Bicyclic heterocyclic amides for combating phytopathogenic fungi

Abstract

The present invention relates to a compound of formula (I), wherein B, D, W, R1, R1a, R2, R3, R4a, R4b, R5 and E are as described in the detailed description. The present invention also relates to a process for preparing the compound of formula (I), compositions or combinations comprising the compound of formula (I), and a method for combating phytopathogenic fungi comprising the compound of formula (I).

Description

[0001] Title: BICYCLIC HETEROCYCLIC AMIDES FOR COMBATING PHYTOPATHOGENIC FUNGI

[0002] FIELD OF THE INVENTION:

[0003] The present invention relates to bicyclic heterocyclic amide compounds of formula (I), which are useful in combating phytopathogenic fungi. The present invention also relates to a process for preparing these bicyclic heterocyclic amide compounds of formula (I), to compositions and combinations comprising these bicyclic heterocyclic amide compounds of formula (I), and to a method for combating phytopathogenic fungi using the same.

[0004] BACKGROUND OF THE INVENTION:

[0005] Bicyclic heterocyclic amide compounds are described as fungicidal agents in WO2022253645A1, WO2023110869A1, W02024068950, WO20241015104 and WO2024115512. The bicyclic heterocyclic amide compounds reported in the above cited literature have disadvantages in certain aspects, such as that they exhibit a narrow spectrum of efficacy or that they do not have a satisfactory fungicidal activity, particularly at low application rates.

[0006] Therefore, there remains a need for the development of new fungicidal compounds, including such that are belonging to the class of the above cited bicyclic heterocyclic amide compounds, to provide compounds being effective against a broader spectrum of fungi, having a lower toxicity, a higher selectivity, and being used at lower dosage rates to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing an effective and long-lasting control of said fungi.

[0007] Therefore, it is an objective of the present invention to provide alternative compounds having an improved / enhanced fungicidal activity and / or a broader efficacy spectrum against phytopathogenic fungi, at the same time, being less toxic and safer to the environment.

[0008] This objective is achieved by providing a compound of formula (I) of the present invention for combating phytopathogenic fungi.

[0009] SUMMARY OF THE INVENTION:

[0010] The present invention relates to a compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof,

[0011]

[0012] Formula (I)

[0013] wherein,

[0014] R1is selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, C3-C8-cycloalkyl or C3-Cs-halocycloalkyl;

[0015] R2is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, C3-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-Ce-alkoxy, or Ci-Ce-haloalkoxy;

[0016] R3is selected from hydrogen, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio or C3-C6.cycloalkylthio;

[0017] R4aand R4bare each independently selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C8-cycloalkyl, Ci-Ce-alkoxy, or Ci-Ce-haloalkoxy; or

[0018] R4aand R4btogether with the carbon atom to which they are attached, may together form an oxo group (=0), a 3- to 6-membered carbocyclic ring, or a 3- to 6-membered heterocyclic ring containing at least one heteroatom / group selected from N, O, S, S(0) or S(O)2, wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to two substituents independently selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0019] R5is selected from the group consisting of hydrogen, Ci-Ce-alkyl, and C1-C6-haloalkyl;

[0020] B represents a phenyl ring or a 5- or 6-membered aromatic heterocyclic ring, which is fused at C3, C4 carbons of the piperidine ring C, wherein said 5- or 6-membered aromatic heterocyclic ring comprises 1 to 3 heteroatoms / groups independently selected from O, N, S, S(O) or S(O)2, wherein said ring B is unsubstituted or substituted with one or more of the same or different substituents selected from R6;

[0021] D is selected from a direct bond, C3-C6 -cycloalkyl, phenyl or a 5- or 6-membered heteroaryl ring, wherein said 5- or 6-membered heteroaryl ring comprises 1, 2, 3 or 4 heteroatoms / groups each independently selected from N, O, S, S(O) and S(O) 2, and wherein said phenyl or 5- or 6-membered heteroaryl ring is unsubstituted or substituted with one or more of the same or different substituents selected from R1band / or R1c;

[0022] ring E is selected from a non-aromatic nitrogen containing 5- or 6-membered saturated or partially saturated heterocyclic ring, wherein the heterocyclic ring may contain 1 to 3 additional heteroatoms / groups independently selected from N, O, S, C(O), S(O) or S(O)2, wherein the heterocyclic ring is unsubstituted or substituted at the ring nitrogen with a substituent selected from RNand at the ring carbon atoms with one to three of the same or different susbstituents selected from R9, wherein said heterocyclic ring is bound to the C=W group either through a carbon atom or a nitrogen atom;

[0023] W is selected from O, S or NR10;

