2-{[2-(phenoxymethyl) pyridin-5-yl] oxy} ethylamine derivatives and related compounds as pest control agents, for example for protecting plants

Abstract

The invention relates to compounds of formula (I), # imgabs0, in which Z, Y, A1, A2, A3, A4, X, R7, R8 and R9 have the meanings described above, to a method for the production thereof, to intermediate products for the production thereof, and to the use thereof for controlling animal pests, in particular insects.

Description

[0001] This application is a divisional application of a Chinese invention patent application (filing date: April 26, 2018; application number: 201880044959.1 (International application number: PCT / EP2018 / 060678); invention name: 2-{[2-(phenoxymethyl)pyridin-5-yl]oxy}ethylamine derivatives and related compounds as pest control agents, for example, for protecting plants).

[0002] The present invention relates to novel heterocyclic compounds, processes for their preparation and intermediates for their preparation, as well as their use for controlling animal pests, particularly insects.

[0003] Heterocyclic derivatives having fungicidal properties have been described in the literature (eg WO 2014 / 179144).

[0004] Heterocyclic derivatives having pharmaceutical properties have been described in the literature (eg WO 2005 / 082089, WO 2008073929, WO 2009 / 145360).

[0005] Modern pesticides must meet numerous requirements, for example, regarding their efficacy, duration of action, spectrum of action, and potential uses. Toxicity issues and compatibility with other active compounds or formulation adjuvants also play a role, as do the costs and complexity involved in synthesizing the active compounds. Furthermore, resistance can develop. For all these reasons alone, the search for new pesticides cannot be considered complete; rather, there is a constant need for new compounds that have improved properties, at least in some respects, compared to known compounds.

[0006] It is an object of the present invention to provide compounds which broaden the pesticide spectrum in various aspects.

[0007] This object, as well as other objects not explicitly stated but discernible or inferable from the connections discussed herein, are achieved by novel compounds of formula (I) and salts, metal complexes, N-oxides and tautomeric forms of compounds of formula (I)

[0008]

[0009]

[0010] Among them (configuration 1)

[0011] Z represents an optionally substituted naphthyl, dibenzo[b,d]furyl, dibenzo[b,d]thienyl, carbazolyl, indanyl, benzothienyl, benzofuranyl, indolyl, fluorenyl, phenanthrenyl, anthracenyl or a phenyl group of the substructure (II)

[0012]

[0013] and the substituted phenyl radical of sub-formula (II) may optionally carry two further substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C3-C6)-cycloalkyl and (C3-C6)-halocycloalkyl,

[0014] Y represents O, S, -CH2, -NR 5 ,

[0015] A 1 Represents N or -CR 1 ,

[0016] A 2 Represents N or -CR 2 ,

[0017] A 3 Represents N or -CR 3 ,

[0018] A 4 Represents N or -CR 4 ,

[0019] wherein at least one and at most two of the atoms A1, A2, A3 and A4 in the aromatic ring represent N,

[0020] X represents oxygen, sulfenyl, sulfinyl, sulfonyl, -CH2, carbonyl, -CHOH or -NR 6 ,

[0021] R 1 、R 2 、R 3 and R 4each independently of one another represents hydrogen, halogen, nitro, cyano, aminocarbonyl, aminosulfonyl, in each case optionally substituted (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, N-mono-(C1-C4)-alkylamino, N-mono-(C3-C6)-cycloalkylamino, N,N-di-(C1-C4)-alkylamino, N,N-di-(C3-C6)- )-cycloalkylamino, N,N-(C3-C6)-cycloalkyl-(C1-C4)-alkylamino, N-(C1-C4)-alkanoylamino, N-(C3-C6)-cycloalkanoylamino, N-(C1-C4)-alkanoyl-N-(C1-C4)-alkylamino, N-(C3-C6)-cycloalkanoyl-N-(C1-C4)-alkylamino, N-(C3-C6)-cycloalkanoyl-N-(C3-C6)-cycloalkylamino, N-(C1-C4)-alkanoyl-N-(C3-C6)-cycloalkylamino, (C1-C4)-alkoxycarbonyl , (C3-C6)-cycloalkyloxycarbonyl, (C1-C4)-alkanoyl, (C3-C6)-cycloalkanoyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, N-(C1-C4)-alkylaminocarbonyl, N-(C3-C6)-cycloalkylaminocarbonyl, N,N-di-(C1-C4)-alkylaminocarbonyl, N,N-di-(C3-C6)-cycloalkylamino carbonyl, N,N-(C3-C6)-cycloalkyl-(C1-C4)-alkylaminocarbonyl, -CH=NO-[(C1-C4)-alkyl], -CH=NO-[(C3-C6)-cycloalkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], -C[(C3-C6)-cycloalkyl]=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C3-C6)-cycloalkyl], -C[(C3-C6)-cycloalkyl]=NO-[(C3-C6)-cycloalkyl],

[0022] R 5 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C3)-alkanoyl,

[0023] R 6 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkanoyl or R 8A closed ring formed by 1 to 3 CH2 groups,

[0024] R 7 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl or 8 A closed ring formed by 1 to 3 CH2 groups,

[0025] R 8 represents hydrogen or represents an optionally substituted (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl or R 6 and R 7 together in a ring formed by 1 to 3 CH2 groups or with R 9 enclosed together in a 4- to 6-membered heterocyclic ring, which in the case of a 5- or 6-membered heterocyclic ring may contain further heteroatoms and which are optionally mono- or polysubstituted by identical or different radicals selected from the group consisting of halogen substituents, cyano or (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy groups, each of which is optionally mono- or polysubstituted by identical or different halogen substituents,

[0026] In R 7 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl or in the case of R 7 With R 8 When forming a 5- or 6-membered ring together, R 9 represents in each case optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylcarbonyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl, or

[0027] In R 7 With R 8 When forming a 4-membered ring together, R 9represents in each case optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, or

[0028] R 8 and R 9 represents a 4- to 6-membered heterocyclic closed ring, which in the case of a 5- or 6-membered heterocyclic ring may contain further heteroatoms and which is optionally mono- or polysubstituted by identical or different radicals selected from the group consisting of halogen substituents, cyano or (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy groups, each of which is optionally mono- or polysubstituted by identical or different halogen substituents,

[0029] R 10represents halogen, nitro, cyano, -SF5, or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylsulfonyl -alkyl], which are optionally mono- or polysubstituted by the same or different substituents selected from the group consisting of halogen, cyano, nitro, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, thiocyanate, , -SF5, (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C2-C4)-alkenyloxy, (C2-C4)-haloalkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C3-C6)-halocycloalkyloxy, (C3-C 6)-cycloalkyl, (C3-C6)-halogenated cycloalkyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-halogenated alkylsulfonyl, (C1-C4)-halogenated alkylthio, (C1-C4)-halogenated alkylsulfinyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, C6-aryl, C 10 -aryl, C 14 -aryl, C6-aryloxy, C 10 -aryloxy, C 14 -aryloxy, benzyl, benzyloxy, benzylthio, C6-arylthio, C 10 -arylthio, C 14 -arylthio, C6-arylamino, C 10 -Arylamino, C 14 - arylamino, benzylamino, heterocyclic and trialkylsilyl groups,

[0030] R 11represents hydrogen, halogen, cyano or nitro, or represents in each case optionally substituted (C1-C4)-alkyl, (C3-C5)-cycloalkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl],

[0031] and

[0032] The proviso was to exclude the compound 1-[4-(6-{2-[3-(chloromethyl)phenyl]ethyl}pyridin-3-yl)piperazin-1-yl]ethanone.

[0033] The excluded compounds are specifically disclosed in WO2009145360 as intermediates for the preparation of pharmaceutically active compounds.

[0034] The compounds of the present invention are broadly defined by formula (I). Preferred substituents or ranges of the radicals given in the formulae mentioned above and below are described below:

[0035] Configuration 2:

[0036] Z preferably represents optionally substituted naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, indan-4-yl, benzothien-4-yl, benzofuran-4-yl, indol-4-yl or represents a substituted phenyl group of the sub-structural formula (II), wherein the phenyl group of the sub-structural formula (II) preferably has an alkyl radical other than R 10 and R 11 It does not carry any other substituents.

[0037] Y preferably represents O, S, -NR 5 ,

[0038] R 1 、R 2 、R 3 and R 4Preferably, each independently of one another represents a substituent selected from hydrogen, halogen, nitro, cyano, or represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkyloxycarbonyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)- 4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl,

[0039] R 5 preferably represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C3)-alkanoyl, which is optionally mono- or polysubstituted by identical or different halogen substituents,

[0040] R 6 Preferably represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C4)-alkanoyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 8 A closed ring formed by 1 to 3 CH2 groups,

[0041] R 7 Preferably represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 8 A closed ring formed by 1 to 3 CH2 groups,

[0042] R 8 Preferably represents hydrogen, or represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different substituents selected from halogen, nitro and cyano, or with R 6 or R 7 Together with 1 to 3 CH2 groups to form a closed ring, or with R 9together to form a 4- to 6-membered heterocyclic closed ring, which in the case of a 5- or 6-membered heterocyclic ring may contain further heteroatoms selected from N and O and which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0043] In R 7 represents hydrogen or (C1-C4)-alkyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents or in the case of R 7 With R 8 When forming a 5- or 6-membered ring, R 9 preferably represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylcarbonyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from halogen, cyano, nitro or (C3-C6)-cycloalkyl, or

[0044] In R 7 With R 8 When forming a 4-membered ring together, R 9 preferably represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C3-C4)-cycloalkyloxy, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, which are in each case optionally mono- or polysubstituted by identical or different substituents selected from halogen, cyano, nitro or (C3-C6)-cycloalkyl, or

[0045] R 8 and R 9 preferably represents a 4- to 6-membered heterocyclic closed ring, which in the case of a 5- or 6-membered heterocyclic ring may contain further heteroatoms selected from N, O and which may optionally be mono- or polysubstituted by identical or different substituents selected from halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0046] R 10Preferably represents halogen, or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkyl thio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl,

[0047] R 11 Preferably represents hydrogen, halogen, cyano or nitro, or represents (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C5)-cycloalkyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkoxy and (C3-C6)-cycloalkyl.

[0048] Substituents not mentioned in Configuration 2 are as defined in Configuration 1.

[0049] Configuration 3:

[0050] Z particularly preferably represents naphthyl, dibenzo[b,d]furyl, dibenzo[b,d]thienyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkylcarbonyl, (C1-C4)-haloalkylcarbonyl, or represents a substituted phenyl group of the subformula (II),

[0051] At least one of the atoms A3 or A4 in the aromatic ring particularly preferably represents nitrogen,

[0052] R 1 、R 2 、R 3 and R 4 each independently of one another particularly preferably represents a substituent selected from the group consisting of hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl and (C1-C4)-alkylsulfonyl,

[0053] R 6 Particularly preferably represents hydrogen, (C1-C4)-alkyl or 8 A closed ring formed by 1 to 3 CH2 groups,

[0054] R 7 Particularly preferably represents hydrogen, (C1-C4)-alkyl, (C3-C4)-cycloalkyl or 8 A closed ring formed by 1 to 3 CH2 groups,

[0055] R 8 Particularly preferably represents hydrogen, or represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different substituents selected from halogen, or with R 6 or R 7 Together with 1 to 3 CH2 groups to form a closed ring, or with R 9 a 4- to 6-membered heterocyclic ring formed together by 3 to 5 CH2 groups, and the heterocyclic ring is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0056] In R 7 represents hydrogen or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl or in the case of R 7 With R 8 When forming a 5- or 6-membered ring together, R 9 Particularly preferably represents (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C1-C6)-alkylcarbonyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro or (C3-C6)-cycloalkyl, or

[0057] In R 7 With R 8 When forming a 4-membered ring together, R 9 Particularly preferably represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro or (C3-C6)-cycloalkyl, or

[0058] R 8 and R 9 Particularly preferably represents a 4- to 6-membered heterocyclic ring closed by 3 to 5 CH2 groups and which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0059] R 10 Particularly preferably represents halogen or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, or represents (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)- )-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro,

[0060] R 11 Particularly preferably represents hydrogen, halogen, cyano or nitro, or represents (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C5)-cycloalkyl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano and (C3-C6)-cycloalkyl.

[0061] Substituents not mentioned in Configuration 3 are as defined in Configuration 1 or Configuration 2.

[0062] Configuration 4:

[0063] Z very particularly preferably represents naphthyl, dibenzo[b,d]furyl, dibenzo[b,d]thienyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C3-C6)-cycloalkyl, or represents a substituted phenyl group of the subformula (II),

[0064] Y very particularly preferably represents oxygen,

[0065] X very particularly preferably represents oxygen or -NR 6 .

[0066] Substituents not mentioned in Configuration 4 are as defined in Configuration 1, Configuration 2 or Configuration 3.

[0067] Configuration 5:

[0068] Z particularly preferably represents naphthyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, or represents unsubstituted dibenzo[b,d]furanyl or dibenzo[b,d]thienyl or represents a substituted phenyl group of the subformula (II),

[0069] R 1 、R 2 、R 3 and R 4 Particularly preferably represents a substituent selected from the group consisting of hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio,

[0070] R 6 Particularly preferably represents hydrogen, (C1-C3)-alkyl or 8 A closed ring formed by 1 to 2 CH2 groups,

[0071] R 7 Especially preferably represents hydrogen or with R 8 A closed ring formed by 1 to 3 CH2 groups,

[0072] R 8Especially preferably represents hydrogen, or represents (C1-C4)-alkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 6 Together with 1 or 2 CH2 groups to form a closed ring or with R 7 Together with 1 to 3 CH2 groups to form a closed ring or with R 9 a 4- to 6-membered heterocyclic ring formed together by 3 to 5 CH2 groups, and the heterocyclic ring is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0073] R 9 Particularly preferably represents (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C1-C6)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano and (C3-C6)-cycloalkyl, or

[0074] R 8 and R 9 Particularly preferably represents a 4- to 6-membered heterocyclic ring closed by 3 to 5 CH2 groups and which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl,

[0075] R 10 particularly preferably represents halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or represents phenyl which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy and (C1-C4)-haloalkoxy,

[0076] R 11 Particularly preferably represents hydrogen, halogen, nitro or cyano, or represents (C1-C4)-alkyl, (C3-C5)-cycloalkyl or (C1-C4)-alkoxy, which are optionally mono- or polysubstituted by identical or different halogen substituents.

[0077] Substituents not mentioned in Configuration 5 are as defined in Configuration 1, Configuration 2, Configuration 3 or Configuration 4.

[0078] Configuration 6:

[0079] Z mainly represents the naphthyl group of the substructure formula (III):

[0080]

[0081] or represents an unsubstituted dibenzo[b,d]furanyl or dibenzo[b,d]thienyl or represents a substituted phenyl group of sub-structural formula (II).

[0082] R 1 Emphasis represents hydrogen, halogen, (C1-C4)-alkyl or (C1-C4)-alkoxy,

[0083] R 2 Emphasis represents hydrogen, halogen or (C1-C4)-haloalkyl,

[0084] R 3 represents hydrogen, halogen, (C1-C4)-alkoxy or (C1-C4)-alkylthio,

[0085] R 4 The key represents hydrogen or halogen,

[0086] R 6 The emphasis represents hydrogen, or with R 8 The piperazine ring is closed.

[0087] R 7 The emphasis represents hydrogen, or with R 8 The pyrrolidine ring is closed.

[0088] R 8 The key represents hydrogen, (C1-C4)-alkyl or R 6 Together with the piperazine closed ring or with R 7 Together with R 9 Together they form a piperidine closed ring,

[0089] R 9 Emphasis represents (C1-C4)-alkyl or (C1-C4)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and cyano, or R 8 and R 9 The key represents the piperidine ring closure,

[0090] R 10 The key represents halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or phenyl of the substructure (IV):

[0091]

[0092] R 11 Emphasis represents hydrogen or halogen or represents (C1-C4)-alkyl or (C1-C4)-alkoxy, which is optionally mono- or polysubstituted by identical or different halogen substituents,

[0093] R 12、R 13 and R 14 The key points each independently represent hydrogen or halogen,

[0094] R 15 The emphasis is on hydrogen, halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy or (C1-C4)-haloalkoxy.

[0095] Substituents not mentioned in Configuration 6 are as defined in Configuration 1, Configuration 2, Configuration 3, Configuration 4 or Configuration 5.

[0096] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0097] wherein Z has the meaning described in configuration (1), and

[0098] Among them, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0099] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0100] wherein Z has the meaning described in configuration (2), and

[0101] Among them, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0102] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0103] wherein Z has the meaning described in configuration (3), and

[0104] Among them, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0105] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0106] wherein Z has the meaning described in configuration (4), and

[0107] Among them, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (5) or configuration (6).

[0108] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0109] wherein Z has the meaning described in configuration (5), and

[0110] Among them, Y, A 1 、A 2 、A3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0111] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0112] wherein Z has the meaning described in configuration (6), and

[0113] Among them, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0114] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0115] wherein Y has the meaning described in configuration (1), and

[0116] Among them, Z, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0117] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0118] wherein Y has the meaning described in configuration (2), and

[0119] Among them, Z, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0120] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0121] wherein Y has the meaning described in configuration (4), and

[0122] Among them, Z, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (5) or configuration (6).

[0123] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0124] Among them A 3 and A 4 has the meanings given in configuration (1), and

[0125] Among them, Z, Y, A1 、A 2 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0126] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0127] Among them A 3 and A 4 has the meanings described in configuration (3), and

[0128] Among them, Z, Y, A 1 、A 2 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0129] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0130] where R 1 、R 2 、R 3 and R 4 has the meanings given in configuration (1), and

[0131] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0132] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0133] where R 1 、R 2 、R 3 and R 4 has the meanings described in configuration (2), and

[0134] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0135] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0136] where R 1 、R 2 、R 3 and R 4 has the meanings described in configuration (3), and

[0137] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0138] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0139] where R 1 、R 2 、R 3 and R 4 has the meanings described in configuration (5), and

[0140] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0141] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0142] where R 1 、R 2 、R 3 and R 4 has the meanings described in configuration (6), and

[0143] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0144] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0145] wherein X has the meaning described in configuration (1), and

[0146] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0147] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0148] wherein X has the meaning described in configuration (3), and

[0149] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0150] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0151] where R 6 has the meanings given in configuration (1), and

[0152] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0153] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0154] where R 6 has the meanings described in configuration (2), and

[0155] Among them, Z, Y, A 1 、A2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0156] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0157] where R 6 has the meanings described in configuration (3), and

[0158] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0159] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0160] where R 6 has the meanings described in configuration (6), and

[0161] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0162] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0163] where R 7 has the meanings given in configuration (1), and

[0164] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0165] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0166] where R 7 has the meanings described in configuration (2), and

[0167] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0168] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0169] where R 7 has the meanings described in configuration (3), and

[0170] Among them, Z, Y, A 1 、A2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0171] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0172] where R 7 has the meanings described in configuration (5), and

[0173] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0174] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0175] where R 7 has the meanings described in configuration (6), and

[0176] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0177] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0178] where R 8 has the meanings given in configuration (1), and

[0179] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0180] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0181] where R 8 has the meanings described in configuration (2), and

[0182] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0183] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0184] where R 8 has the meanings described in configuration (3), and

[0185] Among them, Z, Y, A 1 、A2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0186] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0187] where R 8 has the meanings described in configuration (5), and

[0188] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0189] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0190] where R 8 has the meanings described in configuration (6), and

[0191] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0192] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0193] where R 9 has the meanings given in configuration (1), and

[0194] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0195] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0196] where R 9 has the meanings described in configuration (2), and

[0197] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0198] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0199] where R 9 has the meanings described in configuration (3), and

[0200] Among them, Z, Y, A 1 、A2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0201] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0202] where R 9 has the meanings described in configuration (5), and

[0203] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0204] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0205] where R 9 has the meanings described in configuration (6), and

[0206] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0207] In a preferred embodiment, the present invention relates to compounds of formula (I)

[0208] where R 10 and R 11 has the meanings given in configuration (1), and

[0209] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 has the meanings given above, in particular the meanings given in configuration (2) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0210] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0211] where R 10 and R 11 has the meanings described in configuration (2), and

[0212] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 has the meanings given above, in particular the meanings given in configuration (1) or configuration (3) or configuration (4) or configuration (5) or configuration (6).

[0213] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0214] where R 10 and R 11 has the meanings described in configuration (3), and

[0215] Among them, Z, Y, A1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (4) or configuration (5) or configuration (6).

[0216] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0217] where R 10 and R 11 has the meanings described in configuration (5), and

[0218] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (6).

[0219] In another preferred embodiment, the present invention relates to compounds of formula (I)

[0220] where R 10 and R 11 has the meanings described in configuration (6), and

[0221] Among them, Z, Y, A 1 、A 2 、A 3 、A 4 , X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9has the meanings given above, in particular the meanings given in configuration (1) or configuration (2) or configuration (3) or configuration (4) or configuration (5).

[0222] definition

[0223] Those skilled in the art will appreciate that, unless explicitly stated otherwise, the term "a" or "an" used in this application may mean "one (1)", "one (1) or more" or "at least one (1)", depending on the context.

[0224] It will be apparent to those skilled in the art that the examples given in this application are not to be considered limiting, but merely describe some embodiments in more detail.

[0225] For all structures described herein, such as ring systems and groups, adjacent atoms must not be -OO- or -OS-.

[0226] Structures with a variable number of possible carbon atoms (C atoms) may be referred to herein as C 碳原子的下限 -C 碳原子的上限 Structure (C LL -C UL Example: an alkyl group may consist of 3 to 10 carbon atoms and in this case corresponds to a C3-C 10 -alkyl. A ring structure composed of carbon atoms and heteroatoms may be referred to as a "LL- to UL-membered" structure. An example of a 6-membered ring structure is toluene (a 6-membered ring structure substituted with a methyl group).

[0227] If the collective term for substituents (e.g. C LL -C UL -alkyl) in a composite substituent (e.g., C LL -C UL -cycloalkyl-C LL -C UL -alkyl) at the end of the composite substituent, the component at the starting end (e.g., C LL -C UL -cycloalkyl) may be substituted by a subsequent substituent (C LL -C UL -alkyl) are independently and identically or differently monosubstituted or polysubstituted. All collective terms used in this application for chemical groups, ring systems and cyclic groups can be identified by the addition of the word "C LL -C UL ” or “LL- to UL-members” are more specifically defined. Unless otherwise defined, the definitions of collective terms also apply to these collective terms in composite substituents, for example: C LL -C ULThe definition of -alkyl also applies to composite substituents (e.g. C LL -C UL -cycloalkyl-C LL -C UL -alkyl) part of the C LL -C UL -alkyl.

[0228] In the definitions of the symbols given in the above formulae, collective terms are used which generally represent the following substituents:

[0229] Halogen refers to an element of the seventh main group, preferably fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine and bromine, and still more preferably fluorine and chlorine.

[0230] Examples of heteroatoms are N, O, S, P, B, Si. Preferably, the term "heteroatom" relates to N, S and O.

[0231] Unless defined differently, “alkyl”, by itself or as part of a chemical group, represents a straight or branched hydrocarbon preferably having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. Preference is furthermore given to alkyl radicals having 1 to 4 carbon atoms, such as, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Unless defined differently, “alkenyl” – by itself or as part of a chemical group – represents a straight or branched hydrocarbon preferably having 2 to 6 carbon atoms and at least one double bond, for example ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, Pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl Preference is given to alkenyl groups having 2 to 4 carbon atoms, such as, in particular, 2-propenyl, 2-butenyl or 1-methyl-2-propenyl.

[0232] Unless defined differently, "alkynyl" - by itself or as part of a chemical group - represents a straight-chain or branched hydrocarbon preferably having 2 to 6 carbon atoms and at least one triple bond, for example 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl Alkynyl groups having 2 to 4 carbon atoms are also preferred, such as ethynyl, 2-propynyl or 2-butynyl-2-propenyl.

[0233] Unless otherwise defined, "cycloalkyl"—by itself or as part of a chemical group—represents a monocyclic, bicyclic or tricyclic hydrocarbon preferably having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl. Also preferred are cycloalkyl groups having 3, 4, 5, 6 or 7 carbon atoms, such as, in particular, cyclopropyl or cyclobutyl. Unless otherwise defined, "alkylcycloalkyl" represents a monocyclic, bicyclic or tricyclic alkylcycloalkyl group preferably having 4 to 10 or 4 to 7 carbon atoms, such as, in particular, methylcyclopropyl, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Also preferred are alkylcycloalkyl groups having 4, 5 or 7 carbon atoms, such as, in particular, ethylcyclopropyl or 4-methylcyclohexyl.

[0234] Unless otherwise defined, "hydroxyalkyl" represents a linear or branched alcohol preferably having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. Also preferred are hydroxyalkyl groups having 1 to 4 carbon atoms.

[0235] Unless otherwise defined, "alkoxy" represents a linear or branched O-alkyl group preferably having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Alkoxy groups having 1 to 4 carbon atoms are also preferred. Unless otherwise defined, "alkylthio" represents a linear or branched S-alkyl group preferably having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and tert-butylthio. Alkylthio groups having 1 to 4 carbon atoms are also preferred.

[0236] Unless otherwise defined, "alkylsulfinyl" represents a linear or branched alkylsulfinyl group preferably having 1 to 6 carbon atoms, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl and tert-butylsulfinyl. Alkylsulfinyl groups having 1 to 4 carbon atoms are also preferred.

[0237] Unless otherwise defined, "alkylsulfonyl" represents a linear or branched alkylsulfonyl group preferably having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl. Alkylsulfonyl groups having 1 to 4 carbon atoms are also preferred.

[0238] Unless otherwise defined, "alkylcarbonyl" represents a linear or branched alkyl-C(=O) group preferably having 2 to 7 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl and tert-butylcarbonyl. Alkylcarbonyl groups having 1 to 4 carbon atoms are also preferred.

[0239] Unless defined differently, "alkoxycarbonyl" - by itself or as part of a chemical group - represents a straight-chain or branched alkoxycarbonyl group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy moiety, for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl.

[0240] Unless otherwise defined, "alkylaminocarbonyl" represents a linear or branched alkylaminocarbonyl group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl portion, for example methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, sec-butylaminocarbonyl and tert-butylaminocarbonyl. The alkylaminocarbonyl groups according to the invention may be substituted by one or more identical or different groups.

[0241] Unless defined differently, “N,N-dialkylaminocarbonyl” represents a straight-chain or branched N,N-dialkylaminocarbonyl group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl portion, for example, N,N-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-di(n-propylamino)carbonyl, N,N-di(isopropylamino)carbonyl and N,N-di-(sec-butylamino)carbonyl.

[0242] Unless otherwise defined, "N,N-dialkylamino" represents a linear or branched N,N-dialkylamino group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as N,N-dimethylamino-1, N,N-diethylamino, N,N-di(n-propylamino), N,N-di(isopropylamino), and N,N-di(sec-butylamino). Unless otherwise defined, "alkanoyl" or other "alkylcarbonyl" represents a linear or branched alkyl group having 1 to 6 carbon atoms, which carries a double-bonded oxygen atom at the 1-position and is bonded via the 1-position. Examples include formyl, acetyl, propionyl, n-butyryl, isobutyryl, pivaloyl, and n-hexanoyl.

[0243] Unless defined differently, "aryl" represents a monocyclic, bicyclic or polycyclic aromatic system preferably having 6 to 14, in particular 6 to 10, ring carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, preferably phenyl. Aryl also represents polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, where the binding site is on the aromatic system.

[0244] Examples of substituted aryl are arylalkyl, which may likewise be C1-C4-alkyl and / or C6-C 14 - The aryl moiety is substituted with one or more identical or different groups. Examples of such arylalkyl groups include benzyl and 1-phenylethyl.

[0245] Unless otherwise defined, "heterocycle", "heterocyclic ring" or "heterocyclic ring system" represents a carbocyclic ring system having at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably by a heteroatom selected from N, O, S, P, B, Si, Se, and which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted, with the bonding site being on a ring atom. Unless otherwise defined, the heterocycle preferably comprises 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and contains one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms preferably selected from N, O and S, but no two oxygen atoms should be directly adjacent. The heterocycle generally contains no more than 4 nitrogen atoms and / or no more than 2 oxygen atoms and / or no more than 2 sulphur atoms. If the heterocyclic group or heterocycle is optionally substituted, it may be fused to other carbocyclic or heterocyclic rings. In the case of optionally substituted heterocyclyl, the present invention also includes polycyclic systems, for example 8-azabicyclo[3.2.1]octyl or 1-azabicyclo[2.2.1]heptyl. In the case of optionally substituted heterocyclyl, the present invention also includes spirocyclic systems, for example 1-oxa-5-azaspiro[2.3]hexyl.

[0246] The heterocyclic group of the present invention is, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolanyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, oxiranyl, azetidinyl, oxadiazol ... substituted oxazolidinyl, oxazolidinyl, oxazolidinyl, oxazepanyl, oxazinanyl, azepanyl, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorpholinyl, oxopiperazinyl, and oxepanyl.

[0247] The term "optionally substituted" groups / substituents, such as substituted alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl groups, means, for example, substituted groups derived from an unsubstituted base structure, wherein the substituents are, for example, one (1) substituent or a plurality of substituents, preferably 1, 2, 3, 4, 5, 6 or 7 substituents selected from the group consisting of amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyano, C1-C4-carboxyl, carbonyl, SF5, amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyano, C1-C4-carboxyl, carbonyl, SF5, amino Sulfonyl, C1-C4-alkyl, C3-C4-cycloalkyl, C2-C4-alkenyl, C5-C6-cycloalkenyl, C2-C4-alkynyl, N-mono-C1-C4-alkylamino, N,N-di-C1-C4-alkylamino, N-C1-C4-alkanoylamino, C1-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C3-C4-cycloalkyloxy, C5-C6-cycloalkenyloxy, C1-C4-alkoxycarbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, C6-aryloxycarbonyl, C 10 -aryloxycarbonyl, C 14 -aryloxycarbonyl, C1-C4-alkanoyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl, C6-arylcarbonyl, C 10 -Arylcarbonyl, C 14 -arylcarbonyl, C1-C4-alkylthio, C3-C4-cycloalkylthio, C1-C4-alkylthio, C2-C4-alkenylthio, C5-C6-cycloalkenylthio, C2-C4-alkynylthio, C1-C4-alkylthio (C1-C4-alkylsulfenyl) and C1-C4-alkylsulfinyl (including two enantiomers of C1-C4-alkylsulfinyl), C1-C4-alkylsulfonyl, N-mono-C1-C4-alkylaminosulfonyl, N,N-di-C1-C4-alkylaminosulfonyl, C1-C C1-C4-alkylphosphinyl, C1-C4-alkylphosphinyl (wherein both enantiomers are included for C1-C4-alkylphosphinyl and C1-C4-alkylphosphinyl), N-C1-C4-alkylaminocarbonyl, N,N-di-C1-C4-alkylaminocarbonyl, N-C1-C4-alkanoylaminocarbonyl, N-C1-C4-alkanoyl-N-C1-C4-alkylaminocarbonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl, C6-aryl, C 10 -aryl, C 14 -aryl, C6-aryloxy, C 10 -aryloxy, C 14 -aryloxy, benzyl, benzyloxy, benzylthio, C6-arylthio, C10 -arylthio, C 14 -arylthio, C6-arylamino, C 10 -Arylamino, C 14 - arylamino, benzylamino, heterocyclic and trialkylsilyl groups, substituents linked via a double bond, such as C1-C4-alkylene (e.g. methylene or ethylene), oxo, imino and substituted imino groups. If two or more groups form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, and may also be aromatic and further substituted.

[0248] The substituents mentioned by way of example ("first substituent level"), if they contain a hydrocarbon-containing moiety, optionally have further substitutions therein ("second substituent level"), for example by one or more substituents each independently selected from the group consisting of halogen, hydroxy, amino, nitro, cyano, isocyano, azido, amide, oxo and imino. The term "optionally substituted" group preferably contains exactly one or two substituent levels.

