9.5a.B-1 to I.A-9.5a.B-784; compounds I.B-1.5a.B-1 to I.B-1.5a.B-784, I.B-2.5a.B-1 to I.B-2.5a.B-784, I.B-3.5a.B-1 to I.B-3.5a.B-784, I.B-4.5a.B-1 to I.B-4.5a.B-784, I.B-5.5a.B-1 to I.B-5.5a.B-784, I.B-6.5a.B-1 to I.B-6.5a.B-784, I.B-7.5a.B-1 to I.B-7.5a.B-784, I.B-8.5a.B-1 to I.B-8.5a.B-784, I.B-9.5a.B-1 to I.B-9.5a.B-784; compounds I.C-1.5a.B-1 to I.C-1.5a.B-784, I.C-2.5a.B-1 to I.C-2.5a.B-784, I.C-3.5a.B-1 to I.C-3.5a.B-784, I.C-4.5a.B-1 to I.C-4.5a.B-784, I.C-5.5a.B-1 to I.C-5.5a.B-784, I.C-6.5a.B-1 to I.C-6.5a.B-784, I.C-7.5a.B-1 to I.C-7.5a.B-784, I.C-8.5a.B-1 to I.C-8.5a.B-784, I.C-9.5a.B-1 to I.C-9.5a.B-784; compounds I.D-1.5a.B-1 to I.D-1.5a.B-784, I.D-2.5a.B-1 to I.D-2.5a.B-784, I.D-3.5a.B-1 to I.D-3.5a.B-784, I.D-4.5a.B-1 to I.D-4.5a.B-784, I.D-5.5a.B-1 to I.D-5.5a.B-784, I.D-6.5a.B-1 to I.D-6.5a.B-784, I.D-7.5a.B-1 to I.D-7.5a.B-784, I.D-8.5a.B-1 to I.D-8.5a.B-784, I.D-9.5a.B-1 to I.D-9.5a.B-784; compounds I.D-1.5a.B-1 to I.D-1.5a.B-784, I.D-2.5a.B-1 to I.D-2.5a.B-784, I.D-3.5a.B-1 to I.D-3.5a.B-784, I.D-4.5a.B-1 to I.D-4.5a.B-784, I.D-5.5a.B-1 to I.D-5.5a.B-784, I.D-6.5a.B-1 to I.D-6.5a.B-784, I.D-7.5a.B-1 to I.D-7.5a.B-784, I.D-8.5a.B-1 to I.D - 8.5a.B - 784, I.D - 9.5a.B - 1 to I.D - 9.5a.B - 784; Compounds I.E - 1.5a.B - 1 to I.E - 1.5a.B - 784, I.E - 2.5a.B - 1 to I.E - 2.5a.B - 784, I.E - 3.5a.B - 1 to I.E - 3.5a.B - 784, I.E - 4.5a.B - 1 to I.E - 4.5a.B - 784, I.E - 5.5a.B - 1 to I.E - 5.5a.B - 784, I.E - 6.5a.B - 1 to I.E - 6.5a.B - 784, I.E - 7.5a.B - 1 to I.E - 7.5a.B - 784, I.E - 8.5a.B - 1 to I.E - 8.5a.B - 784, I.E - 9.5a.B - 1 to I.E - 9.5a.B - 784; Compounds I.F - 1.5a.B - 1 to I.F - 1.5a.B - 784, I.F - 2.5a.B - 1 to I.F - 2.5a.B - 784, I.F - 3.5a.B - 1 to I.F - 3.5a.B - 784, I.F - 4.5a.B - 1 to I.F - 4.5a.B - 784, I.F - 5.5a.B - 1 to I.F - 5.5a.B - 784, I.F - 6.5a.B - 1 to I.F - 6.5a.B - 784, I.F - 7.5a.B - 1 to I.F - 7.5a.B - 784, I.F - 8.5a.B - 1 to I.F - 8.5a.B - 784, I.F - 9.5a.B - 1 to I.F - 9.5a.B - 784; Compounds I.G - 1.5a.B - 1 to I.G - 1.5a.B - 784, I.G - 2.5a.B - 1 to I.G - 2.5a.B - 784, I.G - 3.5a.B - 1 to I.G - 3.5a.B - 784, I.G - 4.5a.B - 1 to I.G - 4.5a.B - 784, I.G - 5.5a.B - 1 to I.G - 5.5a.B - 784, I.G - 6.5a.B - 1 to I.G - 6.5a.B - 784; Compounds I.H - 1.5a.B - 1 to I.H - 1.5a.B - 784, I.H - 2.5a.B - 1 to I.H - 2.5a.B - 784, I.H - 3.5a.B - 1 to I.H - 3.5a.B - 784, I.H - 4.5a.B - 1 to I.H - 4.5a.B - 784, I.H - 5.5a.B - 1 to I.H - 5.5a.B - 784, I.H - 6.5a.B - 1 to I.H - 6.5a.B - 784; Compounds I.I - 1.5a.B - 1 to I.I - 1.5a.B - 784, I.I - 2.5a.B - 1 to I.I - 2.5a.B - 784, I.I - 3.5a.B - 1 to I.I - 3.5a.B - 784, I.I - 4.5a.B - 1 to I.I - 4.5a.B-784, I.I-5.5a.B-1 to I.I-5.5a.B-784, I.I-6.5a.B-1 to I.I-6.5a.B-784; compound I.J-1.5a.B-1 to I.J-1.5a.B-784, I.J-2.5a.B-1 to I.J-2.5a.B-784, I.J-3.5a.B-1 to I.J-3.5a.B-784, I.J-4.5a.B-1 to I.J-4.5a.B-784, I.J-5.5a.B-1 to I.J-5.5a.B-784, I.J-6.5a.B-1 to I.J-6.5a.B-784; compound I.K-1.5a.B-1 to I.K-1.5a.B-784, I.K-2.5a.B-1 to I.K-2.5a.B-784, I.K-3.5a.B-1 to I.K-3.5a.B-784, I.K-4.5a.B-1 to I.K-4.5a.B-784, I.K-5.5a.B-1 to I.K-5.5a.B-784, I.K-6.5a.B-1 to I.K-6.5a.B-784; compound I.L-1.5a.B-1 to I.L-1.5a.B-784, I.L-2.5a.B-1 to I.L-2.5a.B-784, I.L-3.5a.B-1 to I.L-3.5a.B-784, I.L-4.5a.B-1 to I.L-4.5a.B-784, I.L-5.5a.B-1 to I.L-5.5a.B-784, I.L-6.5a.B-1 to I.L-6.5a.B-784).
[0292] Table 6a Compounds having the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, wherein R 9 is CHO and X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds in each case to a row of Table B (compounds I.A-1.6a.B-1 to I.A-1.6a.B-784, I.A-2.6a.B-1 to I.A-2.6a.B-784, I.A-3.6a.B-1 to I.A-3.6a.B-784, I.A-4.6a.B-1 to I.A-4.6a.B-784, I.A-5.6a.B-1 to I.A-5.6a.B-784, I.A-6.6a.B-1 to I.A-6.6a.B-784, I.A-7.6a.B-1 to I.A-7.6a.B-784, I.A-8.6a.B-1 to I.A-8.6a.B-784, I.A-9.6a.B-1 to I.A-9.6a.B-784; compounds I.B-1.6a.B-1 to I.B-1.6a.B-784, I.B-2.6a.B-1 to I.B-2.6a.B-784, I.B-3.6a.B-1 to I.B-3.6a.B-784, I.B-4.6a.B-1 to I.B-4.6a.B-784, I.B-5.6a.B-1 to I.B-5.6a.B-784, I.B-6.6a.B-1 to I.B-6.6a.B-784, I.B-7.6a.B-1 to I.B-7.6a.B-784, I.B-8.6a.B-1 to I.B-8.6a.B-784, I.B-9.6a.B-1 to I.B-9.6a.B-784; compounds I.C-1.6a.B-1 to I.C-1.6a.B-784, I.C-2.6a.B-1 to I.C-2.6a.B-784, I.C-3.6a.B-1 to I.C-3.6a.B-784, I.C-4.6a.B-1 to I.C-4.6a.B-784, I.C-5.6a.B-1 to I.C-5.6a.B-784, I.C-6.6a.B-1 to I.C-6.6a.B-784, I.C-7.6a.B-1 to I.C-7.6a.B-784, I.C-8.6a.B-1 to I.C-8.6a.B-784, I.C-9.6a.B-1 to I.C-9.6a.B-784; compounds I.D-1.6a.B-1 to I.D-1.6a.B-784, I.D-2.6a.B-1 to I.D-2.6a.B-784, I.D-3.6a.B-1 to I.D-3.6a.B-784, I.D-4.6a.B-1 to I.D-4.6a.B-784, I.D-5.6a.B-1 to I.D-5.6a.B-784, I.D-6.6a.B-1 to I.D-6.6a.B-784, I.D-7.6a.B-1 to I.D-7.6a.B-784, I.D-8.6a.B-1 to I.D-8.6a.B-784, I.D-9.6a.B-1 to I.D-9.6a.B-784; compounds I.E-1.6a.B-1 to I.E-1.6a.B-784, I.E-2.6a.B-1 to I.E-2.6a.B-784, I.E-3.6a.B-1 to I.E-3.6a.B-784, I.E-4.6a.B-1 to I.E-4.6a.B-784, I.E-5.6a.B-1 to I.E-5.6a.B-784, I.E-6.6a.B-1 to I.E-6.6a.B-784, I.E-7.6a.B-1 to I.E-7.6a.B-784, I.E-8.6a.B-1 to I.E-8.6a.B-784, I.E-9.6a.B-1 to I.E-9.6a.B-784; compounds I.F-1.6a.B-1 to I.F-1.6a.B-784, I.F-2.6a.B-1 to I.F-2.6a.B-784, I.F-3.6a.B-1 to I.F-3.6a.B-784, I.F-4.6a.B-1 to I.F-4.6a.B-784, I.F-5.6a.B-1 to I.F-5.6a.B-784, I.F-6.6a.B-1 to I.F-6.6a.B-784, I.F-7.6a.B-1 to I.F-7.6a.B-784, I.F-8.6a.B-1 to I.F-8.6a.B-784, I.F-9.6a.B-1 to I.F-9.6a.B-784; compounds I.G-1.6a.B-1 to I.G-1.6a.B-784, I.G-2.6a.B-1 to I.G-2.6a.B-784, I.G-3.6a.B-1 to I.G-3.6a.B-784, I.G-4.6a.B-1 to I.G-4.6a.B-784, I.G-5.6a.B-1 to I.G-5.6a.B-784, I.G-6.6a.B-1 to I.G-6.6a.B-784; compounds I.H-1.6a.B-1 to I.H-1.6a.B-784, I.H-2.6a.B-1 to I.H-2.6a.B-784, I.H-3.6a.B-1 to I.H-3.6a.B-784, I.H-4.6a.B-1 to I.H-4.6a.B-784, I.H-5.6a.B-1 to I.H-5.6a.B-784, I.H-6.6a.B-1 to I.H-6.6a.B-784; compounds I.I-1.6a.B-1 to I.I-1.6a.B-784, I.I-2.6a.B-1 to I.I-2.6a.B-784, I.I-3.6a.B-1 to I.I-3.6a.B-784, I.I-4.6a.B-1 to I.I-4.6a.B-784, I.I-5.6a.B-1 to I.I-5.6a.B-784, I.I-6.6a.B-1 to I.I-6.6a.B-784; compound I.J-1.6a.B-1 to I.J-1.6a.B-784, I.J-2.6a.B-1 to I.J-2.6a.B-784, I.J-3.6a.B-1 to I.J-3.6a.B-784, I.J-4.6a.B-1 to I.J-4.6a.B-784, I.J-5.6a.B-1 to I.J-5.6a.B-784, I.J-6.6a.B-1 to I.J-6.6a.B-784; compound I.K-1.6a.B-1 to I.K-1.6a.B-784, I.K-2.6a.B-1 to I.K-2.6a.B-784, I.K-3.6a.B-1 to I.K-3.6a.B-784, I.K-4.6a.B-1 to I.K-4.6a.B-784, I.K-5.6a.B-1 to I.K-5.6a.B-784, I.K-6.6a.B-1 to I.K-6.6a.B-784; compound I.L-1.6a.B-1 to I.L-1.6a.B-784, I.L-2.6a.B-1 to I.L-2.6a.B-784, I.L-3.6a.B-1 to I.L-3.6a.B-784, I.L-4.6a.B-1 to I.L-4.6a.B-784, I.L-5.6a.B-1 to I.L-5.6a.B-784, I.L-6.6a.B-1 to I.L-6.6a.B-784).
[0293] Table 7a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is C(CH3)3 and the X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds in each case to a row of Table B (compounds I.A-1.7a.B-1 to I.A-1.7a.B-784, I.A-2.7a.B-1 to I.A-2.7a.B-784, I.A-3.7a.B-1 to I.A-3.7a.B-784, I.A-4.7a.B-1 to I.A-4.7a.B-784, I.A-5.7a.B-1 to I.A-5.7a.B-784, I.A-6.7a.B-1 to I.A-6.7a.B-784, I.A-7.7a.B-1 to I.A-7.7a.B-784, I.A-8.7a.B-1 to I.A-8.7a.B-784, I.A-9.7a.B-1 to I.A-9.7a.B-784; compounds I.B-1.7a.B-1 to I.B-1.7a.B-784, I.B-2.7a.B-1 to I.B-2.7a.B-784, I.B-3.7a.B-1 to I.B-3.7a.B-784, I.B-4.7a.B-1 to I.B-4.7a.B-784, I.B-5.7a.B-1 to I.B-5.7a.B-784, I.B-6.7a.B-1 to I.B-6.7a.B-784, I.B-7.7a.B-1 to I.B-7.7a.B-784, I.B-8.7a.B-1 to I.B-8.7a.B-784, I.B-9.7a.B-1 to I.B-9.7a.B-784; compounds I.C-1.7a.B-1 to I.C-1.7a.B-784, I.C-2.7a.B-1 to I.C-2.7a.B-784, I.C-3.7a.B-1 to I.C-3.7a.B-784, I.C-4.7a.B-1 to I.C-4.7a.B-784, I.C-5.7a.B-1 to I.C-5.7a.B-784, I.C-6.7a.B-1 to I.C-6.7a.B-784, I.C-7.7a.B-1 to I.C-7.7a.B-784, I.C-8.7a.B-1 to I.C-8.7a.B-784, I.C-9.7a.B-1 to I.C-9.7a.B-784; compounds I.D-1.7a.B-1 to I.D-1.7a.B-784, I.D-2.7a.B-1 to I.D-2.7a.B-784, I.D-3.7a.B-1 to I.D-3.7a.B-784, I.D-4.7a.B-1 to I.D-4.7a.B-784, I.D-5.7a.B-1 to I.D-5.7a.B-784, I.D-6.7a.B-1 to I.D-6.7a.B-784, I.D-7.7a.B-1 to I.D-7.7a.B-784, I.D-8.7a.B-1 to I.D-8.7a.B-784, I.D-9.7a.B-1 to I.D-9.7a.B-784; compounds I.E-1.7a.B-1 to I.E-1.7a.B-784, I.E-2.7a.B-1 to I.E-2.7a.B-784, I.E-3.7a.B-1 to I.E-3.7a.B-784, I.E-4.7a.B-1 to I.E-4.7a.B-784, I.E-5.7a.B-1 to I.E-5.7a.B-784, I.E-6.7a.B-1 to I.E-6.7a.B-784, I.E-7.7a.B-1 to I.E-7.7a.B-784, I.E-8.7a.B-1 to I.E-8.7a.B-784, I.E-9.7a.B-1 to I.E-9.7a.B-784; compounds I.F-1.7a.B-1 to I.F-1.7a.B-784, I.F-2.7a.B-1 to I.F-2.7a.B-784, I.F-3.7a.B-1 to I.F-3.7a.B-784, I.F-4.7a.B-1 to I.F-4.7a.B-784, I.F-5.7a.B-1 to I.F-5.7a.B-784, I.F-6.7a.B-1 to I.F-6.7a.B-784, I.F-7.7a.B-1 to I.F-7.7a.B-784, I.F-8.7a.B-1 to I.F-8.7a.B-784, I.F-9.7a.B-1 to I.F-9.7a.B-784; compounds I.G-1.7a.B-1 to I.G-1.7a.B-784, I.G-2.7a.B-1 to I.G-2.7a.B-784, I.G-3.7a.B-1 to I.G-3.7a.B-784, I.G-4.7a.B-1 to I.G-4.7a.B-784, I.G-5.7a.B-1 to I.G-5.7a.B-784, I.G-6.7a.B-1 to I.G-6.7a.B-784; compounds I.H-1.7a.B-1 to I.H-1.7a.B-784, I.H-2.7a.B-1 to I.H-2.7a.B-784, I.H-3.7a.B-1 to I.H-3.7a.B-784, I.H-4.7a.B-1 to I.H-4.7a.B-784, I.H-5.7a.B-1 to I.H-5.7a.B-784, I.H-6.7a.B-1 to I.H-6.7a.B-784; compounds I.I-1.7a.B-1 to I.I-1.7a.B-784, I.I-2.7a.B-1 to I.I-2.7a.B-784, I.I-3.7a.B-1 to I.I-3.7a.B-784, I.I-4.7a.B-1 to I.I-4.7a.B-784, I.I-5.7a.B-1 to I.I-5.7a.B-784, I.I-6.7a.B-1 to I.I-6.7a.B-784; compounds I.J-1.7a.B-1 to I.J-1.7a.B-784, I.J-2.7a.B-1 to I.J-2.7a.B-784, I.J-3.7a.B-1 to I.J-3.7a.B-784, I.J-4.7a.B-1 to I.J-4.7a.B-784, I.J-5.7a.B-1 to I.J-5.7a.B-784, I.J-6.7a.B-1 to I.J-6.7a.B-784; compounds I.K-1.7a.B-1 to I.K-1.7a.B-784, I.K-2.7a.B-1 to I.K-2.7a.B-784, I.K-3.7a.B-1 to I.K-3.7a.B-784, I.K-4.7a.B-1 to I.K-4.7a.B-784, I.K-5.7a.B-1 to I.K-5.7a.B-784, I.K-6.7a.B-1 to I.K-6.7a.B-784; compounds I.L-1.7a.B-1 to I.L-1.7a.B-784, I.L-2.7a.B-1 to I.L-2.7a.B-784, I.L-3.7a.B-1 to I.L-3.7a.B-784, I.L-4.7a.B-1 to I.L-4.7a.B-784, I.L-5.7a.B-1 to I.L-5.7a.B-784, I.L-6.7a.B-1 to I.L-6.7a.B-784).