[0024] R1ais selected from hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-C6-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-C6-haloalkynyl, C3-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C2-Ce-alkenyloxy, C2-Ce-haloalkenyloxy, C2-C6-alkynyloxy, C2-Ce-haloalkynyloxy, C3-C6-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, C3-Ce-cycloalkylthio, Ci-Ce-alkylsulphinyl, Ci-Ce-haloalkylsulphinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, -N(R7)2, -P(O)(R8)2, -CO-N(R9)2, -S(O)(R8)=NR9, -N=S(O)(R8)2, Si(R8)3or phenyl which is unsubstituted or substituted with one or more of the same or different substituents selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0025] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0026] R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl or hydroxyl;

[0027] R1aand R1b, optionally together along with the phenyl or 5- or 6-membered heteroaryl ring, may form a 8- to 10-membered bicyclic carbocyclic or heterocyclic ring system that is unsubstituted or substituted with one or more of the same or different substituents selected from R1baand / or R1ca, wherein the bicyclic heterocyclic ring system comprises one, two or three heteroatoms / groups independently selected from N, O, S, S(O) or S(O)2, and wherein one or more carbon atom of the bicyclic carbocyclic or heterocyclic ring system may be replaced with C(O);

[0028] R6is selected from hydrogen, halogen, cyano, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio, C3-C8-cycloalkyl, or -N(R7)2; R7represents hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkylcarbonyl, C3-Ce-cycloalkylcarbonyl, Ci-Ce-alkoxycarbonyl or Ci-Ce-alkylsulfonyl;

[0029] R8is selected from hydrogen, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0030] R9is selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl;

[0031] R10is selected from hydrogen, Ci-Ce-alkyl, hydroxy or Ci-Ce-alkoxy; and

[0032] RNis selected from hydrogen, Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, C3-C6-cycloalkyl, Ci-Ce-alkoxy, C(O)Rn, or S(O)2Rn, wherein said Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, C3-C6-cycloalkyl or Ci-Ce-alkoxy, is each unsubstituted or substituted by halogen or cyano;

[0033] R11is selected from hydrogen, halogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C3-C6-cycloalkyloxy, C3-C6-halocycloalkyloxy or -N(R7)2;

[0034] R1bais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy; and

[0035] R1cais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl or hydroxyl.

[0036] The present invention also relates to a process for preparing the compound of formula (I).

[0037] The compounds of formula (I) have been found to be advantageous over the compounds reported in the literature in either of improved fungicidal activity, broader spectrum of biological efficacy, lower application rates, more favourable biological and / or environmental properties, or enhanced plant compatibility.

[0038] The present invention further relates to agrochemical compositions comprising a compound of formula (I) or a compound of formula (I) in combination with one or more further pesticidally active substance(s) for controlling and / or preventing plant diseases, particularly caused by phytopathogenic fungi.

[0039] The present invention still further relates to a method for controlling or preventing an infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I), a composition or a combination thereof, is applied to the plants, to parts thereof or the locus thereof. DETAILED DESCRIPTION OF THE INVENTION:

[0040] DEFINITIONS:

[0041] The definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure.

[0042] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, “contains”, “containing”, “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

[0043] The transitional phrase “consisting of’ excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0044] The transitional phrase “consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.

[0045] Further, unless expressly stated to the contrary, “or” refers to an inclusive “or” and not to an exclusive “or”. For example, a condition A “or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0046] Also, the indefinite articles “a” and “an” preceding an element or component of the present invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. As referred to in this disclosure, the term “invertebrate pests” includes but is not limited to fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and nematodes of economic importance.

[0047] In the context of this disclosure “pest control” means inhibition of invertebrate pest development (including necrosis, retarded growth and / or death), and related expressions are defined analogously. The term “agronomic” refers to the production of field crops such as for food, feed and fiber and includes the growth of com, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).

[0048] The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.

[0049] Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the present invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected. As referred to in the present disclosure and claims, the terms “parasiticidal” and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal. The meaning of various terms used in the description shall now be illustrated.

[0050] The term “Ci-Ce alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” or “cyanoalkyl” refers to a straight-chain or branched Ci to Ce alkyl. Non-limiting examples of “Ci-Ce alkyl” include methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3 -methylbutyl, 2,2-dimethylpropyl, 1- ethylpropyl, hexyl, 1,1 -dimethylpropyl, 1,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1 -dimethylbutyl, 1,2-dimethylbutyl, 1,3 -dimethylbutyl, 2,2-dimethylbutyl, 2,3 -dimethylbutyl, 3, 3 -dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl- 1 -methylpropyl and l-ethyl-2-methylpropyl.