[0249] Unless otherwise defined, the chemical group (for example, alkyl, cycloalkyl or alkoxy) that halogen replaces is halogen monosubstituted or polysubstituted, up to maximum possible substituent number.This class group is also referred to as halogen group (for example, haloalkyl).When being polysubstituted by halogen, halogen atom can be identical or different, and can all be bonded on a carbon atom or can all be bonded on a plurality of carbon atoms.In this article, halogen represents fluorine, chlorine, bromine or iodine especially, preferably fluorine, chlorine or bromine and more preferably fluorine. More specifically, the halogen substituent is a monohalocycloalkyl such as 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl; a monohaloalkyl such as 2-chloroethyl, 2-fluoroethyl, 1-chloroethyl, 1-fluoroethyl, chloromethyl or fluoromethyl; a perhaloalkyl such as trichloromethyl or trifluoromethyl or CF2CF3; a polyhaloalkyl such as difluoromethyl, 2-fluoro-2-chloroethyl, dichloromethyl, 1,1,2,2-tetrafluoroethyl or 2,2,2-trifluoroethyl. Other examples of haloalkyl are trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl and pentafluoro-tert-butyl. Preference is given to haloalkyl groups having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5, identical or different, halogen atoms selected from fluorine, chlorine and bromine. Particular preference is given to haloalkyl groups having 1 or 2 carbon atoms and 1 to 5, identical or different, halogen atoms selected from fluorine and chlorine, such as, in particular, difluoromethyl, trifluoromethyl or 2,2-difluoroethyl.Other examples of compounds substituted with halogen are haloalkoxy such as OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3, OCH2CHF2 and OCH2CH2Cl; haloalkylthio such as difluoromethylthio, trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 1,1,2-tetra ...methylthio, 1,1,2-tetrafluoroethylthio, 1,1,2-tetrafluoroethylthio, fluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl or 2-chloro-1,1,2-trifluoroethylsulfinyl; haloalkylsulfinyl such as difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoro ethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl; haloalkylsulfinyl groups such as difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl; haloalkylsulfonyl such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoroethylsulfonyl.

[0250] Unless otherwise defined, groups having carbon atoms are preferably those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Substituents selected from the group consisting of halogen, such as fluorine and chlorine, (C1-C4)alkyl, preferably methyl or ethyl, (C1-C4)haloalkyl, preferably trifluoromethyl, (C1-C4)alkoxy, preferably methoxy or ethoxy, (C1-C4)haloalkoxy, nitro and cyano are generally preferred. The following substituents are particularly preferred: methyl, methoxy, fluorine and chlorine.

[0251] Unless defined differently, substituted amino, such as mono- or disubstituted amino, is a substituted amino group selected from the group consisting of amino groups, i.e., the amino group is N-substituted, for example, by one or two identical or different groups selected from the group consisting of alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably N-monoalkylamino and N,N-dialkylamino (such as methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino, N,N-di-n-propylamino, N,N-diisopropylamino or N,N-dibutylamino), N-monoalkoxyalkylamino or N,N-di- Alkoxyalkylamino groups (such as N-methoxymethylamino, N-methoxyethylamino, N,N-di(methoxymethyl)amino or N,N-di(methoxyethyl)amino), N-monoarylamino and N,N-diarylamino groups, such as optionally substituted aniline, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; preferably alkyl groups having 1 to 4 carbon atoms; aryl is preferably phenyl or substituted phenyl; acyl is as further defined below, preferably (C1-C4)alkanoyl. The same applies to substituted hydroxyamino or hydrazino groups.

[0252] Substituted amino groups also include quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.

[0253] Unless defined differently, optionally substituted phenyl is preferably unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, cyano, isocyano and nitro, For example, o-tolyl, m-tolyl and p-tolyl, dimethylphenyl, 2-chlorophenyl, 3-chlorophenyl and 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl and 4-fluorophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl and 4-trifluoromethylphenyl and 2-trichloromethylphenyl, 3-trichloromethylphenyl and 4-trichloromethylphenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, 2,5-dichlorophenyl and 2,3-dichlorophenyl, o-methoxyphenyl, m-methoxyphenyl and p-methoxyphenyl, 4-heptafluorophenyl.

[0254] Unless defined differently, optionally substituted cycloalkyl is preferably unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-haloalkoxy, in particular by 1 or 2 C1-C4-alkyl radicals.

[0255] The compounds of the present invention may be present in preferred embodiments. The various embodiments described herein may be combined with one another. Combinations that violate the laws of nature and combinations that a person skilled in the art would exclude based on their expertise are excluded. For example, ring structures having three or more adjacent oxygen atoms are excluded.

[0256] Isomers

[0257] Depending on the nature of the substituents, the compounds of formula (I) may be in the form of geometrical isomers and / or optically active isomers or corresponding isomer mixtures of varying compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometrical isomers. The present invention therefore encompasses both the pure stereoisomers and any desired mixtures of these isomers.

[0258] Methods and uses

[0259] The present invention also relates to a method for controlling animal pests, wherein a compound of formula (I) is allowed to act on the animal pests and / or their habitat. The control of animal pests is preferably carried out in agriculture and forestry, as well as in the protection of materials. This preferably excludes methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body.

[0260] The present invention also relates to the use of the compounds of formula (I) as pesticides, in particular as crop protection compositions.

[0261] In the context of the present application, the term "pesticide" always also includes in each case the term "crop protection composition".

[0262] The compounds of the formula (I) are suitable, due to their good plant tolerance, favorable homeothermic animal toxicity and good environmental compatibility, for the protection of plants and plant organs against biotic and abiotic stress factors, for increasing harvest yields, for improving the quality of harvested products and for combating animal pests, in particular insects, arachnids, helminths, in particular nematodes and molluscs, encountered in agriculture, horticulture, animal husbandry, aquaculture, forestry, gardening and leisure facilities, for the protection of stored products and materials and for hygiene.

[0263] In the context of this patent application, the term "hygiene" is to be understood as meaning any and all measures, methods and processes intended to prevent diseases, in particular infectious diseases, and to protect human and animal health and / or the environment and / or maintain cleanliness. According to the present invention, this particularly includes measures for cleaning, disinfecting and sterilizing surfaces such as textiles or hard surfaces, in particular surfaces made of glass, wood, cement, porcelain, ceramics, plastic or metal, in order to ensure that they are free from hygiene pests and / or their secretions. In this respect, the scope of protection of the present invention preferably excludes surgical or therapeutic treatment methods for the human or animal body, as well as diagnostic methods performed on the human or animal body.

[0264] The term "hygiene sector" includes all areas, technical fields and industrial applications in which these hygiene measures, methods and processes are important, for example hygiene in kitchens, bakeries, airports, bathrooms, swimming pools, department stores, hotels, hospitals, stables, animal husbandry, etc.

[0265] The term "hygiene pest" is therefore understood to mean one or more animal pests whose presence in the hygiene sector is problematic, particularly for health reasons. Therefore, a primary objective is to prevent the presence of hygiene pests and / or to minimize exposure to these pests in the hygiene sector. This can be achieved, in particular, by using pesticides that can be used to prevent both infection and existing infections. Formulations that prevent or reduce exposure to pests can also be used. Examples of hygiene pests include the organisms mentioned below.

[0266] The term "hygienic protection" therefore covers all actions that maintain and / or improve these hygiene measures, precautions and methods.

[0267] The compounds of formula (I) can preferably be used as pesticides. They are active against normally sensitive and resistant species and against all or specific stages of development. The above-mentioned pests include:

[0268] Pests from the phylum Arthropoda, in particular from the class Arachnida, for example Acarus siro (for example Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp., Aculus spp. (for example Aculus fockeui, Aculus schlechtendali), Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp. (for example Brevipalpus phoenicis), Bryobia graminum), Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp. (e.g., Eotetranychus shicoriae), Epitrimerus pyri, Eutetranychus spp. (e.g., Eutetranychus banksi), Eriophyes spp. (e.g., Eriophyes pyri), Glycyphagus domesticus), Halotydeus destructor, Hemitarsonemus spp. (e.g. Hemitarsonemus latus (= Polyphagotarsonemus latus)), Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp.), Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp. (e.g., Oligonychus coffeae, Oligonychus coniferarum, Oligonychus ilicis, Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus syothersi), Ornithodorus spp., Ornithonyssus spp., Panonychus spp. (e.g., Panonychus citri (=Metatetranychus citri)), Panonychus spp. ulmi (= Metatetranychus ulmi), citrus rust mite (Phyllocoptruta oleivora), Platytetranychus multidigituli, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpiomaurus, Stenotarsonemus spp., Stenotarsonemus spinki, Tarsonemus spp. (e.g., Tarsonemus confusus, Tarsonemus pallidus), Tetranychus spp.(e.g., Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae), Trombicula alfreddugesi, Vaejovis spp., and Vasates lycopersici;

[0269] Pests of the class Chilopoda, for example, Geophilus spp. and Scutigera spp.;

[0270] Pests of the order Collembola or class Collembola, for example, Onychiurus armatus; Sminthurus viridis;

[0271] Pests of the class Diplopoda, for example, millipede (Blaniulus guttulatus);

[0272] Pests of the class Insecta, for example, the order Blattodea, such as Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophaea maderae, Loboptera decipiens, Neostylopygarhombifolia, Panchlora spp., Parcoblatta spp., Periplaneta spp. (e.g., Periplaneta americana, Periplaneta australasiae), Pycnoscelus surinamensis, and Supella longipalpa;

[0273] Pests of the order Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethinatumida, Agelastica alni, Agrilus spp., for example (Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus, Agrilus anxius), Agriotes spp. (for example, Agriotes linneatus, Agriotes mancus), Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp.) (e.g., Anoplophora glabripennis), Anthonomus spp. (e.g., Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp. (e.g., Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (e.g., Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata), Ceuthorhynchus spp. (e.g., Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp.(e.g., sweet potato flea beetle (Chaetocnema confinis), American tooth flea beetle (Chaetocnema denticulata), wasteland corn flea beetle (Chaetocnema ectypa)), Cleonus mendicus, Conoderus spp., Cosmopolites spp. (e.g., banana root-necked weevil (Cosmopolites sordidus)), Costelytra zealandica, Ctenicera spp., Curculio spp. (e.g., American walnut weevil (Curculio caryae), large chestnut weevil (Curculio caryatrypes), American hazelnut weevil (Curculio obtusus), small chestnut weevil (Curculio sayi)), Cryptolestes ferrugineus, long-horned corn weevil (Cryptolestes ferrugineus), long-horned corn weevil (Cryptolestes pusillus), Cryptorhynchus lapathi, Cryptorhynchus mangiferae, Cylindrocopturus spp., Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dendroctonus spp. (e.g., Dendroctonus ponderosae), Dermestes spp., Diabrotica spp. (e.g., Diabrotica balteata, Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, Diabrotica spp. (e.g., Diabrotica balteata), ... spp. (e.g., Diabrotica balteata), Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, Diabrotica spp. (e.g., Diabrotica balteata), Diabrotica spp. (e.g., Diabrotica balteata), Diabrotica spp. (e.g., Diabrotica balteata), Diabrotica spp. (e.g., Diabrotica balteata), Diabrotica barberi, virgifera virgifera), Mexican corn root beetle (Diabrotica virgifera zeae), wild borer (Dichocrocis spp.), rice ironclad (Dicladispa armigera), Diloboderus spp., Epicaerus spp., plant-feeding ladybugs (Epilachna spp.(e.g. Epilachna borealis, Epilachna varivestis), Epitrix spp. (e.g. Epitrix cucumeris, Epitrix fuscula, Epitrix hirtipennis, Epitrix subcrinita, Epitrix tuberis), Faustinus spp., Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychusarator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica), Hypomeces squamosus, Hypothenemus spp. (e.g., Hypothenemus hampei, Hypothenemus obscurus, Hypothenemus pubescens), Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa ​​decemlineata, Leucoptera spp. (e.g., Leucoptera coffiella), Limonius ectypus, Lissorhoptrus spp. oryzophilus), Listronotus (=Hyperodes) spp., Lixus spp., Luperodes spp., Luperomorphaxanthodera, Lyctus spp., Megacyllene spp. (e.g. Megacyllene robiniae), Megascelis spp., Melanotus spp.) (e.g. Melanotus longulusoregonensis), Meligethes aeneus, Melolontha spp. (e.g. Melolontha melolontha), Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Neogalerucella spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp. (e.g. Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus), Otiorhynchus rugosostriarus, Otiorhynchus sulcatus), Oulema spp. (e.g., Oulemamelanopus, Oulema oryzae), Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllophagahelleri, Phyllotreta spp. (e.g., Phyllotreta armoraciae, Phyllotreta pusilla, Phyllotreta ramosa, Phyllotreta striolata), Popillia spp. japonica), Premnotrypes spp., Prostephanus truncatus, Psylliodes spp. (e.g., Psylliodes affinis, Psylliodes chrysocephala, Psylliodes punctulata), Ptinus spp.), Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum, Scolytus spp. (e.g. Scolytus multistriatus), Sinoxylon perforans, Sitophilus spp. (e.g. Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais), Sphenophorus spp., Stegobium paniceum, Sternechus spp.) (e.g., Sternechus paludatus), Symphyletes spp., Tanymecus spp. (e.g., Tanymecus dilaticollis, Tanymecus indicus, Tanymecus palliatus), Tenebrio molitor, Tenebrio des mauretanicus, Tribolium spp. (e.g., Tribolium audax, Tribolium castaneum, Tribolium confusum), Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp. (e.g., Zabrus spp. tenebrioides));.

[0274] Pests of the order Dermaptera, for example, Anisolabis maritime, Forficula auricularia, Labidura riparia;

[0275] Pests of the order Diptera, for example, Aedes spp. (e.g., Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans), Agromyza spp. (e.g., Agromyza frontella, Agromyza parvicornis), Anastrepha spp., Anopheles spp. (e.g., Anopheles quadrimaculatus, Anopheles gambiae), Asphondylia spp., Bactrocera spp. (e.g., Bactrocera cucurbitae, Bactrocera orientalis), dorsalis, Bactrocera oleae), Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomya spp., Chrysops spp., Chrysozona pluvialis, Cochliomya spp., Contarinia spp. (e.g., Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia sorghum) sorghicola), Contarinia tritici), Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp. (e.g., Culex pipiens, Culex quinquefasciatus), Culicoides spp., Culiseta spp.), Cuterebra spp., Dacus oleae, Dasineura spp. (e.g., Dasineura brassicae), Delia spp. (e.g., Delia antiqua, Delia coarctata, Delia florilega, Delia platura, Delia radicum), Dermatobia hominis, Drosophila spp. (e.g., Drosphila melanogaster, Drosophila suzukii), Echinocnemus spp., Euleia heraclei, Fannia spp., Gastrophilus spp., Glossina spp.), Haematopota spp., Hydrellia spp., Hydrellia griseola, Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp. (e.g., Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae), Lucilia spp. (e.g., Lucilia cuprina), Lutzomyia spp., Mansonia spp., Musca spp. (e.g., Musca domestica, Musca domestica vicina), Oestrus spp.), Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomya or Pegomyia spp.) (e.g., Pegomya betae, Pegomya hyoscyami, Pegomya rubivora), Phlebotomus spp., Phorbia spp., Phormia spp., Piophila casei, Platyparea poeciloptera, Prodiplosis spp., Psila rosae, Rhagoletis spp. (e.g., Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax, Rhagoletis pomonella), Sarcophaga spp. spp.), Simulium spp. (e.g., Simulium meridionale), Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp. (e.g., Tipula paludosa, Tipula simplex), Toxotrypana curvicauda;

[0276] Pests of the order Hemiptera, for example, Acizzia acaciaebaileyanae, Acizziadodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. (for example, Acyrthosiphon pisum), Acrogonia spp., Aeneolamia spp., Agonascena spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (for example, Amrasca bigutulla, Amrasca devastans), Anuraphis cardui, Aonidiella spp. (e.g., Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp. (e.g., Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis sillinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii, Aphis apple aphid (Aphis nerii), Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis sillinoisensis, Aphis middletoni, Aphis nasturtii, Aphis ner ... pomi), leaf roller aphids (Aphis spiraecola), Aphis viburniphila), grape sawfly (Arboridia apicalis), Arytainilla spp., Aspidiella spp., Aspidiotus spp.) (e.g., Aspidiotus nerii), Atanus spp., Aulacorthum solani, Bemisia tabaci, Blatopsylla occidentalis, Boreoglycaspis melaleucae, Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp. (e.g., Cacopsylla pyricola), Calligypona marginata, Capulinia spp., Carneocephala fulgida, Ceratovacuna laniger, Cercopidae, Ceroplastes spp.), Strawberry Aphid (Chaetosiphon fragaefolii), Sugarcane Snow Shield Scale (Chionaspis tegalensis), Tea Green Sawfly (Chlorita onukii), Taiwan Locust (Chondracris rosea), Walnut Black Spot Aphid (Chromaphis juglandicola), Black Brown Round Shield Scale (Chrysomphalus aonidum), Black Brown Round Shield Scale (Chrysomphalus ficus), Corn Leafhopper (Cicadulinambila), Coccomytilus halli, Coccus spp. (e.g., Brown Soft Scale (Coccus hesperidum), Long Oval Soft Scale (Coccus longulus), Orange Soft Wax Scale (Coccus pseudomagnoliarum), Coffee Green Scale (Coccus viridis)), Cryptomyzus ribis, Cryptonossa spp., Ctenarytaina spp. spp.), Dalbulus spp., Dialeurodes chittendeni, Dialeurodes citri, Diaphorina citri, Diaspis spp., Diuraphis spp., Doralis spp., Drosicha spp., Dysaphis spp.) (e.g., Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae), Dysmicoccus spp., Empoasca spp. (e.g., Empoasca abrupta, Empoasca fabae, Empoasca maligna, Empoasca solana, Empoasca stevensi), Eriosoma spp. (e.g., Eriosoma americanum, Eriosomalanigerum, Eriosoma pyricola), Erythroneura spp., Eucalyptolyma spp., Euphyllura spp.), Euscelis bilobatus, Ferrisia spp., Fiorinia spp., Furcaspis oceanica, Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Hyalopterus pruni, Icerya spp. (e.g., Icerya purchasi), Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp. (e.g., Lecanium corni) (= Parthenolecanium corni), Lepidosaphes spp. (e.g., Lepidosaphes ulmi), Lipaphis erysimi, Lopholeucaspis japonica, Lycorma delicatula, Macrosiphum spp.) (e.g., potato aphid (Macrosiphum euphorbiae), lily aphid (Macrosiphum lilii), rose aphid (Macrosiphum rosae)), two-spotted sawfly (Macrosteles facifrons), Mahanarva spp., sorghum aphid (Melanaphis sacchari), Metcalfiella spp., Metcalfa pruinosa, Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp. (e.g., onion aphid (Myzus ascalonicus), plum aphid (Myzus cerasi), privet aphid (Myzus ligustri), violet aphid (Myzus ornatus), peach aphid (Myzus persicae), tobacco aphid (Myzus nicotianae), lettuce aphid (Nasonovia ribis nigri), Neomaskellia spp., Nephotettix spp. (e.g., Nephotettix cincticeps, Nephotettix nigropictus), Nettigoniclla spectra, brown planthopper (Nilaparvata lugens), Oncometopia spp., Orthezia praelonga, Chinese rice locust (Oxya chinensis), Pachypsylla spp., bayberry whitefly (Parabemisia myricae), Paratrioza spp. (e.g., Paratrioza cockerelli), Parlatoria spp., Pemphigus spp. (e.g., Pemphigus spp. bursarius), Pemphigus populivenae), Corn waxhopper (Peregrinus maidis), Perkinsiella spp., Phenacoccus spp. (e.g., Phenacoccus madeirensis), Yangping winged aphid (Phloeomyzus passerinii), Hubu wart aphid (Phorodon humuli), Grape phylloxera spp.) (e.g., Phylloxera devastatrix, Phylloxera notabilis), Pinnaspis aspidistrae, Planococcus spp. (e.g., Planococcus citri), Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp. (e.g., Pseudococcus calceolariae, Pseudococcus comstocki, Pseudococcus longispinus, Pseudococcus maritimus, Pseudococcus truncatus ... viburni), Psyllopsis spp., Psylla spp. (e.g., Psylla buxi, Psylla mali, Psylla pyri), Pteromalus spp., Pulvinaria spp., Pyrilla spp., Quadraspidiotus spp. (e.g., Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus), Quesada gigas, Rastrococcus spp., Rhopalosiphum spp. (e.g., Rhopalosiphum maidis, Rhopalosiphum oxyacanthae), rice and wheat aphids (Rhopalosiphum padi), red-bellied constriction aphids (Rhopalosiphum rufiabdominale), black-helmeted scales (Saissetia spp.) (e.g., coffee black-helmeted scale (Saissetia coffeae), Saissetia miranda, Saissetia neglecta, black wax scale (Saissetiaoleae)), grape leafhopper (Scaphoideus titanus), wheat aphid (Schizaphis graminum), cycad thorn scale (Selenaspidus articulatus), Sipha flava, wheat aphid (Sitobion avenae), long-lipped planthopper (Sogata spp.), white-backed planthopper (Sogatella furcifera), rice flyhopper (Sogatodes spp.), Stictocephala festina, tree whitefly (Siphoninus phillyreae), Tenalaphara malayensis, Tetragonocephela spp., long-spotted aphid (Tinocallis caryaefoliae), broad-breasted hopper (Tomaspis spp.), sonic aphid (Toxoptera spp.) (e.g., Toxoptera aurantii, Toxoptera citricidus), Trialeurodes vaporariorum, Trioza spp. (e.g., Trioza diospyri), Typhlocyba spp., Unaspis spp., Viteus vitifolii, and Zygina spp.;

[0277] Pests of the suborder Heteroptera, for example, Aelia spp., Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (for example, Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp. (e.g., Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius), Eurydemas spp., Eurygaster spp., Halyomorpha halys, Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis, Leptoglossus occidentalis), Leptoglossus phyllopus, Lygocoris spp. (e.g. Lygocoris pabulinus), Lygus spp. (e.g. Lygus elisus, Lygus hesperus, Lygus lineolaris), Macropes excavatus, Megacopta cribraria, Miridae, Monalonion atratum, Nezara spp.(e.g., green rice stink bug (Nezaraviridula)), Nysius spp., Oebalus spp., Pentomidae, Piesmaquadrata, Piezodorus spp. (e.g., Piezodorus guildinii), Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.;

[0278] Pests of the order Hymenoptera, for example, Acromyrmex spp., Athalia spp. (e.g., Athalia rosae), Atta spp., Camponotus spp., Dolichovespula spp., Diprion spp. (e.g., Diprion similis), Hoplocampa spp. (e.g., Hoplocampa cookei, Hoplocampa testudinea), Lasius spp., Linepithema (Iridiomyrmex) humile, Monomorium pharaonis, Paratrechina spp., Paravespula spp., Plagiolepis spp., Sirex spp.) (e.g., Sirex noctilio), Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa spp. (e.g., Vespa crabro), Wasmannia auropunctata, Xeris spp.);

[0279] Pests of the order Isopoda, for example, Armadillidium vulgare, Oniscusasellus, Porcellio scaber;

[0280] Pests of the order Isoptera, for example, Coptotermes spp. (e.g., Coptotermes formosanus), Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Kalotermes spp., Microtermes obesi, Nasutitermes spp., Odontotermes spp., Porotermes spp., Reticulitermes spp. (e.g., Reticulitermes flavipes, Reticulitermes hesperus);

[0281] Pests of the order Lepidoptera, for example, Achroia grisella, Acronicta major, Adoxophyes spp. (e.g., Adoxophyesorana), Aedia leucomelas, Agrotis spp. (e.g., Agrotissegetum, Agrotis ipsilon), Alabama spp. (e.g., Alabama argillacea), Amyelois transitella, Anarsia spp., Anticarsia spp. (e.g., Anticarsia gemmatalis), Argyroploce spp., Autographa spp.), Barathrabrassicae, Blastodacna atra, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capuareticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp. (e.g., Chilo plejadellus, Chilo suppressalis), Choreutis pariana, Choristoneura spp., Chrysodeixis chalcites, Clysia ambiguella), Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp.) (e.g., Cydia nigricana, Cydia pomonella), Dalaca noctuides, Diaphania spp., Diparopsis spp., Diatraea saccharalis, Dioryctria spp. (e.g., Dioryctriazimmermani), Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp. (e.g., Ephestia elutella, Ephestia kuehniella), Epinotia spp., Epiphyas postvittana), Erannis spp., Erschoviella musculana (Asian walnut moth), Etiella spp., Eudocima spp., Eulia spp., Eupocilia ambiguella, Euproctis spp. (e.g., Euproctis chrysorrhoea), Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp. (e.g., Grapholita molesta, Grapholita prunivora), Hedylepta spp., Helicoverpa spp.) (e.g., Helicoverpa armigera, Helicoverpa zea), Heliothis spp. (e.g., Heliothis virescens), Hofmannophila pseudospretella, Homoeosoma spp., Homona spp.), apple moth (Hyponomeuta padella), persimmon moth (Kakivoria flavofasciata), Lampides spp., Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp. (e.g., Leucoptera coffeella), Lithocolletis spp. (e.g., Lithocolletis blancardella), green fruit armyworm (Lithophane antennata), Lobesia spp. (e.g., Lobesia botrana), bean rootworm (Loxagrotis albicosta), Lymantria spp. (e.g., Lymantria dispar (Lymantria spp.) dispar), Lyonetia spp. (e.g., Lyonetia clerkella), Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Omphisa spp., Operophtera spp., Oria spp., Orthaga spp., Ostrinia spp. (e.g., Ostrinia nubilalis), Panolis flammea), Parnara spp., Pectinophora spp. (e.g., Pectinophora gossypiella), Perileucoptera spp., Phthorimaea spp.) (e.g. potato moth (Phthorimaea operculella)), citrus leafminer (Phyllocnistis citrella), Phyllonorycter spp. (e.g. Phyllonorycter blancardella, Phyllonorycter crataegella), Pieris spp. (e.g. Pieris rapae), Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella (=Plutella maculipennis), Podesia spp. (e.g. Podesia syringae), Prays spp., Prodenia spp., Protoparce spp.), Pseudaletia spp. (e.g., Pseudaletia unipuncta), Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp. (e.g., Schoenobius bipunctifer), Scirpophaga spp. (e.g., Scirpophaga innotata), Scotia segetum, Sesamia spp. (e.g., Sesamia inferens), Sparganothis spp., Spodoptera spp. (e.g., Spodoptera radiana, Spodoptera exigua, Spodoptera frugiperda), Spodoptera spp. (e.g., Spodoptera radiana, Spodoptera exigua, Spodoptera spp. frugiperda), Spodoptera praefica), Stathmopoda spp., Stenoma spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thaumetopoea spp.), soybean armyworm (Thermesiagemmatalis), cork moth (Tinea cloacella), bag moth (Tinea pellionella), curtain moth (Tineola bisselliella), Tortrix spp., felt moth (Trichophaga tapetzella), Trichoplusia spp. (e.g., Trichoplusia ni), yellow-stem borer (Tryporyza incertulas), tomato leafminer (Tuta absoluta), and Virachola spp.;

[0282] Pests of the order Orthoptera or Saltatoria, for example, house crickets (Acheta domesticus), Dichroplus spp., Gryllotalpa spp. (for example Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (for example Locusta migratoria), Melanoplus spp. (for example Melanoplus devastator, Paratlanticus ussuriensis), desert locust (Schistocerca gregaria);

[0283] Pests of the order Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Ptirus pubis, Trichodectes spp.;

[0284] Pests of the order Psocoptera, for example, Lepinatus spp., Liposcelis spp.;

[0285] Pests of the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. (for example Ctenocephalides canis, Ctenocephalides felis), Pulex irritans, Tunga penetrans, Xenopsylla cheopis;

[0286] Pests of the order Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp. (for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi), Haplothrips spp., Heliothrips spp.), greenhouse hedge thrips (Hercinothrips femoralis), card thrips (Kakothrips spp.), grape thrips (Rhipiphorothrips cruentatus), Scirtothrips spp., cardamom thrips (Taeniothrips cardamomi), Thrips spp. (e.g., palm thrips (Thrips palmi), tobacco thrips (Thrips tabaci));

[0287] Pests of the order Zygentoma (=suborder Thysanura), for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica;

[0288] Pests of the class Symphyla, for example, Scutigerella spp. (for example Scutigerella immaculata);

[0289] Pests of the phylum Mollusca, for example, pests of the class Bivalvia, such as Dreissena spp.,

[0290] and pests of the class Gastropoda, such as Arion spp. (e.g. Arion ater rufus), Biomphalaria spp., Bulinus spp., Deroceras spp. (e.g. Deroceras laeve), Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., and Succinea spp.;

[0291] Plant pests of the class Nematoda, i.e. plant-parasitic nematodes, in particular Aglenchus spp. (e.g. Aglenchus agricola), Anguinas spp. (e.g. Anguina tritici), Aphelenchoides spp. (e.g. Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (e.g. Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (e.g. Bursaphelenchus spp. cocophilus), Bursaphelenchus eremus, Bursaphelenchus xylophilus), Cacopaurus spp. (e.g. Cacopaurus pestis), Criconemella spp. (e.g. Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconema xenoplax), Criconemoides spp. (e.g. Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum), Ditylenchus spp. (e.g., Ditylenchus dipsaci), Dolichodorus spp., Globodera spp.) (e.g., Globodera pallida, Globodera rostochiensis), Helicotylenchus spp. (e.g., Helicotylenchus dihystera), Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp. (e.g., Heterodera avenae, Heterodera glycines, Heteroderaschachtii), Hirschmaniella spp., Hoplolaimus spp., Longidorus spp. (e.g., Longidorus africanus), Meloidogyne spp.) (e.g., Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita), Meloinema spp., Nacobbus spp., Neotylenchus spp., Paralongidorus spp., Paraphelenchus spp., Paratrichodorus spp. (e.g., Paratrichodorus minor), Paratylenchus spp., Pratylenchus spp. (e.g., Pratylenchus penetrans penetrans), Pseudohalenchus spp., Psilenchus spp., Punctodera spp., Quinisulcius spp., Radopholus spp. (e.g., Radopholus citrophilus, Radopholus similis), Rotylenchulus spp.), Rotylenchus spp., Scutellonema spp., Subanguina spp., Trichodorus spp. (e.g., Trichodorus obtusus, Trichodorus primitivus), Tylenchorhynchus spp. (e.g., Tylenchorhynchus annulatus), Tylenchulus spp. (e.g., Tylenchulus semipenetrans), Xiphinema spp. (e.g., Xiphinema index).

[0292] Depending on the specific case, at certain concentrations or application rates, the compounds of formula (I) can also be used as herbicides, safeners, growth regulators or agents for improving plant properties, as microbicides or gametocides, for example as fungicides, antifungals, bactericides, viricides (including agents against viroids) or as agents against MLOs (mycoplasma-like organisms) and RLOs (rickettsia-like organisms). Optionally, they can also be used as intermediates or precursors for the synthesis of other active compounds.

[0293] preparation

[0294] The invention also relates to formulations comprising at least one compound of formula (I) and application forms prepared therefrom as pesticides, such as pourings, drips and spraying liquids. Optionally, the application forms contain other pesticides and / or adjuvants to improve the effect, such as penetrants, such as vegetable oils (such as rapeseed oil, sunflower oil), mineral oils (such as paraffin oil), alkyl esters of vegetable fatty acids (such as rapeseed oil methyl ester or soybean oil methyl ester), or alkanol alkoxylates; and / or spreaders, such as alkylsiloxanes and / or salts (such as organic or inorganic ammonium salts or phosphonium salts, such as ammonium sulfate or diammonium hydrogen phosphate); and / or retention promoters, such as dioctyl sulfosuccinate or hydroxypropyl guar polymers; and / or wetting agents, such as glycerol; and / or fertilizers, such as ammonium-, potassium- or phosphorus-containing fertilizers.