[0294] Table 8a Compounds having the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, wherein R 9 is COCH3 and X for each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds in each case to a row of Table B (compounds I.A-1.8a.B-1 to I.A-1.8a.B-784, I.A-2.8a.B-1 to I.A-2.8a.B-784, I.A-3.8a.B-1 to I.A-3.8a.B-784, I.A-4.8a.B-1 to I.A-4.8a.B-784, I.A-5.8a.B-1 to I.A-5.8a.B-784, I.A-6.8a.B-1 to I.A-6.8a.B-784, I.A-7.8a.B-1 to I.A-7.8a.B-784, I.A-8.8a.B-1 to I.A-8.8a.B-784, I.A-9.8a.B-1 to I.A-9.8a.B-784; compounds I.B-1.8a.B-1 to I.B-1.8a.B-784, I.B-2.8a.B-1 to I.B-2.8a.B-784, I.B-3.8a.B-1 to I.B-3.8a.B-784, I.B-4.8a.B-1 to I.B-4.8a.B-784, I.B-5.8a.B-1 to I.B-5.8a.B-784, I.B-6.8a.B-1 to I.B-6.8a.B-784, I.B-7.8a.B-1 to I.B-7.8a.B-784, I.B-8.8a.B-1 to I.B-8.8a.B-784, I.B-9.8a.B-1 to I.B-9.8a.B-784; compounds I.C-1.8a.B-1 to I.C-1.8a.B-784, I.C-2.8a.B-1 to I.C-2.8a.B-784, I.C-3.8a.B-1 to I.C-3.8a.B-784, I.C-4.8a.B-1 to I.C-4.8a.B-784, I.C-5.8a.B-1 to I.C-5.8a.B-784, I.C-6.8a.B-1 to I.C-6.8a.B-784, I.C-7.8a.B-1 to I.C-7.8a.B-784, I.C-8.8a.B-1 to I.C-8.8a.B-784, I.C-9.8a.B-1 to I.C-9.8a.B-784; compounds I.D-1.8a.B-1 to I.D-1.8a.B-784, I.D-2.8a.B-1 to I.D-2.8a.B-784, I.D-3.8a.B-1 to I.D-3.8a.B-784, I.D-4.8a.B-1 to I.D-4.8a.B-784, I.D-5.8a.B-1 to I.D-5.8a.B-784, I.D-6.8a.B-1 to I.D-6.8a.B-784, I.D-7.8a.B-1 to I.D-7.8a.B-784, I.D-8.8a.B-1 to I.D-8.8a.B-784, I.D-9.8a.B-1 to I.D-9.8a.B-784; Compounds I.E-1.8a.B-1 to I.E-1.8a.B-784, I.E-2.8a.B-1 to I.E-2.8a.B-784, I.E-3.8a.B-1 to I.E-3.8a.B-784, I.E-4.8a.B-1 to I.E-4.8a.B-784, I.E-5.8a.B-1 to I.E-5.8a.B-784, I.E-6.8a.B-1 to I.E-6.8a.B-784, I.E-7.8a.B-1 to I.E-7.8a.B-784, I.E-8.8a.B-1 to I.E-8.8a.B-784, I.E-9.8a.B-1 to I.E-9.8a.B-784; Compounds I.F-1.8a.B-1 to I.F-1.8a.B-784, I.F-2.8a.B-1 to I.F-2.8a.B-784, I.F-3.8a.B-1 to I.F-3.8a.B-784, I.F-4.8a.B-1 to I.F-4.8a.B-784, I.F-5.8a.B-1 to I.F-5.8a.B-784, I.F-6.8a.B-1 to I.F-6.8a.B-784, I.F-7.8a.B-1 to I.F-7.8a.B-784, I.F-8.8a.B-1 to I.F-8.8a.B-784, I.F-9.8a.B-1 to I.F-9.8a.B-784; Compounds I.G-1.8a.B-1 to I.G-1.8a.B-784, I.G-2.8a.B-1 to I.G-2.8a.B-784, I.G-3.8a.B-1 to I.G-3.8a.B-784, I.G-4.8a.B-1 to I.G-4.8a.B-784, I.G-5.8a.B-1 to I.G-5.8a.B-784, I.G-6.8a.B-1 to I.G-6.8a.B-784; Compounds I.H-1.8a.B-1 to I.H-1.8a.B-784, I.H-2.8a.B-1 to I.H-2.8a.B-784, I.H-3.8a.B-1 to I.H-3.8a.B-784, I.H-4.8a.B-1 to I.H-4.8a.B-784, I.H-5.8a.B-1 to I.H-5.8a.B-784, I.H-6.8a.B-1 to I.H-6.8a.B-784; Compounds I.I-1.8a.B-1 to I.I-1.8a.B-784, I.I-2.8a.B-1 to I.I-2.8a.B-784, I.I-3.8a.B-1 to I.I-3.8a.B-784, I.I-4.8a.B-1 to I.I-4.8a.B-784, I.I-5.8a.B-1 to I.I-5.8a.B-784, I.I-6.8a.B-1 to I.I-6.8a.B-784; compounds I.J-1.8a.B-1 to I.J-1.8a.B-784, I.J-2.8a.B-1 to I.J-2.8a.B-784, I.J-3.8a.B-1 to I.J-3.8a.B-784, I.J-4.8a.B-1 to I.J-4.8a.B-784, I.J-5.8a.B-1 to I.J-5.8a.B-784, I.J-6.8a.B-1 to I.J-6.8a.B-784; compounds I.K-1.8a.B-1 to I.K-1.8a.B-784, I.K-2.8a.B-1 to I.K-2.8a.B-784, I.K-3.8a.B-1 to I.K-3.8a.B-784, I.K-4.8a.B-1 to I.K-4.8a.B-784, I.K-5.8a.B-1 to I.K-5.8a.B-784, I.K-6.8a.B-1 to I.K-6.8a.B-784; compounds I.L-1.8a.B-1 to I.L-1.8a.B-784, I.L-2.8a.B-1 to I.L-2.8a.B-784, I.L-3.8a.B-1 to I.L-3.8a.B-784, I.L-4.8a.B-1 to I.L-4.8a.B-784, I.L-5.8a.B-1 to I.L-5.8a.B-784, I.L-6.8a.B-1 to I.L-6.8a.B-784).
[0295] Table 9a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2C(CH3)3 and the X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds to a row in Table B in each case (compounds I.A-1.9a.B-1 to I.A-1.9a.B-784, I.A-2.9a.B-1 to I.A-2.9a.B-784, I.A-3.9a.B-1 to I.A-3.9a.B-784, I.A-4.9a.B-1 to I.A-4.9a.B-784, I.A-5.9a.B-1 to I.A-5.9a.B-784, I.A-6.9a.B-1 to I.A-6.9a.B-784, I.A-7.9a.B-1 to I.A-7.9a.B-784, I.A-8.9a.B-1 to I.A-8.9a.B-784, I.A-9.9a.B-1 to I.A-9.9a.B-784; compounds I.B-1.9a.B-1 to I.B-1.9a.B-784, I.B-2.9a.B-1 to I.B-2.9a.B-784, I.B-3.9a.B-1 to I.B-3.9a.B-784, I.B-4.9a.B-1 to I.B-4.9a.B-784, I.B-5.9a.B-1 to I.B-5.9a.B-784, I.B-6.9a.B-1 to I.B-6.9a.B-784, I.B-7.9a.B-1 to I.B-7.9a.B-784, I.B-8.9a.B-1 to I.B-8.9a.B-784, I.B-9.9a.B-1 to I.B-9.9a.B-784; compounds I.C-1.9a.B-1 to I.C-1.9a.B-784, I.C-2.9a.B-1 to I.C-2.9a.B-784, I.C-3.9a.B-1 to I.C-3.9a.B-784, I.C-4.9a.B-1 to I.C-4.9a.B-784, I.C-5.9a.B-1 to I.C-5.9a.B-784, I.C-6.9a.B-1 to I.C-6.9a.B-784, I.C-7.9a.B-1 to I.C-7.9a.B-784, I.C-8.9a.B-1 to I.C-8.9a.B-784, I.C-9.9a.B-1 to I.C-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-784, I.D-8.9a.B-1 to I.D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.D-1.9a.B-1 to I.D-1.9a.B-784, I.D-2.9a.B-1 to I.D-2.9a.B-784, I.D-3.9a.B-1 to I.D-3.9a.B-784, I.D-4.9a.B-1 to I.D-4.9a.B-784, I.D-5.9a.B-1 to I.D-5.9a.B-784, I.D-6.9a.B-1 to I.D-6.9a.B-784, I.D-7.9a.B-1 to I.D-7.9a.B-7D-8.9a.B-784, I.D-9.9a.B-1 to I.D-9.9a.B-784; compounds I.E-1.9a.B-1 to I.E-1.9a.B-784, I.E-2.9a.B-1 to I.E-2.9a.B-784, I.E-3.9a.B-1 to I.E-3.9a.B-784, I.E-4.9a.B-1 to I.E-4.9a.B-784, I.E-5.9a.B-1 to I.E-5.9a.B-784, I.E-6.9a.B-1 to I.E-6.9a.B-784, I.E-7.9a.B-1 to I.E-7.9a.B-784, I.E-8.9a.B-1 to I.E-8.9a.B-784, I.E-9.9a.B-1 to I.E-9.9a.B-784; compounds I.F-1.9a.B-1 to I.F-1.9a.B-784, I.F-2.9a.B-1 to I.F-2.9a.B-784, I.F-3.9a.B-1 to I.F-3.9a.B-784, I.F-4.9a.B-1 to I.F-4.9a.B-784, I.F-5.9a.B-1 to I.F-5.9a.B-784, I.F-6.9a.B-1 to I.F-6.9a.B-784, I.F-7.9a.B-1 to I.F-7.9a.B-784, I.F-8.9a.B-1 to I.F-8.9a.B-784, I.F-9.9a.B-1 to I.F-9.9a.B-784; compounds I.G-1.9a.B-1 to I.G-1.9a.B-784, I.G-2.9a.B-1 to I.G-2.9a.B-784, I.G-3.9a.B-1 to I.G-3.9a.B-784, I.G-4.9a.B-1 to I.G-4.9a.B-784, I.G-5.9a.B-1 to I.G-5.9a.B-784, I.G-6.9a.B-1 to I.G-6.9a.B-784; compounds I.H-1.9a.B-1 to I.H-1.9a.B-784, I.H-2.9a.B-1 to I.H-2.9a.B-784, I.H-3.9a.B-1 to I.H-3.9a.B-784, I.H-4.9a.B-1 to I.H-4.9a.B-784, I.H-5.9a.B-1 to I.H-5.9a.B-784, I.H-6.9a.B-1 to I.H-6.9a.B-784; compounds I.I-1.9a.B-1 to I.I-1.9a.B-784, I.I-2.9a.B-1 to I.I-2.9a.B-784, I.I-3.9a.B-1 to I.I-3.9a.B-784, I.I-4.9a.B-1 to I.I-4.9a.B-784, I.I-5.9a.B-1 to I.I-5.9a.B-784, I.I-6.9a.B-1 to I.I-6.9a.B-784; compounds I.J-1.9a.B-1 to I.J-1.9a.B-784, I.J-2.9a.B-1 to I.J-2.9a.B-784, I.J-3.9a.B-1 to I.J-3.9a.B-784, I.J-4.9a.B-1 to I.J-4.9a.B-784, I.J-5.9a.B-1 to I.J-5.9a.B-784, I.J-6.9a.B-1 to I.J-6.9a.B-784; compounds I.K-1.9a.B-1 to I.K-1.9a.B-784, I.K-2.9a.B-1 to I.K-2.9a.B-784, I.K-3.9a.B-1 to I.K-3.9a.B-784, I.K-4.9a.B-1 to I.K-4.9a.B-784, I.K-5.9a.B-1 to I.K-5.9a.B-784, I.K-6.9a.B-1 to I.K-6.9a.B-784; compounds I.L-1.9a.B-1 to I.L-1.9a.B-784, I.L-2.9a.B-1 to I.L-2.9a.B-784, I.L-3.9a.B-1 to I.L-3.9a.B-784, I.L-4.9a.B-1 to I.L-4.9a.B-784, I.L-5.9a.B-1 to I.L-5.9a.B-784, I.L-6.9a.B-1 to I.L-6.9a.B-784).
[0296] Table 10a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2CH=CH2 and X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combination corresponds to a row in Table B in each case (compounds I.A-1.10a.B-1 to I.A-1.10a.B-784, I.A-2.10a.B-1 to I.A-2.10a.B-784, I.A-3.10a.B-1 to I.A-3.10a.B-784, I.A-4.10a.B-1 to I.A-4.10a.B-784, I.A-5.10a.B-1 to I.A-5.10a.B-784, I.A-6.10a.B-1 to I.A-6.10a.B-784, I.A-7.10a.B-1 to I.A-7.10a.B-784, I.A-8.10a.B-1 to I.A-8.10a.B-784, I.A-9.10a.B-1 to I.A-9.10a.B-784; compounds I.B-1.10a.B-1 to I.B-1.10a.B-784, I.B-2.10a.B-1 to I.B-2.10a.B-784, I.B-3.10a.B-1 to I.B-3.10a.B-784, I.B-4.10a.B-1 to I.B-4.10a.B-784, I.B-5.10a.B-1 to I.B-5.10a.B-784, I.B-6.10a.B-1 to I.B-6.10a.B-784, I.B-7.10a.B-1 to I.B-7.10a.B-784, I.B-8.10a.B-1 to I.B-8.10a.B-784, I.B-9.10a.B-1 to I.B-9.10a.B-784; compounds I.C-1.10a.B-1 to I.C-1.10a.B-784, I.C-2.10a.B-1 to I.C-2.10a.B-784, I.C-3.10a.B-1 to I.C-3.10a.B-784, I.C-4.10a.B-1 to I.C-4.10a.B-784, I.C-5.10a.B-1 to I.C-5.10a.B-784, I.C-6.10a.B-1 to I.C-6.10a.B-784, I.C-7.10a.B-1 to I.C-7.10a.B-784, I.C-8.10a.B-1 to I.C-8.10a.B-784, I.C-9.10a.B-1 to I.C-9.10a.B-784; compounds I.D-1.10a.B-1 to I.D-1.10a.B-784, I.D-2.10a.B-1 to I.D-2.10a.B-784, I.D-3.10a.B-1 to I.D-3.10a.B-784, I.D-4.10a.B-1 to I.D-4.10a.B-784, I.D-5.10a.B-1 to I.D-5.10a.B-784, I.D-6.10a.B-1 to I.D-6.10a.B-784, I.D-7.10a.B-1 to I.D-7.10a.B-784, I.D-8.10a.B-1 to I.D-8.10a.B-784, I.D-9.10a.B-1 to I.D-9.10a.B-784; Compound I.E-1.10a.B-1 to I.E-1.10a.B-784, I.E-2.10a.B-1 to I.E-2.10a.B-784, I.E-3.10a.B-1 to I.E-3.10a.B-784, I.E-4.10a.B-1 to I.E-4.10a.B-784, I.E-5.10a.B-1 to I.E-5.10a.B-784, I.E-6.10a.B-1 to I.E-6.10a.B-784, I.E-7.10a.B-1 to I.E-7.10a.B-784, I.E-8.10a.B-1 to I.E-8.10a.B-784, I.E-9.10a.B-1 to I.E-9.10a.B-784; Compound I.F-1.10a.B-1 to I.F-1.10a.B-784, I.F-2.10a.B-1 to I.F-2.10a.B-784, I.F-3.10a.B-1 to I.F-3.10a.B-784, I.F-4.10a.B-1 to I.F-4.10a.B-784, I.F-5.10a.B-1 to I.F-5.10a.B-784, I.F-6.10a.B-1 to I.F-6.10a.B-784, I.F-7.10a.B-1 to I.F-7.10a.B-784, I.F-8.10a.B-1 to I.F-8.10a.B-784, I.F-9.10a.B-1 to I.F-9.10a.B-784; Compound I.G-1.10a.B-1 to I.G-1.10a.B-784, I.G-2.10a.B-1 to I.G-2.10a.B-784, I.G-3.10a.B-1 to I.G-3.10a.B-784, I.G-4.10a.B-1 to I.G-4.10a.B-784, I.G-5.10a.B-1 to I.G-5.10a.B-784, I.G-6.10a.B-1 to I.G-6.10a.B-784; Compound I.H-1.10a.B-1 to I.H-1.10a.B-784, I.H-2.10a.B-1 to I.H-2.10a.B-784, I.H-3.10a.B-1 to I.H-3.10a.B-784, I.H-4.10a.B-1 to I.H-4.10a.B-784, I.H-5.10a.B-1 to I.H-5.10a.B-784, I.H-6.10a.B-1 to I.H-6.10a.B-784; Compounds I.I-1.10a.B-1 to I.I-1.10a.B-784, I.I-2.10a.B-1 to I.I-2.10a.B-784, I.I-3.10a.B-1 to I.I-3.10a.B-784, I.I-4.10a.B-1 to I.I-4.10a.B-784, I.I-5.10a.B-1 to I.I-5.10a.B-784, I.I-6.10a.B-1 to I.I-6.10a.B-784; Compounds I.J-1.10a.B-1 to I.J-1.10a.B-784, I.J-2.10a.B-1 to I.J-2.10a.B-784, I.J-3.10a.B-1 to I.J-3.10a.B-784, I.J-4.10a.B-1 to I.J-4.10a.B-784, I.J-5.10a.B-1 to I.J-5.10a.B-784, I.J-6.10a.B-1 to I.J-6.10a.B-784; Compounds I.K-1.10a.B-1 to I.K-1.10a.B-784, I.K-2.10a.B-1 to I.K-2.10a.B-784, I.K-3.10a.B-1 to I.K-3.10a.B-784, I.K-4.10a.B-1 to I.K-4.10a.B-784, I.K-5.10a.B-1 to I.K-5.10a.B-784, I.K-6.10a.B-1 to I.K-6.10a.B-784; Compounds I.L-1.10a.B-1 to I.L-1.10a.B-784, I.L-2.10a.B-1 to I.L-2.10a.B-784, I.L-3.10a.B-1 to I.L-3.10a.B-784, I.L-4.10a.B-1 to I.L-4.10a.B-784, I.L-5.10a.B-1 to I.L-5.10a.B-784, I.L-6.10a.B-1 to I.L-6.10a.B-784).
[0297] Table 11a Compounds having the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2CCH and X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combinations corresponds in each case to a row of Table B (compounds I.A-1.11a.B-1 to I.A-1.11a.B-784, I.A-2.11a.B-1 to I.A-2.11a.B-784, I.A-3.11a.B-1 to I.A-3.11a.B-784, I.A-4.11a.B-1 to I.A-4.11a.B-784, I.A-5.11a.B-1 to I.A-5.11a.B-784, I.A-6.11a.B-1 to I.A-6.11a.B-784, I.A-7.11a.B-1 to I.A-7.11a.B-784, I.A-8.11a.B-1 to I.A-8.11a.B-784, I.A-9.11a.B-1 to I.A-9.11a.B-784; compounds I.B-1.11a.B-1 to I.B-1.11a.B-784, I.B-2.11a.B-1 to I.B-2.11a.B-784, I.B-3.11a.B-1 to I.B-3.11a.B-784, I.B-4.11a.B-1 to I.B-4.11a.B-784, I.B-5.11a.B-1 to I.B-5.11a.B-784, I.B-6.11a.B-1 to I.B-6.11a.B-784, I.B-7.11a.B-1 to I.B-7.11a.B-784, I.B-8.11a.B-1 to I.B-8.11a.B-784, I.B-9.11a.B-1 to I.B-9.11a.B-784; compounds I.C-1.11a.B-1 to I.C-1.11a.B-784, I.C-2.11a.B-1 to I.C-2.11a.B-784, I.C-3.11a.B-1 to I.C-3.11a.B-784, I.C-4.11a.B-1 to I.C-4.11a.B-784, I.C-5.11a.B-1 to I.C-5.11a.B-784, I.C-6.11a.B-1 to I.C-6.11a.B-784, I.C-7.11a.B-1 to I.C-7.11a.B-784, I.C-8.11a.B-1 to I.C-8.11a.B-784, I.C-9.11a.B-1 to I.C-9.11a.B-784; compounds I.D-1.11a.B-1 to I.D-1.11a.B-784, I.D-2.11a.B-1 to I.D-2.11a.B-784, I.D-3.11a.B-1 to I.D-3.11a.B-784, I.D-4.11a.B-1 to I.D-4.11a.B-784, I.D-5.11a.B-1 to I.D-5.11a.B-784, I.D-6.11a.B-1 to I.D-6.11a.B-784, I.D-7.11a.B-1 to I.D-7.11a.B-784, I.D-8.11a.B-1 to I.D-8.11a.B-784, I.D-9.11a.B-1 to I.D-9.11a.B-784; Compound I.E-1.11a.B-1 to I.E-1.11a.B-784, I.E-2.11a.B-1 to I.E-2.11a.B-784, I.E-3.11a.B-1 to I.E-3.11a.B-784, I.E-4.11a.B-1 to I.E-4.11a.B-784, I.E-5.11a.B-1 to I.E-5.11a.B-784, I.E-6.11a.B-1 to I.E-6.11a.B-784, I.E-7.11a.B-1 to I.E-7.11a.B-784, I.E-8.11a.B-1 to I.E-8.11a.B-784, I.E-9.11a.B-1 to I.E-9.11a.B-784; Compound I.F-1.11a.B-1 to I.F-1.11a.B-784, I.F-2.11a.B-1 to I.F-2.11a.B-784, I.F-3.11a.B-1 to I.F-3.11a.B-784, I.F-4.11a.B-1 to I.F-4.11a.B-784, I.F-5.11a.B-1 to I.F-5.11a.B-784, I.F-6.11a.B-1 to I.F-6.11a.B-784, I.F-7.11a.B-1 to I.F-7.11a.B-784, I.F-8.11a.B-1 to I.F-8.11a.B-784, I.F-9.11a.B-1 to I.F-9.11a.B-784; Compound I.G-1.11a.B-1 to I.G-1.11a.B-784, I.G-2.11a.B-1 to I.G-2.11a.B-784, I.G-3.11a.B-1 to I.G-3.11a.B-784, I.G-4.11a.B-1 to I.G-4.11a.B-784, I.G-5.11a.B-1 to I.G-5.11a.B-784, I.G-6.11a.B-1 to I.G-6.11a.B-784; Compound I.H-1.11a.B-1 to I.H-1.11a.B-784, I.H-2.11a.B-1 to I.H-2.11a.B-784, I.H-3.11a.B-1 to I.H-3.11a.B-784, I.H-4.11a.B-1 to I.H-4.11a.B-784, I.H-5.11a.B-1 to I.H-5.11a.B-784, I.H-6.11a.B-1 to I.H-6.11a.B-784; Compounds I.I-1.11a.B-1 to I.I-1.11a.B-784, I.I-2.11a.B-1 to I.I-2.11a.B-784, I.I-3.11a.B-1 to I.I-3.11a.B-784, I.I-4.11a.B-1 to I.I-4.11a.B-784, I.I-5.11a.B-1 to I.I-5.11a.B-784, I.I-6.11a.B-1 to I.I-6.11a.B-784; Compounds I.J-1.11a.B-1 to I.J-1.11a.B-784, I.J-2.11a.B-1 to I.J-2.11a.B-784, I.J-3.11a.B-1 to I.J-3.11a.B-784, I.J-4.11a.B-1 to I.J-4.11a.B-784, I.J-5.11a.B-1 to I.J-5.11a.B-784, I.J-6.11a.B-1 to I.J-6.11a.B-784; Compounds I.K-1.11a.B-1 to I.K-1.11a.B-784, I.K-2.11a.B-1 to I.K-2.11a.B-784, I.K-3.11a.B-1 to I.K-3.11a.B-784, I.K-4.11a.B-1 to I.K-4.11a.B-784, I.K-5.11a.B-1 to I.K-5.11a.B-784, I.K-6.11a.B-1 to I.K-6.11a.B-784; Compounds I.L-1.11a.B-1 to I.L-1.11a.B-784, I.L-2.11a.B-1 to I.L-2.11a.B-784, I.L-3.11a.B-1 to I.L-3.11a.B-784, I.L-4.11a.B-1 to I.L-4.11a.B-784, I.L-5.11a.B-1 to I.L-5.11a.B-784, I.L-6.11a.B-1 to I.L-6.11a.B-784).