[0051] The term “Cz-Ce-alkenyl”, used either alone or in compound words refers to straight-chain or branched CT to Ce alkenes. Non-limiting examples of CT-CT, -alken l include ethenyl, 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1 -propenyl, 2-methyl -1-propenyl, l-methyl-2 -propenyl, 2-methyl-2 -propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl- 1-butenyl, 2-methyl- 1-butenyl, 3 -methyl- 1-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, l,l-dimethyl-2-propenyl, 1,2-dimethyl-l -propenyl, l,2-dimethyl-2 -propenyl, 1 -ethyl- 1-propenyl, l-ethyl-2 -propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-l-pentenyl, 2-methyl- 1-pentenyl, 3-methyl- 1-pentenyl, 4-methyl- 1-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3 -pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3 -pentenyl, 1 -methyl -4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, l,l-dimethyl-2-butenyl, l,l-dimethyl-3-butenyl, 1,2-dimethyl-l-butenyl, l,2-dimethyl-2-butenyl, l,2-dimethyl-3-butenyl, 1,3 -dimethyl- 1-butenyl, 1,3-dimethyl-2-butenyl, l,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2, 3-dimethyl- 1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl- 1-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, l,l,2-trimethyl-2 -propenyl, l-ethyl-l-methyl-2 -propenyl, l-ethyl-2 -methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. This definition also applies to alkenyl as a part of a composite substituent, for example haloalkenyl, alkenyloxy or haloalkenyloxy and the like, unless defined specifically elsewhere. The term “Cz-Ce-alkynyl”, used either alone or in compound words refers to straight-chain or branched CT to Ce alkynes. Non-limiting examples of CT-CT-alkyncs include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1 -methyl -2 -propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2 -butynyl, l-methyl-3 -butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1 -dimethyl -2 -propynyl, 1-ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l-pentynyl, 3-methyl-4-pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, l,l-dimethyl-2-butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3 -butynyl, 2,2-dimethyl-3 -butynyl, 3,3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l-ethyl-3 -butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl. This definition also applies to alkynyl as a part of a composite substituent, for example haloalkynyl etc. alkynyloxy, haloalkynyloxy, unless specifically defined elsewhere. The term “alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5 -hexadiynyl.

[0052] The term “C3-Cs-cycloalkyl” means a saturated carbocyclic ring containing 3 to 8 carbon atoms. The term “C3-C6-cycloalkyl” means a saturated carbocyclic ring containing 3 to 6 carbon atoms. Non-limiting examples of C3-Cs-cycloalkyl or C3-C6-cycloalkyl include cyclopropyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example C3-Cs-halocycloalkyl, C3-Ce-halocycloalkyl, cycloalkylalkyl etc., unless specifically defined elsewhere.

[0053] The term “C3-C6-cycloalkoxy”, and “C3-C6-cycloalkylthio” and the like are defined analogously. Non limiting examples of C3-Ce-cycloalkoxy or C3-C6-cycloalkylthio include cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio and cyclohexylthio.

[0054] The term “halogen”, either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “Ci-Ce-haloalkyl”, said Ci-Ce-alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Non-limiting examples of “Ci-Ce-haloalkyl” include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2.2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1-dichloro- 2.2.2-trifluoroethyl, and 1,1,1 -trifluoroprop-2 -yl.

[0055] The terms “Cz-Ce-haloalkenyl”, “Cz-Ce-haloalkynyl” are defined analogously except that, instead of Ci-Ce-alkyl groups, Ci-Ce-alkcnyl and Ci-Ce-alkynyl groups are present as a part of the substituent. The term “Ci-Ce-alkoxy” used either alone or in compound words includes a straight or branched chain Ci-Ce-alkoxy. Examples of Ci-Ce-alkoxy include methoxy, ethoxy, propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy, 1,1 -dimethylethoxy, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1 -methylpentoxy, 2-methylpentoxy, 3 -methylpentoxy, 4-methylpentoxy, 1,1 -dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3 -dimethylbutoxy, 3, 3 -dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1.2.2-trimethylpropoxy, 1 -ethyl- 1 -methylpropoxy and 1-ethyl -2 -methylpropoxy. This definition also applies to alkoxy as a part of a composite substituent, for example haloalkoxy, etc., unless specifically defined elsewhere.

[0056] The term “Ci-Ce-haloalkoxy” means straight-chain or branched Ci-Ce-alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non-limiting examples of Ci-Ce-haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1-bromoethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2, 2-dichloro-2 -fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trifluoroprop-2-oxy. This definition also applies to haloalkoxy as a part of a composite substituent, for example haloalkoxyalkyl etc., unless specifically defined elsewhere. The term “Ci-Ce-alkylthio” includes branched or straight-chain alkylthio moieties with 1 to 6 carbon atoms. Non-limiting examples of Cl-C6-alkylthio include methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1 -methylpropylthio, 2-methylpropylthio, 1,1 -dimethylethylthio, pentylthio, 1 -methylbutylthio, 2-methylbutylthio, 3 -methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1 -dimethylpropylthio, 1,2-dimethylpropylthio, 1 -methylpentylthio, 2-methylpentylthio, 3 -methylpentylthio, 4-methylpentylthio, 1,1 -dimethylbutylthio, 1,2-dimethylbutylthio, 1,3 -dimethylbutylthio, 2,2-dimethylbutylthio, 2,3 -dimethylbutylthio, 3,3-dimethylbutylthio, 1 -ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1 -ethyl- 1 -methylpropylthio and l-ethyl-2-methylpropylthio.