[0295] Conventional formulations include, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS); these formulations and other possible formulation types are described, for example, by Crop Life International and in the following documents: "Pesticide Standards", "Manual on the Establishment and Use of Pesticide Standards by the Food and Agriculture Organization of the United Nations (FAO) and the World Health Organization (WHO)," and "Food and Agriculture Organization of the United Nations (FAO) Plant Production and Protection Document-173 (prepared by the Joint Meeting on Pesticide Specifications of the Food and Agriculture Organization of the United Nations (FAO) / World Health Organization (WHO), 2004, ISBN: 9251048576). In addition to one or more compounds of formula (I), the formulations optionally contain other agrochemically active compounds.

[0296] Preferred are formulations or application forms comprising at least one auxiliary agent, such as an extender, solvent, spontaneity promoter, carrier, emulsifier, dispersant, antifreeze agent, biocide, thickener, and / or other auxiliary agents, such as adjuvants. In the context of the present invention, an adjuvant is a component that enhances the biological efficacy of a formulation without having any biological efficacy itself. Examples of adjuvants are agents that promote retention, spreading, adhesion to foliage, or penetration.

[0297] These preparations are prepared in a known manner, for example by mixing a compound of formula (I) with auxiliaries such as extenders, solvents and / or solid carriers and / or other auxiliaries such as surfactants. The preparations are prepared in suitable equipment or before or during application.

[0298] The auxiliaries used may be substances suitable for imparting particular properties, such as certain physical, technical and / or biological properties, to the formulations of the compounds of formula (I) or to the application forms prepared from these formulations, such as ready-to-use pesticides, such as spray liquids or seed dressing products.

[0299] Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, selected, for example, from the group consisting of: aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which, if appropriate, may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).

[0300] If the extender used is water, organic solvents, for example, can also be used as auxiliary solvents. Useful liquid solvents are primarily: aromatic compounds, such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, such as petroleum fractions, mineral oils and vegetable oils; alcohols, such as butanol or ethylene glycol and their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; highly polar solvents, such as dimethylformamide and dimethyl sulfoxide; and water.

[0301] In principle, all suitable solvents can be used. Examples of suitable solvents are: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons such as cyclohexane, paraffins, petroleum fractions, mineral oils and vegetable oils; alcohols such as methanol, ethanol, isopropanol, butanol or ethylene glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents such as dimethyl sulfoxide; and water.

[0302] In principle, all suitable carriers can be used. Suitable carriers include, for example, ammonium salts and finely ground natural rocks, such as kaolin, aluminum oxide, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth; and finely ground synthetic rocks, such as highly dispersed silica, aluminum oxide, and natural or synthetic silicates; resins; waxes; and / or solid fertilizers. Mixtures of these carriers can also be used. Useful carriers for granules include, for example, crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite; and synthetic granules of inorganic and organic powders; as well as granules of organic materials, such as sawdust, paper, coconut shells, corn cobs, and tobacco stalks.

[0303] Liquefied gaseous extenders or solvents can also be used. Particularly suitable extenders or carriers are those which are gaseous at standard temperature and atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide.

[0304] Examples of emulsifiers and / or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surface-active substances are: salts of polyacrylic acid; salts of ligninsulfonic acid; salts of phenolsulfonic acid or naphthalenesulfonic acid; polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols); salts of sulfosuccinates; taurine derivatives (preferably alkyl taurates); phosphoric acid esters of polyethoxylated alcohols or phenols; fatty acid esters of polyols; and derivatives of compounds containing sulfate, sulfonate and phosphate groups, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, protein hydrolysates, ligninsulfite waste liquors and methylcellulose. The presence of a surfactant is advantageous if one of the compounds of formula (I) and / or one of the inert carriers is insoluble in water and if application is carried out in water.

[0305] Other auxiliaries that may be present in the formulations and the application forms obtained therefrom include dyes, for example inorganic pigments such as iron oxide, titanium oxide and Prussian blue; and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes; and nutrients and trace nutrients, such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts and zinc salts.

[0306] Other components that may be present are stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents that improve chemical and / or physical stability. Foam generators and defoamers may also be present.

[0307] In addition, the preparations and the application forms obtained therefrom may also contain the following substances as additional adjuvants: adhesives such as carboxymethylcellulose; and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate; and natural phospholipids such as cephalin and lecithin and synthetic phospholipids. Other adjuvants may be mineral oils and vegetable oils.

[0308] If appropriate, further adjuvants may also be present in the formulations and the use forms derived therefrom. Examples of such additives are fragrances, protective colloids, binders, adhesives, thickeners, thixotropic agents, penetrants, retention promoters, stabilizers, chelating agents, complexing components, wetting agents, spreaders. In general, the compounds of formula (I) can be combined with any solid or liquid additives customary for formulation purposes.

[0309] Useful retention promoters include all those substances which reduce the dynamic surface tension (such as dioctyl sulfosuccinate) or increase the viscoelasticity (such as hydroxypropyl guar polymers).

[0310] In the context of the present invention, useful penetrants are all substances which are usually used to improve the penetration of agrochemical active compounds into plants. In the context of the present invention, a penetrant is defined by its ability to penetrate from the (usually aqueous) application liquid and / or from the spray coating into the cuticle of the plant, thereby increasing the mobility of the active compound in the cuticle. The methods described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include: alcohol alkoxylates, such as coconut fat ethoxylate (10) or isotridecyl ethoxylate (12); fatty acid esters, such as rapeseed oil methyl ester or soybean oil methyl ester; fatty amine alkoxylates, such as tallowamine ethoxylate (15); or ammonium salts and / or phosphonium salts, such as ammonium sulfate or diammonium hydrogen phosphate.

[0311] The formulation preferably comprises from 0.00000001% to 98% by weight of the compound of formula (I), more preferably from 0.01% to 95% by weight of the compound of formula (I), and most preferably from 0.5% to 90% by weight of the compound of formula (I), based on the weight of the formulation.

[0312] In application forms (especially pesticides) prepared from formulations, the content of the compound of formula (I) can vary within a wide range. In the application form, the concentration of the compound of formula (I) can generally be from 0.00000001% to 95% by weight of the compound of formula (I), preferably from 0.00001% to 1% by weight, based on the weight of the application form. Application is carried out in a conventional manner suitable for the application form.

[0313] mixture

[0314] The compounds of formula (I) can also be used in combination with one or more suitable following substances: fungicides, bactericides, acaricides, molluscicides, nematocides, insecticides, microorganisms, beneficial organisms, herbicides, fertilizers, bird repellents, phytotonics, anti-fertilization agents, safeners, chemical semiochemicals and / or plant growth regulators, thereby, for example, broadening the spectrum of action, prolonging the duration of action, increasing the rate of action, preventing repulsion or preventing the development of resistance. In addition, such active compound compositions can improve plant growth and / or tolerance to abiotic factors, such as tolerance to high or low temperatures, to drought or to high water levels or soil salinity. They can also improve flowering and fruiting performance, optimize germination capacity and root development, promote harvesting and increase harvest yield, influence ripening, improve the quality and / or nutritional value of the harvested product, extend the shelf life and / or improve the processability of the harvested product.

[0315] In addition, the compounds of formula (I) can be mixed with other active compounds or semiochemicals such as attractants and / or bird repellents and / or plant activators and / or growth regulators and / or fertilizers. Similarly, the compounds of formula (I) can be used to improve plant performance, such as growth, yield and quality of harvested products.

[0316] In a particular embodiment of the invention, the compounds of the formula (I) are present in a mixture with other compounds, preferably those mentioned below, in the formulations or in the administration forms prepared from these formulations.

[0317] If one of the compounds mentioned below can exist in different tautomeric forms, these are also included, even if not explicitly mentioned in the individual case. If appropriate, all the mixing components mentioned can also form salts with suitable bases or acids if their functional groups are capable of forming salts.

[0318] Insecticides / Acaricides / Nematicides

[0319] The active compounds referred to herein by their common names are known and described, for example, in The Pesticide Manual (16th edition, British Crop Protection Council 2012) or can be retrieved on the internet (e.g. http: / / www.alanwood.net / pesticides). The classification is based on the IRAC mode of action classification scheme applicable at the time of filing this patent application.

[0320] (1) Acetylcholinesterase (AChE) inhibitors, for example, carbamates, for example, alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb ), isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or organophosphates such as acephate, azamethiphos, azinphos-methyl, phos-ethyl), azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chloropyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethoate thoate), dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion,Malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, piriphos miphos-methyl), profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon-methyl, triazophos, triclorfon, and vamidothion.

[0321] (2) GABA-gated chloride channel blockers, such as cyclopentadienyl organochlorides, such as chlordane and endosulfan; or phenylpyrazoles (fiproles), such as ethiprole and fipronil.

[0322] (3) Sodium channel modulators, such as pyrethroids, for example, acrinathrin, allethrin, d-cis-transallethrin, d-transallethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer isomer), bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans isomer] isomers]), deltamethrin, empenthrin [(EZ)-(1R) isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R)-trans isomers],isomer]), prallethrin, pyrethrine (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin ((1R)isomers], tralomethrin, and transfluthrin; or DDT; or methoxychlor.

[0323] (4) Competitive modulators of nicotinic acetylcholine receptors (nAChRs), for example neonicotinoids, such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.

[0324] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, for example, spinosyns, such as spinetoram and spinosad.

[0325] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, for example, avermectins / milbemycins, such as abamectin, emamectin benzoate, lepimectin and milbemectin.

[0326] (7) Juvenile hormone mimetics, for example, juvenile hormone analogs such as hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.

[0327] (8) Other nonspecific (multi-site) inhibitors, for example alkyl halides, such as methyl bromide and other alkyl halides; or chloropicrin or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators, such as diazomet or metam.

[0328] (9) String organ modulators, such as pymetrozine or flonicamide.

[0329] (10) Mite growth inhibitors, for example clofentezine, hexythiazox and diflovidazin or etoxazole.

[0330] (11) Microbial disruptors of insect gut membranes, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and Bt plant proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, VIP3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1 / 35Ab1.

[0331] (12) Inhibitors of mitochondrial ATP synthase, for example ATP disrupters, such as diafenthiuron or organotin compounds, such as azoxatin, cyclotin and fenbutatin oxide, or propargite or tetradifon.

[0332] (13) Uncouplers of oxidative phosphorylation by blocking the proton gradient, such as chlorfenapyr, dinitrocresol (DNOC), and sulfluramid.

[0333] (14) Nicotinic acetylcholine receptor channel blockers, such as bensultap, cartap hydrochloride, thiocyclam and thiosultap-sodium.

[0334] (15) Chitin biosynthesis inhibitors, type 0, for example, bistrifluron, chlofluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

[0335] (16) Chitin biosynthesis inhibitors, type 1, such as buprofezin.

[0336] (17) Molting disruptors (especially for Diptera), for example cyromazine.

[0337] (18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0338] (19) Octopamine receptor agonists, such as amitraz.

[0339] (20) Mitochondrial complex III electron transport inhibitors, such as hydramethylnone, acequinocyl, or fluacrypyrim.

[0340] (21) Mitochondrial complex I electron transport inhibitors, for example, METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad; or rotenone (Derris).

[0341] (22) Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone.

[0342] (23) Inhibitors of acetyl CoA carboxylase, for example, tetronic acid and tetramic acid derivatives, such as spirodiclofen, spiromesifen and spirotetramat.

[0343] (24) Mitochondrial complex IV electron transport inhibitors, for example phosphines, such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanides, such as calcium cyanide, potassium cyanide and sodium cyanide.

[0344] (25) Mitochondrial complex II electron transport inhibitors, such as β-ketonitrile derivatives, for example, cyenopyrafen and cyflumetofen, and formanilides, such as pyflubumide.

[0345] (28) ryanodine receptor modulators, for example diamides, such as chlorantraniliprole, cyantraniliprole and flubendiamide;

[0346] Other active compounds, such as afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, chloroprallethrin, cryolite, cyclaniliprole, cycloxaprid, cyhalodiamide, dicloromezotiaz, dicofol, epsilonmetofluthrin, epsilon momfluthrin, flometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, fluralaner, fluxametamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, kappabifenthrin, kappa tefluthrin), lotilaner, meperfluthrin, paichongding, pyridalyl, pyrifluquinazon, pyriminostrobin, spirobudiclofen, tetramethylfluthrin, tetraniliprole, tetrachlorantraniliprole, tioxazafen, thiofluoximate, triflumezopyrim, and iodomethane; and preparations based on Bacillus firmus (I-1582, BioNeem, Votivo), and the following compound: 1-{2-fluoro-4-methyl-5-[(2,2,2-(trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO2003 / 106457) (CAS 637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP 2647626) (CAS-1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO 2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP2010 / 018586) (CAS Reg. No. 1204776-60-2), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012 / 029672) (CAS 1363400-41-2), (3E)-3-[1-[(6-chloro-3-pyridinyl)methyl]-2-pyridylidene]-1,1,1-trifluoropropan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-[1-[(6-chloro-3-pyridinyl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012 / 029672) (CAS 1363400-41-2), -chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (from WO 2013 / 050317 A1 known) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide, (+)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide and (-)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propionamide (known from WO 2013 / 162715 A2, WO 2013 / 162716 A2, US 2014 / 0213448A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO 2012 / 034403 A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from WO 2011 / 085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-(2-(dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl cyclopropanecarboxylate (known from CN 103524422 A known) (CAS 1542271-46-4); (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (from CN 102391261 A known) (CAS 1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl-1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US 2014 / 0275503 A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethyl)- 1-Azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-trans)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-cis)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (by WO 2007040280A1, WO 2007040282A1) (CAS 934001-66-8), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]propionamide (known from WO 2015 / 058021 A1, WO 2015 / 058028A1) (CAS 1477919-27-9) and N-[4-(aminothiomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7).

[0347] fungicides

[0348] The active compounds mentioned herein by their common names are known and are described, for example, in the Pesticide Handbook (16th edition, British Crop Protection Council) or can be found on the internet (e.g.: http: / / www.alanwood.net / pesticides )

[0349] All the mixing components mentioned in categories (1) to (15) can optionally form salts with suitable bases or acids, if they are capable of forming salts based on their functional groups. All the fungicidal mixing components mentioned in categories (1) to (15) can optionally include tautomeric forms.

[0350] 1) Ergosterol biosynthesis inhibitors, such as (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamide, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate sulfate), (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) trichlorfonazole triticonazole), (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[ (1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031) (2S) -2- (1-chlorocyclopropyl) -4- [(1R) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.032) (2S) -2- (1-chlorocyclopropyl) -4- [(1S) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.033) (2S) -2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazol-1-yl) propan-2-ol, (1.034) (R) - [3- (4-chloro-2-fluorophenyl) -5- (2,4-difluorophenyl) -1,2-oxazol-4-yl] ( pyridin-3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate Thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[ (2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]- ]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol 1-yl) propan-2-ol, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylthio)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylthio)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylthio)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole N-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]thio}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]thio}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]thio}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]thio}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)thio]phenoxy}phenyl) -N-ethyl-N-methyliminocarboxamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)thio]phenoxy}phenyl)-N-ethyl-N-methyliminocarboxamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarboxamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]thio}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.073) N'-(4-{3-[(difluoromethyl)thio]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarboxamide, (1.074) N′-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methyliminocarboxamide, (1.075) N′-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyliminocarboxamide, (1.076) N′-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.077) N′-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide Carbamylamine, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.081) mefentrifluconazole, (1.082) ipfentrifluconazole.

[0351] 2) Inhibitors of respiratory complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamido, (2.010) pyrazolone isopyrazam (trans epimeric enantiomers 1R, 4S, 9S), (2.011) pyrazolamine (trans epimeric enantiomers 1S, 4R, 9R), (2.012) pyrazolamine (trans epimeric racemates 1RS, 4SR, 9SR), (2.013) pyrazolamine (mixture of cis epimeric racemates 1RS, 4SR, 9RS and trans epimeric racemates 1RS, 4SR, 9SR), (2.014) pyrazolamine (cis epimeric enantiomers 1R, 4S, 9R), (2.015) pyrazolamine (cis epimeric enantiomers 1S, 4R, 9S), (2.016) pyrazolamine (cis (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide 1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1 H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl-)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl-)-N-cyclopentyl Propyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl-)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl-)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) N-(5-chloro-2-isopropylbenzyl-)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro -1,4-methylenenaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methylenenaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxyprop-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl-]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl-]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl-]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl-]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)- )-5-fluoro-N-(2-fluoro-6-isopropylbenzyl-)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl-)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl-)-1-methyl-1H-pyrazole-4-thiocarboxamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl-)-1-methyl-1H-pyrazole-4- Formamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl-)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl-)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl-)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-( 2-Ethyl-5-methylbenzyl-)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl-)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl-)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl-)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide.

[0352] 3) Inhibitors of respiratory complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) oxathiapiprolin, (3.010) oxathiapiprolin, (3.011) oxathiapiprolin, (3.012) oxathiapiprolin, (3.013) oxathiapiprolin, (3.014) oxathiapiprolin, (3.015) oxathiapiprolin, (3.016) oxathiapiprolin, (3.017) oxathiapiprolin, (3.018) oxathiapiprolin, (3.019) oxathiapiprolin, (3.020) oxathiapiprolin, (3.021) oxathiapiprolin, (3.022) oxathiapiprolin, (3.023) oxathiapiprolin, (3.024) oxathiapiprolin, (3.025) oxathiapiprolin, (3.026) oxathiapiprolin, (3.027) oxathiapiprolin, (3.028) oxathiapiprolin, (3.029) oxathiapiprolin, (3.030) oxathiapiprolin, (3.031) oxathiapiprolin, (3.032) oxathiapiprolin, (3.033) oxathiapiprolin, (3.034) oxathiapiprolin, (3.0 moxadon), (3.010) fenamidon, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyraclostrobin rametostrobin), (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R )-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxacyclononan-7-yl 2-methylpropanoate, (3.026) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029)-[methyl{5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate.

[0353] 4) Mitosis and cell division inhibitors, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl -5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H- Pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

[0354] 5) Compounds with multi-site activity, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, oxychloride), (5.009) copper (2+) sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) zinc metiram, (5.017) copper quinoline oxine), (5.018) propineb, (5.019) sulfur and sulfur preparations (including calcium polysulfide), (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0355] 6) Compounds that can trigger host defenses, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, and (6.004) tiadinil.

[0356] 7) Inhibitors of amino acid and / or protein biosynthesis, for example, (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

[0357] 8) ATP production inhibitors, for example (8.001) silthiofam.

[0358] 9) Cell wall synthesis inhibitors, for example, (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0359] 10) Lipid and membrane synthesis inhibitors, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

[0360] 11) Melanin biosynthesis inhibitors, for example (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl {3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.

[0361] 12) Nucleic acid synthesis inhibitors, for example (12.001) benalaxyl, (12.002) kiralaxyl, (12.003) metalaxyl, (12.004) mefenoxam.

[0362] 13) Signal transduction inhibitors, for example, (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, and (13.006) vinclozolin.

[0363] 14) Compounds that can act as uncouplers, for example (14.001) fluazinam and (14.002) meptyldinocap.

[0364] 15) Other compounds, such as (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15. 009) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminum, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate dimethyldithiocarbamate), (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and its salts, (15.025) phosphoric acid and its salts, (15.026) propamocarb-fosetylate, ( 15.027) pyriofenone (chlazafenone) (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzyl-pyridin-2-yl)quinazoline, (15.034) 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5- [2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4 ,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl) 1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) 2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) )quinoline, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene 2-sulfonylhydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.05 3) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.05 7) Phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one.

[0365] Biological pesticides as mixture components

[0366] The compounds of formula (I) may be combined with biological pesticides.

[0367] Biological pesticides include, inter alia, bacteria, fungi, yeasts, plant extracts and products formed by microorganisms, including proteins and secondary metabolites.

[0368] Biological pesticides include bacteria such as spore-forming bacteria, root-colonizing bacteria, and bacteria that act as biological insecticides, fungicides, or nematicides.

[0369] Examples of such bacteria which are or can be used as biological pesticides are:

[0370] Bacillus amyloliquefaciens, strain FZB42 (DSM 231179); or Bacillus cereus, in particular Bacillus cereus strain CNCM I-1562; or Bacillus firmus, strain I-1582 (accession number CNCM I-1582); or Bacillus pumilus, in particular strain GB34 (accession number ATCC 700814) and strain QST2808 (accession number NRRL B-30087); or Bacillus subtilis, in particular strain GB03 (accession number ATCC SD-1397), or Bacillus subtilis strain QST713 (accession number NRRL B-21661) or Bacillus subtilis strain OST 30002 (accession number NRRL Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (accession number ATCC 1276), or B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), or B. thuringiensis subsp. kurstaki strain HD-1, or B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428); Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode))-PR3 (accession number ATCC SD-5834); Streptomyces microflavus strain AQ6121 (=QRD 31.013, NRRL B-50550); Streptomyces galbus strain AQ 6047 (accession number NRRL 30232).

[0371] Examples of fungi and yeasts that are or can be used as biological pesticides are:

[0372] Beauveria bassiana, in particular strain ATCC 74040; Coniothyrium minitans, in particular strain CON / M / 91-8 (accession number DSM-9660); Lecanicillium spp., in particular strain HRO LEC 12; Lecanicillium lecanii (formerly known as Verticillium lecanii), in particular strain KV01; Metarhizium anisopliae, in particular strain F52 (DSM 3884 / ATCC 90448); Metschnikowia fructicola, in particular strain NRRL Y-30752; Paecilomyces fumosoroseus (now known as Isaria fumosorosea), in particular strain IFPC 200613, or strain Apopka 97 (accession number ATCC 20874); Paecilomyces lilacinus, in particular Paecilomyces lilacinus strain 251 (AGAL 89 / 030550); Talaromyces flavus, in particular strain V117b; Trichoderma atroviride, in particular strain SC1 (accession number CBS122089); Trichoderma harzianum, in particular Trichoderma harzianum T39 (accession number CNCM 1-952).

[0373] Examples of viruses that are or can be used as biological pesticides are:

[0374] Adoxophyes orana (summer fruit tortrix) granule virus (GV), Cydia pomonella (codling moth) granule virus (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (African cotton leafworm) NPV.

[0375] Also included are bacteria and fungi that are added to plants or plant parts or plant organs as "inoculants" and that promote plant growth and plant health through their specific properties. Examples include:

[0376] Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp. spp.), Rhizobium spp., especially Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp.

[0377] Examples of plant extracts and products formed by microorganisms (including proteins and secondary metabolites) that are or can be used as biological pesticides are:

[0378] Garlic (Allium sativum), Wormwood (Artemisia absinthium), Azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-mas, Horsetail (Equisetum arvense), Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), Pyrethrum / Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem TM "insecticides", rotenone, ryanodine / ryanodine, Symphytum officinale, Tansy, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, mistletoe, Brassicaceae extracts, especially rapeseed powder or mustard powder.

[0379] As a safener for mixed components

[0380] The compounds of formula (I) may be combined with safeners such as benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadiazole ( ethyl ester)(isoxadifen(-ethyl)), mefenpyr(-diethyl)), naphthalic anhydride, oxabetrinil, 2-methoxy-N-{4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0381] Plants and plant parts

[0382] All plants and plant parts can be processed according to the present invention.In this article, plant should be understood as meaning all plants and plant populations, for example, expectation and undesirable wild plants or crop plants (comprising naturally occurring crop plants), for example cereals (wheat, rice, triticale, barley, rye, oats), corn, soybean, potato, sugar beet, sugar cane, tomato, sweet pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, cabbage (such as cabbage) and other vegetable varieties, cotton, tobacco, rape, and fruit plants (fruit is apple, pear, citrus fruit and grape). Crop plants can be the plants that can be obtained by conventional breeding and optimization method or by biotechnology method and genetic engineering method or the combination of these methods, comprise transgenic plants and can be subject to or not be subject to plant breeder's right (plant breeders'right) protected plant cultivars. Plant should be understood as meaning all developmental stages, for example seed, seedling and early stage (immature) plant until and including mature plant. Plant parts are to be understood as meaning all parts and organs of plants above and below ground, such as buds, leaves, flowers and roots, examples being leaves, needles, stems, branches, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. Plant parts also include harvested plants or harvested plant parts and material for asexual and sexual propagation, for example cuttings, tubers, rhizomes, slips and seeds.

[0383] The treatment of plants and plant parts according to the invention with the compounds of formula (I) is carried out directly by customary treatment methods or by allowing the compounds to act on their environment, habitat or storage space, for example by dipping, spraying, evaporating, atomizing, broadcasting, painting, injection and, in the case of propagation materials, especially seeds, also by applying one or more coatings.

[0384] As mentioned above, all plants and their parts can be processed according to the present invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods such as hybridization or protoplast fusion, and their parts are processed. In another preferred embodiment, transgenic plants and plant cultivars (genetically modified organisms) and their parts obtained by genetic engineering methods, if appropriate, in combination with conventional methods, are processed. The term "parts" or "parts of plants" or "plant parts" has been explained above. Particularly preferably, according to the present invention, plants of commercially available conventional plant cultivars or those plants being used are processed. Plant cultivars are understood to mean plants with new characteristics ("traits") and obtained by conventional breeding, by mutagenesis or by recombinant DNA technology. They can be cultivars, variants, biotypes or genotypes.

[0385] Transgenic plants, seed treatments, and integration events

[0386] Preferred transgenic plants or plant cultivars (those obtained by genetic engineering) to be treated according to the invention include all plants that have received genetic material that imparts particularly advantageous useful properties ("traits") to these plants by genetic modification. Examples of such properties are: better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salinity levels, improved flowering performance, easier harvesting, accelerated maturation, higher harvest yield, higher quality and / or higher nutritional value of the harvested product, better storage capacity and / or processability of the harvested product. Other and particularly emphasized examples of such properties are: enhanced resistance of plants to animal and microbial pests, such as insects, arachnids, nematodes, mites, slugs and snails, due, for example, to toxins formed in plants, in particular those formed in plants by the genetic material of Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and combinations thereof), and enhanced resistance of plants to phytopathogenic fungi, bacteria and / or viruses, caused, for example, by systemically acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins, and enhanced tolerance of plants to certain herbicidally active compounds, such as imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example the "PAT" gene). Genes that confer desired properties ("traits") can also be present in combination with one another in transgenic plants. Examples of transgenic plants include important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas, and other vegetable species, cotton, tobacco, rapeseed, and fruit plants (fruits such as apples, pears, citrus fruits, and grapes), with particular emphasis on corn, soybeans, wheat, rice, potatoes, cotton, sugar cane, tobacco, and rapeseed. Particularly emphasized properties ("traits") are increased resistance of plants to insects, arachnids, nematodes, slugs, and snails.

[0387] Plant protection – types of treatment

[0388] Plants and plant parts are treated with the compounds of formula (I) directly or by acting on their environment, habitat or storage space using customary treatment methods, such as dipping, spraying, atomizing, irrigation, evaporation, dusting, misting, broadcasting, foaming, painting, spreading, injection, watering (drenching), drip irrigation, and in the case of propagation material, especially seeds, also by dry seed treatment, wet seed treatment, slurry treatment, encrustation, by coating with one or more coatings, etc. The compounds of formula (I) can also be applied by the ultra-low volume method or the application forms or the compounds of formula (I) themselves can be injected into the soil.

[0389] A preferred direct treatment of plants is foliar application, ie application of the compounds of formula (I) to the leaves, in which case the frequency of treatment and the application rate should be adjusted to the level of infestation by the pest in question.

[0390] In the case of systemic active compounds, the compound of formula (I) also enters the plant via the root system. The plant is then treated by subjecting the compound of formula (I) to its habitat. This can be accomplished, for example, by watering, or by incorporating it into the soil or nutrient solution, which means that the plant's habitat (e.g., soil or hydroponic system) is impregnated with the compound of formula (I) in liquid form, or by soil application, which means that the compound of formula (I) according to the invention is introduced into the plant's habitat in solid form (e.g., in the form of granules). In the case of rice crops, this can also be accomplished by metering the compound of formula (I) into the rice field in a solid application form (e.g., as granules).

[0391] Seed treatment

[0392] People have long known that by processing plant seeds, prevent and treat animal pests and this is the theme of continuous improvement.Yet seed treatment relates to a series of problems that can not always be solved in a satisfactory manner.Therefore, it is necessary to develop a method for protecting seeds and germinating plants, which method does not need or at least significantly reduces the additional application of agricultural chemicals during storage, after sowing or after plant emergence.In addition, it is also necessary to optimize the amount of employed reactive compound, so that best protection is provided to avoid the infringement of animal pests for seeds and germinating plants, and employed reactive compound can not damage the plant itself.Especially, the method for processing seeds should also take into account the inherent insecticide or nematode characteristics of pest-resistant or pest-tolerant transgenic plants, so that the best protection to seeds and germinating plants is realized with minimum agricultural chemicals.

[0393] Therefore, in particular, the present invention also relates to a method for protecting seeds and germinating plants from pests by treating the seeds with one of the compounds of formula (I). The method of protecting seeds and germinating plants from pests according to the present invention also includes methods for treating seeds with compounds of formula (I) and mixed components simultaneously or sequentially in one operation. It also includes methods for treating seeds with compounds of formula (I) and mixed components at different times.

[0394] The invention also relates to the use of the compounds of formula (I) for treating seed for protecting the seed and the resulting plant from attack by animal pests.

[0395] The present invention also relates to seeds treated with compounds of formula (I) of the present invention to protect them from animal pests. The present invention also relates to seeds treated with compounds of formula (I) and mixed components simultaneously. The present invention also relates to seeds treated with compounds of formula (I) and mixed components at different times. In the case of seeds treated with compounds of formula (I) and mixed components at different times, each substance may be present on the seeds in different layers. In this case, the layers comprising compounds of formula (I) and mixed components may optionally be separated by an intermediate layer. The present invention also relates to seeds to which compounds of formula (I) and mixed components are applied as part of a coating or as another layer or layers in addition to the coating.

[0396] The present invention also relates to seeds which, after treatment with the compound of formula (I), have been subjected to a film coating process to protect the seeds from dust abrasion.

[0397] When the compounds of formula (I) act systemically, one of the advantages that arises is that the treatment of the seed protects not only the seed itself but also the resulting plant from it from attack by animal pests after emergence. In this way, it is not necessary to treat the crop immediately at sowing or shortly thereafter.

[0398] Another advantage is that treatment of seeds with compounds of formula (I) promotes germination and emergence of the treated seeds.

[0399] It is likewise considered advantageous that the compounds of the formula (I) can also be used, in particular, in transgenic seeds.

[0400] The compounds of formula (I) may also be used in combination with signaling technology compositions, leading to better colonization of symbionts (eg rhizobia, mycorrhizae and / or endophytic bacteria or fungi), and / or optimized nitrogen fixation.

[0401] The compound of formula (I) is suitable for protecting the seed of any plant variety used in agriculture, greenhouse, forestry or gardening.More specifically, it is the seed of following plant: cereal (for example wheat, barley, rye, millet and oat), corn, cotton, soybean, rice, potato, sunflower, coffee, tobacco, rape, oilseed rape, beet (for example sugar beet and fodder beet), peanut, vegetables (for example tomato, cucumber, kidney bean, cruciferous vegetables, onion and lettuce), fruit plant, lawn plant and ornamental plant.Particularly important is the seed of processing cereal (wheat, barley, rye, oat), corn, soybean, cotton, rape, oilseed rape, vegetables and rice.