[0298] Table 12a has compounds of the following formula: I.A-1, I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8, I.A-9; I.B-1, I.B-2, I.B-3, I.B-4, I.B-5, I.B-6, I.B-7, I.B-8, I.B-9; I.C-1, I.C-2, I.C-3, I.C-4, I.C-5, I.C-6, I.C-7, I.C-8, I.C-9; I.D-1, I.D-2, I.D-3, I.D-4, I.D-5, I.D-6, I.D-7, I.D-8, I.D-9; I.E-1, I.E-2, I.E-3, I.E-4, I.E-5, I.E-6, I.E-7, I.E-8, I.E-9; I.F-1, I.F-2, I.F-3, I.F-4, I.F-5, I.F-6, I.F-7, I.G-8, I.F-9; I.G-1, I.G-2, I.G-3, I.G-4, I.G-5, I.G-6, I.H-1, I.H-2, I.H-3, I.H-4, I.H-5, I.H-6; I.I-1, I.I-2, I.I-3, I.I-4, I.I-5, I.I-6; I.J-1, I.J-2, I.J-3, I.J-4, I.J-5, I.J-6; I.K-1, I.K-2, I.K-3, I.K-4, I.K-5, I.K-6; I.L-1, I.L-2, I.L-3, I.L-4, I.L-5, I.L-6, where R 9 is CH2C6H5 and the X of each individual compound 1 、X 2 、R 5 、R 6 、R 7 and R 8The meaning of the combination corresponds to a row in Table B in each case (compounds I.A-1.12a.B-1 to I.A-1.12a.B-784, I.A-2.12a.B-1 to I.A-2.12a.B-784, I.A-3.12a.B-1 to I.A-3.12a.B-784, I.A-4.12a.B-1 to I.A-4.12a.B-784, I.A-5.12a.B-1 to I.A-5.12a.B-784, I.A-6.12a.B-1 to I.A-6.12a.B-784, I.A-7.12a.B-1 to I.A-7.12a.B-784, I.A-8.12a.B-1 to I.A-8.12a.B-784, I.A-9.12a.B-1 to I.A-9.12a.B-784; compounds I.B-1.12a.B-1 to I.B-1.12a.B-784, I.B-2.12a.B-1 to I.B-2.12a.B-784, I.B-3.12a.B-1 to I.B-3.12a.B-784, I.B-4.12a.B-1 to I.B-4.12a.B-784, I.B-5.12a.B-1 to I.B-5.12a.B-784, I.B-6.12a.B-1 to I.B-6.12a.B-784, I.B-7.12a.B-1 to I.B-7.12a.B-784, I.B-8.12a.B-1 to I.B-8.12a.B-784, I.B-9.12a.B-1 to I.B-9.12a.B-784; compounds I.C-1.12a.B-1 to I.C-1.12a.B-784, I.C-2.12a.B-1 to I.C-2.12a.B-784, I.C-3.12a.B-1 to I.C-3.12a.B-784, I.C-4.12a.B-1 to I.C-4.12a.B-784, I.C-5.12a.B-1 to I.C-5.12a.B-784, I.C-6.12a.B-1 to I.C-6.12a.B-784, I.C-7.12a.B-1 to I.C-7.12a.B-784, I.C-8.12a.B-1 to I.C-8.12a.B-784, I.C-9.12a.B-1 to I.C-9.12a.B-784; compounds I.D-1.12a.B-1 to I.D-1.12a.B-784, I.D-2.12a.B-1 to I.D-2.12a.B-784, I.D-3.12a.B-1 to I.D-3.12a.B-784, I.D-4.12a.B-1 to I.D-4.12a.B-784, I.D-5.12a.B-1 to I.D-5.12a.B-784, I.D-6.12a.B-1 to I.D-6.12a.B-784, I.D-7.12a.B-1 to I.D-7.12a.B-784, I.D-8.12a.B-1 to I.D-8.12a.B-784, I.D-9.12a.B-1 to I.D-9.12a.B-784; Compound I.E-1.12a.B-1 to I.E-1.12a.B-784, I.E-2.12a.B-1 to I.E-2.12a.B-784, I.E-3.12a.B-1 to I.E-3.12a.B-784, I.E-4.12a.B-1 to I.E-4.12a.B-784, I.E-5.12a.B-1 to I.E-5.12a.B-784, I.E-6.12a.B-1 to I.E-6.12a.B-784, I.E-7.12a.B-1 to I.E-7.12a.B-784, I.E-8.12a.B-1 to I.E-8.12a.B-784, I.E-9.12a.B-1 to I.E-9.12a.B-784; Compound I.F-1.12a.B-1 to I.F-1.12a.B-784, I.F-2.12a.B-1 to I.F-2.12a.B-784, I.F-3.12a.B-1 to I.F-3.12a.B-784, I.F-4.12a.B-1 to I.F-4.12a.B-784, I.F-5.12a.B-1 to I.F-5.12a.B-784, I.F-6.12a.B-1 to I.F-6.12a.B-784, I.F-7.12a.B-1 to I.F-7.12a.B-784, I.F-8.12a.B-1 to I.F-8.12a.B-784, I.F-9.12a.B-1 to I.F-9.12a.B-784; Compound I.G-1.12a.B-1 to I.G-1.12a.B-784, I.G-2.12a.B-1 to I.G-2.12a.B-784, I.G-3.12a.B-1 to I.G-3.12a.B-784, I.G-4.12a.B-1 to I.G-4.12a.B-784, I.G-5.12a.B-1 to I.G-5.12a.B-784, I.G-6.12a.B-1 to I.G-6.12a.B-784; Compound I.H-1.12a.B-1 to I.H-1.12a.B-784, I.H-2.12a.B-1 to I.H-2.12a.B-784, I.H-3.12a.B-1 to I.H-3.12a.B-784, I.H-4.12a.B-1 to I.H-4.12a.B-784, I.H-5.12a.B-1 to I.H-5.12a.B-784, I.H-6.12a.B-1 to I.H-6.12a.B-784; Compounds I.I-1.12a.B-1 to I.I-1.12a.B-784, I.I-2.12a.B-1 to I.I-2.12a.B-784, I.I-3.12a.B-1 to I.I-3.12a.B-784, I.I-4.12a.B-1 to I.I-4.12a.B-784, I.I-5.12a.B-1 to I.I-5.12a.B-784, I.I-6.12a.B-1 to I.I-6.12a.B-784; Compounds I.J-1.12a.B-1 to I.J-1.12a.B-784, I.J-2.12a.B-1 to I.J-2.12a.B-784, I.J-3.12a.B-1 to I.J-3.12a.B-784, I.J-4.12a.B-1 to I.J-4.12a.B-784, I.J-5.12a.B-1 to I.J-5.12a.B-784, I.J-6.12a.B-1 to I.J-6.12a.B-784; Compounds I.K-1.12a.B-1 to I.K-1.12a.B-784, I.K-2.12a.B-1 to I.K-2.12a.B-784, I.K-3.12a.B-1 to I.K-3.12a.B-784, I.K-4.12a.B-1 to I.K-4.12a.B-784, I.K-5.12a.B-1 to I.K-5.12a.B-784, I.K-6.12a.B-1 to I.K-6.12a.B-784; Compounds I.L-1.12a.B-1 to I.L-1.12a.B-784, I.L-2.12a.B-1 to I.L-2.12a.B-784, I.L-3.12a.B-1 to I.L-3.12a.B-784, I.L-4.12a.B-1 to I.L-4.12a.B-784, I.L-5.12a.B-1 to I.L-5.12a.B-784, I.L-6.12a.B-1 to I.L-6.12a.B-784).
[0299] Table B
[0300]
[0301]
[0302]
[0303]
[0304]
[0305]
[0306]
[0307]
[0308]
[0309]
[0310]
[0311]
[0312]
[0313]
[0314]
[0315]
[0316]
[0317]
[0318]
[0319]
[0320] The compounds of the present invention can be prepared as shown in the following schemes, wherein, unless otherwise specified, the definition of each variable is as defined above for the compounds of formula I. The compounds of formula I can be prepared according to the methods described in the prior art or methods similar thereto. The synthesis utilizes starting materials that are commercially available or can be prepared from readily available compounds according to conventional procedures.
[0321] For example, the compounds of formula I can be prepared by alkylating or acylating the benzodiazepines represented by formula (11) with a series of alkyl halides and acyl chlorides, which can be achieved by treating the benzodiazepines Deprotonation of the class (11) is achieved. This reaction is preferably carried out at 0 °C to room temperature. In some cases, the slow reaction is carried out at temperatures up to 60 °C and using 1 - 5 equivalents of base and 1 - 3 equivalents of alkylating / acylating reagent, as described in Chem. Eur. J. [European Chemical Journal] (2016), 22, 10607 - 10613, CN 114349714A, WO 2008 / 118141A2, or US2012 / 184732 A1.
[0322]
[0323] The compound having the formula (11) can also be prepared by reducing the compound (10) with a series of reducing agents such as NaBH4, Na(CN)BH3 and other hydride sources or H2 in the presence of a metal catalyst. Generally, the compound (11) is prepared from (10) using Na(CN)BH3 (1 - 3 equivalents) in the presence of a catalytic amount of acid such as HOAc at room temperature, as described in US2016 / 222028, 2016, A1 or CN 113072542, 2021, A.
[0324]
[0325] The compound having the formula (10) can be prepared via alkylation or acylation of the benzodiazepine class represented by the formula (2) with a series of alkyl halides and acyl chlorides, which can be achieved by deprotonating the benzodiazepine class (2) with a series of organic or inorganic bases such as potassium tert - butoxide or sodium hydride. This reaction is preferably carried out at 0 °C to room temperature. In some cases, the slow reaction is carried out at temperatures up to 60 °C and using 1 - 5 equivalents of base and 1 - 3 equivalents of alkylating / acylating reagent, as described in Chem. Eur. J. [European Chemical Journal] (2016), 22, 10607 - 10613, CN 114349714 A, WO 2008 / 118141A2, or US2012 / 184732A1. The benzodiazepine compound represented by the formula (2) can be prepared by reacting a series of diamines (or their HCl salts) represented by the formula (4) with at least 1 halogen (represented by X
[0326]
[0327] The benzodiazepine represented by the formula (2) 1It is represented that preferably, the F)-substituted quinolinyl / quinoxalinyl / pyridyl / pyrazinyl aryl ketone (3) is prepared by reacting in the presence of a base. This reaction is preferably carried out at room temperature to 120 °C with 1 - 6 equivalents of a base and 1 to 1.5 equivalents of a diamine, similar to the methods described in WO 2016 / 87370A1, Org. Biomol. Chem. [Organic and Biomolecular Chemistry] (2014), 12, 6895 - 6900, WO 2006 / 44753A2, or Heterocycles [Heterocycles] (1994), 38, 125 - 134.
[0328]
[0329] The aryl ketone (3) is commercially available or can be prepared according to the scheme by oxidizing the aryl alcohol 5 using, for example, manganese dioxide, as described in Inorganica Chimica Acta [Inorganic Chemistry Acta] (2012), 382, 72 - 78, WO 2000 / 038618, CN 107879989 A, or Chinese Science Bulletin [Chinese Science Bulletin] 2010, 55(25), 2817 - 2819.
[0330]
[0331] The aryl alcohol (5) can be prepared by isopropylmagnesium chloride-mediated bromine / iodine-magnesium exchange of 7 and subsequent addition to the commercially available aldehyde represented by the general formula (6). This reaction is preferably carried out at 0 °C using an equimolar ratio of iPrMgCl to the aryl halide (7), and the intermediate of this aryl halide is employed at a ratio of 1.2 - 1.3:1 relative to the aldehyde (6), as described in WO 2021 / 71821A1, J. Med. Chem. [Journal of Medicinal Chemistry], (2013), 56, 10158 - 10170, WO 2014 / 102233 A1, or US2016 / 83401A1.
[0332]
[0333] Alternatively, the scaffold represented by formula (2) can also be obtained by reacting aryl ketone (3) with partially protected diamine (8) in the presence of an organic or inorganic base at a temperature up to 200 °C under microwave irradiation, as described in US2006 / 178386A1, Bioorganic & Medicinal Chemistry Letters (2021), 35, 127813, Chem. Sci. (2021), 12, 4519 - 4525, or J. Org. Chem. (2005), 70, 8924 - 8931. The resulting product 9 can then be further reacted at 0 °C in a 1.5:7 mixture of TFA:DCM to produce the condensation product represented by formula 2, as described in US2006 / 3995, J. Bioorg. Med. Chem. Lett. (2007), 17, 2527–2530, WO 2022 / 99011A1, Org Lett. (2012), 14, 5916 - 5919, or J. Med. Chem. (2016), 59, 10661 - 10675. Alkylation / acylation can then be carried out as described above to obtain compound I.
[0334]
[0335] Compound I and its compositions are respectively suitable as fungicides, effectively against a broad spectrum of phytopathogenic fungi, including soil - borne fungi, especially fungi from the classes Plasmodiophoromycetes, Peronosporomycetes (synonym Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (synonym Fungi imperfecti). They can be used as foliar fungicides, seed - dressing fungicides, and soil fungicides in crop protection.
[0336] Compound I and its compositions are preferably useful for controlling phytopathogenic fungi on the following cultivated plants: various cultivated plants such as cereals, for example wheat, rye, barley, triticale, oats or rice; sugar beet, such as sugar beet or fodder beet; fruits, for example pomaceous fruits (apples, pears, etc.), stone fruits (for example plums, peaches, apricots, cherries) or soft fruits, also known as berries (strawberries, raspberries, blackberries, currants, etc.); leguminous plants such as lentils, peas, alfalfa or soybeans; oil plants such as rape, mustard, olives, sunflowers, coconuts, cocoa beans, castor oil plants, oil palms, groundnuts or soybeans; cucurbits, for example pumpkins, cucumbers or melons; fibre plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, gourds or paprika; lauraceous plants such as avocados, cinnamon or camphor; energy and raw material plants, for example maize, soybeans, rape, sugar cane or oil palms; maize; tobacco; nuts; coffee; tea; bananas; grapevines (table grapes and wine grapevines); hops; turf; stevia (also known as stevia rebaudiana); natural rubber plants; or ornamental and forest plants such as flowers, shrubs, broad-leaved trees or evergreens (conifers, eucalyptus, etc.); plant propagation material such as seeds; and crop material of these plants.
[0337] More preferably, compound I and its compositions are used for controlling fungi on the following: field crops such as potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, maize, cotton, soybeans, rape, beans, sunflowers, coffee or sugar cane; fruits; vines; ornamental plants; or vegetables such as cucumbers, tomatoes, green beans or pumpkins.
[0338] The term "plant propagation material" is to be understood as meaning all generative parts of plants, such as seeds; and vegetative plant material which can be used for plant propagation, such as cuttings and tubers (such as potatoes). This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, buds and other parts of plants; including seedlings and young plants which are transplanted after germination or after emergence from the soil.
[0339] Preferably, plant propagation material is treated with compound I and its compositions respectively for controlling fungi on the following: cereals such as wheat, rye, barley and oats; rice, maize, cotton and soybeans.
[0340] According to the invention, all the above-mentioned cultivated plants are to be understood as including all species, subspecies, varieties, cultivars and / or hybrids belonging to the respective cultivated plants, including but not limited to winter and spring varieties, in particular cereals such as wheat and barley, and rape, for example winter wheat, spring wheat, winter barley, etc.
[0341] Maize, also known as Indian corn or Zea mays, includes all types of maize such as forage maize and sweet corn. According to the present invention, it includes all Zea mays or maize subspecies and / or varieties, in particular floury maize (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent maize (Zea mays var. indentata), flint maize (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy maize (Zea mays var. ceratina), high amylose maize (amylomaize) (high amylose Zea mays varieties), pod maize or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).
[0342] Most soybean cultivars can be classified into indeterminate and determinate growth habits, while wild soybean (Glycine soja) (the wild ancestor of soybean) is indeterminate (PNAS 2010, 107(19) 8563 - 856). Indeterminate growth habit (maturity groups, MG 00 to MG 4.9) is characterized by the continuation of vegetative growth after the onset of flowering, while determinate soybean varieties (MG 5 to MG 8) characteristically have completed most of their vegetative growth at the onset of flowering. According to the present invention, it includes all soybean cultivars or varieties, in particular indeterminate and determinate cultivars or varieties.
[0343] The term "cultivated plant" shall be understood to include plants that have been modified by mutagenesis or genetic engineering to provide new traits to the plant or to modify existing traits. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals and also includes targeted mutagenesis to generate mutations at specific loci in the plant genome. Targeted mutagenesis often uses oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs or meganucleases. Genetic engineering typically uses recombinant DNA techniques to generate modifications in the plant genome that cannot be readily obtained by crossing, mutagenesis or natural recombination in the natural environment. Typically, one or more genes are integrated into the plant genome to increase traits or to improve or modify traits. These integrated genes are also referred to as transgenes, and plants containing such transgenes are referred to as transgenic plants. The plant transformation process typically results in a number of transformation events that differ in the genomic loci at which the transgene has been integrated. Plants containing a specific transgene at a specific genomic locus are typically described as containing a specific "event", which is designated by a specific event name. Traits that have been introduced into plants or that have been modified include herbicide tolerance, insect resistance, increased yield, and tolerance to abiotic conditions such as drought.
[0344] Herbicide tolerance has been generated by using mutagenesis and genetic engineering. Plants that have been made tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are available, for example, under the name Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides (such as bromoxynil and ioxynil), sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors (such as isoxaflutole and mesotrione) has been generated by using transgenes.
[0345] Transgenes providing herbicide tolerance traits include: for glyphosate tolerance: cp4epsps, epspsgrg23ace5, mepsps, 2mepsps, gat4601, gat4621, goxv247; for glufosinate tolerance: pat and bar; for 2,4-D tolerance: aad-1, aad-12; for dicamba tolerance: dmo; for oxynil herbicide tolerance: bxn; for sulfonylurea herbicide tolerance: zm-hra, csr1-2, gm-hra, S4-HrA; for ALS inhibitor tolerance: csr1-2; and for HPPD inhibitor tolerance: hppdPF, W336, avhppd-03.
[0346] Transgenic maize events containing herbicide tolerance genes include but are not limited to DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275. Transgenic soybean events containing 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, W62, W98, FG72 and CV127. Transgenic cotton events containing 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 containing 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.
[0347] Transgenes conferring insect resistance are preferably toxin genes of Bacillus species and their synthetic variants, such as cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. Additionally, transgenes of plant origin can be used, such as genes encoding protease inhibitors, such as CpTI and pinII. Another approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
[0348] Transgenic maize events containing insecticidal protein genes 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 containing insecticidal protein genes include, but are not limited to, MON87701, MON87751, and DAS-81419. Transgenic cotton events containing insecticidal protein genes 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, GFMCry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119, and SGK321.
[0349] Cultivated plants with increased yield have been produced by using the transgenes athb17 (e.g., maize event MON87403) or bbx32 (e.g., soybean event MON87712).
[0350] Cultivated plants with improved oil content have been produced by using the following transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A, and fatb1-A (e.g., soybean events 260-05, MON87705, and MON87769).
[0351] Tolerance to abiotic conditions (such as drought) has been achieved by using the transgenes cspB (maize event MON87460) and Hahb-4 (soybean event ) generated.
[0352] Traits are typically combined to produce cultivated plants with stacked traits by combining gene combinations in transformation events or by combining different events during a breeding process. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different species of insects, particularly Lepidoptera and Coleoptera insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield, and combinations of herbicide tolerance and tolerance to abiotic conditions.