[0057] The term “Ci-Ce-haloalkylthio” means straight-chain or branched Ci-Ce-alkylthio group where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1 -chloroethylthio, 1-bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and l,l,l-trifluoroprop-2-ylthio. This definition also applies to haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere.

[0058] The term “Ci-Ce-alkylsulphinyl” includes branched or straight-chain alkylsulphinyl moiety with 1 to 6 carbon atoms. Non-limiting examples of Ci-Ce-alkylsulfinyl include methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2-methylpropylsulphinyl, 1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2-methylbutylsulphinyl, 3 -methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl, 1 -methylpentylsulphinyl, 2-methylpentylsulphinyl. 3 -methylpentylsulphinyl, 4-methylpentylsulphinyl, 1, 1 -dimethylbutylsulphinyl, 1.2-dimethylbutylsulphinyl, 1,3-dimethylbutylsulphinyl, 2,2-dimethylbutylsulphinyl, 2.3 -dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl, 1 -ethylbutylsulphinyl, 2-ethylbutylsulphinyl, 1,1,2-trimethylpropylsulphinyl, 1,2,2-trimethylpropylsulphinyl, 1 -ethyl- 1-methylpropylsulphinyl and 1-ethyl-2-methylpropylsulphinyl. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example Ci-Ce-haloalkylsulphinyl unless specifically defined elsewhere.

[0059] The term “Ci-Ce-alkylsulfonyl” includes branched or straight-chain alkylsulfonyl moiety with 1 to 6 carbon atoms. Non-limiting examples of Ci-Ce-alkylsulfonyl include methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1 -methylethylsulfonyl, butylsulfonyl, 1 -methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1 -dimethylethylsulfonyl, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutylsulfonyl, 3 -methylbutylsulfonyl, 2, 2 -dimethylpropylsulfonyl, 1 -ethylpropylsulfonyl, hexylsulfonyl, 1,1 -dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 1 -methylpentylsulfonyl, 2-methylpentylsulfonyl, 3 -methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1 -dimethylbutylsulfonyl, 1.2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3, 3 -dimethylbutylsulfonyl, 1 -ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1.1.2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1 -ethyl- 1 -methylpropylsulfonyl and l-ethyl-2-methylpropylsulfonyl. This definition also applies to alkylsulfonyl as a part of a composite substituent, for example Ci-Ce-haloalkylsulfonyl unless specifically defined elsewhere.

[0060] The term “Ci-Ce-alkylcarbonyl” includes branched or straight-chain alkylcarbonyl moiety with 1 to 6 carbon atoms. Non-limiting examples of Cl-C6-alkylcarbonyl include methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1 -methylethylcarbonyl, butylcarbonyl, 1 -methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1 -dimethylethylcarbonyl, pentylcarbonyl, 1 -methylbutylcarbonyl, 2-methylbutylcarbonyl, 3 -methylbutylcarbonyl, 2,2-dimethylpropylcarbonyl, 1 -ethylpropylcarbonyl, hexylcarbonyl, 1,1 -dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, 1 -methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3 -dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3 -dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethylpropylcarbonyl, 1,2,2-trimethylpropylcarbonyl, 1 -ethyl- 1 -methylpropylcarbonyl and 1 -ethyl -2 -methylpropylcarbonyl. The term ‘^-Ce-cycloalkylcarbonyl” means -C(O)-C3-Ce-cycloalkyl, wherein C3-C6-cycloalkyl is as defined above. Non-limiting examples include cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl.

[0061] The term “Ci-Ce-alkoxycarbonyl” refers to -C(O)-O-Ci-C6-alkyl group, wherein Ci-Ce-alkyl is as defined above. Non-limiting examples of Ci-Ce-alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl etc.

[0062] The term "heterocyclic ring” includes "an aromatic or a non-aromatic heterocyclic ring comprising at least one heteroatom selected from N, O, and S, wherein the heterocyclic ring may exist in an oxidized form.

[0063] The term “5- or 6-membered aromatic heterocyclic ring or 5- or 6-membered heteroaryl ring” refers to a mono-cyclic 5- or 6-membered aromatic ring which comprises at least one heteroatom selected from N, O or S(0)o-2. Examples include but are not limited to furanyl, pyrrolyl, thienyl, isoxazolyl, pyrazolyl, isothiazolyl, oxazolyl, imidazolyl, thiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, tefrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and tefrazinyl.

[0064] Ther term “a non-aromatic nitrogen containing 5- or 6-membered saturated or partially saturated heterocyclic ring” as used herein includes the 5- or 6-membered fully or partially saturated heterocyclic ring having at least 1 heteroatom selected from nitrogen, which may comprise 1 to 3 additional heteroatoms / groups selected from O, N, S, C(O), S(O) or S(O)2.