[0402] As mentioned above, it is also particularly important to treat transgenic seeds with compounds of formula (I). This includes seeds of plants that generally contain at least one heterologous gene that controls the expression of a polypeptide having, in particular, insecticidal and / or nematocidal properties. The heterologous gene in transgenic seeds can be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly suitable for treating transgenic seeds that contain at least one heterologous gene derived from Bacillus. The heterologous gene is more preferably derived from Bacillus thuringiensis.

[0403] In the context of the present invention, the compound of formula (I) is applied to seeds. Seeds are preferably treated in such a state that they are sufficiently stable so that no damage occurs during the treatment process. Generally, seeds can be treated at any time between harvesting and sowing. Seeds that have been separated from the plant and have removed the cob, shell, stem, pod (coat), hair or pulp are generally used. For example, seeds that have been harvested, cleaned and dried to a moisture content that allows storage can be used. Alternatively, seeds that have been treated with water and then dried (for example, priming) after drying can also be used. In the case of rice seeds, seeds that have been, for example, soaked in water until they reach a certain stage of the rice germ ("endosperm (pigeon breast) stage") can also be used, which results in stimulating germination and more uniform sprouting.

[0404] When treating seed, it is generally necessary to ensure that the amount of compound of formula (I) and / or other additives applied to the seed is selected so that the germination of the seed is not adversely affected or the resulting plant is not damaged. This must be ensured in particular for active compounds that may exhibit phytotoxic effects at certain application rates.

[0405] Typically, the compound of formula (I) is applied to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art.

[0406] The compounds of formula (I) can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.

[0407] These preparations are prepared in a known manner by mixing the compounds of formula (I) with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.

[0408] Suitable dyes that may be present in the seed dressing formulations that can be used according to the invention are all dyes customary for such purposes. Pigments that are sparingly soluble in water or dyes that are soluble in water can be used. Examples include the dyes known under the names Rhodamine B, CI Pigment Red 112, and CI Solvent Red 1.

[0409] Useful wetting ingredients that may be present in the seed dressing formulations which can be used according to the invention are all substances which promote wetting and are customarily used for formulating agrochemically active compounds. Preference is given to using alkyl naphthalenesulfonates, such as diisopropyl naphthalenesulfonate or diisobutyl naphthalenesulfonate.

[0410] Suitable dispersants and / or emulsifiers that may be present in the seed dressing formulations that can be used according to the invention are all nonionic, anionic, and cationic dispersants commonly used for formulating agrochemically active compounds. Preference is given to using nonionic or anionic dispersants, or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include, in particular, ethylene oxide / propylene oxide block polymers, alkylphenol polyglycol ethers, and tristyrylphenol polyglycol ethers, as well as phosphated or sulfated derivatives thereof. Suitable anionic dispersants are, in particular, ligninsulfonates, polyacrylates, and arylsulfonate-formaldehyde condensates.

[0411] Antifoams which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances which are customary for formulating agrochemical active compounds. Silicone antifoams and magnesium stearate can preferably be used.

[0412] Preservatives that may be present in the seed dressing formulations which can be used according to the invention are all substances which can be employed for such purposes in agrochemical compositions. Examples include dichlorophenol and benzyl alcohol hemiformal.

[0413] Useful secondary thickeners that may be present in the seed dressing formulations which can be used according to the invention are all substances which can be employed for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clays and finely divided silicas.

[0414] Useful adhesives that may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used for seed dressing products. Preferred examples include polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and methylcellulose.

[0415] Useful gibberellins that may be present in the seed dressing formulations that can be used according to the invention are preferably gibberellins A1, A3 (= gibberellic acid), A4 and A7; gibberellic acid is particularly preferably used. The gibberellins are known (cf. R. Wegler "Chemieder Pflanzenschutz-und ”, Vol. 2, Springer Verlag, 1970, pp. 401-412).

[0416] The seed dressing formulations that can be used according to the invention can be used directly or after prior dilution with water to treat a wide variety of seed types. For example, concentrates or formulations obtainable therefrom by dilution with water can be used to dress the seeds of cereals (e.g., wheat, barley, rye, oats, and triticale), as well as corn, rice, rapeseed, peas, beans, cotton, sunflower, soybeans, and sugar beets, or various vegetables. The seed dressing formulations that can be used according to the invention, or diluted application forms thereof, can also be used to dress the seeds of transgenic plants.

[0417] For treating seed with the seed dressing formulations that can be used according to the invention or the application forms prepared therefrom by adding water, all conventional mixing devices for seed dressing are suitable. Specifically, the seed dressing process involves placing the seed in a batchwise or continuously operated mixer; adding the specifically desired amount of the seed dressing formulation (as such or after prior dilution with water); and mixing until the formulation is evenly distributed over the seed. If appropriate, this is followed by a drying operation.

[0418] The application rate of the seed dressing formulations that can be used according to the invention can vary within a wide range. This is determined by the specific content of the compound of formula (I) in the formulation and the seed. The application rate of the compound of formula (I) is generally 0.001 to 50 g / kg seed, preferably 0.01 to 15 g / kg seed.

[0419] Animal Health

[0420] In the field of animal health, i.e. veterinary medicine, the compounds of formula (I) are active against animal parasites, in particular ectoparasites or endoparasites. The term "endoparasites" particularly includes helminths and protozoa, such as coccidia. Ectoparasites are generally and preferably arthropods, in particular insects or mites.

[0421] In the field of veterinary medicine, the compounds of formula (I) with favorable homeothermic toxicity are suitable for controlling parasites that occur in animal breeding and animal husbandry in livestock, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals. They are active against all or specific developmental stages of parasites.

[0422] Agricultural livestock include, for example, mammals, such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeer, deer, in particular cattle and pigs; or poultry, such as turkeys, ducks, geese, in particular chickens; or fish or crustaceans, such as in aquaculture; or optionally, insects, such as bees.

[0423] Domestic animals include, for example, mammals, such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, in particular dogs, cats, cage birds; reptiles, amphibians or ornamental fish.

[0424] In one embodiment, the compound of formula (I) is administered to a mammal.

[0425] In another embodiment, the compounds of formula (I) are administered to birds, ie caged birds or in particular poultry.

[0426] The use of compounds of formula (I) for controlling animal parasites aims to reduce or prevent disease, mortality and performance decline (in the case of meat, milk, wool, hides, eggs, honey, etc.), thereby making animal husbandry more economical and simpler and achieving better animal health.

[0427] In the context of this document, with respect to the field of animal health, the term "control" or "controlling" means that the compounds of formula (I) are effective in reducing the incidence of a particular parasite in an animal infected by a parasite to a harmless level. More specifically, in the context of this document, "control" means that the compounds of formula (I) kill the various parasites, inhibit their growth or inhibit their proliferation.

[0428] Arthropods include, but are not limited to, for example:

[0429] From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.;

[0430] From the orders Mallophagida, the suborders Amblycerina and Ischnocerina, for example, Bovicola spp., Damalina spp., Felicola spp., Lepikentron spp., Menopon spp., Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella spp.;

[0431] From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Atylotus spp., Braula spp., Calliphora spp., Chrysomyia spp., Chrysops spp., Culex spp., Culicoides spp., Eusimulium spp., Fannia spp., Gasterophilus spp., Glossina spp., Haematobia spp., Haematopota spp. spp.), Hippobosca spp., Hybomitra spp., Hydrotaea spp., Hypoderma spp., Lipoptena spp., Lucilia spp., Lutzomyia spp., Melophagus spp., Morellia spp., Musca spp., Odagmiaspp., Oestrus spp., Philipomyia spp., Phlebotomus spp., Rhinoestrus spp., Sarcophaga spp., Simulium spp., Stomoxys spp.), Tabanus spp., Tipula spp., Wilhelmia spp., Wohlfahrtia spp.;

[0432] From the order of the Siphonapterida, for example, Ceratophyllus spp., Ctenocephalides spp., Pulex spp., Tunga spp., Xenopsyllas spp.;

[0433] From the order of the Heteropterida, for example, Cimex spp., Panstrongylus spp., Rhodnius spp., Triatoma spp.; and nuisance and hygiene pests from the order of the Blattarida.

[0434] Furthermore, in the case of arthropods, mention should be made of, for example but not limited to, the following Acari:

[0435] Subclass Acari (order Acarina) and Metastigmata, for example, Argasidae such as Argas spp., Ornithodorus spp., Otobius spp., Ixodidae such as Amblyomma spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Ixodes spp., Rhipicephalus (Boophilus) spp., Rhipicephalus spp. (the original genus of multi-host ticks); Order Mesostigmata such as Dermanyssus spp.), Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Tropilelaps spp., Varroa spp.; from the order Actinedida (Prostigmata), for example, Acarapis spp., Cheyletiella spp., Demodex spp., Listrophorus spp., Myobia spp., Neotrombicula spp., Ornithocheyletia spp., Psorergates spp., Trombicula spp.); and from the order of the Acaridida (order Astigmata), for example, Acarus spp., Caloglyphus spp., Chorioptes spp., Cytodites spp., Hypodectes spp., Knemidocoptes spp., Laminosioptes spp., Notoedres spp., Otodectes spp., Psoroptes spp., Pterolichus spp.), Sarcoptes spp., Trixacarus spp., and Tyrophagus spp.

[0436] Examples of parasitic protozoa include, but are not limited to:

[0437] Mastigophora (Flagellata), for example:

[0438] Metamonada: Order Diplomonadida, e.g., Giardia spp., Spironucleus spp.

[0439] Parabasala: order Trichomonadida, for example, Histomonas spp., Pentatrichomonas spp., Tetratrichomonas spp., Trichomonas spp., Tritrichomonas spp.

[0440] Euglenozoa: Trypanosomatida, e.g., Leishmania spp., Trypanosoma spp.

[0441] Subdivision Sarcomastigophora (Rhizopoda), for example, Entamoebidae, for example, Entamoeba spp., Centramoebidae, for example, Acanthamoeba sp., Euamoebidae, for example, Harmanella sp.

[0442] Alveolata, such as Apicomplexa (Sporozoa): for example, Cryptosporidium spp.; Eimeriida, for example, Besnoitia spp., Cystoisospora spp., Eimeria spp., Hammondia spp., Isospora spp., Neospora spp., Sarcocystis spp., Toxoplasma spp.; Adeleida, for example, Hepatozoon spp., Klossiella spp. spp.); Haemosporida, for example, Leucocytozoon spp., Plasmodium spp.; Piroplasmida, for example, Babesia spp., Ciliophora spp., Echinozoon spp., Theileria spp.; Vesibuliferida, for example, Balantidium spp., Buxtonella spp.

[0443] Microspora, for example, Encephalitozoon spp., Enterocytozoon spp., Globidium spp., Nosema spp., and for example, Myxozoa spp.

[0444] Helminths that are pathogenic to humans or animals include, for example, Acanthocephala, nematodes, Pentastoma, and Platyhelminthes (eg, Monogenea, cestodes, and trematodes).

[0445] Exemplary worms include, but are not limited to:

[0446] Monogenea: for example, Dactylogyrus spp., Gyrodactylus spp., Microbothrium spp., Polystoma spp., Troglecephalus spp.

[0447] Tapeworms: Pseudophyllidea, for example, Bothridium spp., Diphyllobothrium spp., Diplogonoporus spp., Ichthyobothrium spp., Ligula spp., Schistocephalus spp., and Spirometra spp.;

[0448] Order of the Cyclophyllidea, for example, Andyra spp., Anoplocephala spp., Avitellina spp., Bertiella spp., Cittotaenia spp., Davainea spp., Diorchis spp., Diplopylidium spp., Dipylidium spp., Echinococcus spp., Echinocotyle spp., Echinolepis spp., Hydatigera spp.), Hymenolepis spp., Joyeuxiella spp., Mesocestoides spp., Moniezias spp., Paranoplocehala spp., Raillietina spp., Stilesia spp., Taenia spp., Thysaniezia spp., Thysanosomsa spp.;

[0449] Trematodes: selected from the class Digenea, for example: Austrobilharzia spp., Brachylaima spp., Calicophoron spp., Catatropis spp., Clonorchis spp., Collyriclum spp., Cotylophoron spp., Cyclocoelum spp., Dicrocoelium spp., Diplostomum spp., Echinochasmus spp., Echinoparyphium spp., Echinostoma spp.), Eurytemas spp., Fasciola spp., Fascioloides spp., Fasciolopsis spp., Fischoederius spp., Gastrothylacus spp., Gigantobilharzia spp., Gigantoctyle spp., Heterophyes spp., Hypoderaeum spp., Leucochloridium spp., Metagonimus spp., Metorchis spp., Nanophyetus spp., Notocotylus spp.), Opisthorchis spp., Ornithobilharzia spp., Paragonimus spp., Paramphistomum spp., Plagiorchis spp., Posthodiplostomum spp., Prosthogonimus spp., Schistosoma spp., Trichobilharzia spp., Troglottrema spp., and Typhlocoelum spp.;

[0450] Nematodes: Order Trichinellida, for example: Capillaria spp., Trichinella spp., Trichomosoides spp., Trichuris spp.;

[0451] From the order of the Tylenchida, for example, Micronema spp., Parastrangyloides spp., Strongyloides spp.;

[0452] From the order of the Rhabditida, for example: Aelurostrongylus spp., Amidostomum spp., Ancylostoma spp., Angiostrongylus spp., Bronchonema spp., Bunostomum spp., Chabertia spp., Cooperia spp., Cooperioides spp., Crenosoma spp., Cyathostomum spp., Cyclococercus spp., Cyclodontostomum spp., Cylicocyclus spp., Cylicostephanus spp., Cylindropharynx spp., Cystocaulus spp.), Dictyocaulus spp., Elaphostrongylus spp., Filaroides spp., Globocephalus spp., Graphidium spp., Gyalocephalus spp., Haemonchus spp., Heligmosomoides spp., Hyostrongylus spp., Marshallagia spp., Metastrongylus spp., Muellerius spp., Necator spp., Nematodirus spp., Neostrongylus spp.), Nippostrongylus spp., Obeliscoides spp., Oesophagodontus spp., Oesophagostomum spp., Ollulanus spp., Ornithostrongylus spp., Oslerus spp., Ostertagia spp., Paracooperia spp.), Paracrenosoma, Parafilaroides spp., Parelaphostrongylus spp., Pneumocaulus spp., Pneumostrongylus spp., Poteriostomum spp., Protostrongylus spp., Spicocaulus spp., Stephanurus spp., Strongylus spp., Syngamus spp., Teladorsagia spp., Trichonema spp., Trichostrongylus spp., Triodontophorus spp., Troglostrongylus spp., Uncinaria spp.);.

[0453] From the order of the Spirurida, for example: Acanthocheilonema spp., Anisakis spp., Ascaridia spp., Ascaris spp., Ascarops spp., Aspiculuris spp., Baylisascaris spp., Brugia spp., Cercopithifilaria spp., Crassicauda spp., Dipetalonema spp., Dirofilaria spp., Dracunculus spp., Drashia spp., Enterobius spp., Filaria spp. spp.), Gnathostoma spp., Gongylonema spp., Habronema spp., Heterakis spp.; Litomosoides spp., Loa spp., Onchocerca spp., Oxyuris spp., Parabronema spp., Parafilaria spp., Parascaris spp., Passalurus spp., Physaloptera spp., Probstmayria spp., Pseudofilaria spp., Setaria spp.), Skjrabinema spp., Spirocerca spp., Stephanofilaria spp., Strongyluris spp., Syphacia spp., Thelazia spp., Toxascaris spp., Toxocara spp., Wuchereria spp.;

[0454] Acanthocephala: Oligacanthorhynchida, for example, Macracanthorhynchus spp., Prosthenorchis spp.; Moniliformida, for example, Moniliformis spp.;

[0455] From the order of the Polymorphida, for example, Filicollis spp.; from the order of the Echinorhynchida, for example, Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.;

[0456] Pentastoma: Porocephalida, e.g. Linguatula spp.

[0457] In the veterinary field and in animal husbandry, the compounds of formula (I) are administered in the form of suitable formulations by methods generally known in the art, such as enteral, parenteral, dermal or nasal routes. Administration can be preventive, metaphylactic or therapeutic.

[0458] Therefore, one embodiment of the present invention relates to compounds of formula (I) for use as medicaments.

[0459] Another aspect relates to compounds of formula (I) for use as anti-endoparasitic agents.

[0460] Another particular aspect of the invention relates to compounds of formula (I) for use as antihelminthics, in particular as nematicides, platyhelmincides, acanthocephalicides or linguicidalides.

[0461] Another specific aspect of the invention relates to compounds of formula (I) for use as antiprotozoal agents.

[0462] A further aspect relates to compounds of the formula (I) for use as anti-ectoparasitic agents, in particular arthropodicides, very particularly insecticides or acaricides.

[0463] Another aspect of the present invention is a veterinary formulation comprising an effective amount of at least one compound of formula (I) and at least one of the following substances: a pharmaceutically acceptable excipient (e.g. a solid or liquid diluent), a pharmaceutically acceptable adjuvant (e.g. a surfactant), in particular a pharmaceutically acceptable excipient conventionally used in veterinary formulations and / or a pharmaceutically acceptable adjuvant conventionally used in veterinary formulations.

[0464] A related aspect of the invention is a method for preparing a veterinary formulation as described herein, comprising the steps of mixing at least one compound of formula (I) with pharmaceutically acceptable excipients and / or adjuvants, in particular with pharmaceutically acceptable excipients and / or adjuvants conventionally used in veterinary formulations.

[0465] Another particular aspect of the present invention is a veterinary preparation selected from ectoparasiticidal and endoparasiticidal preparations, in particular selected from the anthelmintic, antiprotozoal and arthropodicidal preparations of the above aspects, very particularly selected from nematocidal, platyhelmintic, acanthocephalic, linguicidal, insecticidal and acaricidal preparations, and a process for their preparation.

[0466] Another aspect relates to a method for treating parasitic infections, especially infections caused by parasites selected from the ectoparasites and endoparasites mentioned herein, by administering an effective amount of a compound of formula (I) to an animal, especially a non-human animal, in need thereof.

[0467] Another aspect relates to a method for treating parasitic infections, especially infections caused by parasites selected from the group consisting of ectoparasites and endoparasites mentioned herein, by using a veterinary formulation as defined herein in an animal, especially a non-human animal, in need thereof.

[0468] Another aspect relates to the use of a compound of formula (I) for treating parasitic infections in animals, especially non-human animals, especially infections caused by parasites selected from the group consisting of ectoparasites and endoparasites mentioned herein.

[0469] In the animal health or veterinary context of the present invention, the term "treatment" includes prophylactic, remedial or therapeutic treatment.

[0470] In one embodiment, in this way, mixtures of at least one compound of the formula (I) with further active compounds, in particular with endoparasiticides and ectoparasiticides, are provided for use in the veterinary field.

[0471] In the field of animal health, the term "mixture" refers not only to two (or more) different active compounds formulated in a common formulation and used together, but also to products containing separate formulations for each active compound. Thus, when two or more active compounds are used, all may be formulated in a common formulation or as separate formulations; or they may be in a mixed form, with some active compounds formulated together and some formulated separately. Separate formulations allow the active compounds to be administered individually or sequentially.

[0472] The active compounds mentioned herein by their common names are known and are described, for example, in the Pesticide Manual (see above) or can be found on the internet (e.g. http: / / www.alanwood.net / pesticides )

[0473] Exemplary active compounds of the ectoparasiticides as admixture components include, but are not intended to be limited to, the insecticides and acaricides listed in detail above. Other active compounds that can be used are listed below according to the above classification based on the current IRAC mode of action classification scheme: (1) acetylcholinesterase (AChE) inhibitors; (2) GABA-gated chloride channel blockers; (3) sodium channel modulators; (4) nicotinic acetylcholine receptor (nAChR) competitive modulators; (5) nicotinic acetylcholine receptor (nAChR) allosteric modulators; (6) glutamate-gated chloride channel (GluCl) allosteric modulators; (7) juvenile hormone mimetics; (8) other nonspecific (multi-site) inhibitors; (9) chord organ modulators; (10) mite growth inhibitors; (12) mitochondrial ATP synthase inhibitors, such as ATP disrupters; (13) Uncouplers of oxidative phosphorylation by blocking the proton gradient; (14) Nicotinic acetylcholine receptor channel blockers; (15) Chitin biosynthesis inhibitors, type 0; (16) Chitin biosynthesis inhibitors, type 1; (17) Molting disruptors (especially for Diptera); (18) Ecdysone receptor agonists; (19) Octopamine receptor agonists; (21) Mitochondrial complex I electron transport inhibitors; (25) Mitochondrial complex II electron transport inhibitors; (20) Mitochondrial complex III electron transport inhibitors; (22) Voltage-dependent sodium channel blockers; (23) Acetyl CoA carboxylase inhibitors; (28) Rhynchomycin receptor modulators;

[0474] Active compounds with unknown or nonspecific mechanisms of action, such as fentrifanil, fenoxacrim, cycloprene, chlorobenzilate, chlordimeform, flubenzimin, dicyclanil, amidoflumet, quinomethionat, triarathene, clothiazoben, tetrasul, potassium oleate, petroleum, metoxadiazone, gossyplur, flutenzine, brompropylate, and cryolite;

[0475] Other types of compounds, such as butacarb, dimetilan, cloethocarb, phosphocarb, pirimiphos(-ethyl), parathion(-ethyl), methacrifos, isopropylo-salicylate, trichlorfon, sulprofos, propaphos, sebufos, pyridathion, prothoate, dichlofenthion, demeton-S-methyl sulfone), isazofos, cyanofenphos, dialifos, carbophenothion, autathiofos, aromfenvinfos(-methyl), azinphos(-ethyl), chlorpyrifos(-ethyl), fosmethilan, iodofenphos, dioxabenzofos, formothion, fonofos, flupyrazofos, fensulfothion, and etrimfos;

[0476] Organic chlorides, such as camphechlor, lindane, and heptachlor; or phenylpyrazoles, such as acetoprole, pyrafluprole, pyriprole, vaniliprole, and sisapronil; or isoxazolines, such as sarolaner, afoxolaner, lotilaner, and fluralaner;

[0477] Pyrethroids, such as (cis-, trans-)metofluthrin, profluthrin, flufenprox, flubrocythrinate, fubfenprox, fenfluthrin, protrifenbut, pyresmethrin, RU15525, terallethrin, and cis-resmethrin cis-resmethrin, heptafluthrin, bioethanomethrin, biopermethrin, fenpyrithrin, cis-cypermethrin, cis-permethrin, clocythrin, cyhalothrin (lambda-), chlovaporthrin, or halogenated hydrocarbon compounds (HCH),

[0478] Neonicotinoids, such as nithiazine;

[0479] dicloromezotiaz, triflumezopyrim;

[0480] Macrolides (such as nemadectin, ivermectin, latidectin, moxidectin, selamectin, eprinomectin, doramectin, and emamectin benzoate); milbemycin oxime

[0481] Triprene, epofenonane, and diofenolan;

[0482] Biologics, hormones, or pheromones, such as natural products like thuringiensin, codlemone, or neem components

[0483] Dinitrophenols, such as dinocap, dinobuton, and binapacryl;

[0484] Benzoyl ureas, such as fluazuron and penfluron,

[0485] Amidine derivatives, such as chlormebuform, cymiazole, demiditraz

[0486] Beehive varroa acaricide, for example, organic acids such as formic acid and oxalic acid.

[0487] Exemplary active compounds of endoparasiticides as admixtures include, but are not limited to, active anthelmintic compounds and active antiprotozoic compounds.

[0488] Active anthelmintic ingredients include, but are not limited to, the following active nematicidal, trematicidal, and / or cestocidal ingredients:

[0489] Macrolides, such as eprinomectin, abamectin, nemadectin, moxidectin, doramectin, selamectin, lepimectin, latidectin, milbemectin, ivermectin, emamectin, and milbemycin;

[0490] Benzimidazoles and probenzimidazoles, such as oxibendazole, mebendazole, triclabendazole, thiophanate, parbendazole, oxfendazole, netobimin, fenbendazole, febantel, thiabendazole, cyclobendazole, cambendazole, albendazole sulfoxide, albendazole, and flubendazole;

[0491] Depsipeptides, preferably cyclic depsipeptides, especially 24-membered cyclic depsipeptides, such as emodepside and PF1022A;

[0492] Tetrahydropyrimidines, such as morantel, pyrantel, and oxantel;

[0493] Imidazolothiazoles, such as butamisole, levamisole, and tetramisole;

[0494] Aminophenylamidines, such as amidantel, deacylated amidantel (dAMD), and tribendimidine;

[0495] Aminoacetonitriles, such as monepantel;

[0496] paraherquamides, for example, paraherquamide and derquantel;

[0497] Salicylanilides, such as tribromsalan, bromoxanide, brotianide, clioxanide, closantel, niclosamide, oxyclozanide, and rafoxanide;

[0498] Substituted phenols, such as nitroxynil, bithionol, disophenol, hexachlorophene, niclofolan, and meniclopholan;

[0499] Organophosphates, such as trichlorfon, naphthalofos, dichlorvos (DDVP), crufomate, coumaphos, and haloxon;

[0500] Piperazinones / quinolines, such as praziquantel and epsiprantel;

[0501] Piperazines, such as piperazine and hydroxyzine;

[0502] Tetracyclines, such as tetracycline, chlorotetracycline, doxycycline, oxytetracycline, and rolitetracycline;

[0503] Various other types, for example: bunamidine, niridazole, resorantel, omphalotin, oltipraz, nitroscanate, nitroxynil, oxamniquin, mirasan, miracil, lucanthon, hycanthon, hetolin, emetin, diethylcarbamazine, dichlorophen, diamfenetide, clonazepam, bephenium, amoscanate, clorsulon.

[0504] Active antiprotozoal compounds include, but are not limited to, the following active compounds:

[0505] Triazines, such as diclazuril, ponazuril, letrazuril, and toltrazuril;

[0506] Polyether ionophores, such as monensin, salinomycin, maduramicin, and narasin;

[0507] Macrolides, such as milbemycin and erythromycin;

[0508] Quinolones, such as enrofloxacin and pradofloxacin;

[0509] Quinines, such as chloroquine;

[0510] Pyrimidines, such as pyrimethamine;

[0511] Sulfonamides, such as sulfaquinoxaline, trimethoprim, and sulfaclozin;

[0512] Thiamines, such as amprolium;

[0513] Lincosamides, such as clindamycin;

[0514] Carboanilides, such as imidocarb;

[0515] Nitrofurans, such as nifurtimox;

[0516] Quinazolinone alkaloids, such as halofuginone;

[0517] Various other types, such as oxamniquin and paromomycin;

[0518] Vaccines or antigens from microorganisms such as Babesia canis rossi, Eimeria tenella, Eimeria praecox, Eimeria necatrix, Eimeria mitis, Eimeria maxima, Eimeria brunetti, Eimeria acervulina, Babesia canis vogeli, Leishmania infantum, Babesia canis canis, and Dictyocaulus viviparus.

[0519] If appropriate, all mixing components mentioned can also form salts with suitable bases or acids, if they are capable of salt formation based on their functional groups.

[0520] Vector control

[0521] The compounds of formula (I) can also be used for disease vector control. In the context of the present invention, a disease vector is an arthropod, particularly an insect or arachnid, which is capable of transmitting pathogens such as viruses, worms, single-cell organisms, and bacteria from a reservoir (plants, animals, humans, etc.) to a host. Pathogens can be transmitted mechanically to the host (e.g., by non-stinging flies that transmit trachoma) or after injection (e.g., by mosquitoes that transmit Plasmodium).

[0522] Examples of vectors and the diseases or pathogens they transmit are:

[0523] 1)Mosquito

[0524] - Anopheles: malaria, filariasis;

[0525] - Culex spp.: Japanese encephalitis, filariasis, other viral diseases, and other helminthic diseases;

[0526] - Aedes spp.: yellow fever, dengue fever, other viral diseases, filariasis;

[0527] - Simuliidae: worm-borne, especially Onchocerca volvulus;

[0528] -Ceratidae: transmission of leishmaniasis;

[0529] 2) Lice: skin infections, epidemic typhus;

[0530] 3) Fleas: plague, typhus, tapeworms;

[0531] 4) Flies: sleeping sickness (trypanosomiasis); cholera, other bacterial diseases;

[0532] 5) Mites: tick-borne diseases, epidemic typhus, rickettsial pox, tularemia, Saint Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, and borreliosis;

[0533] 6) Ticks: borellioses, such as Borrelia bungdorferi sensu lato., Borrelia duttoni, tick-borne encephalitis, Q fever (Coxiella burnetii), babesia (Babesia canis canis), ehrlichiosis.

[0534] In the context of the present invention, examples of disease vectors are insects, such as aphids, flies, leafhoppers or thrips, which can transmit plant viruses to plants. Other disease vectors capable of transmitting plant viruses are spider mites, lice, beetles and nematodes.

[0535] Further examples of disease vectors in the context of the present invention are insects and arachnids, such as mosquitoes, in particular Aedes, Anopheles, for example A. gambiae, A. arabiensis, A. funestus, A. dirus (malaria) and Culex, Ceratitis, such as Phlebotomus, Lophatherum, lice, fleas, flies, mites and ticks, which can transmit pathogens to animals and / or humans.

[0536] Vector control is also possible if the compounds of the formula (I) are resistance-breaking.

[0537] The compounds of formula (I) are suitable for preventing diseases and / or pathogens borne by vectors. Therefore, another aspect of the invention is the use of the compounds of formula (I) for vector control in, for example, agriculture, horticulture, forestry, gardening and leisure equipment, and in the protection of materials and stored products.

[0538] Protection of industrial materials

[0539] The compounds of the formula (I) are suitable for protecting industrial materials from attack or destruction by insects, for example from the orders Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Pseudocoptera and Zygentoma.

[0540] In the context of the present invention, industrial materials are understood to mean inanimate materials, such as, preferably, plastics, adhesives, glues, paper and card, leather, wood, processed wood products and coating compositions. Particular preference is given to the use according to the invention for protecting wood.

[0541] In another embodiment, the compounds of formula (I) are used together with at least one other insecticide and / or at least one fungicide.

[0542] In another embodiment, the compound of formula (I) is in the form of a ready-to-use pesticide, meaning that it can be applied to the material in question without further modification.Useful other insecticides or fungicides include in particular those mentioned above.

[0543] Surprisingly, it has also been found that the compounds of formula (I) can be used to protect objects that come into contact with saltwater or brackish water, in particular hulls, bulkheads, nets, buildings, moorings and signalling systems, from fouling. The compounds of formula (I) can likewise be used alone or in combination with other active compounds as antifouling compositions.

[0544] Control of animal pests in the health sector

[0545] The compounds of formula (I) are suitable for controlling animal pests in the field of hygiene. More specifically, the present invention can be used in the field of indoor protection, the field of hygiene protection, and the protection of stored products, in particular for controlling insects, arachnids, ticks, and mites encountered in confined spaces, such as homes, factory halls, offices, vehicle cabins, and animal breeding facilities. For the control of animal pests, the compounds of formula (I) are used alone or in combination with other active compounds and / or adjuvants. They are preferably used in indoor insecticide products. The compounds of formula (I) are effective against sensitive and resistant species, as well as all their developmental stages.

[0546] These pests include, for example, the following: Arachnida, Scorpiones, Araneae and Opiliones; Chilopoda and Diplopoda; Insecta, Blattodea, Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psoralea, Saltatoria or Orthoptera, Siphonaptera and Silverfishes; and Isopoda.

[0547] Application is carried out, for example, as aerosols, non-pressure sprayer products such as pump sprayers and atomizing sprayers, automatic atomizing systems, nebulizers, foams, gels, evaporator products with evaporator sheets made of cellulose or plastic, liquid evaporators, gel and film evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth paper, moth bags and moth glue, as granules or dusts, for broadcast baits or bait stations.

[0548] Preparation method

[0549] The compounds of the present invention can be prepared by conventional methods known to those skilled in the art.