[0353] Plants containing single or stacked traits, as well as the genes and events providing such traits, are well known in the art. For example, detailed information on mutagenesis or integration of genes and corresponding events is available from the websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http: / / www.isaaa.org / gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http: / / cera-gmc.org / GMCropDatabase). Additional information on specific events and methods for detecting these events, for canola events MS1, MS8, RF3, GT73, MON88302, KK179, can be found in WO 01 / 031042, WO 01 / 041558, WO 01 / 041558, WO 02 / 036831, WO 11 / 153186, WO 13 / 003558; for cotton events MON1445, MON15985, MON531 (MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701, 81910, can be found in WO 02 / 034946, WO 02 / 100163, WO 02 / 100163, WO 03 / 013224, WO 04 / 072235, WO 04 / 039986, WO 05 / 103266, WO 05 / 103266, WO 06 / 128573, WO 07 / 017186, WO 08 / 122406, WO 08 / 151780, WO 12 / 134808, WO 13 / 112527;For maize 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, they can be found in WO 98 / 044140, US 02 / 102582, US 03 / 126634, WO 04 / 099447, WO 04 / 011601, WO 05 / 103301, WO 05 / 061720, WO 05 / 059103, WO 06 / 098952, WO 06 / 039376, US2007 / 292854, WO07 / 142840, WO 07 / 140256, WO 08 / 112019, WO 09 / 103049, WO 09 / 111263, WO 10 / 077816, WO11 / 084621, WO 11 / 062904, WO 11 / 022469, WO 13 / 169923, WO 14 / 116854, WO 15 / 053998, WO15 / 142571; for potato events E12, F10, J3, J55, V11, X17, Y9, they can be found in WO 14 / 178910, WO 14 / 178913, WO 14 / 178941, WO 14 / 179276, WO 16 / 183445, WO 17 / 062831, WO 17 / 062825; for rice events LLRICE06, LLRICE601, LLRICE62, they can be found in WO 00 / 026345, WO 00 / 026356, WO 00 / 026345;And for the soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751, reference may be made to WO 04 / 074492, WO 06 / 130436, WO06 / 108674, WO 06 / 108675, WO 08 / 054747, WO 08 / 002872, WO 09 / 064652, WO 09 / 102873, WO10 / 080829, WO 10 / 037016, WO 11 / 066384, WO 11 / 034704, WO12 / 051199, WO 12 / 082548, WO13 / 016527, WO 13 / 016516, WO 14 / 201235.;
[0354] The separate use of Compound I and its compositions on cultivated plants can lead to effects specific to cultivated plants comprising a certain transgene or event. Such effects may relate to alterations in growth behavior or altered resistance to biotic or abiotic stress factors. Such effects may in particular include increased yield, increased resistance or tolerance to insect, nematode, fungal, bacterial, mycoplasma, viral or viroid pathogens and early vigour, early or delayed maturity, cold or heat tolerance and altered amino acid or fatty acid profiles or contents.
[0355] Compound I and its compositions are particularly suitable, respectively, for controlling the causative agents of the following plant diseases:
[0356] Species of Albugo (white rust) on ornamental plants, vegetables (e.g., Albugo candida), and sunflowers (e.g., Albugo tragopogonis); species of Alternaria (alternaria leaf spot) on vegetables (e.g., Alternaria dauci or Alternaria porri), rape (Alternaria brassicicola or Alternaria brassicae), sugar beet (Alternaria tenuis), fruits (e.g., Alternaria grandis), rice, soybeans, potatoes, and tomatoes (e.g., Alternaria solani, Alternaria grandis, or Alternaria alternata), tomatoes (e.g., Alternaria solani or Alternaria alternata), and wheat (e.g., Alternaria triticina); species of Aphanomyces on sugar beet and vegetables; species of Ascochyta on cereals and vegetables, such as Ascochyta tritici (anthracnose) on wheat and Ascochyta hordei on barley; Aureobasidium zeae (synonym Kapatiella zeae) on corn; species of Bipolaris and Drechslera (sexual form: species of Cochliobolus), such as southern leaf blight (Drechslera maydis) or northern leaf blight (Bipolaris zeicola) on corn, such as spot blotch (Bipolaris sorokiniana) on cereals and, for example, Bipolaris oryzae on rice and turfgrass; Blumeria graminis (formerly known as Erysiphe graminis) (powdery mildew) on cereals (e.g., wheat or barley); Botrytis cinerea (sexual form: Botryotinia fuckeliana: gray mold) on fruits and berries (e.g., strawberries), vegetables (e.g., lettuce, carrots, celery, and cabbage); Botrytis squamosa or Botrytis allii on the onion family, rape, ornamental plants (e.g., Botrytis elliptica), vines, forest plants, and wheat; Bremia lactucae (downy mildew) on lettuce; species of Ceratocystis (synonym Ophiostoma) (rot or wilt) on broad-leaved and evergreen trees, such as Ceratocystis ulmi on elm treesulmi) (Dutch elm disease); maize (e.g., gray leaf spot: Cercospora zeae-maydis), rice, sugar beet (e.g., Cercospora beticola), sugar cane, vegetables, coffee, soybean (e.g., Cercospora sojina or Cercospora kikuchii) and Cercospora species on rice (Cercospora leafspot); Cladobotryum (synonym Dactylium) species on mushrooms (e.g., Cladobotryum mycophilum).
[0357] (formerly known as Dactylium dendroides), teleomorph: Nectria albertinii, Nectria rosella (synonym Hypomyces rosellus); Cladosporium species on tomato (e.g., C. fulvum: leaf mold) and cereals, such as C. herbarum on wheat (black ear); Claviceps purpurea on cereals (ergot); Cochliobolus (anamorph: Helminthosporium of the genus Bipolaris) species on maize (C. carbonum), cereals (e.g., C. sativus, anamorph: B. sorokiniana) and rice (e.g., C. miyabeanus, anamorph: H. oryzae) (leaf spot); Colletotrichum (teleomorph: Glomerella) species on cotton (e.g., C. gossypii), maize (e.g., C. graminicola: anthracnose stalk rot), soft fruits, potato (e.g., C. coccodes: black dot), common bean (e.g., C. lindemuthianum), soybean (e.g., C. truncatum or C. gloeosporioides), vegetables (e.g., C. lagenarium or C. capsici), fruits (e.g., C. acutatum), coffee (e.g., C. coffeanum or C. kahawae) and various crops (C. gloeosporioides) (anthracnose); Corticium species, such as C. sasakii on rice (sheath blight); Corynespora cassiicola on soybean, cotton and ornamental plants (leaf spot); Cycloconium species, such as C. oleaginum on olive; fruit trees, vines (e.g., CylindrocladiumLiriodendri), sexual form: Neonectria liriodendri: Black Foot Disease) and Cylindrocarpon species on ornamental plants (such as fruit tree canker or young vine decline, sexual form: Nectria or Neonectria species); Dematophora necatrix on soybeans (sexual form: Rosellinia necatrix) (root and stem rot); Diaporthe species, such as D. phaseolorum on soybeans (damping-off); Drechslera (synonym Helminthosporium, sexual form: Pyrenophora) species on corn, cereals such as barley (e.g., D. teres, net blotch) and wheat (e.g., D. tritici-repentis: tan spot), rice and turfgrass; Esca (dieback, apoplexy) on vines, caused by Formitiporia punctata (synonym Phellinus punctata), F. mediterranea, Phaeomoniella chlamydospora (previously known as Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa; Elsinoe species on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae on rice (leaf smut); Epicoccum species on wheat (black mold); Erysiphe betae on sugar beet, Erysiphe species on vegetables (such as E. pisi on peas) such as cucurbits (such as E. cichoracearum on cucumbers), cabbages, oilseeds (such as E. cruciferarum on rape)species of Erysiphe (powdery mildew) on cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, synonym Libertella blepharis) on fruit trees, vines, and ornamental woods; species of Exserohilum (synonym Helminthosporium) on maize (e.g., E. turcicum); species of Fusarium (teleomorph: Gibberella) on various plants (wilt, root or stem rot), such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g., wheat or barley), F. oxysporum on tomato, F. solani (f.sp. glycines, new synonym F. virguliforme) on soybean, and F. tucumaniae and F. brasiliense (both causing sudden death syndrome), and F. verticillioides on maize; Gaeumannomyces graminis (take-all) on cereals (e.g., wheat or barley) and maize; species of Gibberella on cereals (e.g., G. zeae) and rice (e.g., G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits, and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; species of Gymnosporangium on Rosaceae plants and junipers, such as G. sabinae (rust) on pears; species of Helminthosporium (synonym Drechslera, teleomorph: Cochliobolus) on maize, cereals, potatoes, and rice; species of Hemileia, such as H. vastatrix on coffeevastatrix)(coffee leaf rust); Isariopsis clavispora (synonym Cladosporium vitis) on vines; Macrophomina phaseolina (synonym Macrophomina phaseoli) (root and stem rot) on soybeans and cotton; Microdochium nivale (synonym Fusarium nivale) (pink snow mold) on cereals (e.g., wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia species on stone fruits and other Rosaceae plants, such as Monilinia laxa, Monilinia fructicola, and Monilinia fructigena (synonym Monilia species: blossom blight and twig blight, brown rot); Mycosphaerella species on cereals, bananas, soft fruits, and peanuts, such as Mycosphaerella graminicola on wheat (anamorph: Zymoseptoria tritici, previously known as Septoria tritici: Septoria leaf blotch), or Mycosphaerella fijiensis on bananas (synonym Pseudocercospora fijiensis: black Sigatoka disease) and Mycosphaerella musicola, Mycosphaerella arachidicola on peanuts (synonym M. arachidis or Cercospora arachidis), Mycosphaerella berkeleyi, Mycosphaerella pisi on peas, and Mycosphaerella brassiciola on Brassica; Peronospora species on cabbages (e.g., Peronospora brassicae), oilseed rape (e.g., Peronospora parasitica), onions (e.g., Peronospora destructor), tobacco (Peronospora tabacina), and soybeans (e.g., Peronospora manshurica) (downy mildew); Phakopsora pachyrhizi and Phakopsora meibomiae on soybeans (soybean rust); Phialophora species, such as on vines (e.g., Phialophora tracheiphila and Phialophora tetraspora) and soybeans (e.g., Phialophora sojaegregata): stem rot); Phoma lingam (synonyms Leptosphaeria biglobosa and L. maculans: rhizome rot) on rape and cabbage, and Phoma betae (root rot, leaf spot and damping-off) on sugar beet, and P. zeae-maydis (synonym Phyllostica zeae) on maize; Phomopsis species on sunflower, vines (e.g., P. viticola: vine and leaf spot) and soybean (e.g., stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spot) on maize; Phytophthora species on various plants (wilting, root, leaf, fruit and stem rot), such as red pepper and gourd (e.g., P. capsici), soybean (e.g., P. megasperma, synonym P. sojae), potato and tomato (e.g., P. infestans: late blight) and broad-leaved trees (e.g., P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara species, such as P. viticola (downy mildew of grapevine) on vines and P. halstedii on sunflower; Podosphaera species (powdery mildew) on Rosaceae plants, hops, pome and soft fruits, such as P. leucotricha on apple and P. xanthii on gourd; Polymyxa species, such as P. graminis on cereals such as barley and wheat and P. betae on sugar beet, and virus diseases transmitted thereby; Pseudocercosporella herpotrichoides (synonyms Oculimacula yallundae, O. acuformis: eyespot, teleomorph: Tapesia yallundae) on cereals such as wheat or barley; Pseudoperonospora (downy mildew) on various plants, such as P. cubensis on gourdP. cubensis) or P. humili on hops; Pseudopezicula tracheiphila (red fire disease or rotbrenner, anamorph: Phialophora) on vines; Puccinia species (rust) on various plants, such as P. triticina (brown rust or leaf rust) on cereals such as wheat, barley or rye, P. striiformis (strip rust or yellow rust), P. hordei (dwarf rust), P. graminis (stem rust or black rust) or P. recondita (brown rust or leaf rust), P. kuehnii (citrus rust) on sugarcane and P. asparagi on asparagus; Pyrenopeziza species, such as P. brassicae on rapeseed; Pyrenophora tritici-repentis (anamorph: Drechslera tritici-repentis) (tan spot) on wheat or Pyrenophora teres (net blotch) on barley; Pyricularia species, such as P. oryzae (teleomorph: Magnaporthe grisea: rice blast) on rice, and P. grisea on turfgrass and cereals; Pythium species (damping-off) (e.g., P. ultimum or P. aphanidermatum) on turfgrass, rice, corn, wheat, cotton, rapeseed, sunflower, soybean, sugar beet, vegetables and various other plants, and P. oligandrum on mushrooms; Ramularia species, such as R. collo-cygni (Ramularia leaf spot, physiological leaf spot) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beet; Rhizoctonia species on cotton, rice, potato, turfgrass, corn, rapeseed, potato, sugar beet, vegetables and various other plants, such as R. solani (root and stem rot) on soybean, R. solani (sheath blight) on rice, or R. cerealis on wheat or barley (cerealis) (spring leaf blight of cereals); Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbages, vines, and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye, and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia species (stem rot or white mold), such as S. minor and S. sclerotiorum, on vegetables and field crops, e.g., rape, sunflower (e.g., S. sclerotiorum), and soybeans; Sclerotium rolfsii (synonym Athelia rolfsii) on soybeans, peanuts, vegetables, corn, cereals, and ornamental plants; Septoria species on various plants, e.g., Septoria glycines (brown spot) on soybeans, Septoria tritici (synonym Zymoseptoria tritici, Septoria leaf blotch) on wheat, and Septoria nodorum (synonym Stagonospora nodorum (Stagonospora leaf blotch)) on cereals; Uncinula necator (synonym Erysiphe necator) (powdery mildew, anamorph: Oidium tuckeri) on vines; Setosphaeria species (leaf blight) on corn (e.g., Setosphaeria turcicum, synonym Helminthosporium turcicum) and turfgrass; Sphacelotheca species (smut) on corn (e.g., Sphacelotheca reiliana, synonym Ustilago reiliana: head smut), sorghum, and sugarcane; Sphaerotheca fuliginea (synonym Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and the virus diseases transmitted thereby; Stagonospora species on cereals, e.g., Stagonospora nodorum on wheat;nodorum) (Septoria nodorum blotch, teleomorph: Leptosphaeria nodorum [synonym Phaeosphaeria nodorum], synonym Septoria nodorum); Synchytrium endobioticum on potatoes (potato wart disease); Taphrina species, such as Taphrina deformans on peaches (leaf curl) and Taphrina pruni on plums (plum pocket); Thielaviopsis species on tobacco, pome fruits, vegetables, soybeans and cotton (black root rot), such as Thielaviopsis basicola (synonym Chalara elegans); Tilletia species on cereals (common bunt or stinking smut), such as Tilletia tritici on wheat (synonym Tilletia caries, common bunt) and Tilletia controversa on wheat (dwarf bunt); Trichoderma harzianum on mushrooms; Typhula incarnata on barley or wheat (grey snow mold); Urocystis species, such as Urocystis occulta on rye (stem smut); Uromyces species on vegetables such as beans (e.g., Uromyces appendiculatus, synonym Uromyces phaseoli), sugar beets (e.g., Uromyces betae or Uromyces beticola) and dry beans (e.g., Uromyces vignae, Uromyces pisi, Uromyces viciae-fabae and Uromyces fabae) (rust); Ustilago species on cereals (e.g., Ustilago nuda and Ustilago avenae), maize (e.g., Ustilago maydis: corn smut) and sugar cane (loose smut); apples (e.g., Venturiaspecies of Venturia (scab) on pears; and species of Verticillium (wilt) on a variety of plants such as fruit and ornamental plants, vines, soft fruit, vegetables and field crops, such as V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Septoria tritici on cereals.
[0358] Compound I and its compositions are particularly suitable for controlling the pathogenic agents of the following plant diseases, respectively: rust on soybeans and cereals (e.g., Phakopsora pachyrhizi and Phakopsora meibomiae on soybeans; Puccinia triticina and Puccinia striiformis on wheat); mildew on specialty crops, soybeans, oilseed rape and sunflowers (e.g., Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, Sclerotinia minor and Sclerotium rolfsii on oilseed rape, sunflowers and soybeans); Fusarium diseases on cereals (e.g., Fusarium culmorum and Fusarium graminearum on wheat); downy mildew on specialty crops (e.g., Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildew on specialty crops and cereals (e.g., Uncinula necator on vines, species of Erysiphe on various specialty crops, Blumeria graminis on cereals); and leaf spot on cereals, soybeans and maize (e.g., Septoria tritici and Septoria nodorum on cereals, Septoria glycines on soybeans, species of Cercospora on maize and soybeans).
[0359] According to one embodiment, Compounds I.A-1.1a.B-1 to I.A-1.1a.B-180 are particularly suitable for controlling the pathogenic agents of the plant diseases according to List Z.
[0360] According to one embodiment, Compounds I.A-2.1a.B-1 to I.A-2.1a.B-180 are particularly suitable for controlling the pathogenic agents of the plant diseases according to List Z.
[0361] According to one embodiment, Compounds I.A-3.1a.B-1 to I.A-3.1a.B-180 are particularly suitable for controlling the pathogenic agents of the plant diseases according to List Z.
[0362] According to one embodiment, Compounds I.A-4.1a.B-1 to I.A-4.1a.B-180 are particularly suitable for controlling the pathogenic agents of the plant diseases according to List Z.
[0363] According to one embodiment, compounds I.A-5.1a.B-1 to I.A-5.1a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0364] According to one embodiment, compounds I.A-6.1a.B-1 to I.A-6.1a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0365] According to one embodiment, compounds I.A-1.2a.B-1 to I.A-1.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0366] According to one embodiment, compounds I.A-2.2a.B-1 to I.A-2.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0367] According to one embodiment, compounds I.A-3.2a.B-1 to I.A-3.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0368] According to one embodiment, compounds I.A-4.2a.B-1 to I.A-4.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0369] According to one embodiment, compounds I.A-5.2a.B-1 to I.A-5.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0370] According to one embodiment, compounds I.A-6.2a.B-1 to I.A-6.2a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0371] According to one embodiment, compounds I.A-1.3a.B-1 to I.A-1.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0372] According to one embodiment, compounds I.A-2.3a.B-1 to I.A-2.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0373] According to one embodiment, compounds I.A-3.3a.B-1 to I.A-3.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0374] According to one embodiment, compounds I.A-4.3a.B-1 to I.A-4.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0375] According to one embodiment, compounds I.A-5.3a.B-1 to I.A-5.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0376] According to one embodiment, compounds I.A-6.3a.B-1 to I.A-6.3a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0377] According to one embodiment, compounds I.A-1.4a.B-1 to I.A-1.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0378] According to one embodiment, compounds I.A-2.4a.B-1 to I.A-2.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0379] According to one embodiment, compounds I.A-3.4a.B-1 to I.A-3.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0380] According to one embodiment, compounds I.A-4.4a.B-1 to I.A-4.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0381] According to one embodiment, compounds I.A-5.4a.B-1 to I.A-5.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0382] According to one embodiment, compounds I.A-6.4a.B-1 to I.A-6.4a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0383] According to one embodiment, compounds I.A-1.5a.B-1 to I.A-1.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0384] According to one embodiment, compounds I.A-2.5a.B-1 to I.A-2.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0385] According to one embodiment, compounds I.A-3.5a.B-1 to I.A-3.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0386] According to one embodiment, compounds I.A-4.5a.B-1 to I.A-4.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0387] According to one embodiment, compounds I.A-5.5a.B-1 to I.A-5.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0388] According to one embodiment, compounds I.A-6.5a.B-1 to I.A-6.5a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0389] According to one embodiment, compounds I.A-1.6a.B-1 to I.A-1.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0390] According to one embodiment, compounds I.A-2.6a.B-1 to I.A-2.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0391] According to one embodiment, compounds I.A-3.6a.B-1 to I.A-3.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0392] According to one embodiment, compounds I.A-4.6a.B-1 to I.A-4.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0393] According to one embodiment, compounds I.A-5.6a.B-1 to I.A-5.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0394] According to one embodiment, compounds I.A-6.6a.B-1 to I.A-6.6a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0395] According to one embodiment, compounds I.A-1.7a.B-1 to I.A-1.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0396] According to one embodiment, compounds I.A-2.7a.B-1 to I.A-2.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0397] According to one embodiment, compounds I.A-3.7a.B-1 to I.A-3.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0398] According to one embodiment, compounds I.A-4.7a.B-1 to I.A-4.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0399] According to one embodiment, compounds I.A-5.7a.B-1 to I.A-5.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0400] According to one embodiment, compounds I.A-6.7a.B-1 to I.A-6.7a.B-180 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0401] According to one embodiment, compounds Ex-1 to Ex-92 are particularly suitable for controlling the pathogenic agents of plant diseases according to list Z.