[0065] Examples of non-aromatic nitrogen containing 5-membered saturated or partially saturated heterocyclic ring include but are not limited to pyrrolidinyl, pyrazolidinyl, isoxazolidinyl, isothiazolidinyl, imidazolidinyl, oxazolidinyl, thiazolidinyl, triazolidinyl, oxadiazolidinyl, thiadiazolidinyl, tefrazolidinyl, dihydropyrrolyl, dihydropyrazolyl, dihydroisoxazolyl, dihydrothiozolyl, dihydroimidazolyl, dihydroxazolyl, dihydrothiazolyl, dihydrotriazolyl, dihydrooxadiazolyl, dihydrothiadiazolyl, dihydrotetrazolyl or their oxidized form thereof.

[0066] Examples of non-aromatic 6-membered saturated or partially saturated heterocyclic ring include but are not limited to piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyridine, dihydropyridazine, dihydropyrimidine, dihydropyrazine, dihydrofriazine, tefrahydropyridine, tefrahydropyridazinyl, tefrahydropyrimidinyl, tefrahydropyrazinyl or their oxidized form.

[0067] The term “oxidized form” as used herein in the present specification includes the heterocyclic ring comprising C(O), S(O) or S(O)2 group. When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript m in (R)mindicates an integer ranging from for example 0 to 4 then the number of substituents may be selected from the integers between 0 and 4 inclusive.

[0068] When a group contains a substituent which can be hydrogen, then, when this substituent is taken as hydrogen, it is recognized that said group is being un-substituted.

[0069] Optionally substituted groups may be mono- or polysubstituted, where the substituents in the case of polysubstitutions may be the same or different.

[0070] The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skilled in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.

[0071] The description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and / or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

[0072] Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.

[0073] The numerical values mentioned in the description and the description / claims though might form a critical part of the present invention, any deviation from such numerical values shall still fall within the scope of the present invention if that deviation follows the same scientific principle as that of the present invention disclosed in the present invention.

[0074] The inventive compound of the present invention may, if appropriate, be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example E and Z, threo and erythro, and also optical isomers, but if appropriate also of tautomers. Both the E and the Z isomers, but also the threo and erythro isomers, and the optical isomers, and any desired mixtures of these isomers and the possible tautomeric forms are disclosed and claimed.

[0075] The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of cocrystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by formula (I), or formula (I-A) to Formula (I-H) can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by formula (I), or formula (I-A) to Formula (I-H). The preparation and isolation of a particular polymorph of a compound represented by formula (I), or formula (I-A) to Formula (I-H) can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.

[0076] The term “pest” for the purpose of the present disclosure includes but is not limited to fongi, stramenopiles (oomycetes) and bacteria.

[0077] The term “plant” is understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders’ rights.

[0078] For the purpose of the present disclosure the term “plant” includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, fems, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis.

[0079] Examples of “plant” for the purpose of the present invention include but are not limited to agricultural crops such as wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits and fruit trees, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit and citrus frees, such as oranges, lemons, grapefruits or mandarins; any horticultural plants, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; cucurbitaceae; oleaginous plants; energy and raw material plants, such as cereals, com, soybean, other leguminous plants, rape, sugar cane or oil palm; tobacco; nuts; coffee; tea; cacao; bananas; peppers; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved frees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

[0080] Preferably, the plant for the purpose of the present invention includes but is not limited to cereals, com, rice, soybean and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and vegetables, ornamentals, any floricultural plants and other plants for the use of humans and animals.

[0081] The term “plant parts” is understood to mean all parts and organs of plants above and below the ground. For the purpose of the present disclosure the term plant parts include but is not limited to cuttings, leaves, twigs, tubers, flowers, seeds, branches, roots including taproots, lateral roots, root hairs, root apex, root cap, rhizomes, slips, shoots, fruits, fruit bodies, bark, stem, buds, auxiliary buds, meristems, nodes and internodes.

[0082] The term “locus thereof’ includes soil, surroundings of plant or plant parts and equipment or tools used before, during or after sowing / planting a plant or a plant part.

[0083] Application of the compounds of the present disclosure or the compound of the present disclosure in a composition optionally comprising other compatible compounds to a plant or a plant material or locus thereof includes application by a technique known to a person skilled in the art which includes but is not limited to spraying, coating, dipping, fumigating, impregnating, injecting and dusting.

[0084] The term “applied” means adhered to a plant or plant part either physically or chemically including impregnation.