[0550] Reaction Scheme I - Method A

[0551]

[0552] Compounds of formula (I) can be prepared, for example, in one or two steps according to Reaction Scheme I. Group A 1 、A 2 、A 3 、A 4 , Z, X, R 5 、R 7 、R 8 and R 9 has the above meanings and optionally other meanings related to the preparation method, which are obvious from the text or context. Y represents O, S or NR 5 . Hal represents chlorine or bromine.

[0553] For example, using a halogenating agent, an alcohol of formula (AI) can be converted into a benzyl halide of formula (A-II). These are then reacted in a second reaction step with a compound of formula (A-III) in a nucleophilic substitution reaction in the presence of a basic reaction auxiliary to obtain a compound of formula (I).

[0554] For compounds of formula (I) in which Y represents oxygen, the reaction can alternatively be carried out in a one-step process. Here, a benzyl alcohol of formula (AI) is activated in situ in the presence of a trialkylphosphine or triarylphosphine and an azodicarboxylate and reacted with an alcohol of formula (A-IV) in a nucleophilic substitution reaction to give the compound of formula (I).

[0555] Method A - Step 1: Compounds of formula (AI) are known (e.g. [6-(4-ethylpiperazin-1-yl)pyridin-3-yl]methanol in WO2010 / 132999, tert-butyl 4-[3-chloro-5-(hydroxymethyl)pyridin-2-yl]piperazine-1-carboxylate in EP2050734, and tert-butyl 3-{[3-fluoro-5-(hydroxymethyl)pyridin-2-yl]amino}pyrrolidine-1-carboxylate in US2006 / 0052599) or can be obtained by known preparation methods. Other preparation methods for them are described in this application, in particular (6-{2-[methoxy(methyl)amino]ethoxy}pyridin-3-yl)methanol and (3-fluoro-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol (see also Schemes II and VI).

[0556] Many reaction conditions have been described for halogenation reactions. They are known to those skilled in the art. Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Volume V / 3 (Georg Thieme Verlag Stuttgart), page 760 provides an overview of Hal=Cl, and Houben-Weyl, Methoden der Organischen Chemie, Volume V / 4 (Georg Thieme Verlag Stuttgart), page 361 provides an overview of Hal=Br. Preferably, benzyl chlorides of formula (A-II) are prepared in which Hal represents chlorine. These can be prepared, for example, from benzyl alcohols of formula (AI) in the presence of thionyl chloride. The reaction can be carried out in a suitable inert solvent or diluent such as toluene or dichloromethane and optionally in the presence of a catalytic amount of N,N-dimethylformamide (see, for example, 5-(chloromethyl)-2-(2,2,3,3-tetrafluoropropoxy)pyridine in WO 2013 / 161312).

[0557] Method A - Step 2: Compounds of formula (A-III) are known, commercially available or can be obtained by known preparation methods (see, for example, 5,6-dichloro-1-naphthol in WO2002017712). Other methods for their preparation have been described in this application (see, for example, the preparation of 6-fluoro-3'-(trifluoromethoxy)biphenyl-3-ol and 4-chloro-3-methoxyphenol).

[0558] By heating in the presence of a basic reaction auxiliary such as potassium carbonate or cesium carbonate, a halide of formula (A-II) reacts with a compound of formula (A-III) to undergo a nucleophilic substitution reaction to obtain a compound wherein Y represents O, S or NR 5The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that may be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone and acetonitrile. For Y=O or NR 5 The reaction is preferably carried out at a temperature of 50-120°C. For Y=S, the reaction is preferably carried out at room temperature (see WO2015 / 089139 for Y=O, and WO2015 / 089139 for Y=NR 5 WO2013 / 019621 and WO2005 / 049572 regarding Y=S, WO2012 / 082566 regarding Y=S).

[0559] Method A - Step 3: Compounds of formula (A-IV) are known, commercially available or can be obtained by known preparation methods. Other methods for their preparation are described herein (see, for example, the preparation of 6-fluoro-3'-(trifluoromethoxy)biphenyl-3-ol or 4-chloro-3-methoxyphenol).

[0560] The benzyl alcohol of formula (AI) reacts with an alcohol of formula (A-IV) in the presence of a trialkylphosphine or triarylphosphine and an azodicarboxylate in a nucleophilic substitution reaction to give a compound of formula (I) in which Y represents oxygen. This reaction is known to those skilled in the art as the "Mitsunobureaction". The phosphine used is preferably triphenylphosphine, and the azodicarboxylate used is preferably diethyl azodicarboxylate. The reaction is carried out in the presence of an inert solvent or diluent (e.g., tetrahydrofuran) (see, for example, WO2016 / 044789).

[0561] Reaction Scheme II - Method B

[0562]

[0563] Compounds of formula (IB) can be prepared, for example, according to Reaction Scheme II. Group A 1 、A 2 、A 3 、A 4 , Z, R 5 、R 8 and R 9 With the above meaning (wherein the method does not allow R 8 and R 6 or R 7 Y represents O, S or NR 5 Hal represents chlorine or bromine. Alk represents (C1-C3)-alkyl.

[0564] For example, an alcohol of formula (BI) can be reacted with 1,2-dibromoethane in a nucleophilic substitution reaction in the presence of an alkaline reaction auxiliary to obtain a compound of formula (B-II). In a subsequent step, the alkyl ester functional group in the compound of formula (B-II) can be reduced using a reducing agent to obtain a benzyl alcohol of formula (B-III). Using a halogenating agent, the benzyl alcohol of formula (B-III) can then be converted into a benzyl halide of formula (B-IV). Then, in another reaction step, they can then be reacted with a compound of formula (BV) in a nucleophilic substitution reaction in the presence of an alkaline reaction auxiliary to obtain a compound of formula (B-VI). In another nucleophilic substitution reaction, an amine of formula (B-VII) can be reacted with a bromide of formula (B-VI) to obtain a compound of formula (IB).

[0565] Method B - Step 1:

[0566] Compounds of the formula (BI) are known, commercially available or can be obtained by known preparation methods (see, for example, methyl 3-fluoro-5-hydroxypyridine-2-carboxylate in WO 2011 / 044181).

[0567] The alcohol of formula (BI) is reacted with 1,2-dibromoethane in a nucleophilic substitution reaction in the presence of a basic auxiliary agent (such as potassium carbonate or cesium carbonate) and optionally in the presence of a catalytic amount of potassium iodide. The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that may be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone and acetonitrile. The reaction is carried out at an elevated temperature, preferably at 50°C to 120°C (for example, wherein A 1 To A 4 represents -CH, see for example WO 1998 / 48800).

[0568] Method B - Step 2:

[0569] The ester of formula (B-II) is reacted in the presence of a suitable reducing agent (e.g., sodium borohydride or diisobutylaluminum hydride) to obtain the benzyl alcohol of formula (B-III). If the reaction is carried out in the presence of sodium borohydride, a suitable solvent or diluent, such as ethanol or methanol, is used. Here, the reaction is preferably carried out at a temperature of 0°C to 50°C. If diisobutylaluminum hydride is used, the reaction is carried out in a suitable inert solvent (e.g., toluene or dichloromethane). Here, the reaction is preferably carried out at a temperature of -78°C to +30°C (see, for example, the synthesis of methyl 5-(2-bromoethoxy)-3-fluoropyridine-2-carboxylate described in this application). If diisobutylaluminum hydride is used, a mixture of the benzyl alcohol of formula (B-III) and a similar benzaldehyde can be obtained. In this case, in a second step, the aldehyde functional group is reduced to obtain the benzyl alcohol of formula (B-III). This reaction can be carried out in the presence of sodium hydride under the above conditions.

[0570] Method B - Step 3:

[0571] Many reaction conditions have been described for halogenation reactions. They are known to those skilled in the art and are described in step 1 of method A.

[0572] Method B - Step 4: Compounds of formula (BV) are known, commercially available or can be obtained by known preparation methods. Other methods for their preparation are described herein (see, for example, the preparation of 6-fluoro-3'-(trifluoromethoxy)biphenyl-3-ol or 4-chloro-3-methoxyphenol).

[0573] The halide of formula (B-IV) reacts with the compound of formula (BV) in a nucleophilic substitution reaction to obtain the compound of formula (B-VI) by heating in the presence of a basic reaction auxiliary (e.g., potassium carbonate or cesium carbonate). The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone, and acetonitrile. The reaction is preferably carried out at a temperature of 50° C. to 120° C.

[0574] Method B - Step 5: Compounds of formula (B-VII) are known, commercially available or can be obtained by known preparation methods (see, for example, 1-(aminooxy)propane in EP 0 678 504). Some are also known as their hydrochloride or hydrobromide salts and are commercially available.

[0575] Under heating, the bromide of formula (B-VI) and the compound of formula (B-VII) undergo a nucleophilic substitution reaction to obtain a compound of formula (IB). The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, and tetrahydrofuran. The reaction is optionally carried out in the presence of an alkaline reaction auxiliary (e.g., potassium carbonate, cesium carbonate, or N,N-diisopropylethylamine). The reaction is preferably carried out at a temperature of 10°C to 120°C (without an alkaline reaction auxiliary: WO2006 / 078619, in the presence of K2CO3: WO2010 / 071885, in the presence of N,N-diisopropylethylamine: WO2006 / 105304).

[0576] Method B - Step 6:

[0577] Under heating, the bromide of formula (B-III) reacts with the compound of formula (B-VII) in a nucleophilic substitution reaction to give the compound of formula (B-VIII). The reaction conditions correspond to the reaction conditions described in step 5. They can be converted to compounds of formula (IB) using method A.

[0578] Reaction Scheme III - Method C

[0579]

[0580] Compounds of formula (IC) can be prepared, for example, according to reaction scheme III. Group A 1 、A 2 、A 3 、A 4 , Z, R 5 、R 7 、R 8 and R 9 has the above meanings and optionally other meanings related to the preparation method, which are obvious from the text or context. Y represents O, S or NR 5 Hal represents chlorine or bromine. LG represents fluorine or chlorine. Alk represents (C1-C5)-alkyl.

[0581] For example, a compound of formula (CI) can be reacted with a compound of formula (C-II) in a nucleophilic substitution reaction in the presence of an alkaline reaction auxiliary to obtain a compound of formula (C-III). In a subsequent step, the compound of formula (C-III) can be directly converted with a compound of formula (C-IV) in a nucleophilic aromatic substitution reaction to obtain a compound of formula (IC). Alternatively, the compound of formula (C-III) can be reacted with a compound of formula (CV) in a nucleophilic aromatic substitution reaction to obtain a compound of formula (C-VI). These compounds can be condensed with an amine of formula (C-VII) or its hydrochloride or hydrobromide to obtain a compound of formula (C-VIII). The compound of formula (C-VIII) can then be reduced in a first step and reacted with an aldehyde of formula (C-IX) in a reductive amination reaction in a second step to obtain a compound of formula (IC).

[0582] According to another route to prepare compounds of formula (C-VIII), a benzyl alcohol of formula (CX) can be reacted with a chloride of formula (C-XI), which first gives a compound of formula (C-XII). After the alcohol is converted to a halogen with a halogenating agent, the halogenated intermediate can be reacted with a compound of formula (C-II) in a nucleophilic substitution reaction to give a compound of formula (C-VIII).

[0583] Method C - Step 1: Benzyl halides of formula (CI) are known, commercially available or can be obtained by known preparation methods (see for example 2-chloro-5-(chloromethyl)pyridine of EP0366085 or 5-(bromomethyl)-2-chloropyrimidine of WO2014 / 028669).

[0584] By heating in the presence of an alkaline reaction auxiliary agent (such as potassium carbonate or cesium carbonate), the benzyl halide of formula (CI) and the compound of formula (C-II) are reacted in a nucleophilic substitution reaction to obtain a compound of formula (C-III). The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone and acetonitrile. The reaction is preferably carried out at a temperature of 10°C to 120°C (see, for example, US 2003 / 0092739).

[0585] Method C - Step 2: Alcohols of formula (C-IV) are known, commercially available or can be obtained by known preparation methods (see for example 2-[methoxy(methyl)amino]ethanol in Journal of Organic Chemistry, 1957, 22, 579).

[0586] In the presence of a basic reaction auxiliary (e.g., sodium hydride), the compound of formula (C-III) is reacted with the alcohol of formula (C-IV) in a nucleophilic aromatic substitution reaction to give the compound of formula (IC). The reaction is carried out in the presence of an inert solvent or diluent. Examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, and tetrahydrofuran. The reaction is preferably carried out at a temperature of 0°C to 120°C (see, for example, LG=Cl in EP 2236507 or LG=F in EP 0135894).

[0587] Method C - Step 3: Reacting a compound of formula (C-III) with a compound of formula (CV) in a nucleophilic aromatic substitution reaction to give an acetal of formula (C-VI). This reaction is carried out under the conditions described in Method C, Step 2.

[0588] Method C - Step 4: Compounds of formula (C-VII) are known, commercially available or can be obtained by known preparation methods (see, for example, 1-(aminooxy)propane in EP 0 678 504). Some are also known as their hydrochloride or hydrobromide salts and are commercially available.

[0589] The acetal of formula (C-VI) is optionally reacted with a compound of formula (C-VII) or its hydrochloride or hydrobromide in a condensation reaction in the presence of an acid (e.g., p-toluenesulfonic acid) (see, e.g., WO2012 / 038851) or a dehydrating agent (e.g., magnesium sulfate) (see, e.g., WO2010 / 054024) to obtain a compound of formula (C-VIII). The reaction is carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are ethanol, methanol, acetonitrile, tetrahydrofuran and water, and mixtures of these solvents. The reaction is preferably carried out at a temperature of 10° C. to 80° C.

[0590] Method C - Step 5: Aldehydes of formula (C-IX) are known, commercially available or can be obtained by known preparation methods.

[0591] The compound of formula (C-VIII) can be converted to the compound of formula (IC) in a two-step one-pot reaction. In the first step, the compound of formula (C-VIII) is first reacted in the presence of a reducing agent (e.g., sodium cyanoborohydride) to obtain a compound wherein R 8 The intermediate of general formula (IC) represents hydrogen. The reaction is carried out at a temperature of 10°C to 80°C in the presence of a solvent or diluent such as acetic acid.

[0592] In the second step, this intermediate is reacted with an aldehyde of formula (C-IX) in the presence of a reducing agent in a reductive alkylation reaction to give 8 The compound of formula (IC) represents a (C1-C6)-alkyl group which is optionally substituted on C2 to C6. The reaction is carried out at a temperature of 10°C to 80°C in the presence of a solvent or diluent such as acetic acid.

[0593] Method C - Step 6: Compounds of formula (CX) and (C-XI) are known, commercially available, or can be obtained by known preparation methods. Other methods for their preparation are described in this application, such as the preparation of 2-fluoro-6-(hydroxymethyl)pyridin-3-ol.

[0594] In the presence of an alkaline reaction auxiliary (e.g., potassium carbonate or cesium carbonate), the compound of formula (CX) reacts with the chloride of formula (C-XI) in a nucleophilic substitution reaction to obtain a compound of formula (C-XII). The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone, and acetonitrile. The reaction is preferably carried out at a temperature of 20°C to 120°C.

[0595] Method C - Step 7: After converting the alcohol functional group to a halogen, the benzyl alcohol of formula (C-XII) can be reacted with a compound of formula (C-II) in a nucleophilic substitution reaction to give a compound of formula (C-VIII). This reaction is carried out under the conditions described in steps 1 and 2 of method A.

[0596] Reaction Scheme IV - Method D

[0597]

[0598] Compounds of formula (ID) can be prepared, for example, according to reaction scheme IV. Group A 1 、A 2 , X, Y, Z, R 7 、R 8 and R 9Hal represents chlorine or fluorine. D represents O or S. Alk represents optionally substituted (C1-C4)-alkyl.

[0599] Compounds of formula (ID') can be obtained by known preparation methods or by methods analogous to those described in the present application. Thiols and aldehydes (DI) and their sodium salts are known, commercially available or can be obtained by known preparation methods. In the presence of a basic reaction auxiliary (such as sodium hydride), compounds of formula (ID') are reacted with alcohols and thiols of formula (DI) in a nucleophilic aromatic substitution reaction to obtain compounds of formula (ID). Sodium salts of alcohols and thiols of formula (DI) can also be used directly. In this case, the addition of a base is superfluous. The reaction is carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and tetrahydrofuran. The reaction is preferably carried out at a temperature of 0°C to 80°C.

[0600] Reaction Scheme V - Method E

[0601]

[0602] Compounds of formula (IE) can be prepared, for example, according to Reaction Scheme V. Group A 1 、A 2 、A 3 、A 4 , X, Y, R 7 、R 8 、R 9 and R 11 has the above meanings and optionally further meanings relevant to the preparation methods, which are apparent from the text or context. Hal represents bromine or iodine. Ar represents, in each case, optionally substituted phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiophene-2-yl or thiophene-3-yl.

[0603] In principle, compounds of the formula (IE') can be obtained by known preparation methods or analogously to the preparation methods described in this application. Boronic esters (EI) and boronic acids (E-II) are known, commercially available or can be obtained by known preparation methods.

[0604] The compound of formula (IE') is reacted with an optionally substituted arylboronic acid (E-II) or arylboronic acid pinacol ester (EI) in the presence of a suitable coupling catalyst (e.g., tetrakis(triphenylphosphine)palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)) in the presence of a base (e.g., potassium carbonate or sodium carbonate) to give a compound of formula (IE) (see, e.g., WO2014 / 201206 or WO2016 / 059097). The reaction is carried out in an inert solvent or diluent. Examples that may be mentioned are 1,4-dioxane, toluene or tetrahydrofuran, in each case optionally in combination with water. The reaction is preferably carried out at a temperature of 40°C to 120°C.

[0605] Reaction Scheme VI - Method F

[0606]

[0607] Compounds of formula (F-VIII) and (F-IV) can be prepared, for example, according to reaction scheme VI. Group A 1 、A 2 、A 3 、A 4 、R 6 、R 7 、R 8 and R 9 has the above meanings and optionally other meanings related to the preparation method, which are obvious from the text or context. 6 or S. LG 1 Represents chlorine or fluorine. LG 2 represents chlorine or bromine. Alk represents an optionally substituted (C1-C5)-alkyl group. D represents a cyano group, a (C1-C3)-alkoxycarbonyl group, a formyl group, or a CH2OPG group. PG represents a protecting group, for example, tert-butyldimethylsilyl. Protective groups for alcohols, their introduction and removal are known to those skilled in the art. For example, a review is provided in TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 3rd edition, 1999 (Wiley-Interscience).

[0608] Method F - Step 1: Compounds of formula (FI) and formula (F-II) are known, commercially available or can be obtained by known preparation methods (see for example 2-[methoxy(methyl)amino]ethanol in Journal of Organic Chemistry, 1957, 22, 579).

[0609] In the presence of a basic reaction auxiliary (e.g., sodium hydride or potassium carbonate), a compound of formula (FI) is reacted with a compound of formula (F-II) in a nucleophilic aromatic substitution reaction to give a compound of formula (F-III). The reaction is carried out in the presence of an inert solvent or diluent. Examples that may be mentioned are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and acetonitrile. The reaction is preferably carried out at a temperature between 0°C and 100°C (see, for example, the syntheses of the following substances described in this application: 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carbonitrile, 6-{2-[methoxy(methyl)amino]ethoxy}nicotinaldehyde, 3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridine-2-carboxylic acid methyl ester), and 5-(4-ethylpiperazin-1-yl)-3-fluoropyridine-2-carboxylic acid ethyl ester).

[0610] Method F - Step 2: Depending on the substituent D, compounds of formula (F-III) can be converted into compounds of structure (F-IV) by a one-step or optionally multi-step process.

[0611] If D represents a cyano group, the cyano functional group can be hydrolyzed in the presence of an alkali (such as sodium hydroxide) to obtain an acid functional group. The reaction is carried out in the presence of an inert solvent or a diluent. Examples that can be mentioned are ethanol, methanol, tetrahydrofuran and water, or optionally a mixture of these substances. The reaction is preferably carried out at a temperature of 20 ℃ to 120 ℃ (see, for example, the synthesis of (6-methoxypyridin-3-yl) methanol in WO2010 / 043377 or the synthesis of 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-methyl-formiate in the present application). Then, the acid functional group can be converted into a compound of formula (F-III) in the presence of an inorganic acid (such as sulfuric acid) and an alkanol of (C1-C3) chain length, wherein D represents a (C1-C3)-alkoxycarbonyl group (see, for example, the synthesis of 3-bromopyridine-2-methyl carboxylate in WO2003 / 084917 or the synthesis of 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-methyl carboxylate in the present application). The reaction is preferably carried out in the presence of an excess of (C1-C3)-alkanol as a solvent or diluent, optionally as a mixture with another solvent or diluent. The reaction is preferably carried out at a temperature of 40°C to 100°C.

[0612] If D represents a (C1-C3)-alkoxycarbonyl group, the ester function can be reduced in the presence of a suitable reducing agent (such as sodium borohydride or diisobutylaluminum hydride) to give the benzyl alcohol of formula (F-IV). If the reaction is carried out in the presence of sodium borohydride, a suitable solvent or diluent, such as ethanol or methanol, is used. The reaction is preferably carried out at a temperature of 0°C to 50°C. If diisobutylaluminum hydride is used, the reaction is carried out in a suitable inert solvent (such as toluene or dichloromethane). The reaction is preferably carried out at a temperature of -78°C to +30°C (see, for example, the syntheses of (5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridin-2-yl)methanol) and (3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol described herein).

[0613] If D represents a formyl group, the formyl group can be reduced in the presence of a suitable reducing agent (e.g., sodium borohydride) to give the benzyl alcohol of formula (F-IV). If the reaction is carried out in the presence of sodium borohydride, a suitable solvent or diluent is used, such as ethanol or methanol, optionally as a mixture with tetrahydrofuran. The reaction is preferably carried out at a temperature of 0° C. to 50° C.

[0614] If D represents -CH2OPG, then can remove protecting group under different conditions according to its property.The conditions for removing alcohol protecting group are known to those skilled in the art.For example, in TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, the 3rd edition, 1999 (Wiley-InterScience) provides a review.

[0615] Method F - Step 3: Halides of formula (F-VI) are known, commercially available or can be obtained by the preparation methods described in this application (see, for example, the preparation of 2-bromo-N-methoxy-N-methylethanamine hydrobromide (1:1)). Compounds of formula (FV) are known, commercially available or can be obtained by known preparation methods (see, for example, the preparation of 2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-ol described in this application).

[0616] In the presence of a basic reaction auxiliary (such as potassium carbonate) and optionally in the presence of sodium iodide, the compound of formula (F-VI) is reacted with the alcohol of formula (FV) in a nucleophilic substitution reaction to obtain a compound of formula (F-VII). The reaction is carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone and tetrahydrofuran. The reaction is preferably carried out at a temperature of 0°C to 100°C (see, for example, the reaction of 2-bromo-N,N-dimethylethylamine with 5-bromopyridine-3-ol in WO2016 / 040185).

[0617] Method F - Step 4: Depending on the substituent D, the compound of formula (F-VII) can be converted into the compound of structure (F-VIII) in a single or optionally multi-step process. The reaction conditions correspond to the reaction conditions described for the reaction of the compound of formula (F-III) to the compound of formula (F-IV) in step 2.

[0618] Method F - Step 5: Compounds of formula (F-IX) are known, commercially available or can be obtained by known preparation methods.

[0619] In the presence of an alkaline reaction auxiliary agent (such as potassium carbonate or cesium carbonate), the compound of formula (FV) is reacted with the chloride of formula (F-IX) in a nucleophilic substitution reaction to obtain a compound of formula (FX). The reaction is optionally carried out in the presence of an inert solvent or diluent. Examples that can be mentioned are N,N-dimethylformamide, N-methyl-2-pyrrolidone and acetonitrile. The reaction is preferably carried out at a temperature of 20° C. to 120° C. (see, for example, the synthesis of 3-fluoro-5-[2-(methoxyimino)ethoxy]pyridine-2-methylformate described in the present application).

[0620] Method F - Step 6: Aldehydes of formula (F-XI) are known, commercially available or can be obtained by known preparation methods.

[0621] The compound of formula (FX) can be converted to the compound of formula (F-VIII) in a two-step one-pot reaction. In the first step, the compound of formula (FX) is first reacted in the presence of a reducing agent (e.g., sodium cyanoborohydride) to give 8 The intermediate of formula (F-VIII) represents hydrogen. The reaction is carried out at a temperature of 10°C to 80°C in the presence of a solvent or diluent such as acetic acid.

[0622] In the second step, this intermediate is reacted with an aldehyde of formula (F-XI) in the presence of a reducing agent in a reductive alkylation reaction to give a compound of formula (F-VIII) wherein R 8represents (C1-C6)-alkyl optionally substituted on C2 to C6. The reaction is carried out at a temperature of 10°C to 80°C in the presence of a solvent or diluent (eg acetic acid).

[0623] Reaction Scheme VII - Method G

[0624]

[0625] Compounds of formula (IG) can be prepared, for example, according to reaction scheme VII. Group A 1 、A 2 、A 3 、A 4 、R 7 、R 8 , X, Y and Z have the above meanings and optionally other meanings related to the preparation method, which are obvious from the text or context. 6 represents an optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkanoyl or 8 A closed ring formed by 1 to 3 CH2 groups. 5 represents an optionally substituted (C1-C4)-alkyl group. 9 represents an optionally substituted (C1-C6)-alkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-alkylsulfonyl or (C1-C6)-alkoxycarbonyl group. Alk represents an optionally substituted (C1-C6)-alkyl group. Alk' represents an optionally substituted (C1-C5)-alkyl group. LG represents a leaving group, such as a halogen or a sulfonate.

[0626] Method G - Step 1: Compounds of formula (GI) can be obtained by the methods shown in Reaction Schemes I and III.

[0627] The tert-butoxycarbonyl group of the compound of formula (GI) can be removed under acidic conditions. The acid used is preferably hydrogen chloride or trifluoroacetic acid. The reaction is optionally carried out in the presence of an inert solvent or diluent or in pure trifluoroacetic acid. Exemplary solvents that may be mentioned are 1,4-dioxane, dichloromethane and water. The reaction is preferably carried out at a temperature of 0°C to 60°C. (See, for example, the synthesis of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(pyrrolidin-3-yloxy)pyridine described herein or US2015 / 238641).

[0628] Method G - Step 2: Depends on the substituent R 9 , the compound of formula (G-II) can be converted to the compound of structure (1-G) in a one-step process.

[0629] a) Where R 9Compounds of structure (IG) representing optionally substituted (C1-C6)-alkyl groups are obtained by reacting a compound of formula (G-II) with an alkylating agent of general structure (G-III) in the presence of a basic reaction auxiliary (e.g., potassium carbonate or triethylamine). Preferred leaving groups LG are halogens such as chlorine, bromine, or iodine, or sulfonates such as methanesulfonate or p-toluenesulfonate. The reaction is optionally carried out in the presence of an inert solvent or diluent (e.g., acetonitrile, dichloromethane, or N,N-dimethylformamide). The reaction is preferably carried out at a temperature of 0°C to 100°C (see, for example, WO2014 / 207240 or WO2014 / 116684).

[0630] Alternatively, a compound of formula (G-II) is reacted with an aldehyde of formula (G-IV) in the presence of a reducing agent (e.g. sodium cyanoborohydride) in a reductive alkylation reaction to give a compound of formula (IG) wherein R 9 represents (C1-C6)-alkyl optionally substituted on C2 to C6. The reaction is carried out at a temperature of 10°C to 80°C in the presence of a solvent or diluent such as acetic acid.

[0631] b) Where R 9 The compound of structure (IG) representing an optionally substituted (C1-C6)-alkylcarbonyl, (C1-C6)-alkylsulfonyl or (C1-C6)-alkoxycarbonyl group is obtained by reacting a compound of formula (G-II) with an acyl chloride of general structure (GV) or with a sulfonyl chloride of general structure (G-VI) or with a chloroformate of general structure (G-VII). The reaction is preferably carried out in the presence of a basic reaction auxiliary (such as triethylamine or diisopropylethylamine) and an inert solvent or diluent (such as dichloromethane, tetrahydrofuran or acetonitrile). The reaction is preferably carried out at a temperature of 0°C to 100°C (see, for example, the reaction with an acyl chloride in US2015 / 259317, the reaction with a sulfonyl chloride in WO2004 / 041264 or the reaction with a chloroformate in WO2004 / 089925).

[0632] Another embodiment of the present invention is directed to intermediates and includes compounds of formula (Va) or (Vb) below:

[0633]

[0634] in

[0635] A 1 represents N or CH,

[0636] A 2 represents N or CH, at least A 1 or A 2 Represents N and preferably A 1 Represents N and A2 Represents CH,

[0637] R 16 represents hydrogen, methyl, fluorine or methoxy,

[0638] R 17 represents a cyano group, a hydroxymethyl group, a methylcarboxyl group, an ethylcarboxyl group or a 3-bromophenoxymethyl group,

[0639] R 18 In the compounds of formula (Va) represents the group:

[0640] or bromine,

[0641] The following compounds are excluded:

[0642]

[0643] In a preferred embodiment of the present invention, R 18 Representative groups:

[0644]

[0645] In another preferred embodiment of the present invention, the compound of formula (Vb) represents:

[0646]

[0647] Furthermore, a particularly preferred embodiment of the present invention relates to compounds of the formulae (Va-1 to Va-14) and (Vb-1):

[0648]

[0649] The above-described preparation process provides, inter alia, compounds of formula (I) as described in Table 1.

[0650] Table 1

[0651] Compounds of formula (Ia)

[0652]

[0653] The substituents Z, Y, A 1 、A 2 、A 3 、A 4 and * have the following meanings:

[0654]

[0655]

[0656]

[0657]

[0658]

[0659]

[0660]

[0661]

[0662]

[0663]

[0664]

[0665]

[0666]

[0667] 2-[(5-fluoro-6-{[(6-fluorobiphenyl-3-yl)oxy]methyl}pyridin-3-yl)oxy]-N-methoxy-N-methyl Preparation of ethylamine

[0668]

[0669] Under argon, 58 mg (0.42 mmol) of potassium carbonate, 49 mg (42 μmol) of tetrakis(triphenylphosphine)palladium, 1 ml of water, and 51 mg (0.42 mmol) of phenylboronic acid were added to a solution of 85 mg (0.21 mmol) of 2-({6-[(3-bromo-4-fluorophenoxy)methyl]-5-fluoropyridin-3-yl}oxy)-N-methoxy-N-methylethanamine in 5 ml of tetrahydrofuran. The reaction mixture was freed of dissolved oxygen by passing through an argon stream and then stirred at 80° C. overnight. Silica gel was then added and the solvent removed under reduced pressure. The residue was chromatographed first on silica gel by MPLC (gradient: ethyl acetate / cyclohexane) and then by HPLC (gradient: H 2 O / acetonitrile). 80 mg of 2-[(5-fluoro-6-{[(6-fluorobiphenyl-3-yl)oxy]methyl}pyridin-3-yl)oxy]-N-methoxy-N-methylethylamine were obtained.

[0670] 1H-NMR (400.0MHz, d6-DMSO): δ = 8.2304 (2.2); 8.2263 (2.2); 7.5763 (1.4); 7.5681 (2.6); 7.5640 (1 .8);7.5471(4.3);7.4984(1.9);7.4804(3.7);7.4611(2.0);7.4291(0.8);7.4259(1.4);7.4227( 0.9); 7.4135(0.5); 7.4076(1.7); 7.3895(0.6); 7.2630(1.2); 7.2404(1.7); 7.2374(1.6); 7.2147(1.5); 7.1731(1.2); 7.1653(1.4); 7.1570(1.3); 7.1492(1.4); 7.0680(0.8); 7.0587(1.3); 7.050 3(0.8);7.0456(0.8);7.0367(1.0);7.0280(0.6);5.1873(4.3);5.1829(4.6);4.2340(1.9);4.2203(4.0);4.2066(2.1);3.4025(19.6);3.3189(19.4);2.9769(1.8);2.9633(3.6);2.9495(1.8); 2.6708(0.4); 2.5643(16.0); 2.5409(36.2); 2.5239(0.9); 2.5104(22.3); 2.5061(46.1); 2.5016(61.5); 2.4971(45.7); 2.4929(23.3); 2.3283(0.4); 0.0079(1.5); -0.0002(41.0); -0.0084(1.9).