[0402] List Z:
[0403] Species of Albugo (white rust) on ornamental plants, vegetables (e.g., Albugo candida), and sunflowers (e.g., Albugo tragopogonis); species of Alternaria (alternaria leaf spot) on vegetables (e.g., Alternaria dauci or Alternaria porri), oilseed rape (Alternaria brassicicola or Alternaria brassicae), sugar beet (Alternaria tenuis), fruits (e.g., Alternaria grandis), rice, soybeans, potatoes, and tomatoes (e.g., Alternaria solani, Alternaria grandis, or Alternaria alternata), tomatoes (e.g., Alternaria solani or Alternaria alternata), and wheat (e.g., Alternaria triticina); species of Aphanomyces on sugar beet and vegetables; species of Ascochyta on cereals and vegetables, such as Ascochyta tritici (anthracnose) on wheat and Ascochyta hordei on barley; Aureobasidium zeae (synonym Kapatiella zeae) on maize; species of Bipolaris and Drechslera (sexual form: species of Cochliobolus), such as southern leaf blight (Drechslera maydis) or northern leaf blight (Bipolaris zeicola) on maize, such as spot blotch (Bipolaris sorokiniana) on cereals and Bipolaris oryzae on rice and turfgrass; Blumeria graminis (formerly known as Erysiphe graminis) (powdery mildew) on cereals (e.g., wheat or barley); Botrytis cinerea (sexual form: Botryotinia fuckeliana: gray mold) on fruits and berries (e.g., strawberries), vegetables (e.g., lettuce, carrots, celery, and cabbages); Botrytis squamosa or Botrytis allii on the onion family, oilseed rape, ornamental plants (e.g., Botrytis elliptica), vines, forest plants, and wheat; Bremia lactucae (downy mildew) on lettuce; species of Ceratocystis (synonym Ophiostoma) (rot or wilt) on broad-leaved and evergreen trees, such as Ceratocystis ulmi on elm treesulmi)(Dutch elm disease); maize (e.g., gray leaf spot: Cercospora zeae-maydis), rice, sugar beet (e.g., Cercospora beticola), sugar cane, vegetables, coffee, soybean (e.g., Cercospora sojina or Cercospora kikuchii) and Cercospora species on rice (Cercospora leafspot); Cladobotryum (synonym Dactylium) species on mushrooms (e.g., Cladobotryum mycophilum).
[0404] (formerly known as Dactylium dendroides), teleomorph: Nectria albertinii, Nectria rosella (synonym Hypomyces rosellus); Cladosporium species on tomato (e.g., C. fulvum: leaf mold) and cereals, e.g., C. herbarum on wheat (black ear); Claviceps purpurea on cereals (ergot); Cochliobolus species (anamorph: Helminthosporium of the genus Bipolaris) on maize (C. carbonum), cereals (e.g., C. sativus, anamorph: B. sorokiniana) and rice (e.g., C. miyabeanus, anamorph: H. oryzae) (leaf spot); Colletotrichum (teleomorph: Glomerella) species on cotton (e.g., C. gossypii), maize (e.g., C. graminicola: anthracnose stalk rot), soft fruits, potato (e.g., C. coccodes: black dot), bean (e.g., C. lindemuthianum), soybean (e.g., C. truncatum or C. gloeosporioides), vegetables (e.g., C. lagenarium or C. capsici), fruits (e.g., C. acutatum), coffee (e.g., C. coffeanum or C. kahawae) and various crops (C. gloeosporioides) (anthracnose); Corticium species, e.g., C. sasakii on rice (sheath blight); Corynespora cassiicola on soybean, cotton and ornamental plants (leaf spot); Cycloconium species, e.g., C. oleaginum on olive trees; fruit trees, vines (e.g., Cylindrocladiumliriodendri), sexual form: Neonectria liriodendri: Black Foot Disease) and Cylindrocarpon species on ornamental plants (such as fruit tree canker or young vine decline, sexual form: Nectria or Neonectria species); Dematophora necatrix on soybeans (sexual form: Rosellinia necatrix) (root and stem rot); Diaporthe species, such as D. phaseolorum on soybeans (damping-off); Drechslera (synonym Helminthosporium, sexual form: Pyrenophora) species on corn, cereals such as barley (e.g., D. teres, net blotch) and wheat (e.g., D. tritici-repentis: tan spot), rice, and turfgrass; Esca (dieback, apoplexy) on vines, caused by Formitiporia punctata (synonym Phellinus punctata), F. mediterranea, Phaeomoniella chlamydospora (previously known as Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum, and / or Botryosphaeria obtusa; Elsinoe species on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose), and vines (E. ampelina: anthracnose); Entyloma oryzae on rice (leaf smut); Epicoccum species on wheat (black mold); Erysiphe betae on sugar beets, Erysiphe pisi on vegetables (such as peas), for example, Erysiphe cichoracearum on cucurbits (such as gourds), cabbage, rape (such as Erysiphe cruciferarum),species of Erysiphe (powdery mildew) on cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, synonym Libertella blepharis) on fruit trees, vines and ornamental woods; species of Exserohilum (synonym Helminthosporium) on maize (e.g., Exserohilum turcicum); species of Fusarium (teleomorph: Gibberella) on various plants (wilt, root or stem rot), such as Fusarium graminearum or Fusarium culmorum (root rot, scab or head blight) on cereals (e.g., wheat or barley), Fusarium oxysporum on tomatoes, Fusarium solani (f.sp. glycines, new synonym Fusarium virguliforme) on soybeans and F. tucumaniae and F. brasiliense (both causing sudden death syndrome), and Fusarium verticillioides on maize; Gaeumannomyces graminis (take-all) on cereals (e.g., wheat or barley) and maize; species of Gibberella on cereals (e.g., Gibberella zeae) and rice (e.g., Gibberella fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and Glomerella gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; species of Gymnosporangium on Rosaceae plants and junipers, such as Gymnosporangium sabinae (rust) on pears; species of Helminthosporium (synonym Drechslera, teleomorph: Cochliobolus) on maize, cereals, potatoes and rice; species of Hemileia, such as Hemileia vastatrix on coffeevastatrix)(coffee leaf rust); Isariopsis clavispora (synonym Cladosporium vitis) on vines; Macrophomina phaseolina (synonym Macrophomina phaseoli) (root and stem rot) on soybeans and cotton; Microdochium nivale (synonym Fusarium nivale) (pink snow mold) on cereals (e.g., wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia species on stone fruits and other Rosaceae plants, such as Monilinia laxa, Monilinia fructicola, and Monilinia fructigena (synonym Monilia species: blossom blight and twig blight, brown rot); Mycosphaerella species on cereals, bananas, soft fruits, and peanuts, such as Mycosphaerella graminicola on wheat (anamorph: Zymoseptoria tritici, previously known as Septoria tritici: Septoria leaf blotch), or Mycosphaerella fijiensis on bananas (synonym Pseudocercospora fijiensis: black Sigatoka disease) and Mycosphaerella musicola, Mycosphaerella arachidicola on peanuts (synonym M. arachidis or Cercospora arachidis), Mycosphaerella berkeleyi, Mycosphaerella pisi on peas, and Mycosphaerella brassiciola on Brassica; Peronospora species (downy mildew) on cabbages (e.g., Peronospora brassicae), oilseed rape (e.g., Peronospora parasitica), onions (e.g., Peronospora destructor), tobacco (Peronospora tabacina), and soybeans (e.g., Peronospora manshurica); Phakopsora pachyrhizi and Phakopsora meibomiae (soybean rust) on soybeans; Phialophora species, such as on vines (e.g., Phialophora tracheiphila and Phialophora tetraspora) and soybeans (e.g., Phialophora sojaegregata): stem rot); Phoma lingam (synonyms Leptosphaeria biglobosa and L. maculans: root and stem rot) on rape and cabbage, and Phoma betae (root rot, leaf spot and damping-off) on sugar beet, as well as P. zeae-maydis (synonym Phyllostica zeae) on maize; Phomopsis species on sunflower, vines (e.g. P. viticola: canes and leaf spot) and soybean (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spot) on maize; Phytophthora species on various plants (wilt, root, leaf, fruit and stem rot), such as red pepper and gourd (e.g. P. capsici), soybean (e.g. P. megasperma, synonym P. sojae), potato and tomato (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara species, such as P. viticola (downy mildew of grapevine) on vines and P. halstedii on sunflower; Podosphaera species (powdery mildew) on Rosaceae plants, hops, pome and soft fruits, such as P. leucotricha on apple and P. xanthii on gourd; Polymyxa species, such as P. graminis on cereals such as barley and wheat and P. betae on sugar beet, and virus diseases transmitted thereby; Pseudocercosporella herpotrichoides (synonyms Oculimacula yallundae, O. acuformis: eyespot, teleomorph: Tapesia yallundae) on cereals such as wheat or barley; Pseudoperonospora (downy mildew) on various plants, such as P. cubensis on gourdP. cubensis) or P. humili on hops; Pseudopezicula tracheiphila (red fire disease or rotbrenner, anamorph: Phialophora) on vines; Puccinia species (rust) on various plants, such as P. triticina (brown rust or leaf rust) on cereals such as wheat, barley or rye, P. striiformis (strip rust or yellow rust), P. hordei (dwarf rust), P. graminis (stem rust or black rust) or P. recondita (brown rust or leaf rust), P. kuehnii (citrus rust) on sugarcane and P. asparagi on asparagus; Pyrenopeziza species, such as P. brassicae on rape; Pyrenophora tritici-repentis (anamorph: Drechslera tritici-repentis) (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia species, such as P. oryzae on rice (teleomorph: Magnaporthe grisea: rice blast), and P. grisea on turfgrass and cereals; Pythium species (damping-off) (e.g., P. ultimum or P. aphanidermatum) on turfgrass, rice, maize, wheat, cotton, rape, sunflower, soybean, sugar beet, vegetables and various other plants, and P. oligandrum on mushrooms; Ramularia species, such as R. Collo-cygni on barley (Ramularia leaf spot, physiological leaf spot), R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beet; Rhizoctonia species on cotton, rice, potato, turfgrass, maize, rape, potato, sugar beet, vegetables and various other plants, such as R. solani (rhizome rot) on soybean, R. solani (sheath blight) on rice, or R. cerealis on wheat or barley (cerealis) (spring leaf blight of Rhizoctonia); Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbages, vines and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia species (stem rot or white mold), such as S. minor and S. sclerotiorum, on vegetables and field crops, such as rapeseed, sunflowers (e.g., Sclerotinia) and soybeans; Sclerotium rolfsii (synonym Athelia rolfsii) on soybeans, peanuts, vegetables, corn, grains and ornamental plants; Septoria species on various plants, such as Septoria glycines (brown spot) on soybeans, Septoria tritici (synonym Zymoseptoria tritici, Septoria leaf blotch) on wheat and Septoria nodorum (synonym Stagonospora nodorum (Stagonospora leaf blotch)) on grains; Uncinula necator (synonym Erysiphe necator) (powdery mildew, anamorph: Oidium tuckeri) on vines; Setosphaeria species (leaf blight) on corn (e.g., Setosphaeria turcicum, synonym Helminthosporium turcicum) and turfgrass; Sphacelotheca species (smut) on corn (e.g., Sphacelotheca reiliana, synonym Ustilago reiliana: head smut), sorghum and sugarcane; Sphaerotheca fuliginea (synonym Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and the virus diseases transmitted thereby; Stagonospora species on grains, such as Stagonospora nodorum on wheat (S.nodorum) (Stagonospora nodorum, sexual stage: Leptosphaeria nodorum [synonym Phaeosphaeria nodorum], synonym Septoria nodorum); Synchytrium endobioticum on potatoes (potato wart disease); Taphrina species, such as Taphrina deformans on peaches (leaf curl) and Taphrina pruni on plums (plum pocket); Thielaviopsis species on tobacco, pome fruits, vegetables, soybeans, and cotton (black root rot), such as Thielaviopsis basicola (synonym Chalara elegans); Tilletia species on cereals (common bunt or stinking smut), such as Tilletia tritici on wheat (synonym Tilletia caries, common bunt) and Tilletia controversa on wheat (dwarf bunt); Trichoderma harzianum on mushrooms; Typhula incarnata on barley or wheat (grey snow mold); Urocystis species, such as Urocystis occulta on rye (stem smut); Uromyces species on vegetables such as kidney beans (e.g., Uromyces appendiculatus, synonym Uromyces phaseoli), sugar beets (e.g., Uromyces betae or Uromyces beticola), and dry beans (e.g., Uromyces vignae, Uromyces pisi, Uromyces viciae-fabae, and Uromyces fabae) (rust); Ustilago species on cereals (e.g., Ustilago nuda and Ustilago avenae), corn (e.g., Ustilago maydis: corn smut), and sugarcane (loose smut); Venturia inaequalis on apples (e.g., apple scab);species of Venturia (scab) on pears; and species of Verticillium (wilt) on various plants such as fruits and ornamental plants, vines, soft fruits, vegetables and field crops, such as V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Septoria tritici on cereals.
[0405] Compound I and its compositions are also suitable for controlling harmful microorganisms in the protection of stored products or harvested crops and in the protection of materials, respectively.
[0406] The term "stored products or harvested crops" should be understood to mean natural substances of plant or animal origin and their processed forms required for long-term protection. Stored products of plant origin, such as stalks, leaves, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed forms such as pre-dried, moistened, crushed, ground, pressed or baked (this processing is also referred to as post-harvest treatment). Also falling under the definition of stored products is wood, whether in the form of logs, such as construction timber, transmission towers and fences, or in the form of finished products, such as furniture or objects made of wood. Stored products of animal origin are hides, leather, furs, hairs, etc. Preferably, the "stored products" should be understood to mean natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pome fruits, stone fruits, soft fruits and citrus fruits and their processed forms, where the application of Compound I and its compositions can also prevent adverse effects such as rot, discoloration or mould.
[0407] The term "protection of materials" should be understood to mean protecting industrial and non-living materials such as adhesives, glues, wood, paper, cardboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fibres or fabrics against infestation and destruction by harmful microorganisms such as fungi and bacteria.
[0408] When used in the protection of materials or stored products, the amount of the active substance applied depends on the type of application area and the desired effect. The amount usually applied in the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic metre of treated material.
[0409] Compound I and its compositions can be used, respectively, to improve the health of plants. The invention also relates to a method for improving the health of plants by treating plants, their propagation materials and / or the places where plants are growing or will grow with an effective amount of Compound I and its compositions, respectively.
[0410] The term "plant health" should be understood to denote the condition of plants and / or their products, which is determined by a plurality of parameters, either individually or in combination with one another, such as yield (e.g., increased biomass and / or increased content of valuable constituents), plant vigor (e.g., improved plant growth and / or greener leaves ("greening effect")), quality (e.g., improved content or composition of certain constituents), and tolerance to abiotic and / or biotic stress. The parameters for determining the plant health condition as defined above may be interdependent or may influence one another.
[0411] Compound I is used as such or in the form of a composition by treating fungi, plants, plant propagation material (such as seeds), soil, surfaces, materials, or rooms to be protected against fungal attack with a fungicidally effective amount of the active substance. Application can be carried out before and after the plants, plant propagation material (such as seeds), soil, surfaces, materials, or rooms are infected with fungi.
[0412] The agrochemical composition comprises a fungicidally effective amount of Compound I. The term "fungicidally effective amount" denotes an amount of the composition or of Compound I which is sufficient for controlling harmful fungi on cultivated plants, or for the protection of stored products or harvests, or of materials, and which does not cause substantial damage to the treated plants, treated stored products or harvests, or to the treated materials. Such amounts can vary within a wide range and depend on various factors, such as the fungal species to be controlled, the cultivated plants, stored products, harvests or materials treated, the climatic conditions, and the specific Compound I used.
[0413] Plant propagation material can be prophylactically treated with Compound I itself or with a composition comprising at least one Compound I at the time of planting or transplanting or before planting or transplanting.
[0414] When used in plant protection, depending on the type of effect desired, the amount of the active substance applied is from 0.001 to 2 kg / ha, preferably from 0.005 to 2 kg / ha, more preferably from 0.05 to 0.9 kg / ha, and in particular from 0.1 to 0.75 kg / ha.
[0415] In the treatment of plant propagation material (such as seeds), for example by dusting, coating, or soaking, an amount of the 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) is required.
[0416] The user usually applies the agrochemical composition by means of a pre-application device, a knapsack sprayer, a spray tank, a crop spraying aircraft, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and / or additional adjuvants to the desired application concentration, and thus a ready-to-use spray liquor or agrochemical composition according to the invention is 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.
[0417] Compound I, its N-oxides and salts can be converted into agrochemical compositions of common types, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, tablets, capsules, and mixtures thereof. Examples of composition types (see also "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Edition, 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, pills, wettable powders or powders (e.g., WP, SP, WS, DP, DS), tablets (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal articles (e.g., LN), and gel formulations (e.g., GF) for treating plant propagation materials such as seeds. These compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The invention also relates to an agrochemical composition comprising an adjuvant and at least one compound I.
[0418] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, fungicides, antifreezes, antifoaming agents, colorants, tackifiers, and binders.
[0419] Suitable solvents and liquid carriers are water and organic solvents, such as medium- to high-boiling mineral oil fractions, such as kerosene, diesel oil; oils of vegetable or animal origin; aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and aromatic hydrocarbons, such as toluene, paraffin wax, tetrahydronaphthalene, and alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, ethylene glycol; DMSO; ketones, such as cyclohexanone; esters, such as lactates, carbonates, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
[0420] Suitable solid carriers or fillers are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, such as cereal flour, bark powder, wood powder, nut shell powder, and mixtures thereof.
[0421] 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 emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Examples of surfactants are listed in McCutcheon’s, Volume 1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Edition or North American Edition).
[0422] Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecylbenzene and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids, oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.
[0423] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, glycosyl surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents of alkylene oxide. Ethylene oxide and / or propylene oxide can be used for 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 glycerol monoesters. Examples of glycosyl surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homologues or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.
[0424] Suitable cationic surfactants are quaternary ammonium surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing polyethylene oxide and polypropylene oxide blocks, or A-B-C type block polymers containing alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamine or polyethylenamine.
[0425] Suitable adjuvants are compounds that themselves have negligible or even no pesticidal activity and can enhance the biological performance of Compound I against the target. Examples are surfactants, mineral oils or vegetable oils and other adjuvants. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.
[0426] Suitable thickeners are polysaccharides (such as xanthan gum, carboxymethyl cellulose), inorganic clays (organo-modified or unmodified), polycarboxylates, and silicates.
[0427] Suitable fungicides are bronopol and isothiazolone derivatives such as alkyl isothiazolones and benzisothiazolones.
[0428] Suitable antifreezes are ethylene glycol, propylene glycol, urea, and glycerol.
[0429] Suitable defoamers are silicones, salts of long-chain alcohols, and fatty acids.
[0430] Suitable colorants (such as red, blue, or green) are poorly water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (such as iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (such as alizarin, azo, and phthalocyanine colorants).
[0431] Suitable thickening agents or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.
[0432] Agrochemical compositions generally contain from 0.01% to 95% by weight, preferably from 0.1% to 90% by weight, more preferably from 1% to 70% by weight, and especially from 10% to 60% by weight of an active ingredient (such as at least one compound I). Agrochemical compositions generally contain from 5% to 99.9% by weight, preferably from 10% to 99.9% by weight, more preferably from 30% to 99% by weight, and especially from 40% to 90% by weight of at least one auxiliary agent. The active ingredient (such as compound I) is employed with a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectra).
[0433] For the purpose of treating plant propagation material, especially seeds, solutions for seed treatment (LS), suspension emulsions (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 generally used. After dilution 2 to 10 times, the concentration of the active ingredient in the ready-to-use preparation of the composition in question is from 0.01% to 60% by weight, preferably from 0.1% to 40% by weight. Application can be carried out before or during sowing. Methods for applying compound I and its compositions to plant propagation material, especially seeds, respectively, include seed dressing, coating, granulation, dusting, soaking, and in-furrow application methods. Preferably, compound I or its composition is applied to the plant propagation material separately by a method that does not induce germination, such as by seed dressing, granulation, coating, and dusting.
[0434] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and additional pesticides (such as fungicides, growth regulators, herbicides, insecticides, safeners) can be added to Compound I or its composition as a premix, or added just prior to use (tank mix). These reagents can be admixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
[0435] A pesticide is generally a chemical or biological agent (such as a pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial agent or disinfectant) that prevents, disables, kills or otherwise frustrates pests by its effects. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microorganisms that damage property, cause nuisances, spread diseases or are vectors for diseases. The term "pesticide" also includes plant growth regulators that alter the expected growth, flowering or reproductive rate of plants; defoliants that cause leaves or other foliage to fall off plants, usually to facilitate harvesting; desiccants that promote the drying of living tissue, such as the above-ground parts of unwanted plants; plant activators that activate plant physiological functions to defend against certain pests; safeners that reduce the unwanted herbicidal effects of pesticides on crop plants; and plant growth promoters that affect plant physiological functions, for example, to enhance plant growth, biomass, yield or any other quality parameter of the harvestable product of crop plants.
[0436] Biopesticides are defined as pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or in the form of 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 main categories, microbial and biochemical pesticides:
[0437] (1) Microbial pesticides consist of bacteria, fungi or viruses (and usually include metabolites produced by bacteria and fungi). Entomopathogenic nematodes are also classified as microbial pesticides, although they are multicellular.