[0085] The present invention provides a compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof,

[0086]

[0087] Formula (I)

[0088] wherein,

[0089] R1is selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, C3-C8-cycloalkyl or CT-CT-halocycloalkyl:

[0090] R2is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, C3-C’s-cycloalkyl, CT-CT-halocycloalkyl. Ci-Ce-alkoxy, or Ci-Ce-haloalkoxy;

[0091] R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkcnyl. CT-CT-haloalkenyl, Ci-Ce-alkynyl. Ci-Ce-haloalkynyl. C3-Cs-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio or C3-C6-cycloalkylthio;

[0092] R4aand R4bare each independently selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, CT-G-cycloalkyl. Ci-Ce-alkoxy, or Ci-Ce-haloalkoxy; or

[0093] R4aand R4btogether with the carbon atom to which they are attached, may together form an oxo group (=0), a 3- to 6-membered carbocyclic ring or a 3- to 6-membered heterocyclic ring containing at least one heteroatom / group selected from N, O, S, S(0) or SiO)?. wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to two substituents independently selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0094] R5is selected from the group consisting of hydrogen, Ci-Ce-alkyl and C1-C6-haloalkyl; B represents a phenyl ring or a 5- or 6-membered aromatic heterocyclic ring, which is fused at C3, C4 carbons of the piperidine ring C, wherein said 5- or 6-membered aromatic heterocyclic ring comprises 1 to 3 heteroatoms / groups independently selected from O, N, S, S(O) or SlOfr wherein said ring B is unsubstituted or substituted with one or more of the same or different substituents selected from R6;

[0095] D is selected from a direct bond, C3-C6 -cycloalkyl, phenyl or a 5- or 6-membered heteroaryl ring, wherein said 5- or 6-membered heteroaryl ring comprises 1, 2, 3 or 4 heteroatoms / groups each independently selected from N, O, S, S(O) and S(O) 2, and wherein said phenyl or 5- or 6-membered heteroaryl ring is unsubstituted or substituted with one or more of the same or different substituents selected from R1band / or R1c;

[0096] ring E is selected from a non-aromatic nitrogen containing 5- or 6-membered saturated or partially saturated heterocyclic ring, wherein the heterocyclic ring may contain 1 to 3 additional heteroatoms / groups independently selected from N, O, S, C(O), S(O) or S(O)2, wherein the heterocyclic ring is unsubstituted or substituted at the ring nitrogen with a substituent selected from RNand at the ring carbon atoms with one to three of the same or different substituents selected from R9, wherein said heterocyclic ring is bound to the C=W group either through a carbon atom or a nitrogen atom;

[0097] W is selected from O, S or NR10;

[0098] R1ais selected from hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-C6-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-C6-haloalkynyl, C3-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C2-Ce-alkenyloxy, C2-Ce-haloalkenyloxy, C2-C6-alkynyloxy, C2-Ce-haloalkynyloxy, C3-C6-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, C3-Ce-cycloalkylthio, Ci-Ce-alkylsulphinyl, Ci-Ce-haloalkylsulphinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, -N(R7)2, -P(O)(R8)2, -CO-N(R9)2, -S(O)(R8)=NR9, -N=S(O)(R8)2, Si(R8)3or phenyl which is unsubstituted or substituted with one or more of the same or different substituents selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0099] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0100] R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, or hydroxyl; R1aand R1b, optionally together along with the phenyl or 5- or 6-membered heteroaryl ring, may form a 8- to 10-membered bicyclic carbocyclic or heterocyclic ring system that is unsubstituted or substituted with one or more of the same or different substituents selected from R1baand / or R1ca, wherein the bicyclic heterocyclic ring system comprises one, two or three heteroatoms / groups independently selected from N, O, S, S(O) or S(O)?, and wherein one or more carbon atom of the bicyclic carbocyclic or heterocyclic ring system may be replaced with C(O);

[0101] R6is selected from hydrogen, halogen, cyano, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio, C3-Cs-cycloalkyl, or -N(R7)z;

[0102] R7represents hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkylcarbonyl, C3-Ce-cycloalkylcarbonyl, Ci-Ce-alkoxycarbonyl or Ci-Ce-alkylsulfonyl;

[0103] R8is selected from hydrogen, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0104] R9is selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl;

[0105] R10is selected from hydrogen, Ci-Ce-alkyl, hydroxy or Ci-Ce-alkoxy;

[0106] RNis selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-alkcnyl. C3-Ce-alkynyl, C3-C6-cycloalkyl, Ci-Ce-alkoxy, C(O)Rn, or S(O)2Rn, wherein said Ci-Ce-alkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, C3-C6-cycloalkyl or Ci-Ce-alkoxy, is each unsubstituted or substituted by halogen or cyano;

[0107] R11is selected from hydrogen, halogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C3-C6-cycloalkyloxy, C3-C6-halocycloalkyloxy or -N(R7)2;

[0108] R1bais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy; and

[0109] Rlcais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, or hydroxyl.

[0110] In an embodiment of the present invention, for the compound of formula (I), B is preferably selected from a phenyl or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, and said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6.

[0111] In another embodiment of the present invention, for the compound of formula (I), E is preferably a non-aromatic nitrogen containing 5 -membered saturated or partially saturated heterocyclic ring, which is selected from pyrrolidinyl, pyrazolidinyl, isoxazolidinyl, isothiazolidinyl, imidazolidinyl, oxazolidinyl, thiazolidinyl, triazolidinyl, oxadiazolidinyl, thiadiazolidinyl, tefrazolidinyl, dihydropyrrolyl, dihydropyrazolyl, dihydroisoxazolyl, dihydrothiozolyl, dihydroimidazolyl, dihydroxazolyl, dihydrothiazolyl, dihydrotriazolyl, dihydrooxadiazolyl, dihydrothiadiazolyl, dihydrotefrazolyl or their oxidized form thereof, wherein said ring is unsubstituted or substituted at the ring nitrogen(s) with substituent selected from RNand at the ring carbon atoms with one to three of the same or different substituents selected from R9.