[0671] 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-ethoxypyridin-3-yl)oxy]-N-methoxy- Preparation of N-methylethylamine

[0672]

[0673] At room temperature, 9.6 mg (0.14 mmol) of sodium ethoxide were added to a solution of 20 mg (47 μmol) of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxy-N-methylethanamine in 1 ml of dimethylacetamide. The reaction mixture was stirred overnight and then chromatographed by HPLC (gradient: H2O / acetonitrile). This gave 7 mg of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-ethoxypyridin-3-yl)oxy]-N-methoxy-N-methylethanamine.

[0674] 1 H-NMR(400.0MHz,d6-DMSO):δ=9.9594(0.4);8.2457(2.4);8.2230(2.6);7.7922(1.9);7.7708(2.7);7.6965(3.2);7.6791(1.9);7.6739(3.3);7.6593(2.4);7.6384(1.3);7.3698(2.4);7.3498(2.8);7.2878(2.3);7.2684(2.1);7.1449(2.7);7.1251(2.3);5.2364(7.8);4.5171(0.3);4.3665(1.3);4.3490(4.1);4.3315(4.2);4.3139(1.4);4.1371(2.1);4.1226(4.5);4.1080(2.3);3.4096(18.6);3.4001(2.0);3.3204(31.9);2.9799(2.3);2.9655(4.6);2.9511(2.3);2.6709(0.6);2.5723(16.0);2.5558(1.6);2.5058(75.0);2.5019(95.4);2.4980(72.3);2.3286(0.5);1.3184(4.2);1.3009(8.7);1.2834(4.2);1.2308(0.6);0.1457(0.5);-0.0004(99.6);-0.1499(0.5)。

[0675] 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methylpyridin-3-yl}oxy)-N-methoxy Preparation of 4-Methyl-N-ethylethylamine

[0676]

[0677] Step 1: Preparation of 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carbonitrile

[0678] A solution of 1.38 g (13.1 mmol) of 2-[methoxy(methyl)amino]ethanol in 4 ml of N-methyl-2-pyrrolidone was slowly added dropwise to a cold suspension of 686 mg (15.7 mmol) of sodium hydride (55% strength dispersion in mineral oil) in 32 ml of N-methyl-2-pyrrolidone. The reaction mixture was stirred at room temperature for 30 minutes, after which a solution of 2.00 g (13.1 mmol) of 5-chloro-3-methylpyridine-2-carbonitrile in 4 ml of N-methyl-2-pyrrolidone was added dropwise. Stirring was continued at room temperature overnight, after which 20 ml of ethyl acetate was added. After 5 minutes, water was added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was adsorbed onto RP silica gel and chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). This gave 1.20 g of 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carbonitrile.

[0679] 1 H-NMR (400.0MHz, CDCl3): δ = 8.7253 (0.4); 8.7197 (0.4); 8.2526 (1.8); 8.2459 (1.9); 7.7789 (0.3 );7.7733(0.3);7.2654(4.4);7.1286(1.7);7.1221(1.7);4.2396(1.4);4.2259(2.9);4.2122(1 .6); 3.9097(0.7); 3.5168(16.0); 3.0561(2.1); 3.0424(4.0); 3.0286(2.0); 2.7222(0.6); 2.6748(14.6); 2.6247(1.3); 2.5715(0.4); 2.5393(11.4); 2.0097(3.7); 1.6280(0.5); -0.0002(3.7).

[0680] Steps 2 & 3: Preparation of methyl 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carboxylate

[0681] 2.17 g (54.3 mmol) of sodium hydroxide, 2.7 ml of water, and 2.7 ml of ethanol were added to a solution of 1.20 g (5.43 mmol) of 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carbonitrile in 5.4 ml of tetrahydrofuran, and the mixture was stirred at 70°C for 12 hours. The reaction mixture was then diluted with water, acidified with 1 M hydrochloric acid, and repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. 245 mg of a residue was obtained. The aqueous phase was likewise concentrated under reduced pressure, and the residue was azeotropically dried with CHCl. ​​4.28 g of a residue was obtained, which was dissolved in 45 ml of methanol and a catalytic amount of sulfuric acid was added. The reaction solution was heated under reflux for 5 days, and then the solvent was removed under reduced pressure. Saturated NaHCO solution was added to the residue, and the resulting solution was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. This gave 787 mg of methyl 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carboxylate.

[0682] 1 H-NMR (400.0MHz, CDCl3): δ = 8.2899 (1.8); 8.2832 (1.8); 7.2673 (4.3); 7.1065 (1.6 );7.1003(1.6);5.3010(0.6);4.2446(1.2);4.2311(2.5);4.2174(1.4);4.0111(1 .3); 3.9793(1.3); 3.9549(15.8); 3.9047(0.5); 3.5244(16.0); 3.0596(1.9); 3.0459(3.7); 3.0322(1.9); 2.6789(14.2); 2.6359(11.1); 1.6127(0.4); -0.0002(2.9).

[0683] Step 4: Preparation of (5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridin-2-yl)methanol

[0684] At -78°C, 14.8 ml (14.8 mmol) of a 1M diisobutylaluminum hydride solution was added dropwise to a solution of 750 mg (2.95 mmol) of methyl 5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridine-2-carboxylate in 32 ml of toluene. The reaction solution was stirred at -10°C for 60 minutes, 50 ml of a saturated potassium sodium tartrate solution was added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was dissolved in 10 ml of methanol, cooled with ice, and 64 mg (1.7 mmol) of sodium borohydride was added. The solution was stirred at room temperature for 2 hours. The solvent was removed under reduced pressure. Water was added to the residue, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. 498 mg of (5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridin-2-yl)methanol was obtained.

[0685] 1 H-NMR (400.0MHz, CDCl3): δ = 8.1296 (1.7); 8.1232 (1.8); 7.2654 (3.6); 7.1012 ( 1.6);7.0955(1.6);4.6307(3.8);4.5215(0.5);4.1966(1.3);4.1829(2.6);4. 1692(1.4);3.8572(0.5);3.5324(16.0);3.0446(2.0);3.0308(3.9);3.0171(2.0);2.6788(14.8);2.2275(0.4);2.2064(10.4);1.6595(0.9);-0.0002(2.0).

[0686] Step 5: Preparation of 2-{[6-(chloromethyl)-5-methylpyridin-3-yl]oxy}-N-methoxy-N-methylethylamine

[0687] At 0° C., 0.23 ml (1.3 mmol) of diisopropylethylamine and 34 μl (0.44 mmol) of methanesulfonyl chloride were added to a solution of 100 mg (442 μmol) of (5-{2-[methoxy(methyl)amino]ethoxy}-3-methylpyridin-2-yl)methanol in 3 ml of CHCl. ​​The reaction solution was stirred at room temperature overnight, then diluted with CHCl and washed with saturated NaHCO solution and water. The organic phase was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. This gave 102 mg of 2-{[6-(chloromethyl)-5-methylpyridin-3-yl]oxy}-N-methoxy-N-methylethylamine.

[0688] 1H-NMR (400.0MHz, CDCl3): δ = 8.1510 (1.8); 8.1442 (1.8); 7.2641 (5.4); 7.0808 (1.7);7.0743(1.7);4.7037(0.5);4.6904(9.1);4.1959(1.4);4.1823(2.7);4 .1686(1.5); 3.8559(0.5); 3.5265(16.0); 3.0400(2.0); 3.0263(3.8); 3.0125(2.0); 2.6738(14.6); 2.4657(0.4); 2.4289(11.1); 1.6500(0.9); -0.0002(3.5)

[0689] Step 6: 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methylpyridin-3-yl}oxy)-N- Preparation of methoxy-N-methylethylamine

[0690] 61 mg (0.33 mmol) of dibenzo[b,d]furan-2-ol and 227 mg (1.64 mmol) of KCO were added to a solution of 100 mg (409 μmol) of 2-{[6-(chloromethyl)-5-methylpyridin-3-yl]oxy}-N-methoxy-N-methylethanamine in 3 ml of N,N-dimethylformamide. The reaction mixture was stirred at 70°C for 4 hours and at room temperature overnight. Water was then added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed by HPLC (gradient: H2O / acetonitrile). This gave 93 mg of 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methylpyridin-3-yl}oxy)-N-methoxy-N-methylethanamine.

[0691] 1H-NMR(400.0MHz,CDCl3):δ=8.2065(2.0);8.1997(2.0);7.9262(1.5);7.9069(1.6);7.5833(2.4);7.5768(2.5);7.5423(1.4);7.5217(2.2);7.4626(2.3);7.4559(1.0);7.4536(0.9);7.4401(3.2);7.4172(0.8);7.3375(1.2);7.3184(1.8);7.3000(0.8);7.2610(7.7);7.1522(1.4);7.1457(1.4);7.1299(1.3);7.1233(1.4);7.1162(1.9);7.1096(1.8);5.2523(8.4);4.2062(1.4);4.1927(2.7);4.1790(1.5);3.8629(0.5);3.5287(16.0);3.0459(1.9);3.0323(3.8);3.0186(1.9);2.6759(14.0);2.4599(11.8);2.0045(1.6);1.6104(5.7);-0.0002(5.0)。

[0692] 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methoxypyridin-3-yl}oxy)-N-methoxy Preparation of 4-Methyl-N-ethylethylamine

[0693]

[0694] Step 1: Preparation of methyl 3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridine-2-carboxylate

[0695] A solution of 1.35 g (12.9 mmol) of 2-[methoxy(methyl)amino]ethanol in 10 ml of N,N-dimethylformamide was added dropwise to a suspension of 673 mg (15.4 mmol) of sodium hydride (55% dispersion in mineral oil) in 80 ml of N,N-dimethylformamide. The reaction solution was stirred at room temperature for 30 minutes, followed by the dropwise addition of a solution of 2.38 g (12.9 mmol) of methyl 5-fluoro-3-methoxypyridine-2-carboxylate in 10 ml of N,N-dimethylformamide. The reaction mixture was stirred at room temperature overnight, water was added, and the mixture was extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed by HPLC (gradient: H2O / acetonitrile). 2.76 g of crude product was obtained, which was further purified by chromatography by HPLC (gradient: H2O / acetonitrile). 1.43 g of methyl 3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}picolinate (purity about 69%) was obtained as a mixture with 2-[methoxy(methyl)amino]ethyl-3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}picolinate.

[0696] 1 H-NMR (400.0MHz, CDCl3): δ = 8.0372 (1.9); 8.0315 (1.9); 8.0009 (0.9); 7.9951 (0.9); 7.2691 (3.6); 6.92 42(1.7);6.9186(1.7);6.8404(0.8);6.8346(0.8);4.2815(1.0);4.2681(1.9);4.2547(1.1);3.9713(0 .6); 3.9495(16.0); 3.9380(6.1); 3.9351(6.2); 3.9249(10.7); 3.9142(0.6); 3.5489(0.5); 3.5312(11.7); 3.0632(1.4); 3.0497(2.7); 3.0362(1.4); 2.6847(10.4); 2.6366(0.4); 1.6400(2.2); -0.0002(3.8).

[0697] Step 2: Preparation of (3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol

[0698] At -78 ° C, 3.3 ml (3.3 mmol) of 1M diisobutylaluminum hydride solution was added dropwise to a solution of 1.43 g (5.29 mmol) of 3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridine-2-carboxylic acid methyl ester in 56 ml of toluene. The reaction solution was stirred at 0 ° C overnight. At 0 ° C, 10.6 ml (10.6 mmol) of 1M diisobutylaluminum hydride solution was then added. After stirring at 0 ° C for 1 hour, 3 ml of methanol was added dropwise, and 5 minutes later, 56 ml of saturated potassium sodium tartrate solution was added. The mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was dissolved in 5 ml of methanol, cooled with ice, and 114 mg (3.02 mmol) of sodium borohydride was added. The solution was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, water was added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed by HPLC (gradient: H2O / acetonitrile). 949 mg of (3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol were obtained.

[0699] 1 H-NMR (400.0MHz, CDCl3): δ = 7.8658 (0.8); 7.2645 (3.4); 6.8295 (2.2); 6.8242 ( 2.2);4.6788(2.4);4.6682(2.5);4.2230(1.2);4.2096(2.3);4.1962(1.3);4. 0111(0.5); 3.9995(0.9); 3.9882(0.4); 3.8247(14.4); 3.5389(16.0); 3.0482(1.8); 3.0347(3.5); 3.0212(1.9); 2.6855(14.5); 1.6298(0.8); -0.0002(3.3.)

[0700] Step 3: 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methoxypyridin-3-yl}oxy)- Preparation of N-methoxy-N-methylethylamine

[0701] To 100 mg (413 μmol) of (3-methoxy-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol were added 246 mg (2.06 mmol) of SOCl2 and a catalytic amount of N,N-dimethylformamide. The reaction mixture was stirred at room temperature for 4 hours and then concentrated under reduced pressure. The residue was dissolved in 2 ml of N,N-dimethylformamide, and 61 mg (0.33 mmol) of dibenzo[b,d]furan-2-ol and 285 mg (2.06 mmol) of K2CO3 were added. The reaction mixture was stirred at 70°C for 4 hours and at room temperature for 3 days, absorbed onto RP silica gel, and chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). This gave 48 mg of 2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-methoxypyridin-3-yl}oxy)-N-methoxy-N-methylethanamine.

[0702] 1 H-NMR (400.0MHz, CDCl3): δ=7.9991(2.4); 7.9934(2.7); 7.9143(1.4); 7.8 951(1.5);7.6111(2.2);7.6049(2.5);7.5409(1.3);7.5202(2.1);7.4563( 2.1); 7.4506(1.1); 7.4471(1.0); 7.4336(3.0); 7.4295(2.1); 7.4115(0.8); 7.4083(0.8); 7.3311(1.0); 7.3289(1.0); 7.3104(1.6); 7.2936(0.7); 7. 2916(0.7); 7.2605(8.3); 7.1897(1.4); 7.1832(1.5); 7.1673(1.2); 7.1609(1.3); 6.8950(2.2); 6.8894(2.5); 5.2982(2.7); 5.2508(8.2); 4.2445(1. 3); 4.2311(2.5); 4.2178(1.4); 3.8825(14.1); 3.5365(16.0); 3.0517(1.8); 3.0383(3.5); 3.0248(1.8); 2.6834(13.9); 1.5841(6.1); -0.0002(7.8).

[0703] Preparation of (5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol

[0704]

[0705] Step 1: Preparation of 5-[2-(methoxyimino)ethoxy]pyridine-2-carbaldehyde

[0706] At room temperature, 4.42g (32.0mmol) of KCO and a solution of 2-chloro-N-methoxyethylamine (22.4mmol) in 30ml of acetonitrile were added to a solution of 1.97g (16.0mmol) of 5-hydroxypyridine-2-carboxaldehyde in 30ml of acetonitrile. The reaction mixture was heated under reflux for 40 hours and stirred at room temperature for another 4 days. The precipitation was filtered out, the filtrate was concentrated under reduced pressure, and residue was dissolved in 15ml of acetonitrile. The mixture was filtered again, and the filtrate was concentrated under reduced pressure. 1.91g of 5-[2-(methoxyimino)ethoxy]pyridine-2-carboxaldehyde was obtained as residue.

[0707] 1 H-NMR (400.0MHz, CDCl3): δ = 10.0000 (4.9); 8.4785 (2.5); 8.4717 (2.5); 8.4568 (0.8); 8.4500 (0.8); 7.9809 (2.4); 7.9592 (2 .5);7.5613(1.3);7.5469(2.6);7.5328(1.4);7.3812(1.3);7.3743(1.3);7.3594(1.2);7.3530(1.2);7.3203(0.4);7.3136 (0.4); 7.2985(0.4); 7.2918(0.4); 7.2652(6.8); 6.9597(0.4); 6.9506(0.8); 6.9413(0.4); 4.9494(1.7); 4.9403(1.7); 4.7838(5.2); 4.7695(5.1); 3.9757(5.0); 3.9550(0.3); 3.9161(16.0); 3.9032(1.0); 3.8898(0.4); 1.6375(3.0); -0.0001(3.9).

[0708] Step 2: Preparation of (5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol

[0709] At 10°C, 926 mg (14.7 mmol) of sodium cyanoborohydride was added to a solution of 1.91 g (9.83 mmol) of 5-[2-(methoxyimino)ethoxy]pyridine-2-carbaldehyde in 15 ml of acetic acid, and the mixture was stirred at room temperature for 2 hours. After cooling, 12.1 g (147 mmol) of a 36.5% aqueous formaldehyde solution was added at 20°C. After 10 minutes, another 926 mg (14.7 mmol) of sodium cyanoborohydride was added. The reaction mixture was stirred at room temperature overnight, and the solvent was then removed under reduced pressure. 50 ml of water was added to the residue, the pH was adjusted to 10 with 50% sodium hydroxide solution, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed on silica gel by MPLC (gradient: ethyl acetate / cyclohexane). This gave 1.08 g of 5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol.

[0710] 1 H-NMR (400.0MHz, CDCl3): δ = 8.2963 (2.0); 8.2894 (2.0); 7.2869 (1.1); 7.2799 (1. 0);7.2697(2.7);7.2657(2.0);7.2585(1.7);7.2065(2.4);7.1852(1.4);4.9625( 0.5); 4.7643(0.5); 4.7038(7.6); 4.2049(1.5); 4.1912(2.9); 4.1775(1.6); 3.5311(16.0); 3.0514(2.2); 3.0377(4.2); 3.0239(2.1); 2.6800(15.3); -0.0002(1.2).

[0711] 2-{[6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-(methylthio)pyridin-3-yl]oxy}-N-methyl Preparation of oxy-N-methylethylamine

[0712]

[0713] 14.6 mg (0.21 mmol) of sodium methylthiolate was added to a solution of 46 mg (0.10 mmol) of 2-[(2-chloro-6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}pyridin-3-yl)oxy]-N-methoxy-N-methylethanamine in dimethylacetamide, and the mixture was stirred at room temperature overnight. A further 7.3 mg (0.10 mmol) of sodium methylthiolate was then added. After 2 hours at room temperature, a further 7.3 mg (0.10 mmol) of sodium methylthiolate was added, and the reaction mixture was stirred overnight. Water was added to the reaction mixture, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed by HPLC (gradient: H2O / acetonitrile). This gave 3 mg of 2-{[6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-(methylthio)pyridin-3-yl]oxy}-N-methoxy-N-methylethylamine.

[0714] 1 H-NMR (601.6MHz, CDCl3): δ = 8.2606 (1.7); 8.2455 (1.8); 7.8618 (1.6); 7.8475 (1.7); 7.5069 (1.2); 7.5011 (2.6); 7.4936 (1 .8);7.4861(2.4);7.4797(1.2);7.2589(26.6);7.1854(1.7);7.1718(2.0);7.0330(2.2);7.0193(1.9);6.9921(1.7);6.9 793(1.6); 5.3152(6.8); 4.2239(1.9); 4.2140(4.0); 4.2041(2.0); 3.5268(16.0); 3.1054(2.2); 3.0956(4.4); 3.0857(2.1); 2.6824(14.6); 2.5371(15.1); 1.5443(15.4); 1.2554(1.0); 0.0691(3.3); 0.0051(0.6); -0.0002(16.0); -0.0056(0.7).

[0715] 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxy-N-methylethylamine preparation

[0716]

[0717] Step 1: Preparation of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridine

[0718] 6.22 g (34.8 mmol) of 4-chloro-1-naphthol and 14.4 g (104 mmol) of KCO were added to a solution of 5.64 g (34.8 mmol) of 2-chloro-5-(chloromethyl)pyridine in 40 ml of N,N-dimethylformamide. The reaction mixture was stirred at 70°C for 16 hours and then concentrated under reduced pressure. The residue was dissolved in ethyl acetate, and the solution was washed with water and saturated ammonium chloride solution. The organic phase was then extracted with saturated ammonium chloride solution, and the combined aqueous phases were repeatedly extracted with ethyl acetate. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was adsorbed on silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 9.72 g of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridine.

[0719] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.6347 (4.5); 8.6289 (4.7); 8.2855 (3.6); 8.2647 (3.9); 8.1440 (3.6) ;8.1229(4.0);8.0817(2.7);8.0759(2.7);8.0612(2.9);8.0553(2.9);7.7505(1.7);7.7325(3.3);

[0720] 7.7140(2.2); 7.6592(2.5); 7.6462(6.3); 7.6409(3.8); 7.6256(6.5); 7.6154(5.7); 7.5948(5.0); 7.1313(5.5); 7.1104(5.1); 5.3830(16.0); 3.3373(32.0); 2.5096(30.8); 2.5056(39.6); 2.5016(30.3); 0.0074(0.9); -0.0002(21.8).

[0721] Step 2: Preparation of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(2,2-diethoxyethoxy)pyridine

[0722] 359 mg (8.22 mmol) of sodium hydride (55% dispersion in mineral oil) was added to a solution of 882 mg (6.58 mmol) of 2,2-diethoxyethanol in tetrahydrofuran, and the mixture was stirred at room temperature for 30 minutes. Then, 1.00 g (3.29 mmol) of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridine dissolved in 20 ml of tetrahydrofuran was added, and the reaction solution was stirred at 60°C for 4 hours and at room temperature for 12 hours. An additional 359 mg (8.22 mmol) of sodium hydride (55% dispersion in mineral oil) was then added, and the mixture was stirred at 60°C for an additional 6 hours and at room temperature overnight. Water and ethyl acetate were added to the reaction mixture, and the phases were separated. The organic phase was washed with water, and the aqueous phase was repeatedly extracted with ethyl acetate. The organic phases were combined and washed with saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was adsorbed onto silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 128 mg of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(2,2-diethoxyethoxy)pyridine and 891 mg of a contaminated fraction. This fraction was chromatographed on RP silica gel by MPLC (gradient: acetonitrile / H2O). This gave a further 652 mg of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(2,2-diethoxyethoxy)pyridine.

[0723] 1H-NMR(400.0MHz,d6-DMSO):δ=8.3586(1.9);8.3534(2.0);8.2309(1.4);8.2103(1.5);8.1313(1.5);8.1105(1.6);7.9306(1.2);7.9246(1.2);7.9094(1.3);7.9034(1.3);7.7362(0.7);7.7333(0.7);7.7190(1.1);7.7158(1.4);7.7124(0.8);7.6980(0.9);7.6950(0.9);7.6373(2.8);7.6166(3.5);7.5971(0.7);7.5944(0.6);7.1480(2.2);7.1271(2.0);6.9259(2.1);6.9047(2.0);5.2679(5.9);4.8430(1.1);4.8297(2.5);4.8165(1.2);4.2634(4.4);4.2501(4.2);3.7038(0.5);3.6861(1.6);3.6798(0.9);3.6684(1.8);3.6622(2.5);3.6507(0.7);3.6445(2.4);3.6269(0.7);3.5846(0.7);3.5670(2.3);3.5608(0.7);3.5494(2.4);3.5430(1.8);3.5318(0.9);3.5254(1.6);3.5078(0.5);3.3325(27.3);2.5258(0.6);2.5122(12.8);2.5081(24.9);2.5036(32.0);2.4991(23.6);2.4951(11.9);1.1454(7.9);1.1278(16.0);1.1102(7.6);0.0079(0.8);-0.0002(20.6);-0.0083(0.9)。

[0724] Step 3: Preparation of 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxyethylamine

[0725] A solution of 125 mg (1.49 mmol) of O-methylhydroxylamine hydrochloride in 3 ml of water was added to a solution of 200 mg (498 μmol) of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(2,2-diethoxyethoxy)pyridine in 20 ml of ethanol, and the mixture was stirred at 65°C overnight. The solvent was then removed under reduced pressure. Water and CH2Cl2 were added to the reaction mixture, and the phases were separated. The organic phase was washed with water, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was adsorbed on silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 160 mg of 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxyethylamine.

[0726] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.3813 (2.0); 8.3765 (3.2); 8.2340 (2.3); 8.2131 (2.4); 8.1323 (2. 4);8.1114(2.7);7.9720(0.9);7.9659(1.0);7.9608(1.3);7.9546(1.3);7.9510(1.1);7.9446(1. 1); 7.9395(1.3); 7.9335(1.2); 7.7372(1.2); 7.7344(1.2); 7.7200(1.8); 7.7169(2.3); 7.6990(1.5); 7.6960(1.4); 7.6766(1.2); 7.6628(2.4); 7.6490(1.3); 7.6398(4.3); 7.6193(5.6); 7.5989(1. 1); 7.5963(1.0); 7.1515(3.4); 7.1306(3.2); 7.0390(0.8); 7.0298(1.8); 7.0208(0.9); 6.9829(1.5); 6.9616(1.5); 6.9545(2.0); 6.9332(1.9); 5.2769(9.9); 5.0632(3.8); 5.0541(3.8); 4.9043(4 .8); 4.8905(4.8); 3.8585(11.2); 3.7910(16.0); 3.3331(34.8); 2.5260(0.9); 2.5083(35.1); 2.5039(45.3); 2.4994(33.8); 1.9903(1.2); 1.1934(0.3); 1.1756(0.6); 0.0078(1.4); -0.0002(33.0).

[0727] Step 4: 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxy-N-methyl Preparation of ethylamine

[0728] 49 mg (0.79 mmol) of sodium cyanoborohydride were added to a solution of 140 mg (392 μmol) of 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxyethanamine in 20 ml of acetic acid, and the mixture was stirred at room temperature for 1 hour. A further 49 mg (0.79 mmol) of sodium cyanoborohydride were then added. After 30 minutes at room temperature, 2.98 ml (39.2 mmol) of 36.5% aqueous formaldehyde solution were added, and after a further 20 minutes, 74 mg (1.2 mmol) of sodium cyanoborohydride were added. The reaction mixture was stirred at room temperature for 2 hours. Saturated aqueous NaHCO3 solution was then added, and the reaction mixture was repeatedly extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was adsorbed on silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 78 mg of 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]-N-methoxy-N-methylethylamine.

[0729] 1H-NMR(400.0MHz,d6-DMSO):δ=8.3630(5.1);8.3579(5.5);8.2317(3.9);8.2108(4.1);8.1311(4.0);8.1102(4.3);7.9169(3.2);7.9109(3.2);7.8956(3.3);7.8896(3.3);7.7361(1.8);7.7335(2.0);7.7160(3.8);7.6980(2.3);7.6953(2.4);7.6387(6.2);7.6180(8.4);7.5966(1.7);7.5943(1.8);7.1509(5.6);7.1300(5.2);6.9034(5.4);6.8821(5.2);5.2613(16.0);4.8123(1.3);4.7872(1.6);4.6588(1.7);4.4268(5.1);4.4124(10.6);4.3979(5.4);3.4092(42.0);3.3340(86.0);3.2821(2.8);2.9629(4.6);2.9486(9.2);2.9341(4.6);2.6773(0.4);2.6731(0.6);2.6687(0.4);2.5578(36.3);2.5082(62.5);2.5039(81.9);2.4997(64.1);2.3307(0.5);1.3969(1.8);1.2317(2.8);0.8527(0.4);0.0077(0.8);-0.0002(16.2)。

[0730] Preparation of {3-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]pyrrolidin-1-yl}acetonitrile

[0731]

[0732] Step 1: Preparation of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(pyrrolidin-3-yloxy)pyridine

[0733] At 0°C, 1.54 ml (6.16 mmol) of a 4M solution of hydrochloric acid in 1,4-dioxane was added to a solution of 280 mg (615 μmol) of tert-butyl 3-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]pyrrolidine-1-carboxylate in 6 ml of CHCl. ​​The reaction solution was stirred overnight at room temperature, 5 ml of water was added, and the pH was adjusted to 8 using saturated aqueous NaHCO. The phases were separated, and the aqueous phase was extracted twice with 5 ml of CHCl. ​​The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. This gave a further 249 mg of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(pyrrolidin-3-yloxy)pyridine.

[0734] 1H-NMR(400.0MHz,d6-DMSO):δ=8.3634(1.8);8.3580(1.7);8.2375(1.3);8.2173(1.4);8.1393(1.4);8.1186(1.6);7.9133(1.1);7.9073(1.0);7.8920(1.1);7.8860(1.1);7.7434(0.7);7.7405(0.7);7.7262(1.0);7.7229(1.3);7.7051(0.9);7.7021(0.8);7.6448(2.6);7.6241(3.3);7.6044(0.6);7.6018(0.6);7.1562(2.1);7.1353(1.9);6.8639(1.8);6.8427(1.7);5.4316(0.5);5.4174(0.7);5.4022(0.4);5.2648(5.3);3.5757(16.0);3.5001(0.3);3.4806(0.4);3.4702(0.4);3.3656(2.6);3.1757(0.6);3.1619(0.6);3.1449(0.8);3.1311(0.7);2.9862(0.6);2.9784(0.4);2.9593(0.8);2.9406(0.4);2.9270(0.8);2.9223(0.8);2.8958(1.0);2.8838(0.6);2.8750(0.5);2.8635(0.5);2.8569(0.4);2.5318(0.8);2.5183(17.8);2.5140(35.3);2.5095(47.3);2.5050(34.4);2.5007(16.0);2.0926(0.4);2.0759(0.5);2.0575(0.6);2.0415(0.5);1.8551(0.4);1.8380(0.4);1.8210(0.4)。

[0735] Step 2: {3-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]pyrrolidin-1-yl}acetonitrile Preparation

[0736] 35 μl (0.25 mmol) of triethylamine and 18 μl (0.25 mmol) of bromoacetonitrile were added to a solution of 90 mg (0.25 mmol) of 5-{[(4-chloro-1-naphthyl)oxy]methyl}-2-(pyrrolidin-3-yloxy)pyridine in 3 ml of tetrahydrofuran, and the mixture was stirred at 70°C for 30 minutes. The solvent was then removed under reduced pressure. The residue was adsorbed on silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 75 mg of {3-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}pyridin-2-yl)oxy]pyrrolidin-1-yl}acetonitrile.

[0737] 1H-NMR(400.0MHz,d6-DMSO):δ=8.3569(3.4);8.3518(3.4);8.3142(4.9);8.2335(2.5);8.2124(2.7);8.1313(2.6);8.1106(2.9);7.9180(2.2);7.9119(2.1);7.8967(2.2);7.8906(2.2);7.7358(1.2);7.7328(1.4);7.7187(1.8);7.7154(2.5);7.7119(1.4);7.6976(1.6);7.6945(1.6);7.6371(5.9);7.6164(7.2);7.5985(1.2);7.5958(1.2);7.1484(3.9);7.1275(3.6);6.8863(3.6);6.8650(3.5);5.7544(3.1);5.4337(0.4);5.4264(0.9);5.4188(1.0);5.4112(1.2);5.4074(1.3);5.3999(1.1);5.3921(0.9);5.3850(0.5);5.2594(10.2);3.8567(16.0);3.3186(33.8);3.2947(1.9);3.0038(1.5);2.9886(1.6);2.9775(2.0);2.9623(1.8);2.8469(0.6);2.8263(1.3);2.8108(1.4);2.7907(0.8);2.7530(1.7);2.7463(1.7);2.7267(1.4);2.7201(1.4);2.6757(0.3);2.6712(0.5);2.6667(0.4);2.5830(0.8);2.5628(1.6);2.5464(1.6);2.5420(1.2);2.5249(1.9);2.5111(25.9);2.5067(53.8);2.5022(74.6);2.4977(57.1);2.4934(28.5);2.3698(0.4);2.3506(0.8);2.3356(1.5);2.3164(1.4);2.3016(0.9);2.2820(0.4);2.0742(1.4);1.9166(0.4);1.9096(0.5);1.8961(0.7);1.8821(0.8);1.8750(0.8);1.8605(0.6);1.8472(0.4);1.8408(0.4);-0.0002(6.6)。

[0738] 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}-6-fluoropyridin-2-yl)oxy]-N-methoxy-N-methylethyl Preparation of amines

[0739]

[0740] 43 mg (0.98 mmol) of sodium hydride (55% dispersion in mineral oil) was added to a solution of 52 mg (0.49 mmol) of 2-[methoxy(methyl)amino]ethanol in 3 ml of tetrahydrofuran and 0.5 ml of N,N-dimethylformamide. A solution of 100 mg (327 mmol) of 3-{[(4-chloro-1-naphthyl)oxy]methyl}-2,6-difluoropyridine in 3 ml of tetrahydrofuran was added dropwise. The reaction mixture was stirred at room temperature for 2 days, ice was added, and the mixture was extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was adsorbed on RP silica gel and chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). This gave 7 mg of 2-[(5-{[(4-chloro-1-naphthyl)oxy]methyl}-6-fluoropyridin-2-yl)oxy]-N-methoxy-N-methylethylamine.