[0438] (2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
[0439] Mixing compound I or a composition comprising them, in the form of use as a fungicide, with other fungicides in many cases results in an extension of the fungicidal activity spectrum or prevents the development of fungicide resistance. Furthermore, in many cases, a synergistic effect (synergistic mixture) is obtained.
[0440] The following list of pest control agents II which can be used in combination with compound I is intended to illustrate the possible combinations but does not limit them:
[0441] A) Respiratory inhibitors
[0442] - At Q o Site complex III inhibitors: azoxystrobin (A.1.1), dimoxystrobin (A.1.2), carylystrobin (A.1.3), kresoxim-methyl (A.1.4), enestroburin (A.1.5), enaminostrobin (A.1.6), fenoxystrobin / flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyribencarb (A.1.15), pyributicarb (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), pyrimethanil (A.1.19), triclopyricarb / chlorodincarb (A.1.20), fenamidone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxymethyl]phenyl]-N-methoxy-carbamate (A.1.22), tetraconazole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), pyrimidifen (A.1.36), picarbutrazox (A.1.37), 2-(o-((2,5-dimethylphenyl-oxymethylene)phenyl)-3-methoxy-acrylic acid methyl ester (A.1.38);
[0443] - At Q iComplex III inhibitors at the site: Cyazofamid (A.2.1), Indaziflam (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxytetrahydrobenzodiazepin-2-one)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), Fenpicoxamid (A.2.4), Picoxystrobin (A.2.5), Metarylpicoxamid (A.2.6); - Complex II inhibitors: Carboxin (A.3.1), Benzovindiflupyr (A.3.2), Bixafen (A.3.3), Boscalid (A.3.4), Carboxin (A.3.5), Furametpyr (A.3.6), Fluopyram (A.3.7), Flutolanil (A.3.8), Fluxapyroxad (A.3.9), Fupyradifurone (A.3.10), Iprovalicarb (A.3.11), Isopyrazam (A.3.12), Metsulfovax (A.3.13), oxycarboxin (A.3.14), Fluxametamide (A.3.15), Pyriofenone (A.3.16), Fluxapyroxad (A.3.17), Bipyrazonamide (A.3.18), Flutriafol (A.3.19), Tricyclazole (A.3.20), Thifluzamide (A.3.21), Inpyrfluxam (A.3.22), Pyrapropoyne (A.3.23), Fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxamide (A.3.29), (E)-methyl 2-[2-[(5-cyano-2-methylphenoxy)methyl]phenyl]-3-methoxyprop-2-enoate (A.3.30), Isoflucypram (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.35)
[0444] - Complex II inhibitors: Carboxin (A.3.1), Benzovindiflupyr (A.3.2), Bixafen (A.3.3), Boscalid (A.3.4), Carboxin (A.3.5), Furametpyr (A.3.6), Fluopyram (A.3.7), Flutolanil (A.3.8), Fluxapyroxad (A.3.9), Fupyradifurone (A.3.10), Iprovalicarb (A.3.11), Isopyrazam (A.3.12), Metsulfovax (A.3.13), oxycarboxin (A.3.14), Fluxametamide (A.3.15), Pyriofenone (A.3.16), Fluxapyroxad (A.3.17), Bipyrazonamide (A.3.18), Flutriafol (A.3.19), Tricyclazole (A.3.20), Thifluzamide (A.3.21), Inpyrfluxam (A.3.22), Pyrapropoyne (A.3.23), Fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxamide (A.3.29), (E)-methyl 2-[2-[(5-cyano-2-methylphenoxy)methyl]phenyl]-3-methoxyprop-2-enoate (A.3.30), Isoflucypram (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.35) - 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.35) - 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.35) - 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]tetrahydro-1,4-benzodiazepine-3-carboxamide (A.3.35) - 3 - formamide (A.3.35), 2 - (difluoromethyl) - N - (1,1 - dimethyl - 3 - propyl - indan - 4 - yl) tetrahydrobenzodiazepine - 3 - formamide (A.3.36), 2 - (difluoromethyl) - N - [(3R) - 1,1 - dimethyl - 3 - propyl - indan - 4 - yl] tetrahydrobenzodiazepine - 3 - formamide (A.3.37), 2 - (difluoromethyl) - N - (3 - isobutyl - 1,1 - dimethyl - indan - 4 - yl) tetrahydrobenzodiazepine - 3 - formamide (A.3.38), 2 - (difluoromethyl) - N - [(3R) - 3 - isobutyl - 1,1 - dimethyl - indan - 4 - yl] tetrahydrobenzodiazepine - 3 - formamide (A.3.39), trifluoropyridinamine (A.3.24);
[0445] - Other respiratory inhibitors: diflurin (A.4.1); Nitrophenyl derivatives: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), dicofol (A.4.6), ferimzone (A.4.7); Organometallic compounds: triphenyltin salts, such as fentin acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); amisulbrom (A.4.11); silthiofam (A.4.12);
[0446] B) Sterol biosynthesis inhibitors (SBI fungicides)
[0447] -C14 demethylase inhibitors: Triazoles: penconazole (B.1.1), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazol (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23),simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.31), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.33), ipfentrifluconazole (B.1.37), chlorfluzolam (B.1.38), (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, 2-(chloromethyl)-2-methyl-5-((p-tolyl)methyl)-1-((1,2,4-triazol-1-yl)methyl)cyclopentanol (B.1.43); Imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizole (B.1.47); Pyrimidines, tetrahydrobenzodiazepines Classes, piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.52), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.53), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.54), 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.55);
[0448] -δ14-reductase inhibitors: 4-dodecyl-2,6-dimethylmorpholine (aldimorph) (B.2.1), dodemorph (B.2.2), dodemorph acetate (B.2.3), fenpropimorph (B.2.4), pyrifenox (B.2.5), fenpropidin (B.2.6), tridemorph (B.2.7), spiroxamine (B.2.8);
[0449] -3-ketoreductase inhibitors: fenhexamid (B.3.1);
[0450] -Other sterol biosynthesis inhibitors: dichlobutrazol (B.4.1);
[0451] C) Nucleic acid synthesis inhibitors
[0452] -Phenylamide or acylamino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
[0453] -Other nucleic acid synthesis inhibitors: hymexazol (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), ethirimol sulfate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenylmethoxy)pyrimidin-4-amine (C.2.8);
[0454] D) Cell division and cytoskeleton inhibitors
[0455] - Tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridachlometyl (D.1.6), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthio-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthio-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methylthio-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16);
[0456] - Other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), fenfuram (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7), cyanotilide (D.2.8);
[0457] E) Amino acid and protein synthesis inhibitors
[0458] - Methionine synthesis inhibitors: cyprodinil (E.1.1), fenarimol (E.1.2), pyrimethanil (E.1.3);
[0459] - Protein synthesis inhibitors: blastcidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride hydrate (E.2.3), validamycin (E.2.4), streptomycin (E.2.5), oxytetracycline (E.2.6);
[0460] F) Signal transduction inhibitors
[0461] -MAP / Histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5);
[0462] -G protein inhibitors: quinoxyfen (F.2.1);
[0463] G) Lipid and membrane synthesis inhibitors
[0464] -Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), isoprothiolane (G.1.2), hymexazol (G.1.3), isoprobenfos (G.1.4);
[0465] -Lipid peroxidation: dichlofluanid (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), ethaboxam (G.2.7), thiazole zinc (G.2.8);
[0466] -Phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), fenpyrazamine (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);
[0467] -Compounds and fatty acids affecting cell membrane permeability: propamocarb (G.4.1);
[0468] -Oxysterol-binding protein inhibitors: flutriafol (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-difluoromethyl-5-methyl-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-tetrahydrobenzodiazepine -2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-tetrahydrobenzodiazepine -2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-tetrahydrobenzodiazepine -2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-tetrahydrobenzodiazepine -2-formamide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-1,2,3,4-tetrahydro-1,5-benzodiazepine -2-formamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-1,2,3,4-tetrahydro-1,5-benzodiazepine -2-formamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-1,2,3,4-tetrahydro-1,5-benzodiazepine -2-formamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-1,2,3,4-tetrahydro-1,5-benzodiazepine -2-formamide (G.5.11);
[0469] H) Inhibitors with multi-site action
[0470] - Inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7);
[0471] - Thio- and dithiocarbamates: ferric dimethyldithiocarbamate (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam-sodium (H.2.4), metiram (H.2.5), zinc methyl dithiocarbamate (H.2.6), thiram (H.2.7), zinc dithiocarbamate (H.2.8), zinc dimethyldithiocarbamate (H.2.9);
[0472] - Organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorophenol (H.3.9) and its salts, tecnazene (H.3.10), tolylfluanid (H.3.11);
[0473] - Guanidine and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), guazatine-amine (H.4.6), guazatine-amine triacetate (H.4.7), bis-guazotridecylbenzenesulfonate (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (H.4.10);
[0474] I) Cell wall synthesis inhibitors
[0475] - Glucan synthesis inhibitors: validamycin (I.1.1), polyoxin (I.1.2);
[0476] - Melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), blastoxamide (I.2.5);
[0477] J) Plant defense inducers
[0478] - Benzoic acid S-methyl ester (J.1.1), thiabendazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1.5); Phosphonates: ethylic acid (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)-1,2,4-thiadiazole-5-carboxamide (J.1.10);
[0479] K) Unknown mode of action
[0480] -Bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), iminoctadine (K.1.6), diclocymet (K.1.7), pyridinitril (K.1.8), barban (K.1.9), barban-methylsulfate (K.1.10), diphenylamine (K.1.11), diflufenican (K.1.12), amisulbrom (K.1.13), flumetover (K.1.14), sulfanilamide (K.1.15), fluopyram (K.1.16), harpin protein (K.1.17), sulfallate (K.1.18), 3,5,6-trichloro-2-pyridinol (K.1.19), phthalide (K.1.20), tolprocarb (K.1.21), copper quinolate (K.1.22), propoxyquinoline (K.1.23), tebufloquin (K.1.24), tetrachloroisophthalodinitrile (K.1.25), pyrazophos (K.1.26), N’-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.27), N’-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.28), N’-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N’-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N’-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N’-[5-bromo-6-(4-isopropylcyclohexyloxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N’-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N’-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilyl-propoxy)phenyl)-N-ethyl-N-methylformamidine (K.1.34), N’-(5-difluoromethyl-2-methyl-4-(3-trimethylsilyl-propoxy)-phenyl)-N-ethyl-N-methyl-formamidine (K.1.35), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-tetrahydro-1,4-benzodiazepine (Picoxystrobin)(K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-tetrahydro-1,4-benzodiazepine (K.1.38), 5-chloro-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-1H-benzimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenylacrylate (K.1.40), tetraconazole (K.1.41), N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]pentylcarbamate (K.1.42), N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]but-3-ynylcarbamate (K.1.43), ipflufenoquin (K.1.44), quinofumelin (K.1.47), thiabendazole (K.1.48), bromothalonil (K.1.49), 2-(6-benzylpyridin-2-yl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (K.1.53), amisulbrom (K.1.54), fluoxastrobin (K.1.55), N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)pyridin-3-yl]-N-ethyl-N-methylformamidine (K.1.56), N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine (K.1.57), N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (K.1.58), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide (K.1.59), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (WO 2018 / 177894, WO 2020 / 212513);
[0481] L) Biocidal pest control agents
[0482] L1) Microbial pest control agents with fungicidal, bactericidal, virucidal and / or plant defense activator activities: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, Bacillus amyloliquefaciens, Bacillus amyloliquefaciens subsp. plantarum (also known as Bacillus velezensis), Bacillus megaterium, Bacillus mojavensis, Bacillus mycoides, Bacillus pumilus, Bacillus simplex, Bacillus salarius, Bacillus subtilis, Bacillus subtilis var. amyloliquefaciens, Bacillus velezensis, Candida oleophila, Candida saitoana, Clavibacter michiganensis (phage), Coniothyrium minitans, Cryptocline parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also known as Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, Lysobacter enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Mycosphaerella sp., Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, Paenibacillus polymyxa, Pantoea agglomerans, Penicillium bilaiae, Phellinus igniarius, Pseudomonas spp., Pseudomonas chlororaphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, Streptomyces lydicus, Streptomyces violaceoniger, Talaromyces flavus, Trichoderma asperelloides, Trichoderma asperellum, Trichoderma atroviride, Trichoderma apical, Trichoderma gamsii, Trichoderma harzianum, Trichoderma polysporum, Trichoderma stromaticum, Trichoderma virens, Trichoderma viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahliae, Zucchini yellow mosaic virus (avirulent strain);
[0483] L2) Biochemical pest control agents with fungicidal, bactericidal, virucidal and / or plant defense activator activities: Hypersensitive protein, Reynoutria japonica extract;
[0484] L3) Microbial pest control agents with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, Bacillus firmus, Bacillus thuringiensis, Bacillus thuringiensis aizawai, Bacillus thuringiensis israelensis, Bacillus thuringiensis galleriae, Bacillus thuringiensis kurstaki, Bacillus thuringiensis tenebrionis, Beauveria bassiana, Beauveria brongniartii, Burkholderia species, Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium species, Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Heliothis zea nucleopolyhedrovirus (HzNPV), Heliothis zea single nucleocapsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, Lecanicillium muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, Metarhizium anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, Paecilomyces lilacinus, Paenibacillus popilliae, Pasteuria species, Pasteuria nishizawae, Pasteuria penetrans, Pasteuria ramosa, Pasteuria thornei, Pasteuria usgae, Pseudomonas fluorescens, Spodoptera litura nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, Steinernema feltiae, Streblocera nematode, Streptomyces gilvosporeus, Streptomyces microflavus;
[0485] L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-ethyl 2,4-decadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavandulyl senecioate, cis-jasmone, 2-methyl-1-butanol, methyleugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-yl acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, termite pheromone (pentatermanone), (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, neem oil, Quillay extract;
[0486] L5) Microbial pesticides with plant stress reduction, plant growth regulator, plant growth promotion and / or yield increase activity: Azospirillum amazonense, Azospirillum brasilense, Azospirillum lipoferum, Azospirillum iraquense, Azospirillum halopraeferens, Bradyrhizobium spp., Bradyrhizobium elkanii, Bradyrhizobium japonicum, Bradyrhizobium liaoningense, Bradyrhizobium lupini, Delftia acidovorans, Arbuscular mycorrhizal fungi, Mesorhizobium spp., Rhizobium leguminosarum biovar phaseoli, Rhizobium leguminosarum biovar trifolii, Rhizobium leguminosarum biovar viciae, Rhizobium tropici, Sinorhizobium meliloti;
[0487] O) Insecticides from classes O.1 to O.29
[0488] O.1 Acetylcholinesterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, cyphenothrin, dichlofenthion, dimethoate, ethion, fenthion, fenamiphos, fosthiazate, heptenophos, imicyafos, isopropylamine phosphate, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propargite, propaphos, pyraclofos, pyridaphenthion, quinalphos, sulprofos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;
[0489] O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, butene-fipronil, pyrafluprole, pyriprole;
[0490] O.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, k-bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flubrocythrinate, tau-fluvalinate, flumethrin, heptaflumethrin, imiprothrin, metofluthrin, metofluthrin epsilon, permethrin, phenothrin, propargite, propachlor, pyrethrum, resmethrin, silafluofen, heptafluthrin, k-heptafluthrin, tetraflumethrin, tetramethrin, tralomethrin, tetramethylfluthrin; DDT, methoxychlor;
[0491] O.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, epoxiconazole, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylideneaminoguanidine; 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroimidazo[1,2-a]tetrahydrobenzodiazepine Nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate, (3S)-3-(6-chloro-3-pyridinyl)-8-methyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate, (3S)-8-methyl-5-oxo-6-phenyl-3-pyrimidin-5-yl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate, (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-5-oxo-6-[3-(trifluoromethyl)phenyl]-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate; (3R)-3-(2-chlorothiazol-5-yl)-6-(3,5-dichlorophenyl)-8-methyl-5-oxo-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate, (3R)-3-(2-chlorothiazol-5-yl)-8-ethyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-phenolate;
[0492] O.5 Allosteric activators of nicotinic acetylcholine receptors: spinosad, spinetoram;
[0493] O.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemycin;
[0494] O.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
[0495] O.8 Various non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
[0496] O.9 Chordotonal organ TRPV channel modulators: pymetrozine, flupyrimin;
[0497] O.10 Mite growth inhibitors: clofentezine, hexythiazox, flufenzine; etoxazole;
[0498] O.11 Microbial Disruptors of the Midgut Membrane of Insects: Bacillus thuringiensis, Bacillus sphaericus, and Insecticidal Proteins Produced by Them: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt Crop Proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;
[0499] O.12 Mitochondrial ATP Synthase Inhibitors: Diafenthiuron; Azocyclotin, Cyhexatin, Fenbutatin Oxide, Propargite, Chlorfenson;
[0500] O.13 Oxidative Phosphorylation Decouplers Interfering via the Proton Gradient: Chlorfenapyr, DNOC, Sulfluramid;
[0501] O.14 Nicotinic Acetylcholine Receptor (nAChR) Channel Blockers: Bensultap, Cartap, Thiosultap-sodium, Bisultap;
[0502] O.15 Chitin Biosynthesis Inhibitors Type 0: Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron, Chlorbenzuron;
[0503] O.16 Chitin Biosynthesis Inhibitors Type 1: Buprofezin;
[0504] O.17 Molting Disruptors: Cyromazine;
[0505] O.18 Ecdysone Receptor Agonists: Methoxyfenozide, Tebufenozide, Chlorantraniliprole, Fufenozide, Chromafenozide;
[0506] O.19 Octopamine Receptor Agonists: Amitraz;
[0507] O.20 Mitochondrial Complex III Electron Transport Inhibitors: Hydramethylnon, Acequinocyl, Fluacrypyrim, Bifenazate;
[0508] O.21 Mitochondrial Complex I electron transport inhibitors: fenpyroximate, fenazaquin, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;
[0509] O.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide, N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]hydrazinecarboxamide;
[0510] O.23 Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, methoprene;
[0511] O.24 Mitochondrial Complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanides;
[0512] O.25 Mitochondrial Complex II electron transport inhibitors: cyenopyrafen, cyflumetofen;
[0513] O.26 Ryanodine receptor modulators: flubendiamide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, flonicamid; (R)-3-chloro-N 1 -{2-methyl-4-[1,2,2,2–tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N 2 -(1-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-N 1 -{2-methyl-4-[1,2,2,2–tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N 2-(1-Methyl-2-methylsulfonylethyl)phthalamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1,2-dimethylhydrazinecarboxylate; N-[4,6-dichloro-2-[(diethyl-λ4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-λ4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(di-2-propyl-λ4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dichloro-2-[(di-2-propyl-λ4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(diethyl-λ4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide; 3-chloro-1-(3-chloropyridin-2-yl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole-5-carboxamide; tetrachlorantraniliprole; N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide; chlorantraniliprole-fluoro;
[0514] O.27: Chordotonal organ modulators - unspecified target site: flonicamid;
[0515] O.28. Insecticidal compounds with unknown or uncertain mode of action: bipropyl dicylclopropionate, afoxolaner, azadirachtin, flufenerim, bromopropylate, broflanilide, bromopropylate, chinomethionat, sodium fluoroaluminate, cyflumetofen, dichlorothymid, dicofol, clofentezine, flonicamid, fluralaner, oxydemethon-methyl, piperonyl butoxide, pyrazolecarboxanilide, pyriproxyfen, sulfluramid, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxo-9-aza-dispiro[4.2.4.2]tetradec-11-en-10-one, 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]Dec-3-en-2-one, 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine, Bacillus firmus I-1582; flupyrimin; fluoxastrobin; 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole; 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide; N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 2-(1,3-dioxolan-2-yl)-6-[2-(3-pyridyl)-5-thiazolyl]-tetrahydrobenzodiazepine. 2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; N-Methylsulfonyl-6-[2-(3-pyridinyl)thiazol-5-yl]tetrahydrobenzodiazepine -2-carboxamide; N-Methylsulfonyl-6-[2-(3-pyridinyl)thiazol-5-yl]tetrahydrobenzodiazepine -2-carboxamide; 1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1,2-a]tetrahydrobenzodiazepine 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol; 1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N,5-dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methylethyl)pyrazole-4-carboxamide; 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-ethyl-1-(2-fluoro-1-methylpropyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(1,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-[1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-methyl-1-(2-fluoro-1-methylpropyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide; methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide; N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide, tyclopyrazoflor; sarolaner, lotilaner, N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide;2-(3-Ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine; 2-[3-Ethylsulfonyl-5-(trifluoromethyl)-2-pyridinyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine Isoxazid, N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; Acynonapyr; Benzpyrimoxan; Tigolaner; Chlorine-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide, Oxasulfuron, [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxytetrahydropyran-2-yl]-N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl]N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxytetrahydropyran-2-yl]-N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl]-N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, (2Z)-3-(2-Isopropylphenyl)-2-[(E)-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylidenehydrazino]thiazolidin-4-one; 2-(6-Chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-(6-Bromo-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-(3-Ethylsulfonyl-6-iodo-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-[3-Ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-(7-Chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-(3-Ethylsulfonyl-7-iodo-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 3-Ethylsulfonyl-6-iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]imidazo[1,2-a]tetrahydrobenzodiazepine -8-Carbonitrile, 2-[3-Ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-[3-Ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethylsulfinyl)imidazo[4,5-b]tetrahydrobenzodiazepine 2-[3-Ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]tetrahydrobenzodiazepine 2-(6-Bromo-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]tetrahydrobenzodiazepine
[0516] The active substance known as Component 2, its preparation and its activity against harmful fungi, for example, are known (see: http: / / www.alanwood.net / pesticides / ); these substances are commercially available. Compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (see Can. J. Plant Sci. [Canadian Journal of Plant Science] 48(6), 587 - 94, 1968; EP - A 141 317; EP - A 152 031; EP - A 226 917; EP - A 243 970; EP - A256503; EP - A 428 941; EP - A 532 022; EP - A 1 028 125; EP - A 1 035 122; EP - A 1 201648; EP - A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US3,296,272; US 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, CN1456054, 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 Numbers, which are split into three parts by hyphens, the first part consisting of two to seven digits, the second part consisting of two digits, and the third part consisting of a single digit.;
[0517] According to the invention, the solid material (dry matter) of a biopesticide (except for oils such as neem oil, etc.) is considered to be the active ingredient (obtained, for example, in the case of a liquid formulation of a microbial pesticide after drying or evaporation of the extraction or suspension medium). The weight ratios and percentages used for biological extracts such as soapbark extract are based on the total weight of the dry content (solid material) of the corresponding extract.