[0112] In another embodiment of the present invention, for the compound of formula (I), E is preferably a non-aromatic nitrogen containing 6-membered saturated or partially saturated heterocyclic ring, which is selected from piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyridine, dihydropyridazine, dihydropyrimidine, dihydropyrazine, dihydrofriazine, tefrahydropyridine, tefrahydropyridazinyl, tefrahydropyrimidinyl, tetrahydropyrazinyl or their oxidized form, wherein said ring is unsubstituted or substituted at the ring nitrogen (s) with substituent selected from RNand at the ring carbon atoms with one to three of the same or different substituents selected from R9. In another embodiment of the present invention, for the compound of formula (I), E is more preferably selected from dihydroisoxazolyl, particularly 4,5 -dihydroisoxazolyl, dihydroisothiazolyl, isoxazolindinyl, dihydrooxazolyl, oxazolidinyl, 2-oxo-pyrrolidinyl, or 4H-pyrazolyl wherein said ring is attached to the C=W group through a carbon atom or a nitrogen, and said ring is unsubstituted or substituted with one to two of the same or different substituents selected from R9.

[0113] In another preferred embodiment of the present invention, for the compound of formula (I), E is selected from:

[0114]

[0115] wherein R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

[0116] In another embodiment of the present invention, for the compound of formula (I), D is preferably selected from a direct bond, phenyl, pyridyl, thiophenyl, or cyclohexyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with R1band / or R1c.

[0117] In another embodiment of the present invention, for the compound of formula (I), W = O. In one preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I -A):

[0118]

[0119] Formula (l-A)

[0120] wherein n = 1-3; and B, Rla-Rlc, R1, R2, R3, R4a, R4b, R5and E are as defined above for the compound of formula (I).

[0121] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-B):

[0122]

[0123] wherein n = 1-3, preferably n = 1; and Rla-Rlc, R1, R2, R3, R4a, R4b, R5and E are as defined above for the compound of formula (I); Z1, Z2, Z3and Z4, are each independently selected from C-R6or N. R6is as defined above for the compound of formula (I).

[0124] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-C):

[0125]

[0126] wherein n = 1-3, preferably n = 1; Rla-Rlc, R1, R2, R3, R4a, R4b, R5, and R6are as defined above for the compound of formula (I); and E is selected from:

[0127]

[0128] wherein R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

[0129] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-D):

[0130]

[0131] Formula (l-D)

[0132] wherein n = 1-3, preferably n = 1; Rla-Rlc, R1, R2, R3, R4a, R4b, R5, and R6, are as defined above for the compound of formula (I); Q is selected from NH, O or S, preferably S; and E is selected from:

[0133]

[0134] wherein R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

[0135] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-E):

[0136]

[0137] Formula (l-E)

[0138] wherein n = 1-3, preferably n = 1; Rla-Rlc, R2, R3, R4a, R4b, and R5, are as defined above for the compound of formula (I); and Q is selected from NH, O or S. E is as defined above for the compound of formula (I-D).

[0139] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-F):

[0140]

[0141] wherein n = 1-3, preferably n = 1; Rla-Rlc, R2, R3, R4a, R4b, and R5, are as defined above for the compound of formula (I); and Q is selected from NH, O or S. E is as defined above for the compound of formula (I-D).

[0142] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-G):

[0143]

[0144] Formula (l-G)

[0145] wherein n = 1-3, preferably n = 1; Rla-Rlc, R2, R3, R4a, R4b, and R5, are as defined above for the compound of formula (I); and Q is selected from NH, O or S; and E is as defined above for the compound of formula (I-D).

[0146] In another preferred embodiment of the present invention, the compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof, is represented as a compound of formula (I-H):

[0147]

[0148] wherein n = 1-3, preferably n = 1; and Rla-Rlc, R2, R3, R4a, R4b, and R5, are as defined above for the compound of formula (I); and Q is selected from NH, O or S; and E is as defined above for the compound of formula (I-D).

[0149] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0150] R1ais selected from hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkenyl, Ci-Ce-haloalkcnyl. Ci-Ce-alkynyl. Ci-Ce-haloalkynyl. C3-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkcnyloxy. Ci-Ce-haloalkcnyloxy. Ci-Ce-alkynyloxy, Ci-Ce-haloalkynyloxy. C3-C6-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, C3-Ce-cycloalkylthio, Ci-Ce-alkylsulphinyl, Ci-Ce-haloalkylsulphinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, -N(R7)2, -P(O)(R8)2, -CO-N(R9)2, -S(O)(R8)=NR9, -N=S(O)(R8)2, Si(R8)3, or phenyl which is unsubstituted or substituted with one or more different or identical substituents selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy. Preferably, Rlais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Ce-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce-alkylsulfonyl. More preferably, Rlais selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, tert-butyl, trifluoromethyl, OMe, OCF3, or cyclopropyl.