[0741] 1H-NMR(400.0MHz,d6-DMSO):δ=8.3185(0.4);8.2012(3.8);8.1806(4.1);8.1441(2.6);8.1346(4.3);8.1235(3.5);8.1186(3.5);8.1138(5.0);8.0986(2.6);7.7379(2.0);7.7351(2.0);7.7207(3.0);7.7176(3.8);7.7141(2.1);7.6997(2.6);7.6967(2.4);7.6441(6.7);7.6338(3.0);7.6312(3.0);7.6234(7.6);7.6165(2.7);7.6133(4.0);7.6105(2.9);7.5956(1.9);7.5930(1.8);7.1689(6.1);7.1480(5.6);6.8636(4.3);6.8431(4.2);5.2692(16.0);5.2479(0.4);4.3869(4.7);4.3729(9.7);4.3588(5.1);3.8703(3.1);3.4562(0.4);3.4080(45.7);3.3516(5.1);3.3445(5.1);3.2886(0.4);3.2287(0.3);2.9594(4.3);2.9454(8.5);2.9314(4.4);2.6770(0.7);2.6724(0.9);2.6680(0.7);2.5584(37.8);2.5257(2.1);2.5120(53.0);2.5079(106.6);2.5034(139.2);2.4989(102.1);2.4949(52.0);2.3874(0.4);2.3346(0.7);2.3302(1.0);2.3256(0.7);1.2984(0.5);1.2584(0.8);1.2318(2.7);0.1460(0.3);0.0079(2.7);-0.0002(78.0);-0.0084(3.4);-0.1496(0.4)。

[0742] Preparation of (6-{2-[methoxy(methyl)amino]ethoxy}pyridin-3-yl)methanol

[0743]

[0744] Step 1: Preparation of 6-{2-[methoxy(methyl)amino]ethoxy}nicotinaldehyde

[0745] Under stirring at room temperature, 686 mg (15.7 mmol) of sodium hydride (55% dispersion in mineral oil) was added to a solution of 1.64 g (13.1 mmol) of 6-fluoronicotinaldehyde in 30 ml of acetonitrile. After 10 minutes at room temperature, a solution of 1.38 g (13.1 mmol) of 2-[methoxy(methyl)amino]ethanol in 5 ml of acetonitrile was added dropwise. The reaction mixture was stirred overnight, then ethyl acetate and water were added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). 50 mg of 6-{2-[methoxy(methyl)amino]ethoxy}nicotinaldehyde was obtained.

[0746] 1 H-NMR (400.0MHz, d6-DMSO): δ = 9.9600 (16.0); 8.7610 (8.6); 8.7555 (8.3); 8.3457 (1.0); 8.1297 (5.1 );8.1241(4.9);8.1081(5.5);8.1024(5.9);8.0814(0.6);8.0752(0.5);8.0607(0.4);7.6942(0.5); 7.6887(0.5); 7.6727(0.6); 7.6671(0.5); 7.2136(0.7); 7.2067(0.6); 7.1927(0.6); 7.1859(0.5); 7.0042(7.5); 6.9826(7.2); 6.8655(0.9); 6.8443(0.8); 5.3751(2.9); 5.1906(0.6); 5.1765(1.0); 5.16 23(0.5); 4.8916(0.4); 4.5316(7.1); 4.5175(14.4); 4.5033(7.6); 4.4439(1.6); 4.4299(1.5); 3.4326(0.9); 3.4004(56.2); 3.3517(0.7); 3.3210(24.3); 2.9809(6.7); 2.9668(12.9); 2.9526(6.7); 2.9 050(0.4);2.6761(0.5);2.6720(0.6);2.5761(1.0);2.5563(50.5);2.5068(89.3);2.5025(113.6);2.4984(85.1);2.3338(0.5);2.3295(0.7);2.0957(0.8);2.0391(1.0);0.0038(9.9);-0.0004(50.2).

[0747] Step 2: Preparation of (6-{2-[methoxy(methyl)amino]ethoxy}pyridin-3-yl)methanol

[0748] A solution of 100 mg (476 μmol) of 6-{2-[methoxy(methyl)amino]ethoxy}nicotinaldehyde was dissolved in a mixture of 15 ml of methanol and 25 ml of tetrahydrofuran, and 27 mg (0.71 mmol) of sodium borohydride was added at 0°C. The reaction solution was stirred at room temperature for 1 hour. Water was then added, the organic solvent was removed under reduced pressure, and the aqueous phase was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. This yielded 90 mg of 6-{2-[methoxy(methyl)amino]ethoxy}pyridin-3-yl)methanol.

[0749] 1 H-NMR (400.0MHz, d6-DMSO): δ = 6.7875 (0.4); 6.7660 (0.3); 5.1460 (0.5); 4.4268 (0.7);4.4128(0.6);4.3792(0.4);4.3647(0.8);4.3501(0.4);3.3975(3.3);3.3 805(1.3); 3.3196(12.3); 3.3030(4.8); 3.2951(0.5); 3.2853(3.6); 2.9374(0.4); 2.9228(0.7); 2.9083(0.3); 2.6950(16.0); 2.5447(2.8); 2.5236(0.4); 2.5103 (8.4); 2.5059(17.3); 2.5014(23.1); 2.4968(16.9); 2.4926(8.6); 2.1965(1.8); 2.1765(3.5); 2.1560(2.4); 1.9887(1.4); 1.9379(0.9); 1.9203(2.2); 1.9174(1 .8);1.9117(0.5);1.9017(2.5);1.8914(0.4);1.8819(2.0);1.8621(0.6);1.3551(0.5);1.2351(0.4);1.1924(0.4);1.1746(0.7);1.1568(0.4);-0.0001(2.2).

[0750] Preparation of 6-fluoro-3'-(trifluoromethoxy)biphenyl-3-ol

[0751]

[0752] A mixture of 5.0 g (26 mmol) of 3-bromo-4-fluorophenol, 7.00 g (34.0 mmol) of [3-(trifluoromethoxy)phenyl]boronic acid, 7.60 g (55.0 mmol) of potassium carbonate, 35 ml of tetrahydrofuran, and 7 ml of water was freed of dissolved oxygen by the introduction of an argon stream, followed by the addition of 0.50 g (0.43 mmol) of tetrakis(triphenylphosphine)palladium. The reaction mixture was stirred at 80°C overnight and then concentrated under reduced pressure. The pH was adjusted to 1 using 1 M hydrochloric acid. Water and ethyl acetate were added, the phases were separated, and the aqueous phase was repeatedly extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). This yielded 4.85 g of 6-fluoro-3'-(trifluoromethoxy)biphenyl-3-ol.

[0753] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.3185 (1.1); 7.6289 (0.4); 7.6203 (1.7); 7.6 006(4.7);7.5807(3.6);7.5675(0.4);7.5484(2.9);7.5453(3.0);7.5287(1. 6); 7.5257(1.5); 7.4457(3.0); 7.4083(1.8); 7.4056(1.9); 7.4028(1.6); 7.3882(1.5); 7.3855(1.6); 7.3826(1.4); 7.1303(2.2); 7.1081(2.7); 7.1037(2. 5); 7.0815(2.6); 6.8504(2.1); 6.8429(2.6); 6.8339(2.1); 6.8264(2.6); 6.7931(1.5); 6.7833(2.0); 6.7755(1.3); 6.7710(1.4); 6.7614(1.6); 6.7535(1. 0); 2.5257(0.5); 2.5123(15.4); 2.5079(32.4); 2.5034(43.5); 2.4989(31.4); 2.4945(15.1); 2.0760(16.0); 0.0080(0.7); -0.0002(21.3); -0.0085(0.8).

[0754] Preparation of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyrimidine

[0755]

[0756] Step 1: Preparation of 5-(bromomethyl)-2-chloropyrimidine

[0757] A solution of 200 mg (1.56 mmol) of 2-chloro-5-methylpyrimidine, 277 mg (1.56 mmol) of N-bromosuccinimide, and 26 mg (0.16 mmol) of 2,2'-azobis(2-methylpropionitrile) in 17.6 ml of chlorobenzene was heated under reflux for 16 hours. The reaction solution was then washed with aqueous Na2SO3 and saturated aqueous NaHCO3, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 76 mg of 5-(bromomethyl)-2-chloropyrimidine.

[0758] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.9119 (1.1); 8.8913 (15.0); 8.8619 (0.7); 8.8222 (1.3); 8. 6390(1.4);5.5539(0.5);5.3766(0.9);4.8528(2.2);4.7481(16.0);4.7234(1.3);3.3281( 67.0); 2.6718(0.4); 2.5248(0.8); 2.5114(23.6); 2.5071(48.7); 2.5027(64.9); 2.4983(46.7); 2.4941(22.6); 2.3295(0.4); 2.2725(2.8); 2.2461(0.6); 1.4376(0.4); -0.0002(0.7).

[0759] Step 2: Preparation of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyrimidine

[0760] A suspension of 38 mg (0.21 mmol) of 4-chloro-1-naphthol and 60 mg (0.43 mmol) of potassium carbonate in 1 ml of acetonitrile was stirred at room temperature for 1 hour. The mixture was cooled to 0°C, and a solution of 76 mg (0.27 mmol) of 5-(bromomethyl)-2-chloropyrimidine in acetonitrile was added dropwise. The reaction mixture was stirred at room temperature overnight, after which water and saturated NaHCO₃ solution were added. The mixture was repeatedly extracted with ethyl acetate. The combined organic phases were washed with water and saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 70 mg of 2-chloro-5-{[(4-chloro-1-naphthyl)oxy]methyl}pyrimidine.

[0761] 1H-NMR (400.0MHz, d6-DMSO): δ = 9.0173 (16.0); 8.9478 (1.4); 8.8875 (0.4); 8.3 103(2.7);8.2893(2.8);8.1476(2.8);8.1269(3.1);7.7565(1.4);7.7534(1. 6); 7.7393(2.2); 7.7359(2.9); 7.7323(1.5); 7.7183(2.0); 7.7150(1.9); 7.6608(6.9); 7.6439(1.8); 7.6402(8.3); 7.6231(1.4); 7.6202(1.3); 7.1554(4.4 );7.1485(0.6);7.1345(4.1);7.1276(0.5);5.4057(11.9);5.3819(1.1);4.8531(0.5);3.3215(34.5);2.6719(0.4);2.5254(1.0);2.5206(1.5);2.5120(25 .1); 2.5075(54.3); 2.5029(73.9); 2.4983(52.7); 2.4938(24.5); 2.3297(0.4); 0.1459(0.4); 0.0080(3.4); -0.0002(106.7); -0.0085(3.6); -0.1498(0.4).

[0762] Preparation of 4-chloro-3-methoxyphenol and 2-chloro-5-methoxyphenol

[0763]

[0764] At 0°C, 342 mg (2.54 mmol) of sulfonyl chloride were added to a solution of 300 mg (2.42 mmol) of 3-methoxyphenol in 2 ml of CHCl. ​​The reaction solution was stirred at 0°C for 1 hour, after which water and CHCl were added. The phases were separated, and the aqueous phase was repeatedly extracted with CHCl. ​​The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure. The residue was adsorbed on RP silica gel and chromatographed on RP silica gel by MPLC (gradient: HO / acetonitrile). This gave 125 mg of 4-chloro-3-methoxyphenol and 194 mg of 2-chloro-5-methoxyphenol.

[0765] 4-Chloro-3-methoxyphenol:

[0766] 1H-NMR (400.0MHz, d6-DMSO): δ = 9.6746 (2.2); 7.1593 (2.9); 7.1379 (3.1); 7.0630 (0.3); 7.0428 (0.5); 6.5162 (2.7); 6.5096 (2.8); 6.3642 (1.8); 6.3576 (1.7); 6.3484 (0.4); 6.3427 (1.7); 6.3362 (1.7); 6.3152 (0.4); 6. 3094(0.4);3.7876(0.8);3.7744(16.0);3.7390(0.5);3.6885(0.6);3.6800(2.9);3.3248(6.3);2.5240(0.4);2.5064(18.8);2.5021(24.2);2.4978(17.3);2.0253(0.4);0.0078(0.5);-0.0002(11.6);-0.0073(0.4).

[0767] 2-Chloro-5-methoxyphenol:

[0768] 1 H-NMR (400.0MHz, d6-DMSO): δ = 10.1114 (4.9); 7.2062 (2.6); 7.1843 (2.8); 6.5256 (2.6); 6.5185 (2.9); 6.4149 (1.6); 6.407 7(1.4); 6.3929(1.5); 6.3857(1.3); 3.6893(16.0); 3.3297(3.7); 2.5112(4.3); 2.5071(8.6); 2.5028(11.2); 2.4984(7.9).

[0769] Preparation of 5-[2-(diethylamino)ethoxy]pyridine-2-carboxaldehyde

[0770]

[0771] A suspension of 1.0 g (8.1 mmol) of 5-hydroxypyridine-2-carboxaldehyde and 3.4 g (25 mmol) of KCO in 25 ml of N,N-dimethylformamide was stirred at 65°C for 2 hours. Subsequently, 13 mg (81 μmol) of potassium iodide and 2.43 g (9.14 mmol) of 2-bromo-N,N-diethylethanamine hydrobromide (1:1) were added at 30°C, and the reaction mixture was stirred at 65°C for 16 hours. 1.27 g (4.87 mmol) of 2-bromo-N,N-ethylethanolamine hydrobromide (1:1), 1.7 g (12 mmol) of potassium carbonate, and 13 mg (81 μmol) of potassium iodide were added, and the mixture was stirred at 65°C for a further 20 hours. The reaction mixture was filtered through Celite, and the solvent was removed under reduced pressure. The residue was chromatographed on RP silica gel by MPLC (gradient: H2O / acetonitrile). After removing the solvent under reduced pressure, water was added to the residue, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. 803 mg of 5-[2-(diethylamino)ethoxy]pyridine-2-carbaldehyde was obtained.

[0772] 1 H-NMR (400.0MHz, d6-DMSO): δ = 9.8858 (4.6); 8.4862 (2.4); 8.4793 (2.5); 7.9378 (2.3); 7.9161 (2.6); 7.6 092(1.2);7.6024(1.3);7.5874(1.1);7.5807(1.1);4.2358(2.2);4.2208(4.6);4.2059(2.3);3.3230(1 0.4); 2.8232(2.2); 2.8083(4.5); 2.7933(2.2); 2.5739(2.3); 2.5561(7.3); 2.5383(7.5); 2.5205(3.2); 2.5073(16.8); 2.5030(22.2); 2.4987(17.2); 0.9826(8.0); 0.9649(16.0); 0.9471(7.7); -0.0002(20.2).

[0773] Preparation of ethyl 5-(4-ethylpiperazin-1-yl)-3-fluoropyridine-2-carboxylate

[0774]

[0775] In a microwave reactor, a suspension of 1.98 g (17.4 mmol) of 1-ethylpiperazine, 2.50 g (13.4 mmol) of ethyl 3,5-difluoropyridine-2-carboxylate and 2.40 g (17.4 mmol) of potassium carbonate in 21 ml of N,N-dimethylacetamide was heated at 70°C for 2 hours. Water was then added to the reaction mixture, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate + 1% v / v triethylamine). 1.46 g of ethyl 5-(4-ethylpiperazine-1-yl)-3-fluoropyridine-2-carboxylate was obtained.

[0776] 1 H-NMR (400.0MHz, d6-DMSO): δ=8.2421(2.7); 8.2374(4.2); 7.2262(2.2); 7.2203(2.2); 7.1891(2.2); 7.1832(2.2); 4.2963(2.2); 4.2786 (7.0);4.2608(7.1);4.2431(2.3);3.4222(6.1);3.4097(7.9);3.39 67(6.4);3.3230(23.9);2.9455(4.4);2.7859(3.6);2.5080(21.5);2 .5036(28.6);2.4992(21.7);2.4833(6.8);2.4705(8.4);2.4579(6.3);2.3926(1.9);2.3746(6.1);2.3566(6.2);2.3387(2.1);1.9587(3.8);1.3048(7.7);1.2870(16.0);1.2693(7.5);1.0464(6.7);1.0284(13.9);1.0105(6.4);0.0079(0.8);-0.0002(18.1);-0.0082(0.8).

[0777] 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxy-N-methyl Preparation of ethylamine

[0778]

[0779] Step 1: Preparation of {6-fluoro-5-[2-(methoxyimino)ethoxy]pyridin-2-yl}methanol

[0780] 334 mg (3.97 mmol) of sodium bicarbonate are added to a solution of 300 mg (2.65 mmol) of 2-fluoropyridin-3-ol in 2.3 ml of water, and the mixture is stirred at room temperature for 15 minutes. After heating to 90° C., 696 μl (9.28 mmol) of a 37% aqueous formaldehyde solution are added a little at a time, and the mixture is stirred at 90° C. for 2.5 hours and at room temperature for a further 16 hours. After adding 2 g of ice, the pH of the mixture is adjusted to 1 using a 6N aqueous hydrochloric acid solution and repeatedly extracted with ethyl acetate. The combined organic extracts are dried over sodium sulfate, filtered, and the solvent is removed under reduced pressure. The residue is dissolved in dichloromethane and filtered, and the solvent is removed under reduced pressure. The intermediate 2-fluoro-6-(hydroxymethyl)pyridin-3-ol obtained in this manner was dissolved in 9 ml of acetonitrile, and 579 mg (4.19 mmol) of potassium carbonate and 413 mg (3.07 mmol, 80% purity) of 2-chloro-N-methoxyethylamine were added. The mixture was then heated under reflux for 4 hours and stirred at room temperature for an additional 16 hours. After filtering to remove the precipitate, the filtrate was adsorbed onto silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 205 mg of a mixture of (E,Z) isomers of {6-fluoro-5-[2-(methoxyimino)ethoxy]pyridin-2-yl}methanol.

[0781] 1 H-NMR (400.0MHz, d6-DMSO): δ=7.7277(0.9); 7.7073(1.0); 7.7015(1.0); 7.6810(1.0); 7.6596(1.1); 7.6456(2.5); 7.6316(1.2); 7.6227 (0.4);7.6167(0.4);7.5963(0.4);7.3251(1.6);7.3048(1.4);7.1226(0.4);7.1133(0.9);7.1040(0.4);5.4528(0.7);5.4500(1.3);5. 4382(1.6); 5.4352(2.8); 5.4235(0.8); 5.4205(1.4); 4.9464(1.8); 4.9371(1.8); 4.7654(4.5); 4.7514(4.4); 4.4156(4.5); 4.4009(4.4); 3.8674(5.9); 3.7989(16.0); 3.3316(17.6); 2.5251(0.4); 2.5112(9.1); 2.5072(18.1); 2.5028(23.6); 2.4983(17.5); -0.0002(4.4).

[0782] Step 2: 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxy Preparation of ethylamine

[0783] 194 μl (2.66 mmol) of thionyl chloride and a catalytic amount of N,N-dimethylformamide were added to a solution of 190 mg (0.88 mmol) of a mixture of (E,Z) isomers of {6-fluoro-5-[2-(methoxyimino)ethoxy]pyridin-2-yl)methanol in 6 ml of toluene. The reaction mixture was stirred at room temperature for 3.5 hours and then concentrated under reduced pressure. The residue was dissolved in 6 ml of N,N-dimethylformamide, and 246 mg (1.15 mmol) of 5,6-dichloro-1-naphthol and 368 mg (2.66 mmol) of potassium carbonate were added. The reaction mixture was stirred at 70°C for 50 minutes and then concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 332 mg of a mixture of (E,Z) isomers of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxyethylamine.

[0784] 1H-NMR(400.0MHz,d6-DMSO):δ=8.2461(1.6);8.2385(0.8);8.2236(1.8);8.2158(0.9);8.1528(0.4);8.1300(0.4);7.8100(1.9);7.8011(0.8);7.7885(2.7);7.7808(1.1);7.7752(0.8);7.7546(0.9);7.7077(3.1);7.6876(3.4);7.6849(3.5);7.6688(4.6);7.6549(1.2);7.6479(1.4);7.6134(0.6);7.5859(1.7);7.5663(2.1);7.5548(0.4);7.5472(0.6);7.5357(0.4);7.2592(2.2);7.2397(2.0);7.1517(0.5);7.1424(1.1);7.1331(0.5);7.0119(0.3);5.2828(7.5);4.9992(2.0);4.9899(2.0);4.8222(4.0);4.8083(3.9);3.8747(6.9);3.8067(16.0);3.3316(25.0);2.6729(0.3);2.5260(0.9);2.5125(20.4);2.5083(41.0);2.5038(53.8);2.4993(39.3);2.4950(19.3);2.3305(0.4);1.3971(0.4);0.0079(0.6);-0.0002(16.4);-0.0084(0.6)。

[0785] Step 3: 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxy N-methylethylamine

[0786] 68 mg (1.08 mmol) of sodium cyanoborohydride were added to a solution of 295 mg (0.72 mmol) of a mixture of the (E,Z) isomers of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxyethanamine in 6.2 ml of acetic acid. After 30 minutes at room temperature, 1.08 ml (14.4 mmol) of 37% aqueous formaldehyde solution were added, and 5 minutes later, 68 mg (1.08 mmol) of sodium cyanoborohydride were added. The reaction mixture was stirred at room temperature for 30 minutes and concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 236 mg of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-2-fluoropyridin-3-yl)oxy]-N-methoxy-N-methylethanamine.

[0787] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.2363 (2.0); 8.2351 (2.0); 8.2136 (2.2) ;8.2124(2.2);7.8066(1.6);7.7851(3.2);7.7646(1.2);7.7589(1.0);7 .7384(1.1);7.7052(3.3);7.6877(1.6);7.6825(3.2);7.6679(2.1);7. 6468(1.3);7.5581(2.0);7.5379(1.7);7.2605(1.9);7.2413(1.8);5.27 40(6.6); 4.2559(1.9); 4.2421(4.0); 4.2282(2.0); 3.4043(19.9); 3.3348(27.4); 2.9998(1.7); 2.9861(3.5); 2.9722(1.7); 2.5742(16.0); 2.52 73(0.4);2.5139(10.8);2.5095(22.1);2.5050(29.0);2.5005(21.1);2.4961(10.3);1.3968(0.4);0.0079(0.5);-0.0002(15.7);-0.0084(0.5).

[0788] 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N-methoxy-N-methyl Preparation of ethylamine

[0789]

[0790] Step 1: Preparation of methyl 3-fluoro-5-[2-(methoxyimino)ethoxy]pyridine-2-carboxylate

[0791] At room temperature, 18.39 g (133 mmol) of potassium carbonate and 59.1 ml (44.4 mmol) of a 0.75 M solution of 2-chloro-N-methoxyethylamine in acetonitrile were added to a solution of 7.59 g (44.4 mmol) of 3-fluoro-5-hydroxypyridine-2-carboxylic acid methyl ester in 253 ml of acetonitrile. The reaction mixture was heated under reflux for 27 hours and stirred at room temperature for an additional 3 days. After removing the precipitate by filtration, the filtrate was concentrated under reduced pressure. This gave 5.17 g of a mixture of (E,Z) isomers of 3-fluoro-5-[2-(methoxyimino)ethoxy]pyridine-2-carboxylic acid methyl ester.

[0792] 1 H-NMR (400.0MHz, d6-DMSO): δ=8.3132(1.5); 8.3107(1.6); 8.3074(1.7); 8.3004(0.7); 8.2977(0.7); 8.2942(0.7); 7.6847(1. 0);7.6710(3.1);7.6648(1.2);7.6574(1.1);7.6391(1.0);7.6331(1.1);7.6238(0.4);7.6178(0.4);7.5925(0.4);7.5864(0. 4); 7.1439(0.4); 7.1344(0.8); 7.1251(0.4); 5.0357(1.5); 5.0263(1.5); 4.8625(4.0); 4.8488(3.9); 3.8787(5.0); 3.8551(16.0); 3.8083(14.4); 3.3195(2.3); 2.5068(17.8); 2.5024(23.4); 2.4981(17.5); 0.0079(0.6); -0.0002(18.6); -0.0085(0.9).

[0793] Step 2: Preparation of methyl 3-fluoro-5-{2-[methoxy(methyl)amino]ethoxy}pyridine-2-carboxylate

[0794] 2.01 g (32.0 mmol) of sodium cyanoborohydride was added to a solution of 5.17 g of a mixture of (E,Z) isomers of methyl 3-fluoro-5-[2-(methoxyimino)ethoxy]pyridine-2-carboxylate in 180 ml of acetic acid. After 1 hour at room temperature, 32.0 ml (427 mmol) of 37% aqueous formaldehyde solution was added, and 15 minutes later, 2.01 g (32.0 mmol) of sodium cyanoborohydride was added. The reaction mixture was stirred at room temperature for 1 hour and then concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 4.61 g of methyl 3-fluoro-5-{2-[methoxy(methyl)amino]ethoxy}pyridine-2-carboxylate.

[0795] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.2901 (1.6); 8.2874 (2.2); 8.2844 (2.2); 8.2817 (2.1); 7.6473 (1.3); 7.6414 (1.4);7.6153(1.3);7.6094(1.4);4.2890(2.2);4.2754(4.2);4.2617(2.2);3.8498(16.0);3.4048(19.4);3 .3192(5.5);2.9915(1.8);2.9779(3.7);2.9643(1.9);2.5678(16.0);2.5202(0.5);2.5112(8.5);2.5070(18.4);2.5025(25.4);2.4981(19.5);1.9893(0.4);1.9092(6.7);0.0079(0.6);-0.0002(18.8);-0.0083(0.9).

[0796] Step 3: Preparation of (3-fluoro-5-{2-(methoxy(methyl)amino)ethoxy}pyridin-2-yl)methanol

[0797] At 10 ° C, 2.78 g (73.6 mmol) of sodium borohydride was added to a solution of 7.84 g (30.4 mmol) of 3-fluoro-5-{2-[methoxy(methyl)amino)ethoxy}pyridine-2-carboxylic acid methyl ester in 78 ml of ethanol, and the reaction mixture was stirred at 10 ° C for 1 hour and then at room temperature for another 16 hours. After adding 100 ml of ice-cooled water, the mixture was stirred at room temperature for 20 minutes. Subsequently, most of the ethanol was removed under reduced pressure, and the residue was repeatedly extracted with ethyl acetate. The combined organic phases were washed with saturated sodium chloride aqueous solution, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. 5.31 g of (3-fluoro-5-{2-(methoxy(methyl)amino)ethoxy}pyridin-2-yl)methanol was obtained.

[0798] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.1383 (2.4); 8.1339 (2.4); 7.4605 (1.4); 7.4548 (1.4); 7.4312 (1.4); 7.4254(1.4);5.1829(1.2);5.1683(2.5);5.1537(1.2);4.5150(2.9);4.5095(3.0);4.5004(2.9);4. 4950(2.8);4.2006(2.3);4.1868(4.6);4.1730(2.4);3.4028(18.6);3.3203(16.8);2.9662(2.1);2.9525(4.1);2.9386(2.1);2.5626(16.0);2.5058(38.8);2.5016(49.8);2.4974(37.0);-0.0002(8.2).

[0799] Step 4: 2-[(6-[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N-methoxy Preparation of 4-Methyl-N-ethylethylamine

[0800] 20 ml (273 mmol) of thionyl chloride and a catalytic amount of N,N-dimethylformamide were added to 1.0 g (4.34 mmol) of (3-fluoro-5-{2-[methoxy(methyl)amino]ethoxy}pyridin-2-yl)methanol. The reaction mixture was stirred at room temperature for 80 minutes and then concentrated under reduced pressure. The residue was dissolved in 26 ml of N,N-dimethylformamide, and 787 mg (3.69 mmol) of 5,6-dichloro-1-naphthol and 2.55 g (18.5 mmol) of potassium carbonate were added. The reaction mixture was stirred at 70°C for 4 hours and 20 minutes, then stirred at room temperature for an additional 15 hours and then concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 1.16 g of 2-[(6-[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N-methoxy-N-methylethylamine.

[0801] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.2575 (2.3); 8.2531 (2.4); 8.0842 (2.2); 8.061 5(2.5);7.8056(1.7);7.7842(2.6);7.7031(1.6);7.6833(2.3);7.6593(3.7);7 .6365(3.1);7.6107(1.4);7.6047(1.3);7.5811(1.4);7.5752(1.4);7.3719(2.2);7.3525(1.9);5.3891(4.6);5.3853(4.7);4.2479(2.0);4.2342(4.2);4.22 04(2.1); 3.4116(19.6); 3.3190(60.2); 2.9871(1.9); 2.9735(3.7); 2.9597(1.9); 2.6759(0.5); 2.6712(0.7); 2.6670(0.5); 2.5718(16.0); 2.5244(2.2); 2.51 08(43.8);2.5066(86.7);2.5022(117.2);2.4978(89.0);2.3336(0.5);2.3291(0.7);2.3247(0.5);1.9000(0.4);0.0079(1.3);-0.0001(31.9);-0.0081(1.4).

[0802] {[2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-fluoropyridin-3-yl}oxy)ethyl](methyl Preparation of 1,2-dimethylaminoacetonitrile

[0803]

[0804] Step 1: Preparation of methyl 5-(2-bromoethoxy)-3-fluoropyridine-2-carboxylate

[0805] At room temperature, 7.07 g (51.1 mmol) of potassium carbonate and 8.9 ml (103 mmol) of 1,2-dibromoethane were added to a solution of 3.50 g (20.5 mmol) of methyl 3-fluoro-5-hydroxypyridine-2-carboxylate in 100 ml of acetonitrile. The reaction mixture was stirred at 80°C overnight and then adsorbed onto silica gel. The product was chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 1.96 g of methyl 5-(2-bromoethoxy)-3-fluoropyridine-2-carboxylate.

[0806] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.3079 (1.6); 8.3054 (1.8); 8.3021 (1.8); 7.6591 (1.2); 7.65 32(1.2);7.6275(1.2);7.6215(1.2);4.5409(2.1);4.5277(2.7);4.5142(2.3);3.8715(2.4 );3.8545(16.0);3.8449(2.6);3.3192(14.1);2.5107(13.3);2.5064(27.3);2.5019(37.7);2.4975(28.6);2.4932(14.4);1.3979(0.8);0.0080(0.4);-0.0002(10.4);-0.0083(0.5).

