Heterocyclic pyridines as novel fungicides

Abstract

The present disclosure relates to heterocyclic pyridine compounds, methods and intermediates for preparing these compounds, and the use of these compounds for controlling phytopathogenic microorganisms (such as phytopathogenic fungi).

Claims

1. Compounds of formula (I), their salts, hydrates, and hydrates of said salts: wherein A is O, C(=O), NR 1 or CR 2A R R2B , wherein R 1 is hydrogen, methyl or formyl, R 2A and R 2B are each independently hydrogen, m is 0, 1 or 2, T is hydrogen, R 3 and R 4 are independently hydrogen, fluorine, chlorine, methyl, ethyl, methylcarbonyloxy, ethylcarbonyloxy, cyclopropyl or cyclobutyl, R 5 is hydrogen, methyl or ethyl, L is a direct bond, methylene or ethylene, wherein the methylene or ethylene group is optionally substituted by 1 or 2 substituents L SA substituted, wherein L SA is fluorine or methyl, or Two substituents L bonded to the same carbon atom SA together with the carbon atom to which they are attached form a cyclopropyl or cyclobutyl ring, R 6 is an indanyl, phenyl, naphthyl, dihydrobenzofuranyl, dihydrobenzodioxinyl, thienyl or indolyl group, wherein the indanyl, phenyl, naphthyl, dihydrobenzofuranyl, dihydrobenzodioxinyl, thienyl and indolyl groups are optionally substituted with one or two R 6S substituents, where R 6S independently selected from fluorine, chlorine, bromine, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkoxy, difluoromethoxy, trifluoromethoxy, C2-C4-alkenyl, methylcarbonyl, ethylcarbonyl, C2-C4-alkynyl, cyclopropyl, cyclobutyl, oxetanyl, tetrahydrofuranyl and pyrazolyl, wherein the cyclopropyl, cyclobutyl, oxetanyl, tetrahydrofuranyl and pyrazolyl are optionally substituted by 1 or 2 substituents independently selected from: fluorine and methyl, R 7 is hydrogen, fluorine, chlorine, cyano, hydroxy, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, phenylthio, C3-C6-cycloalkyl, pyridyl, pyrrolidinyl, tetrahydrofuryl or -N(R 20 )2, wherein the C2-C4-alkynyl is optionally substituted by 1 substituent -Si(CH3)3, wherein the phenylthio group, phenyl group and pyridyl group are optionally substituted by 1 or 2 R 7Sc substituents, and wherein R 20 independently hydrogen or C1-C4-alkyl, R 7Sc independently is fluorine, methyl, ethyl, difluoromethyl or trifluoromethyl, and R 8 is hydrogen, fluorine, iodine, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkoxy, difluoromethoxy, trifluoromethoxy, C3-C6-cycloalkyl, phenyl, -N(R 30 )2 or -SR 31 , wherein the C1-C4-alkoxy is optionally substituted by 1 substituent C1-C4-alkoxy, and wherein R 30 independently hydrogen, C1-C4-alkyl or C2-C4-alkenyl, R 31 is a C1-C4-alkyl group, R 9 is hydrogen, fluorine or chlorine, Q is phenyl, naphthyl, 3-bicyclo[4.2.0]octa-1,3,5-trienyl, indanyl, dihydrobenzofuranyl, 1,3-benzodioxolyl, 6,7-dihydro-5H-cyclopenta[b]pyridinyl, thiophenyl, pyridinyl or benzothiophenyl, wherein the phenyl, naphthyl, 3-bicyclo[4.2.0]octa-1,3,5-trienyl, indanyl, dihydrobenzofuranyl, 1,3-benzodioxolyl, 6,7-dihydro-5H-cyclopenta[b]pyridyl, thienyl, pyridyl and benzothienyl are optionally substituted by 1 or 2 substituents Q S substituted, wherein Q S independently selected from halogen, cyano, formyl, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkylcarbonyl, C1-C4-alkoxy, difluoromethoxy, trifluoromethoxy, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylthio, difluoromethylthio, trifluoromethylthio, C1-C4-alkylsulfonyl, C3-C6-cycloalkyl, oxetanyl, tetrahydrofuranyl, phenyl, pyridyl, -O(C=O)R 33 and -N(R 43 )2, wherein the C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylthio and C1-C4-alkylsulfonyl are in turn optionally substituted by 1 or 2 substituents independently selected from: hydroxy, C1-C4-alkoxy and C1-C4-alkoxycarbonyl, the C3-C6-cycloalkyl, oxetanyl, tetrahydrofuranyl, phenyl and pyridinyl are in turn optionally substituted by 1 or 2 substituents independently selected from: halogen and C1-C4-alkyl, and wherein R 33 is a C1-C4-alkyl group, R 43 Independently is hydrogen or a C1-C4-alkyl group.