[0518] The total weight ratio of a composition containing at least one microbial pesticide in the form of live microbial cells (including dormant forms) can be determined by calculating the total weight of the corresponding active ingredient using the amount of CFU of the corresponding microorganism with the following equation: 1×10 10 CFU is equal to the total weight of one gram of the corresponding active ingredient. Colony forming unit is a measure of live microbial cells. In addition, "CFU" can also be understood as the number of (juvenile) individual nematodes in the case of nematode biopesticides such as Steinernema feltiae.
[0519] In a binary mixture, the weight ratio of component 1) to component 2) usually depends on the properties of the components used, and generally it is in the range of 1:10,000 to 10,000:1, often in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, even more preferably in the range of 1:4 to 4:1, and especially in the range of 1:2 to 2:1. According to another embodiment, the weight ratio of component 1) to component 2) is usually in the range of 1000:1 to 1:1, often in the range of 100:1 to 1:1, frequently in the range of 50:1 to 1:1, preferably in the range of 20:1 to 1:1, more preferably in the range of 10:1 to 1:1, even more preferably in the range of 4:1 to 1:1, and especially in the range of 2:1 to 1:1. According to another embodiment, the weight ratio of component 1) to component 2) is usually in the range of 20,000:1 to 1:10, often in the range of 10,000:1 to 1:1, frequently in the range of 5,000:1 to 5:1, preferably in the range of 5,000:1 to 10:1, more preferably in the range of 2,000:1 to 30:1, even more preferably in the range of 2,000:1 to 100:1, and especially in the range of 1,000:1 to 100:1. According to another embodiment, the weight ratio of component 1) to component 2) is usually in the range of 1:1 to 1:1000, often in the range of 1:1 to 1:100, frequently in the range of 1:1 to 1:50, preferably in the range of 1:1 to 1:20, more preferably in the range of 1:1 to 1:10, even more preferably in the range of 1:1 to 1:4, and especially in the range of 1:1 to 1:2. According to another embodiment, the weight ratio of component 1) to component 2) is usually in the range of 10:1 to 1:20,000, often in the range of 1:1 to 1:10,000, frequently in the range of 1:5 to 1:5,000, preferably in the range of 1:10 to 1:5,000, more preferably in the range of 1:30 to 1:2,000, even more preferably in the range of 1:100 to 1:2,000, and especially in the range of 1:100 to 1:1,000.
[0520] In a ternary mixture, i.e., a composition comprising component 1) and component 2) and compound III (component 3), the weight ratio of component 1) to component 2) depends on the properties of the active substances used, and generally it is in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, and especially in the range of 1:4 to 4:1, and the weight ratio of component 1) to component 3) is usually in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, and especially in the range of 1:4 to 4:1. If desired, any additional active component is added to component 1) at a ratio of 20:1 to 1:20. These ratios are also suitable for mixtures applied by seed treatment.
[0521] When a mixture containing a microbial pestcide is used for crop protection, the application rate ranges from 1×10 6 to 5×10 16 (or greater) CFU / ha, preferably from 1×10 8 to 1×10 13 CFU / ha, and even more preferably from 1×10 9 to 5×10 15 CFU / ha, and especially from 1×10 12 to 5×10 14 CFU / ha. In the case of nematodes as microbial pestcides (e.g., Steinernema carpocapsae), the application rate range is often from 1×10 5 to 1×10 12 (or greater), preferably from 1×10 8 to 1×10 11 , more preferably from 5×10 8 to 1×10 10 individuals (e.g., in the form of eggs, larvae or any other living stage, preferably in the non-reproductive (infetive) larval stage) / ha.
[0522] When a mixture containing a microbial pestcide is used for seed treatment, the application rate range is generally from 1×10 6 to 1×10 12 (or greater) CFU / seed, preferably from 1×10 6 to 1×10 9 CFU / seed. In addition, the application rate range for seed treatment is generally from 1×10 7 to 1×10 14 (or greater) CFU / 100 kg of seeds, preferably from 1×10 9 to 1×10 12 CFU / 100 kg of seeds.
[0523] Preferably, a mixture containing at least one active substance as component 2), the at least one active substance being selected from group A) in Q oComplex III inhibitors at the site, 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).
[0524] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from the complex III inhibitors in group A) at Q i Complex III inhibitors at the site, 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).
[0525] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from the complex II inhibitors 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).
[0526] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from other respiratory inhibitors of group A), more preferably selected from compounds (A.4.5) and (A.4.11); in particular (A.4.11).
[0527] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from C14-demethylase inhibitors of 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).
[0528] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from δ14-reductase inhibitors of 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).
[0529] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from phenylamide and acyl amino acid fungicides of 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).
[0530] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from other nucleic acid synthesis inhibitors of group C), more preferably selected from compounds (C.2.6), (C.2.7) and (C.2.8).
[0531] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being 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).
[0532] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); particularly (E.1.3).
[0533] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5).
[0534] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being 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); particularly selected from (G.3.1), (G.5.1) and (G.5.3).
[0535] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being 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).
[0536] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group I), more preferably selected from compounds (I.2.2) and (I.2.5).
[0537] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being 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); particularly (J.1.5).
[0538] Also preferably, a mixture comprising at least one active substance as component 2), the at least one active substance being 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).
[0539] The biopesticides from group L1) and / or L2) may also have insecticidal, acaricidal, molluscicidal, pheromonal, nematicidal, plant stress reducing, plant growth regulating, plant growth promoting and / or yield increasing activities. The biopesticides from group L3) and / or L4) may also have fungicidal, bactericidal, virucidal, plant defense activating, plant stress reducing, plant growth regulating, plant growth promoting and / or yield increasing activities. The biopesticides from group L5) may also have fungicidal, bactericidal, virucidal, plant defense activating, insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activities.
[0540] Microbial biopesticides, particularly those from groups L1), L3) and L5), include not only isolated pure cultures of the corresponding microorganisms as defined herein, but also their cell-free extracts, their suspensions in whole broth cultures and media containing metabolites, or purified metabolites obtained from whole broth cultures of the microorganisms.
[0541] Many of these biopesticides are deposited under the accession numbers mentioned herein (prefixes such as ATCC or DSM refer to the initials of the corresponding culture collections, for details see, for example, http: / / www.wfcc.info / ccinfo / collection / by_acronym / ), are mentioned in the literature, are registered and / or are commercially available: a mixture of Aureobasidium pullulans DSM14940 and DSM 14941 was isolated in Konstanz, Germany in 1989 (e.g., blastospores, from bio-ferm GmbH, Austria ), Azospirillum brasilense Sp245 was initially isolated at least before 1980 in the wheat-growing region of southern Brazil (Passo Fundo) (BR 11005; e.g., from BASF Agricultural Specialties Ltd., Brazil Gramíneas), Azospirillum brasilense strains Ab-V5 and Ab-V6 (e.g., AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quartelúpolis, Brazil or PlantSoil 331, 413 - 425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331; US 8,445,255); Bacillus amyloliquefaciens subsp. plantarum strains, sometimes formerly also referred to as Bacillus subtilis, recently reclassified together with Bacillus methylotrophicus and Bacillus velezensis as Bacillus velezensis (Int. J. Syst. Evol. Microbiol. [International Journal of Systematic and Evolutionary Microbiology] 66, 1212–1217, 2016); Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis D747 isolated from the air in Kikugawa, Japan (US20130236522 A1; FERM BP-8234; e.g., Double Nickel TM 55WDG) from Certis LLC, USA), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis FZB24 isolated from soil in Brandenburg, Germany (also known as SB3615; DSM 96-2; J. Plant Dis. Prot. [Journal of Plant Diseases and Protection] 105, 181 - 197, 1998; e.g., ) from Novozyme Biologicals, Inc., USA), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. [Journal of Plant Diseases and Protection] 105, 181 - 197, 1998; e.g., Rhizo 42) from AbiTEP GmbH, Germany), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis MBI600 (also known as 1430; NRRL B-50595; US2012 / 0149571A1) isolated from Vicia faba in Sutton Bonington, Nottinghamshire, UK at least before 1988; e.g., ) from BASF Corporation, USA), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis QST-713 (NRRL B-21661) isolated from a peach orchard in California, USA in 1995; e.g., MAX), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis TJ1000 (also known as 1BE; ATCC BAA-390; CA 2471555 A1; e.g., QuickRoots from TJ Technologies, Watertown, South Dakota, USA TM ); Bacillus firmus CNCM I-1582, a variant of the parental strain EIP-N1 isolated from soil in the Central Region of Israel (CNCM I-1556) (WO 2009 / 126473, US 6,406,690; e.g., from Bayer CropScience LP, USA ), Bacillus pumilus GHA180 isolated from the rhizosphere of apple trees in Mexico (IDAC 260707-01; e.g., from Premier Horticulture, Quebec, Canada BX), Bacillus pumilus INR-7, also known as BU-F22 and BU-F33, isolated from cucumbers infected with Erwinia tracheiphila at least before 1993 (NRRL B-50185, NRRL B-50153; US 8,445,255), Bacillus pumilus KFP9F isolated from the rhizosphere of grass 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), Bacillus pumilus QST2808 isolated from soil collected in Pohnpei, Federated States of Micronesia in 1998 (NRRL B-30087; e.g., from Bayer CropScience, USA or (Plus), Bacillus simplex ABU 288 (NRRL B-50304; US 8,445,255), also known as UD 1022 or UD10-22, Bacillus subtilis FB17 was isolated from red beetroot in North America (ATCC PTA-11857; System Appl Microbiol [System and Applied Microbiology] 27, 372-379, 2004; US2010 / 0260735; WO2011 / 109395); Bacillus thuringiensis subsp. aizawai ABTS-1857 was isolated in 1987 from soil taken from a lawn in Ephraim, Wisconsin, USA (also known as ABG-6346; ATCC SD-1372; e.g., from BioFa AG, Münsingen, Germany of ), Bacillus thuringiensis subsp. kurstaki ABTS-351 is equivalent to HD-1 isolated in 1967 from black larvae of the cotton bollworm, Pectinophora gossypiella, in Brownsville, Texas, USA (ATCC SD-1275; e.g., from Valent BioSciences, Illinois, USA of DF), Bacillus thuringiensis subsp. kurstaki SB4 was isolated from the cadavers of larvae of the African sugarcane borer (E. saccharina) (NRRL B-50753; e.g., from BASF Agricultural Specialities (Pty) Ltd., South Africa of Beta ), Bacillus thuringiensis subsp. tenebrionis NB-176-1, a mutant of strain NB-125, was isolated in 1982 from the dead pupae of the beetle Tenebrio molitor (DSM 5480; EP 585 215B1; e.g., from Valent BioSciences, Switzerland of ), Beauveria bassiana GHA (ATCC 74250; e.g., from Laverlam Int. Corp., USA of 22WGP), Beauveria bassiana JW-1 (ATCC 74040; e.g., from CBC (Europe) S.r.l., Italy of ), Beauveria bassiana PPRI 5339 was isolated from the larvae of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e.g., from BASF Agricultural Specialities (Pty) Ltd., South Africa of ),The Bradyrhizobium elkanii strain SEMIA 5019 (also known as 29W) was isolated in Rio de Janeiro, Brazil and SEMIA 587 was isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with North American isolates, and has been used for commercial inoculants since 1968 (Appl. Environ. Microbiol. [Applied and Environmental Microbiology] 73(8), 2635, 2007; e.g., GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), and Bradyrhizobium japonicum 532c was isolated from a field in Wisconsin, USA (Nitragin 61A152; Can. J. Plant Sci. [Canadian Journal of Plant Sciences] 70, 661 - 666, 1990; e.g., (Super), Bradyrhizobium japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. [European Journal of Soil Biology] 45, 28 - 35, 2009; Biol. Fertil. Soils [Biology and Fertility of Soils] 47, 81–89, 2011); Bradyrhizobium japonicum strains known to be deposited at SEMIA by Appl. Environ. Microbiol. [Applied and Environmental Microbiology] 73(8), 2635, 2007: Bradyrhizobium japonicum SEMIA5079 was isolated from soil by Embrapa-Cerrados in the Cerrados region of Brazil and has been used for commercial inoculants since 1992 (CPAC 15; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), Bradyrhizobium japonicum SEMIA 5080 was obtained under laboratory conditions by Embrapa-Cerrados in Brazil and has been used for commercial inoculants since 1992 and is a natural variant of SEMIA 586 (CB1809) originally isolated in the United States (CPAC 7; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia species A396 was 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 was isolated from Brassica napus (WO 1996 / 021358; DSM 9660; e.g., WG, WG), hypersensitive protein (α-β) protein (Science [Science] 257, 85 - 88, 1992; e.g., Messenger from Plant Health Care plc, UK TM or HARP-N-Tek), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol [Journal of Invertebrate Pathology]. 107, 112 - 126, 2011; e.g., from Koppert, Brazil From AgBiTech Pty Ltd., Queensland, Australia Max), Helicoverpa zea single nucleocapsid nucleopolyhedrovirus (HzSNPV) (e.g., from Certis LLC, USA ), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e.g., from AgBiTech Pty Ltd., Queensland, Australia ), Heterorhabditis bacteriophora (e.g., from BASF Agricultural Specialities Limited, UK G), Isaria fumosorosea Apopka-97 isolated from mealybugs on Begonia fimbristipula in Apopka, Florida, USA (ATCC 20874; Biocontrol Science Technol [Biocontrol Science and Technology]. 22(7), 747-761, 2012; e.g., PFR-97 from Certis LLC, USA TM or ), Metarhizium anisopliae var. anisopliae F52, also known as 275 or V275, isolated from Cydia pomonella in Austria (DSM 3884, ATCC 90448; e.g., Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central region of Israel (US 6,994,849; NRRL Y-30752; e.g., previously from Agrogreen, Israel ), Paecilomyces lilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89 / 030550; WO 1991 / 02051; Crop Protection [Crop Protection] 27, 352-361, 2008; e.g., from Bayer CropScience AG, Germany and from Certis, USA ) The Paenibacillus alvei NAS6G6 was isolated from the rhizosphere of grass roots in South Africa at least before 2008 (WO 2014 / 029697; NRRL B-50755; for example, BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa), and Paenibacillus strains isolated from soil samples in various European regions including Germany: Paenibacillus adhaerens Lu17015 (WO 2016 / 020371; DSM 26971), Paenibacillus polymyxa subsp. plantarum Lu16774 (WO 2016 / 020371; DSM 26969), Paenibacillus polymyxa subsp. plantarum strain Lu17007 (WO 2016 / 020371; DSM 26970); Pasteuria nishizawae Pn1 was isolated from a soybean field in Illinois, USA in the mid-2000s (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; for example, Clariva from Syngenta Crop Protection, LLC, USA) TM PN), Penicillium bilaiae (also known as P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851, and / or ATCC 22348 (= ATCC 74318) were originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1), 91-102, 1998; US 5,026,417, WO 1995 / 017806; for example, Jump from Novozymes Biologicals BioAg Group, Canada) ) Extract of Reynoutria japonica (EP 0307510 B1; for example, SC from Marrone BioInnovations, Davis, CA, USA or ) from BioFa AG, Germany), Steinernema carpocapsae (for example, ) from BASF Agricultural Specialities Limited, UK), Steinernema feltiae (for example, from BASF Agricultural Specialities Limited, UK ), Streptomyces microflavus NRRL B-50550 (WO2014 / 124369; Bayer CropScience AG), Trichoderma asperellum JM41R isolated in South Africa (NRRL 50759; also known as Trichoderma apicalis; e.g., from BASF Agricultural Specialities (Pty) Ltd., South Africa ), Trichoderma harzianum T-22 also known as KRL-AG2 (ATCC 20847; BioControl 57,687-696, 2012; e.g., from BioWorks Inc., USA or SabrEx from Advanced Biological Marketing Inc., Van Wert, Ohio, USA TM ).
[0542] According to another embodiment of the mixture, at least one pesticidal agent II is selected from groups L1) to L5):
[0543] L1) Microbial pest control agents with fungicidal, bactericidal, virucidal and / or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus amyloliquefaciens AP-188 (L.1.2), Bacillus amyloliquefaciens subsp. plantarum D747 (L.1.3), Bacillus amyloliquefaciens subsp. plantarum FZB24 (L.1.4), Bacillus amyloliquefaciens subsp. plantarum FZB42 (L.1.5), Bacillus amyloliquefaciens subsp. plantarum MBI600 (L.1.6), Bacillus amyloliquefaciens subsp. QST-713 (L.1.7), Bacillus amyloliquefaciens subsp. TJ1000 (L.1.8), Bacillus pumilus GB34 (L.1.9), Bacillus pumilus GHA 180 (L.1.10), Bacillus pumilus INR-7 (L.1.11), Bacillus pumilus KFP9F (L.1.12), Bacillus pumilus QST 2808 (L.1.13), Bacillus simplex ABU 288 (L.1.14), Bacillus subtilis FB17 (L.1.15), Coniothyrium minitans CON / M / 91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paenibacillus alvei NAS6G6 (L.1.18), Paraburkholderia epiphytica Lu17015 (L.1.25), Paenibacillus polymyxa subsp. plantarum Lu16774 (L.1.26), Paenibacillus polymyxa subsp. strain Lu17007 (L.1.27), Penicillium bilaiae ATCC 22348 (L.1.19), Penicillium bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRLB-50550 (L.1.22), Trichoderma pseudokoningii JM41R (L.1.23), Trichoderma harzianum T-22 (L.1.24);
[0544] L2) Biochemical pest control agents with fungicidal, bactericidal, virucidal and / or plant defense activator activity: harpins (L.2.1), Reynoutria japonica extract (L.2.2);
[0545] L3) Microbial pest control agents with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Bacillus firmus I-1582 (L.3.1); Bacillus thuringiensis subsp. aizawai ABTS-1857 (L.3.2), Bacillus thuringiensis subsp. kurstaki ABTS-351 (L.3.3), Bacillus thuringiensis subsp. kurstaki SB4 (L.3.4), Bacillus thuringiensis subsp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), Beauveria bassiana JW-1 (L.3.7), Beauveria bassiana PPRI 5339 (L.3.8), Burkholderia species A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Heliothis zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Heliothis zea single nucleocapsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var. anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae (L.3.18), Steinernema feltiae (L.3.19);
[0546] L4) Biochemical pest control agents with insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillaja saponaria extract (L.4.3);
[0547] L5) Microbial pest control agents with plant stress reduction, plant growth regulator, plant growth promotion and / or yield increase activity: Azospirillum brasilense Ab-V5 and Ab-V6 (L.5.1), Azospirillum brasilense Sp245 (L.5.2), Bradyrhizobium elkanii SEMIA 587 (L.5.3), Bradyrhizobium elkanii SEMIA 5019 (L.5.4), Bradyrhizobium japonicum 532c (L.5.5), Bradyrhizobium japonicum E-109 (L.5.6), Bradyrhizobium japonicum SEMIA 5079 (L.5.7), Bradyrhizobium japonicum SEMIA 5080 (L.5.8).
[0548] Furthermore, the present invention relates to agrochemical compositions comprising a mixture of the following: at least one compound I (component 1) and at least one biopesticide selected from group L) (component 2), in particular at least one biopesticide selected from groups L1) and L2) as described above, and (if desired) at least one suitable adjuvant.