[0807] Step 2: Preparation of [5-(2-bromoethoxy)-3-fluoropyridin-2-yl]methanol

[0808] Under ice cooling, 3.19 g (84.4 mmol) of sodium borohydride was added to a solution of 9.39 g (33.8 mmol) of 5-(2-bromoethoxy)-3-fluoropyridine-2-carboxylic acid methyl ester in 300 ml of ethanol, and the reaction mixture was stirred under ice cooling for 1 hour and then stirred at room temperature overnight. After adding 250 ml of ice-cooled water, the mixture was stirred at room temperature for 40 minutes, most of the ethanol was removed under reduced pressure, and the residue was repeatedly extracted with ethyl acetate. The combined organic phases were washed with a saturated sodium chloride aqueous solution, dried over sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. 5.96 g of [5-(2-bromoethoxy)-3-fluoropyridin-2-yl]methanol (purity 88%) was obtained.

[0809] 1H-NMR(400.0MHz,d6-DMSO):δ=8.1532(11.0);8.1489(10.9);8.1037(0.9);8.0999(0.9);7.4823(6.6);7.4763(6.8);7.4532(6.7);7.4473(6.8);7.3980(0.6);7.3921(0.6);7.3686(0.6);7.3625(0.6);6.5251(0.4);5.2083(5.5);5.1936(11.9);5.1789(6.3);5.1624(1.1);5.1480(0.5);4.5215(12.7);4.5161(14.0);4.5069(13.8);4.5016(13.5);4.4908(1.7);4.4486(11.6);4.4354(15.8);4.4218(12.8);4.3831(0.6);4.3710(0.8);4.3578(0.7);4.1452(0.6);4.1279(1.7);4.1104(1.7);4.0930(0.6);3.9835(0.7);3.9703(0.8);3.9581(0.6);3.8396(13.2);3.8260(16.0);3.8128(12.1);3.3216(53.4);2.6750(0.7);2.6709(0.9);2.5061(112.3);2.5017(151.1);2.4974(118.2);2.3326(0.6);2.3286(0.8);1.3559(1.8);1.3385(3.6);1.3210(1.7);0.1459(0.6);0.0079(5.5);-0.0002(130.8);-0.1497(0.6)。

[0810] Step 3: Preparation of 5-(2-bromoethoxy)-2-[(dibenzo[b,d]furan-2-yloxy)methyl]-3-fluoropyridine

[0811] 11.1 ml (152 mmol) of thionyl chloride and a catalytic amount of N,N-dimethylformamide were added to 516 mg (2.06 mmol) of [5-(2-bromoethoxy)-3-fluoropyridin-2-yl]methanol. The reaction mixture was stirred at room temperature for 80 minutes and then concentrated under reduced pressure. The residue was dissolved in 14 ml of N,N-dimethylformamide, and 388 mg (2.10 mmol) of dibenzo[b,d]furan-2-ol and 1.43 g (10.3 mmol) of potassium carbonate were added. The reaction mixture was stirred at 70°C for 2 hours and 40 minutes and then concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed onto silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This yielded 120 mg of 5-(2-bromoethoxy)-2-[(dibenzo[b,d]furan-2-yloxy)methyl]-3-fluoropyridine.

[0812] 1H-NMR(400.0MHz,d6-DMSO):δ=8.2654(7.9);8.2602(7.8);8.1324(5.7);8.1134(6.2);7.8764(9.5);7.8698(9.6);7.6849(6.7);7.6643(8.7);7.6304(10.0);7.6131(5.3);7.6079(15.2);7.5841(4.8);7.5781(4.6);7.5414(3.2);7.5384(3.2);7.5205(6.1);7.5025(3.4);7.4996(3.2);7.4159(4.5);7.3969(7.2);7.3785(3.2);7.1949(5.8);7.1883(5.6);7.1726(5.2);7.1659(5.1);5.2553(15.8);5.2507(16.0);4.4973(7.8);4.4843(10.2);4.4706(8.4);4.4321(0.5);4.4199(0.6);4.4066(0.5);4.0096(0.6);3.9968(0.7);3.9842(0.5);3.8650(8.7);3.8513(10.3);3.8383(7.9);3.5441(0.3);3.5294(0.4);3.3607(1876.4);2.6834(1.1);2.6791(1.5);2.6747(1.1);2.5321(3.9);2.5187(89.6);2.5143(185.4);2.5099(255.8);2.5055(190.1);2.5013(91.8);2.3411(1.0);2.3368(1.4);2.3327(1.0);1.4029(0.4);1.2389(0.3)。

[0813] Step 4: {[2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-fluoropyridin-3-yl}oxy)ethyl methyl]amino}acetonitrile

[0814] 99 mg (1.41 mmol) of (methylamino)acetonitrile was added to a solution of 117 mg (0.28 mmol) of 5-(2-bromoethoxy)-2-[(dibenzo[b,d]furan-2-yloxy)methyl]-3-fluoropyridine in 2 ml of dimethylformamide, and the mixture was stirred at 80° C. for 4 hours. The reaction mixture was then adsorbed onto silica gel and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). This gave 95 mg of {[2-({6-[(dibenzo[b,d]furan-2-yloxy)methyl]-5-fluoropyridin-3-yl}oxy)ethyl](methyl)amino}acetonitrile.

[0815] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.2459 (2.6); 8.2408 (2.7); 8.0776 (2.6) ;8.0549(2.9);7.8046(1.9);7.7832(2.9);7.7018(1.8);7.6818(2.6); 7.6614(5.2);7.6389(3.4);7.5845(1.5);7.5786(1.5);7.5550(1.5);7 .5491(1.5);7.3692(2.5);7.3496(2.2);5.3903(5.1);5.3868(5.2);4.2 442(2.3); 4.2307(4.4); 4.2171(2.3); 3.8084(10.6); 3.3201(14.6); 2.8214(2.3); 2.8079(4.2); 2.7943(2.2); 2.6761(0.4); 2.6717(0.6); 2.66 78(0.4); 2.5247(1.3); 2.5069(68.8); 2.5026(94.4); 2.4983(71.4); 2.3426(16.0); 2.3298(0.8); 0.0078(1.2); -0.0002(33.8); -0.0077(1.4).

[0816] 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N,N-diethylethyl Preparation of amines

[0817]

[0818] Step 1: Preparation of {5-[2-(diethylamino)ethoxy]-3-fluoropyridin-2-yl}methanol

[0819] 918 μl (8.88 mmol) of diethylamine were added to a solution of 740 mg (2.96 mmol) of [5-(2-bromoethoxy)-3-fluoropyridin-2-yl]methanol in 2 ml of dimethylformamide, and the mixture was stirred at 75° C. for 5 hours. The reaction mixture was chromatographed on RP silica gel by MPLC (gradient: water / acetonitrile). This gave 613 mg of {5-[2-(diethylamino)ethoxy]-3-fluoropyridin-2-yl}methanol.

[0820] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.1056 (2.0); 8.1019 (2.0); 7.4256 (1.2); 7.4196 (1.2); 7.3961 (1.2); 7.3901 (1.3); 5.1 802(0.5);5.1657(0.9);5.1512(0.5);4.5038(2.1);4.4959(2.1);4.1224(2.1);4.1074(4.6);4.0923(2.2);3.3237(7 .8);2.7819(2.2);2.7669(4.4);2.7518(2.0);2.5614(2.3);2.5436(7.3);2.5258(7.9);2.5064(26.0);2.5019(33.3);2.4974(24.8);1.9039(1.0);0.9769(7.9);0.9592(16.0);0.9414(7.5);0.0079(1.1);-0.0002(28.0);-0.0083(1.3).

[0821] Step 2: 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N,N-dichloro- Preparation of ethylethylamine

[0822] 1.0 ml (13.7 mmol) of thionyl chloride and a catalytic amount of N,N-dimethylformamide were added to a solution of 634 mg (2.62 mmol) of {5-[2-(diethylamino)ethoxy]-3-fluoropyridin-2-yl}methanol in 30 ml of dichloromethane, and the mixture was stirred at room temperature for 90 minutes. After adding 30 ml of toluene, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 12 ml of N,N-dimethylformamide, and one-sixth of this solution was added to 79 mg (0.37 mmol) of 5,6-dichloro-1-naphthol and 428 mg (1.31 mmol) of cesium carbonate. The reaction mixture was stirred at 80°C overnight and then chromatographed on RP silica gel by MPLC (gradient: water / acetonitrile). This gave 144 mg of 2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]-N,N-diethylethanamine.

[0823] 1 H-NMR (400.0MHz, d6-DMSO): δ = 8.2239 (2.2); 8.2196 (2.2); 8.0771 (2.1); 8.0 544(2.3);7.8029(1.6);7.7815(2.3);7.7006(1.5);7.6807(2.1);7.6591(4. 2); 7.6363(2.8); 7.5745(1.2); 7.5687(1.3); 7.5449(1.2); 7.5391(1.2); 7.3669(2.0); 7.3476(1.8); 5.3842(4.2); 5.3808(4.4); 4.1683(1.9); 4.1533(4. 1); 4.1383(2.0); 3.3230(39.8); 2.8013(1.8); 2.7865(3.8); 2.7714(1.8); 2.6720(0.4); 2.6675(0.3); 2.5675(2.1); 2.5497(6.7); 2.5319(7.2); 2.5071( 57.4); 2.5027(75.6); 2.4983(56.7); 2.3294(0.4); 2.3249(0.3); 0.9792(7.8); 0.9615(16.0); 0.9437(7.5); 0.0078(2.3); -0.0002(54.0); -0.0081(2.7).

[0824] N-{2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]ethyl}-N,2- Dimethylpropane-2-ammonium chloride and N-{2-[(6-[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy Preparation of 1,2-dimethyl]ethyl}-N,2-dimethylpropane-2-amine

[0825]

[0826] 1.0 ml (13.7 mmol) of thionyl chloride and a catalytic amount of N,N-dimethylformamide were added to a solution of 596 mg (2.33 mmol) of (5-{2-[tert-butyl(methyl)amino]ethoxy}-3-fluoropyridin-2-yl)methanol in 20 ml of dichloromethane, and the mixture was stirred at room temperature for 90 minutes. After adding 30 ml of toluene, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 12 ml of N,N-dimethylformamide, and one-sixth of this solution was added to 70 mg (0.33 mmol) of 5,6-dichloro-1-naphthol and 378 mg (1.16 mmol) of cesium carbonate. The reaction mixture was stirred at 80°C overnight and then chromatographed on RP silica gel using MPLC (gradient: water / acetonitrile). During the injection of the reaction mixture liquid into the MPLC, after the addition of ethanol and water, the solid precipitated in the syringe was redissolved by adding acetonitrile and 1N aqueous hydrochloric acid. This gave 99 mg of N-{2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]ethyl}-N,2-dimethylpropane-2-ammonium chloride (purity 78%) and 29 mg of N-{2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]ethyl}-N,2-dimethylpropane-2-amine.

[0827] N-{2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]ethyl}-N,2-dimethylpropane-2-ammonium chloride (purity 78%):

[0828] 1H-NMR (400.0MHz, d6-DMSO): δ = 9.6357 (0.4); 8.3034 (1.2); 8.2990 (1.2); 8.0 670(1.2);8.0443(1.3);7.8101(1.0);7.7885(1.4);7.7061(0.8);7.6863(1. 3); 7.6764(1.9); 7.6653(0.8); 7.6537(2.2); 7.6362(0.5); 7.6235(1.3); 7.3742(1.2); 7.3549(1.0); 5.7570(0.8); 5.4187(2.5); 5.2320(0.6); 4.5213(1. 4); 4.5096(1.0); 3.8081(0.4); 3.7953(0.4); 3.7817(0.4); 3.7708(0.4); 3.3260(52.0); 2.8122(2.7); 2.8002(2.9); 2.6758(0.3); 2.6716(0.4); 2.5068(6 0.7); 2.5024(79.5); 2.4980(60.3); 2.3292(0.4); 2.3249(0.4); 1.3720(16.0); 0.1460(0.3); 0.0077(3.4); -0.0002(73.8); -0.0083(4.0); -0.1498(0.3).

[0829] N-{2-[(6-{[(5,6-dichloro-1-naphthyl)oxy]methyl}-5-fluoropyridin-3-yl)oxy]ethyl}-N,2-dimethylpropane-2-amine:

[0830] 1H-NMR (400.0MHz, d6-DMSO): δ=8.2188(1.1); 8.2144(1.1); 8.0759(1.0); 8.0532(1.2); 7.8031(0.8); 7.7816(1.2); 7.7000(0) .8);7.6800(1.1);7.6602(2.0);7.6378(1.4);7.5625(0.6);7.5566(0.6);7.5326(0.6);7.5268(0.6);7.3651(1.0);7.3459(0) .9); 5.3811(2.2); 4.1263(0.8); 4.1109(1.6); 4.0956(0.8); 3.3230(51.0); 2.7359(0.7); 2.7206(1.4); 2.7050(0.7); 2.6712(0.4); 2.5064(54.4); 2.5021(71.6); 2.4977(54.5); 2.3288(0.4); 2.2272(4.9); 1.0083(16.0); 0.0077(2.8); -0.0003(64.9).

[0831] 2-[(2-{[(4-chloro-1-naphthyl)oxy]methyl}pyrimidin-5-yl)oxy]-N-methoxy-N-methylethylamine preparation

[0832]

[0833] Step 1: 5-(Benzyloxy)-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidine

[0834] 616 mg (4.10 mmol) of tert-butyldimethylsilyl chloride was added to a solution of 744 mg (3.44 mmol) of [5-(benzyloxy)pyrimidin-2-yl]methanol (D. Bensen et al., WO2014 / 043272) and 341 mg (5.0 mmol) of imidazole in 3.5 ml of N,N-dimethylformamide, and the mixture was stirred at room temperature for 30 minutes. After adding ethyl acetate, the mixture was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in dichloromethane, adsorbed on silica gel, and chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). 0.83 g of 5-(benzyloxy)-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidine was obtained.

[0835] 1H-NMR (400.0MHz, CDCl3): δ=8.3222(3.5); 7.2949(1.8); 7.2883(1.2); 7.2807(1.3); 7.1373(2.4); 5.0288(2.9); 4.7408(3) .4); 1.4579 (1.2); 0.8133 (0.7); 0.8061 (16.0); 0.7990 (0.9); 0.0076 (0.4); -0.0002 (11.7); -0.0079 (0.5); -0.1235 (2.7).

[0836] Step 2: 2-{[2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-yl]oxy}-N-methyl Preparation of oxy-N-methylethylamine

[0837] exist In a hydrogenation reactor, a solution of 470 mg (1.42 mmol) of 5-(benzyloxy)-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidine in 40 ml of methanol was hydrogenated at 1 bar over 10% Pd / C at a flow rate of 2 ml / min. The reaction solution was then concentrated under reduced pressure. This yielded 328 mg of unpurified 2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-ol as an intermediate. A solution of 150 mg of the unpurified intermediate 2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-ol in 1.5 ml of N,N-dimethylformamide was added to 224 mg (1.62 mmol) of potassium carbonate and 202 mg (0.81 mmol) of 2-bromo-N-methoxy-N-methylethanamine hydrobromide (1:1), and the mixture was stirred at 50°C for 15 hours. After adding another 62 mg (0.25 mmol) of 2-bromo-N-methoxy-N-methylethanamine hydrobromide (1:1), the reaction mixture was stirred at 50° C. for a further 3 hours and then concentrated under reduced pressure. Water was added to the residue, and the mixture was repeatedly extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was chromatographed on silica gel by MPLC (gradient: cyclohexane / ethyl acetate). 43 mg of 2-{[2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-yl]oxy}-N-methoxy-N-methylethanamine was obtained.

[0838] 1H-NMR (400.0MHz, d6-DMSO): δ = 8.5493 ​​(3.9); 4.7338 (3.3); 4.2697 (0.7); 4.2559 (1 .5);4.2421(0.8);3.3996(6.2);3.3184(2.0);2.9778(0.7);2.9640(1.3);2.9502( 0.7); 2.5641(5.3); 2.5066(8.9); 2.5021(12.5); 2.4978(9.6); 0.8740(16.0); 0.8639(1.7); 0.0677(0.5); 0.0602(11.7); 0.0439(1.0); -0.0002(8.8); -0.0080(0.4).

[0839] Step 3: 2-[(2-{[(4-chloro-1-naphthyl)oxy]methyl}pyrimidin-5-yl)oxy]-N-methoxy-N-methyl Preparation of ethylamine

[0840] 250 μl (0.25 mmol) of a 1M tetrabutylammonium fluoride solution in tetrahydrofuran was added to a solution of 40 mg (0.12 mmol) of (2-{[2-({[tert-butyl(dimethyl)silyl]oxy}methyl)pyrimidin-5-yl]oxy}-N-methoxy-N-methylethanamine) in 0.7 ml of tetrahydrofuran, and the mixture was stirred at room temperature for 30 minutes. After adding saturated aqueous ammonium chloride, the mixture was repeatedly extracted with ethyl acetate, the combined organic phases were dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 1 ml of toluene, and 25 μl (0.34 mmol) of thionyl chloride and a catalytic amount of N,N...

Claims

1. Compounds of formula (I), and salts, metal complexes, N-oxides and tautomeric forms of compounds of formula (I) in Z represents an optionally substituted naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, carbazolyl, indanyl, benzothienyl, benzofuranyl, indolyl, fluorenyl, phenanthryl, anthracenyl, or a phenyl radical of the substructure formula (II): and the substituted phenyl of sub-formula (II) may optionally carry two other substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C3-C6)-cycloalkyl and (C3-C6)-halocycloalkyl, Y represents O, S, -CH2, -NR 5 , A 1 Represents N or -CR 1 , A 2 Represents N or -CR 2 , A 3 Represents N or -CR 3 , A 4 Represents N or -CR 4 , wherein at least one and at most two of the atoms A1, A2, A3 and A4 in the aromatic ring represent N, X represents oxygen, sulfhydryl, sulfinyl, sulfonyl, -CH2, carbonyl, -CHOH or -NR 6 , R 1 , R 2 , R 3 and R 4 each independently of one another represents hydrogen, halogen, nitro, cyano, aminocarbonyl, aminosulfonyl, in each case optionally substituted (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, N-mono-(C1-C4)-alkylamino, N-mono-(C3-C6)-cycloalkylamino, N,N-di-(C1-C4)-alkylamino, N,N-di-(C3-C6)-cycloalkyl )-cycloalkylamino, N,N-(C3-C6)-cycloalkyl-(C1-C4)-alkylamino, N-(C1-C4)-alkanoylamino, N-(C3-C6)-cycloalkanoylamino, N-(C1-C4)-alkanoyl-N-(C1-C4)-alkylamino, N-(C3-C6)-cycloalkanoyl-N-(C1-C4)-alkylamino, N-(C3-C6)-cycloalkanoyl-N-(C3-C6)-cycloalkylamino, N-(C1-C4)-alkanoyl-N-(C3-C6)-cycloalkylamino, (C1-C4)-alkoxycarbonyl , (C3-C6)-cycloalkyloxycarbonyl, (C1-C4)-alkanoyl, (C3-C6)-cycloalkanoyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, N-(C1-C4)-alkylaminocarbonyl, N-(C3-C6)-cycloalkylaminocarbonyl, N,N-di-(C1-C4)-alkylaminocarbonyl, N,N-di-(C3-C6)-cycloalkylamino carbonyl, N,N-(C3-C6)-cycloalkyl-(C1-C4)-alkylaminocarbonyl, -CH=NO-[(C1-C4)-alkyl], -CH=NO-[(C3-C6)-cycloalkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], -C[(C3-C6)-cycloalkyl]=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C3-C6)-cycloalkyl], -C[(C3-C6)-cycloalkyl]=NO-[(C3-C6)-cycloalkyl], R 5 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C3)-alkanoyl, R 6 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkanoyl or R 8 Through the closed ring formed by 1 to 3 CH2 groups, R 7 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl or 8 Through the closed ring formed by 1 to 3 CH2 groups, R 8 represents hydrogen or represents an optionally substituted (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl or R 6 and R 7 together in a ring formed by 1 to 3 CH2 groups or with R 9 enclosed together in a 4- to 6-membered heterocyclic ring which, in the case of a 5- to 6-membered heterocyclic ring, may contain further heteroatoms and which are optionally mono- or polysubstituted by identical or different radicals selected from the group consisting of halogen substituents, cyano or (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy groups which are each optionally mono- or polysubstituted by identical or different halogen substituents, In R 7 represents hydrogen or optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl or in the case of R 7 With R 8 When forming a 5- or 6-membered ring, R 9 represents in each case optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylcarbonyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl, or In R 7 With R 8 When forming a 4-membered ring, R 9 represents in each case optionally substituted (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, or R 8 and R 9 represents a 4- to 6-membered heterocyclic closed ring which, in the case of a 5- to 6-membered heterocyclic ring, may contain further heteroatoms and which is optionally mono- or polysubstituted by identical or different radicals selected from the group consisting of halogen substituents, cyano or (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy groups which are each optionally mono- or polysubstituted by identical or different halogen substituents, R 10 represents halogen, nitro, cyano, -SF5, or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylsulfonyl, -C1-C4)-alkyl], which are optionally substituted or polysubstituted by the same or different substituents selected from the group consisting of halogen, cyano, nitro , -SF5, (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C2-C4)-alkenyloxy, (C2-C4)-haloalkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C3-C6)-halocycloalkyloxy, (C3-C4)-halo 6)-cycloalkyl, (C3-C6)-halogenated cycloalkyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-halogenated alkylsulfonyl, (C1-C4)-halogenated alkylthio, (C1-C4)-halogenated alkylsulfonyl, (C1-C4)-halogenated alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, C6-aryl, C 10 -Aryl, C 14 -aryl, C6-aryloxy, C 10 -Aryloxy, C 14 -aryloxy, benzyl, benzyloxy, benzylthio, C6-arylthio, C 10 -Arylthio, C 14 -Arylthio, C6-arylamino, C 10 -Arylamino, C 14 - arylamino, benzylamino, heterocyclic and trialkylsilyl groups, R 11 represents hydrogen, halogen, cyano or nitro, or represents, in each case optionally substituted, (C1-C4)-alkyl, (C3-C5)-cycloalkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], and The proviso was to exclude the compound 1-[4-(6-{2-[3-(chloromethyl)phenyl]ethyl}pyridin-3-yl)piperazin-1-yl]ethanone.

2. A compound of formula (I) according to claim 1, wherein Z represents an optionally substituted naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, indan-4-yl, benzothien-4-yl, benzofuran-4-yl, indol-4-yl, or represents a substituted phenyl group of sub-structural formula (II) and the phenyl group of sub-structural formula (II) is substituted except for R 10 and R 11 It does not carry any other substituents. Y represents O, S, -NR 5 , R 1 , R 2 , R 3 and R 4 Each independently of one another represents a substituent selected from hydrogen, halogen, nitro, cyano, or represents a (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkyloxycarbonyl, N-mono-(C1-C4)-alkylamino, N,N-di-(C1-C4)-alkylamino, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkyloxycarbonyl ...1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alk )-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, each of which is optionally substituted or polysubstituted by the same or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, R 5 represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C3)-alkanoyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, R 6 represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C4)-alkanoyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 8 Through the closed ring formed by 1 to 3 CH2 groups, R 7 represents hydrogen, or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 8 Through the closed ring formed by 1 to 3 CH2 groups, R 8 represents hydrogen, or represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C4)-cycloalkyl, which is optionally substituted or polysubstituted by the same or different substituents selected from halogen, nitro and cyano, or with R 6 or R 7 Together with 1 to 3 CH2 groups to form a closed ring, or with R 9 together with a 4- to 6-membered heterocyclic ring closure which, in the case of a 5- to 6-membered heterocyclic ring, may contain further heteroatoms selected from N and O and which are optionally mono- or polysubstituted by identical or different substituents selected from halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, In R 7 represents hydrogen or (C1-C4)-alkyl, (C3-C4)-cycloalkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents or in the case of R 7 With R 8 When forming a 5- or 6-membered ring, R 9 represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylcarbonyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl, each of which is optionally mono- or polysubstituted by the same or different substituents selected from halogen, cyano, nitro or (C3-C6)-cycloalkyl, or In R 7 With R 8 When forming a 4-membered ring, R 9 represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C3-C4)-cycloalkyloxy, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, which are in each case optionally mono- or polysubstituted by identical or different substituents selected from halogen, cyano, nitro or (C3-C6)-cycloalkyl, or R 8 and R 9 represents a 4- to 6-membered heterocyclic closed ring which, in the case of a 5- to 6-membered heterocyclic ring, may contain further heteroatoms selected from N, O and which may optionally be mono- or polysubstituted by identical or different substituents selected from halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, R 10 represents halogen, or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio -C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, R 11 represents hydrogen, halogen, cyano or nitro, or represents (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C5)-cycloalkyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl], which are optionally mono- or poly-substituted by the same or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkoxy and (C3-C6)-cycloalkyl.

3. A compound of formula (I) according to claim 1 or 2, wherein Z represents naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkylcarbonyl, (C1-C4)-haloalkylcarbonyl, or represents a substituted phenyl of the sub-formula (II), At least one of the atoms A3 or A4 in the aromatic ring represents nitrogen, R 1 , R 2 , R 3 and R 4 each independently of one another represents a substituent selected from the group consisting of hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl and (C1-C4)-alkylsulfonyl, R 6 represents hydrogen, (C1-C4)-alkyl or 8 Through the closed ring formed by 1 to 3 CH2 groups, R 7 represents hydrogen, (C1-C4)-alkyl, (C3-C4)-cycloalkyl or 8 Through the closed ring formed by 1 to 3 CH2 groups, R 8 represents hydrogen, or represents (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C4)-cycloalkyl, which is optionally substituted or polysubstituted by the same or different substituents selected from halogen, or with R 6 or R 7 Together with 1 to 3 CH2 groups to form a closed ring, or with R 9 a 4- to 6-membered heterocyclic ring formed together by 3 to 5 CH2 groups, and the heterocyclic ring is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, In R 7 represents hydrogen or represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl or in the case of R 7 With R 8 When forming a 5- or 6-membered ring, R 9 represents (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C1-C6)-alkylcarbonyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro or (C3-C6)-cycloalkyl, or In R 7 With R 8 When forming a 4-membered ring, R 9 represents (C1-C4)-alkyl, (C3-C4)-cycloalkyl, (C1-C4)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro or (C3-C6)-cycloalkyl, or R 8 and R 9 represents a 4- to 6-membered heterocyclic ring closed by 3 to 5 CH2 groups and which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, R 10 represents halogen or represents phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thien-2-yl, thien-3-yl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, or represents (C1-C4)-alkyl, (C1-C4)-alkenyl, (C1-C4)-alkynyl, (C3-C6)-cycloalkyl, (C1-C4)- alkoxy, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, (C3-C6)-cycloalkyloxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylthio, (C3-C6)-cycloalkylsulfinyl, (C3-C6)-cycloalkylsulfonyl, -CH=NO-[(C1-C4)-alkyl], -C[(C1-C4)-alkyl]=NO-[(C1-C4)-alkyl, which are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, R 11 represents hydrogen, halogen, cyano or nitro, or represents (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C5)-cycloalkyl, which is optionally mono- or poly-substituted by the same or different substituents selected from the group consisting of halogen, cyano and (C3-C6)-cycloalkyl.

4. A compound of formula (I) according to any one of claims 1 to 3, wherein Z represents naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C3-C6)-cycloalkyl, or represents a substituted phenyl of the sub-formula (II), Y represents oxygen, X represents oxygen or -NR 6 .

5. A compound of formula (I) according to any one of claims 1 to 4, wherein Z represents naphthyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, or represents unsubstituted dibenzo[b,d]furanyl or dibenzo[b,d]thienyl or represents a substituted phenyl of the sub-formula (II), R 1 , R 2 , R 3 and R 4 represents a substituent selected from the group consisting of hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio, R 6 represents hydrogen, (C1-C3)-alkyl or 8 The closed ring is formed by 1 to 2 CH2 groups. R 7 Represents hydrogen or with R 8 Through the closed ring formed by 1 to 3 CH2 groups, R 8 represents hydrogen, or represents (C1-C4)-alkyl, which is optionally mono- or polysubstituted by identical or different halogen substituents, or with R 6 Through the closed ring formed by 1 to 2 CH2 groups or with R 7 Through the closed ring formed by 1 to 3 CH2 groups or with R 9 a 4- to 6-membered heterocyclic ring formed together by 3 to 5 CH2 groups, and the heterocyclic ring is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, R 9 represents (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C1-C6)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano and (C3-C6)-cycloalkyl, or R 8 and R 9 represents a 4- to 6-membered heterocyclic ring closed by 3 to 5 CH2 groups and which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, (C1-C4)-alkyl and (C1-C4)-haloalkyl, R 10 represents halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, or represents phenyl, which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy and (C1-C4)-haloalkoxy, R 11 represents hydrogen, halogen or cyano, or represents (C1-C4)-alkyl, (C3-C5)-cycloalkyl or (C1-C4)-alkoxy, which is optionally mono- or polysubstituted by identical or different halogen substituents.

6. A compound of formula (I) according to any one of claims 1 to 5, wherein Z represents a naphthyl group of the substructure formula (III): or represents an unsubstituted dibenzo[b,d]furanyl or dibenzo[b,d]thienyl or represents a substituted phenyl group of the substructure formula (II), R 1 represents hydrogen, halogen, (C1-C4)-alkyl or (C1-C4)-alkoxy, R 2 represents hydrogen, halogen or (C1-C4)-haloalkyl, R 3 represents hydrogen, halogen, (C1-C4)-alkoxy or (C1-C4)-alkylthio, R 4 represents hydrogen or halogen, R 6 represents hydrogen, or represents 8 The piperazine ring is closed. R 7 represents hydrogen, or represents 8 The pyrrolidine ring is closed. R 8 represents hydrogen, (C1-C4)-alkyl or represents 6 The piperazine closed ring formed together or represents R 7 The pyrrolidine closed ring formed together or represents the R 9 Together they form a piperidine closed ring, R 9 represents (C1-C4)-alkyl or (C1-C4)-alkoxy, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and cyano, or R 8 and R 9 represents the piperidine ring closure, R 10 represents halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy or represents phenyl of the sub-formula (IV): R 11 represents hydrogen or halogen, or represents (C1-C4)-alkyl or (C1-C4)-alkoxy, which is optionally mono- or polysubstituted by identical or different halogen substituents, R 12 , R 13 and R 14 each independently represents hydrogen or halogen, R 15 represents hydrogen, halogen, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy or (C1-C4)-haloalkoxy.

7. A preparation comprising a compound of formula (I) as claimed in any one of claims 1 to 6 and at least one auxiliary agent.

8. The formulation according to claim 7, which additionally comprises a further agrochemically active compound.

9. Compounds of formula (Va) or (Vb-1): in A 1 represents N or CH, A 2 represents N or CH, at least A 1 or A 2 represents N and preferably A 1 Represents N and A 2 Represents CH, R 16 represents hydrogen, methyl, fluorine or methoxy, R 17 represents cyano, hydroxymethyl, methylcarboxyl, ethylcarboxyl or 3-bromophenoxymethyl, R 18 In the compounds of formula (Va) represents the following groups: or bromine, provided that the following compounds are excluded:

10. A method for controlling animal pests, characterized in that: The compound of formula (I) according to any one of claims 1 to 6 or the formulation according to claim 7 or 8 is allowed to act on animal pests and / or their habitat.

11. Use of a compound of formula (I) as claimed in any one of claims 1 to 6 or a formulation as claimed in claim 7 or 8 for controlling animal pests.

12. The use according to claim 11, wherein the animal pest is a mosquito.

13. The method according to claim 10 or the use according to claim 11 or 12, excluding surgical, therapeutic and diagnostic treatment of the human or animal body.

14. Use of a compound of formula (I) as claimed in any one of claims 1 to 6 or a formulation as claimed in claim 7 or 8 for the preparation of a medicament for controlling ectoparasites on an animal.

15. A method for controlling animal pests, characterized in that: The compound of formula (I) according to any one of claims 1 to 6 or the formulation according to claim 7 or 8 is allowed to act on animal pests and / or their habitat.

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