2. The compound of formula (I) according to claim 1, wherein L is a direct bond, methylene, monofluoromethylene or difluoromethylene.

3. The compound of formula (I) according to claim 1 or 2, wherein R 6 is wherein § 1 is the point connected to L R 6S1 and R 6S2 are each independently hydrogen or R 6S , wherein R 6S selected from fluorine, chlorine, bromine, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkoxy, difluoromethoxy, trifluoromethoxy, C2-C4-alkenyl, methylcarbonyl, ethylcarbonyl, C2-C4-alkynyl, cyclopropyl, cyclobutyl, oxetanyl, tetrahydrofuranyl and pyrazolyl, wherein the cyclopropyl, cyclobutyl, oxetanyl, tetrahydrofuranyl and pyrazolyl are optionally substituted by 1 or 2 substituents independently selected from: fluorine and methyl, The condition is R 6S1 and R 6S2 at least one of which is different from hydrogen.

4. The compound of formula (I) according to claim 1 or 2, wherein Q is phenyl, wherein The phenyl group is substituted by 1 or 2 substituents Q independently selected from the following S Substituted: halogen, cyano, formyl, C1-C4-alkyl, difluoromethyl, trifluoromethyl, C1-C4-alkylcarbonyl, C1-C4-alkoxy, difluoromethoxy, trifluoromethoxy, C2-C4-alkynyl, cyclopropyl and cyclobutyl, wherein the cyclopropyl and cyclobutyl are in turn optionally substituted by 1 or 2 substituents independently selected from fluorine or methyl.

5. A composition for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) according to any one of claims 1 to 4 and at least one carrier and / or surfactant.

6. A method for controlling phytopathogenic harmful fungi in crop protection and material protection, characterized in that, Applying at least one compound of formula (I) according to any one of claims 1 to 4 and / or the composition according to claim 5 to phytopathogenic harmful fungi and / or their habitats.

7. Use of one or more compounds of formula (I) according to any one of claims 1 to 4 and / or the composition according to claim 5 for controlling phytopathogenic harmful fungi in crop protection and material protection.

8. A method for preparing a compound of formula (I-a-1) by where Q, L, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 as defined in any one of claims 1 to 4, and A is O, T is hydrogen, m is 1 or 2, reacting a compound of formula (1) where Q, R 7 , R 8 and R 9 are as defined above, and U 1 is a hydroxyl group, a halogen or a C1-C6-alkoxy group, with a compound of formula (2) where m, A, L, R 3 , R 4 , R 5 and R 6 are defined as described above, and W is hydrogen, an amino protecting group, and the amino protecting group is tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, to obtain a compound of formula (3) where m, A, Q, L, W, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are defined as described above, Removing the phthalimide group from the compound of formula (3) to obtain a compound of formula (4) where m, A, Q, L, W, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are defined as described above, The compound of formula (4) is then cyclized in the following manner When W is hydrogen, the compound of formula (4) is treated with a dehydrating agent, optionally in the presence of a base, to directly obtain the compound of formula (I-a-1). or When W is an amino protecting group which is tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, the compound of formula (4) is treated with a dehydrating agent, optionally in the presence of a base, and then subjected to a deprotection step to obtain the compound of formula (I-a-1).

9. A process for preparing the compound of formula (I-a-1) by the following method where Q, L, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are defined in any one of claims 1 to 4, and A is O, T is hydrogen, m is 1 or 2, First, the compound of formula (5) wherein R 7 , R 8 and R 9 are as defined above, and X 1 is a halogen, U 1 is hydroxy, halogen or C1-C6-alkoxy, is reacted with the compound of formula (2) where m, A, L, R 3 , R 4 , R 5 and R 6 are defined as previously described, and W is hydrogen or an amino protecting group which is tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, to obtain the compound of formula (6a) where m, A, L, X 1 , R 3 , R 4 , R 5 and R 6 are defined as described above, The phthalimide group in the compound of formula (6a) is removed and the resulting amine is cyclized to obtain the compound of formula (7). where m, A, L, X 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are defined as described above, The compound of formula (7) is reacted with the compound of formula (8) in the presence of an organic or inorganic base and optionally in the presence of a suitable copper salt or complex to obtain the compound of formula (I-a-1), wherein Q is as defined above.

10. The method of claim 9, wherein X 1 is bromine.

11. The compound of formula (4): where m, A, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , L and Q are as defined in claim 1, and W represents hydrogen, tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl.

12. The compound of formula (7): where m, A, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and L are as defined in claim 1, and W is hydrogen, tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, X 1 is a halogen.

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