[0549] Furthermore, the present invention relates to agrochemical compositions comprising a mixture of the following: at least one compound I (component 1) and at least one biopesticide selected from group L) (component 2), in particular at least one biopesticide selected from groups L3) and L4) as described above, and (if desired) at least one suitable adjuvant.
[0550] Also preferred are mixtures comprising a biopesticide as pesticidal agent II (component 2), which biopesticide is selected from groups L1), L3) and L5), preferably selected from the strains designated 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 treating propagation material, i.e. for seed treatment purposes, and are equally suitable for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, maize and leguminous plants such as soybeans.
[0551] Also preferred are mixtures comprising a biopesticide as pesticidal agent II (component 2), which biopesticide is selected from group L1), L3) and L5), preferably from those denoted above as (L1.1), (L1.2), (L1.3), (L1.6), (L1.7), (L1.9), (L1.11), (L1.12), (L1.13), (L1.14), (L1.15), (L1.17), (L1.18), (L1.22), (L1.23), (L1.24), (L1.25), (L1.26), (L1.27), (L2.2); (L3.2), (L3.3), (L3.4), (L3.5), (L3.6), (L3.7), (L3.8), (L3.10), (L3.11), (L3.12), (L3.13), (L3.14), (L3.15), (L3.18), (L3.19); (L4.2), even more preferably from (L1.2), (L1.7), (L1.11), (L1.13), (L1.14), (L1.15), (L1.18), (L1.23), (L3.3), (L3.4), (L3.6), (L3.7), (L3.8), (L3.10), (L3.11), (L3.12), (L3.15) and (L4.2). These mixtures are particularly suitable for the foliar treatment of cultivated plants, preferably vegetables, fruits, vines, cereals, maize and leguminous crops such as soya beans.
[0552] Compositions comprising mixtures of active ingredients can be prepared by customary means, for example by the means given for the compositions of compound I.
[0553] When live microorganisms such as pesticidal agents II from group L1), L3) and L5) form part of the composition, such compositions can be prepared by customary means (for example H.D. Burges: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008 / 002371, US 6,955,912, US 5,422,107).
[0554] I. Synthesis examples
[0555] Example 1: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepin-3,1'-cyclopropane] -3,1'-cyclopropane
[0556] Step 1: Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol At 0 °C, under N2, i-PrMgCl (2 M) (36 mL, 0.073 mol) was added to a solution of 1,2-difluoro-3-iodobenzene (16.8 g, 0.07 mol) in THF (150 mL), and the mixture was stirred at 0 °C for 30 min. Then, at 0 °C, 6-(difluoromethyl)-5-methylnicotinaldehyde (10 g, 0.058 mol) in THF was added, and the mixture was stirred at 0 °C to 20 °C under N2 for 4 h. TLC (PE:EtOAc = 3:1) showed completion of the reaction. The reaction mixture was quenched with an aqueous NH4Cl solution (200 mL), extracted with EtOAc (150 mL), and washed with brine (200 mL). The organic layer was dried over Na2SO4 and concentrated to give (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol (16.7 g, crude) as a yellow solid. The title compound was used directly without further purification.
[0557] 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.38 (s, 1H) 7.54 (s, 1H) 7.20 - 7.25 (m, 1H) 7.02 - 7.09 (m, 2H) 6.45 - 6.75 (m, 1H) 6.14 (s, 1H) 2.40 - 2.44 (m, 3H).
[0558] Step 2: Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone
[0559] MnO2 (51 g, 0.59 mol) was added to a solution of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol (16.7 g, 0.059 mol) in THF (200 mL), and the mixture was stirred at 80 °C for 16 h. TLC (PE:EtOAc = 3:1) showed completion of the reaction. The reaction mixture was filtered and the filtrate was concentrated, purified by column (PE:EtOAc = 7:1) to give (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone (12.5 g, 75%) as a yellow oil. The title compound was used directly without further purification.
[0560] 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.69 (s, 1H) 7.95 (s, 1H) 7.27 - 7.41 (m, 2H) 7.19 - 7.24 (m, 1H) 6.49 - 6.84 (m, 1H) 2.53 (s, 3H).
[0561] Step 3: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1,2-dihydrospiro[benzo[e][1,4]diazepine -3,1'-cyclopropane]
[0562] At 25 °C, Na2CO3 (2.2 g, 20.8 mmol) and 1-(aminomethyl)cyclopropan-1-amine dihydrochloride (1.1 g, 6.9 mmol) were added to a solution of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone (1.63 g, 5.8 mmol) in nBuOH (40 mL), and the mixture was stirred at 120 °C under N2 for 16 h. TLC (PE:EtOAc = 1:1) showed completion of the reaction. The mixture was quenched with H2O (50 mL) and extracted with EtOAc (30 mL × 3). The organic layer was washed with brine (20 mL × 2), dried over Na2SO4 and concentrated. The residue was purified by column (PE:EtOAc = 3:1 to 1:1) to give the title compound (1.1 g) as a yellow oil.
[0563] 1 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.47 (s, 1H) 7.72 (s, 1H) 7.05 (ddd, J = 11.19, 7.94, 1.25 Hz, 1H) 6.51 - 6.87 (m, 4H) 4.85 (br s, 1H) 3.60 (d, J = 4.13 Hz, 2H) 2.53 (s, 3H) 1.09 - 1.14 (m, 2H) 0.97 - 1.02 (m, 2H).
[0564] Step 4: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2-dihydrospiro[benzo[e][1,4]diazepine -3,1'-cyclopropane]
[0565] At 0 °C, to 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1,2-dihydrospiro[benzo[e][1,4]diazepine A solution of [[2.2 g, 6.6 mmol]] of [[3,1'-bicyclopropyl]] in [[20 mL]] of [[DMF]] was added to [[NaH]] (approx. [[60%]]) [[398 mg, 10 mmol]] and stirred for [[15 min]] at [[0 °C]] under [[N₂]]. Then, [[MeI]] [[2.3 g, 16.6 mmol]] was added at [[0 °C]] and stirred for [[16 h]] at [[0 °C - 25 °C]] under [[N₂]]. TLC ([[PE:EtOAc = 3:1]]) showed approximately [[65%]] of the desired product and approximately [[30%]] of the starting material in the reaction. The mixture was quenched with an aqueous [[NH₄Cl]] solution [[(30 mL)]], extracted with [[EtOAc]] [[(15 mL × 3)]]. The organic layer was washed with brine [[(15 × 2 mL)]], dried over [[Na₂SO₄]] and concentrated. The residue was purified by column ([[PE:EtOAc = 3:1 to 1:1]]) to give [[5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2-dihydrospiro[benzo[e][1,4]diazepine]] [[(1.7 g, 74.6%)]].
[0566] 1 ¹H NMR ([[400 MHz]], [[CDCl₃]]) δ [[[ppm]]] = [[8.52 (s, 1H)]] [[7.91 (br s, 1H)]] [[7.12 (br dd, J = 11.38, 7.25 Hz, 1H)]] [[6.93 (td, J = 7.88, 4.75 Hz, 1H)]] [[6.56 - 6.86 (m, 2H)]] [[3.55 (s, 2H)]] [[2.99 (d, J = 6.38 Hz, 3H)]] [[2.53 (s, 3H)]] [[0.77 (br s, 4H)]].
[0567] Step 5: Preparation of [[5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepine]] [[3,1'-bicyclopropyl]]
[0568] At [[25 °C]], to [[5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2-dihydrospiro[benzo[e][1,4]diazepine]] A solution of -3,1'-cyclopropane](1.7 g, 4.9 mmol) in MeOH (20 mL) was added to Na(CN)BH3 (466 mg, 7.4 mmol) and HOAc (1 drop). The mixture was stirred at 25 °C for 2 h. TLC (PE:EtOAc = 5:1) showed the reaction was complete. The mixture was concentrated and quenched with H2O (10 mL), and extracted with EtOAc (10 mL × 3). The organic layer was dried over Na2SO4 and concentrated. The residue was purified by preparative HPLC (NH4HCO3) to give 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepin
[0569] 1 H NMR (400 MHz, CDCl3) δ [ppm] = 8.41 (s, 1H) 7.62 (br s, 1H) 6.97 (dd, J = 12.07, 8.19 Hz, 1H) 6.59 - 6.86 (m, 2H) 6.26 (br d, J = 7.25 Hz, 1H) 5.61 (s, 1H) 3.20 (br d, J = 12.88 Hz, 1H) 3.11 (d, J = 5.00 Hz, 3H) 3.01 (br d, J = 12.13 Hz, 1H) 2.52 (s, 3H) 0.63 - 0.69 (m, 1H) 0.48 - 0.55 (m, 2H) 0.28 - 0.33 (m, 1H).
[0570] Step 6: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1,4-dimethyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepin -3,1'-cyclopropane]
[0571] At 0 °C, under N2, to 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepin A solution of -3,1'-cyclopropane (250 mg, 0.7 mmol) and MeI (504 mg, 3.5 mmol) in DMF (3 mL) was added to NaH (ca. 60%) (58 mg, 1.4 mmol). The mixture was stirred under N2 at 0 °C to 25 °C for 16 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The mixture was quenched with aqueous NH4Cl solution (6 mL) and extracted with EtOAc (3 mL × 3). The organic layer was washed with brine (3 mL × 2), dried over Na2SO4 and concentrated. The residue was purified by preparative HPLC to give 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1,4-dimethyl-1,2,4,5-tetrahydrospiro[benzo[e][1,4]diazepin -3,1'-cyclopropane (115 mg, yield: 44%).
[0572] 1 1H NMR (400 MHz, DMSO-d6) δ [ppm] = 8.37 (s, 1H) 7.68 (s, 1H) 6.86 - 7.12 (m, 2H) 6.81 - 6.85 (m, 1H) 6.10 (br d, J = 7.63 Hz, 1H) 5.21 (s, 1H) 3.86 (br dd, J = 5.60, 2.98 Hz, 1H) 3.06 - 3.06 (m, 1H) 3.05 (s, 3H) 2.46 (s, 3H) 2.32 (s, 3H) 0.51 - 0.56 (m, 1H) 0.38 - 0.44 (m, 1H) 0.22 (brd, J = 3.81 Hz, 1H) 0.01 - 0.07 (m, 1H).
[0573] The compounds listed in Table I were prepared in a similar manner.
[0574] Table I: Compounds Ex-1 to Ex-6 having the formula I, where R 5 、R 6 、R 7 、R 8 and R 9′ are defined as in each row.
[0575] *HPLC: High Performance Liquid Chromatography; HPLC - column Kinetex XB C18 1,7 μ (50 × 2,1 mm); eluent: acetonitrile / water + 0.1% trifluoroacetic acid (gradient from 5:95 to 100:0 in 1.5 min at 60 °C, flow rate gradient from 0.8 to 1.0 ml / min in 1.5 min);
[0576] *LCMS: Liquid Chromatography-Mass Spectrometry; Shimadzu Nexera LC-30LCMS-2020 (ESI+), using HPLC-column Kinetex XB C18 1,7 μ (50×2,1 mm); Eluent: acetonitrile / water + 0.1% trifluoroacetic acid (gradient from 5:95 to 100:0 in 1.5 min at 60 °C, flow rate gradient from 0.8 to 1.0 ml / min in 1.5 min);
[0577] R t : Retention time in minutes.
[0578]
[0579] #imgpt186#
[0580] II. Biological examples
[0581] Greenhouse
[0582] Dissolve the compound in a mixture of acetone and / or dimethyl sulfoxide and the ethoxylated alkylphenol-based wetting agent / emulsifier Wettol in a solvent-emulsifier ratio (by volume) of 99:1 to give a total volume of 5 ml. Subsequently, add water to a total volume of 100 ml.
[0583] Then dilute this stock solution with the solvent-emulsifier-water mixture to the final concentrations given in the table below.
[0584] Example 1 - Preventive fungicidal control of Botrytis cinerea on green pepper leaves
[0585] Green pepper seedlings were grown in pots to the 4- to 5-leaf stage. These plants were sprayed to runoff with the aforementioned spray solution containing the active ingredient or mixture at the concentrations mentioned in the table below. The next day, the plants were inoculated with a biological malt aqueous solution or DOB solution containing a suspension of Botrytis cinerea spores. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 °C to 24 °C and saturated relative humidity, the degree of fungal infestation on the leaves was visually evaluated as % diseased leaf area.
[0586] In this test, the sample treated with 125 ppm of the active substance from Example Ex-9 showed a 0% pathogen growth rate, while 90% of the untreated plants were infected.
[0587] Microtest
[0588] The active compound was formulated separately as a stock solution at a concentration of 10,000 ppm in dimethyl sulfoxide.
[0589] Example 1 - Activity against Botrytis cinerea in microtiter plate tests
[0590] The stock solutions were mixed in proportion, pipetted onto a microtiter plate (MTP) and diluted with water to the specified concentration. Then a spore suspension of Botrytis cinerea in an aqueous solution of biomalts or a yeast - bacterium peptone - sodium acetate solution was added. The plates were placed in a water - vapor - saturated chamber at a temperature of 18 °C. The MTP was measured at 405 nm 7 days after inoculation using an absorption photometer.
[0591] In this test, samples treated with 125 ppm of the active substances from Examples Ex - 2 and Ex - 5 respectively showed a pathogen growth rate of 21%.
[0592] In this test, samples treated with 31 ppm of the active substances from Examples Ex - 7, Ex - 8, Ex - 9, Ex - 10, Ex - 11, Ex - 12, Ex - 13 and Ex - 14 respectively showed a pathogen growth rate of 12%.
[0593] Example 2 - Activity against Colletotrichum orbiculare in microtiter plate tests
[0594] The active compounds were formulated individually as stock solutions at a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed in proportion, pipetted onto a microtiter plate (MTP) and diluted with water to the specified concentration. Then a spore suspension of a Colletotrichum orbiculare isolate in DOB medium (pH 7) was added.
[0595] In this test, samples treated with 125 ppm of the active substances from Examples Ex - 1, Ex - 2, Ex - 5 and Ex - 6 respectively showed a pathogen growth rate of up to 17%.
[0596] Example 3 - Activity against Corynespora cassiicola in microtiter plate tests
[0597] The active compounds were formulated individually as stock solutions at a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed in proportion, pipetted onto a microtiter plate (MTP) and diluted with water to the specified concentration. Then a spore suspension of a Corynespora cassiicola isolate in DOB medium (pH 7) was added.
[0598] In this test, samples treated with 125 ppm of the active substance from Example Ex - 2 showed a pathogen growth rate of up to 4%.
[0599] Example 4 - Anti-Pyricularia oryzea Activity in Microtiter Plate Tests
[0600] Mix the stock solutions in proportion, pipette them onto a microtiter plate (MTP) and dilute with water to the specified concentration. Then add Pyricularia oryzae a spore suspension in aqueous biological malt or yeast-bacterial peptone-glycerol or DOB solution. Place these plates in a water vapor-saturated chamber at a temperature of 18 °C. Measure the MTP at 405 nm 7 days after inoculation using an absorption photometer.
[0601] In this test, samples treated with 125 ppm of the active substances from Examples Ex-1, Ex-2, Ex-3, Ex-5 and Ex-6 respectively showed a pathogen growth rate of 10%.
[0602] Example 5 - Anti-Fusarium culmorum Activity in Microtiter Plate Tests
[0603] Mix the stock solutions in proportion, pipette them onto a microtiter plate (MTP) and dilute with water to the specified concentration. Then add a spore suspension of Fusarium culmorum in aqueous biological malt or yeast-bacterial peptone-glycerol or DOB solution. Place these plates in a water vapor-saturated chamber at a temperature of 18 °C. Measure the MTP at 405 nm 7 days after inoculation using an absorption photometer.
[0604] In this test, samples treated with 31 ppm of the active substances from Examples Ex-10 and Ex-14 respectively showed a pathogen growth rate of 16%.
Claims
1. A compound of formula I or its N-oxide, tautomer, stereoisomer or agriculturally acceptable salt Y is N, CR 1 ; R 1 independently selected from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl in each case; R 2 independently selected in each case from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, O-C1-C6-alkyl, O-C2-C6-alkenyl, O-C2-C6-alkynyl, C3-C6-cycloalkyl, S-C1-C6-alkyl, S-C2-C6-alkenyl, S-C2-C6-alkynyl; R 3 independently selected in each case from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, O-C1-C6-alkyl, O-C2-C6-alkenyl, O-C2-C6-alkynyl, C3-C6-cycloalkyl, S-C1-C6-alkyl, S-C2-C6-alkenyl, S-C2-C6-alkynyl; and R 2 and R 3 together with the carbon atom to which they are bonded form a phenyl group which is unsubstituted or bears 1, 2 or 3 substituents R 23a ; wherein Each R 23a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl; R 4 independently selected from H, halogen, CN, C1-C4-alkyl, C1-C4-haloalkyl in each case; R 5 independently selected in each case from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 5a ; where Each R 5a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl; R 6 independently selected in each case from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 6a ; where Each R 6a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl; or R 5 and R 6 together form an oxo group (=O); or a thio group (=S); or R 5 and R 6 together with the carbon atom to which they are bonded form a 3-, 4-, 5- or 6-membered saturated carbon ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1, 2 or 3 heteroatoms selected from O and S as ring members; wherein the carbon ring or heterocyclic ring is unsubstituted or bears 1, 2 or 3 substituents R 56 wherein Each R 56 independently is halogen, C1-C6-alkyl or C1-C6-haloalkyl; R 7 independently selected, in each case, from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 7a ; where Each R 7a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl; R 8 independently selected in each case from hydrogen, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, a five- or six-membered heteroaryl or a five- or six-membered CH2-heteroaryl; where the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and where these aliphatic or aromatic groups are unsubstituted or carry 1, 2 or 3 substituents R 8a ; where Each R 8a independently is halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl or O-C1-C6-alkyl; or R 7 and R 8 together form an oxo group (=O) or a thio group (=S); or R 7 and R 8 together with the carbon atoms to which they are bonded form a 3-, 4-, 5- or 6-membered saturated carbon ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1, 2 or 3 heteroatoms selected from O and S as ring members; R 9 independently selected in each case from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a , a five- or six-membered heteroaryl, aryl or benzyl; wherein the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; wherein the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; wherein the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen; wherein R 9a is a C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, where the benzene ring in the last two mentioned groups is unsubstituted or carries 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; R 9′ independently selected in each case from H, CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)C1-C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)-N(H)C1-C4-alkyl, -C(=O)-N(C1-C4-alkyl)2, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -S(=O)2-R 9a , a five- or six-membered heteroaryl, aryl or benzyl; wherein the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S as ring members; wherein the benzene ring in the aryl and benzyl is unsubstituted or bears 1, 2, 3, 4 or 5 substituents selected from the group consisting of: CN, halogen, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; wherein the benzene ring in the benzyl is unsubstituted or bears 1, 2 or 3 substituents selected from the group consisting of: CN and halogen; wherein R 9′a is a C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl or benzyl, where the benzene ring in the last two mentioned groups is unsubstituted or bears 1, 2 or 3 substituents each independently selected from the group consisting of: halogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; X is independently selected in each case from halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, phenyl, benzyl, phenoxy, benzyloxy, C1-C6-thioalkyl; N is 0, 1, 2 or 3.
2. The compound according to claim 1, wherein Y is CR 1 and R 1 is H.
3. The compound according to any one of claims 1 to 2, wherein R 2 is a C1-C6-alkyl group.
4. The compound according to any one of claims 1 to 3, wherein, R 2 is CH3.
5. The compound according to any one of claims 1 to 4, wherein, R 3 selected from C1-C6-alkyl, C1-C6-haloalkyl.
6. The compound according to any one of claims 1 to 5, wherein, R 3 is CH3 or CHF2.
7. The compound according to any one of claims 1 to 6, wherein R 2 and R 3 forms a phenyl group with the C atom.
8. The compound according to any one of claims 1 to 7, wherein, R 4 is H.
9. A compound according to any one of claims 1 to 8, wherein, R 5 and R 6 is H or a C1-C6-alkyl group.
10. The compound according to any one of claims 1 to 9, wherein, R 5 and R 6 together with the C atom to which they are bonded form a C3-C6-cycloalkyl or a (=O) group.
11. The compound according to any one of claims 1 to 10, wherein R 7 and R 8 is H or a C1-C6-alkyl group.
12. The compound according to any one of claims 1 to 11, wherein, R 6 and R 7 together with the carbon atom to which they are bonded form a (=O) group.
13. A composition comprising a compound of formula I as defined in any one of claims 1 to 12, its N-oxide or an agriculturally acceptable salt.
14. A method for combating phytopathogenic fungi, which method comprises treating the fungi or the material, plant, soil or seed to be protected against fungal attack with an effective amount of at least one compound of formula I as defined in any one of claims 1 to 12, or with a composition as defined in any one of claims 13.
15. A seed coated with 0.1 to 10 kg / 100 kg of seed amount of at least one compound of formula I as defined in any one of claims 1 to 12 or its agriculturally acceptable salt, or a composition as defined in any one of claims 13.
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