[0151] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0152] wherein, R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C8-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy. Preferably, R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6-cycloalkyl. More preferably, Rlbis selected from hydrogen, fluoro, chloro, bromo, cyano, methyl, trifluoromethyl and cyclopropyl.

[0153] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0154] wherein, R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C8-cycloalkyl. Preferably, R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl or Ci-Ce-haloalkyl. More preferably, Rlcis selected from hydrogen, halogen such as fluoro, chloro or bromo or cyano.

[0155] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0156] wherein, R1is selected from halogen, cyano or Ci-Ce-alkyl. Preferably, R1is Ci-Ce-alkyl. More preferably, R1is methyl.

[0157] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0158] wherein, R2is selected from hydrogen, Ci-Ce-alkyl, or Ci-Ce-haloalkyl. Preferably, R2is hydrogen. According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0159] wherein, R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkcnyl. Ci-Ce-alkynyl. Ci-Ce-alkoxy, Ci-Ce -haloalkoxy, or Ci-Ce-alkylthio. Preferably, R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, or Ci-Ce-alkylthio. More preferably, R3is selected from hydrogen, chloro, bromo, cyano, methyl, CH2CI, or -SMe. According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0160] wherein, R4aand R4bare each independently selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl or together with the carbon atom to which they are attached, may form an oxo group (=0) or a 3- to 6-membered carbocyclic ring.

[0161] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0162] wherein, R4ais preferably selected from hydrogen or Ci-Ce-alkyl. More preferably, R4ais selected from hydrogen or methyl.

[0163] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0164] wherein, R4bis preferably selected from hydrogen or Ci-Ce-alkyl and more preferably, R4bis hydrogen.

[0165] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0166] wherein, R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring.

[0167] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H):

[0168] wherein, R5is selected from hydrogen or Ci-Ce-alkyl. Preferably, R5is selected from hydrogen or methyl.

[0169] According to any of the above embodiments of the present invention, the compound of formula (I) or formula (I -A), wherein:

[0170] B is preferably selected from a phenyl or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, and said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6.

[0171] According to any of the above embodiments of the present invention, the compound of formula (I), wherein:

[0172] D is preferably selected from a direct bond, phenyl, pyridyl, thiophenyl, or cyclohexyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with R1band / or R1c. According to any of the above embodiments of the present invention, the compound of formula (I), to formula (I-H), wherein:

[0173] E is preferably selected from a non-aromatic nitrogen containing 5 -membered saturated or partially saturated heterocyclic ring, which is selected from dihydroisoxazolyl, dihydroisothiazolyl, pyrrolidinyl-2-one, or 4H-pyrazolyl, wherein the ring carbon atoms are unsubstituted or substituted with one to three of the same or different substituents selected from R9, wherein R9is preferably selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl. More preferably, E is selected from:

[0174]

[0175] E-1 E-2 E-3 E-4

[0176] wherein R9is selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl;

[0177] According to any of the above embodiments of the present invention, the compound of formula (I), wherein:

[0178] W = O.

[0179] According to any of the above embodiments of the present invention, the compound of formula (I), to formula (I-H), wherein:

[0180] R6is preferably selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Cs-cycloalkyl, or -N(R7)2.

[0181] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0182] R7is preferably selected from hydrogen, Ci-Ce-alkyl, C3-Cs-cycloalkyl, Ci-Ce-alkylcarbonyl, or C3-Ce-cycloalkylcarbonyl.

[0183] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0184] R8is preferably selected from hydrogen, halogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy.

[0185] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein: R9is preferably selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl.

[0186] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0187] RNis preferably selected from the group consisting of hydrogen, Ci-Ce-alkyl, C3-C6 -cycloalkyl, Ci-Ce-alkoxy, C(O)Rn, and S(O)2Rn, wherein said Ci-Ce-alkyl or Ci-Ce-alkoxy, is each unsubstituted or substituted by one to three halogen.

[0188] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0189] R11is preferably selected from hydrogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy or -N(R7)2.

[0190] According to any of the above embodiments of the present invention, the compound of formula (I) to formula (I-H), wherein:

[0191] Rlaand Rlboptionally together along with the phenyl ring may form an 9- to 10-membered bicyclic carbocyclic or heterocyclic ring system that can be optionally substituted with one or more of the same or different substituents selected from R1baand / or R1ca, wherein the bicyclic heterocyclic ring system comprises one or more heteroatoms / groups independently selected from nitrogen, oxygen, S, S(O) or S(O)2.

[0192] According to any of the above embodiments of the present invention, the compound of formula (I-A) to formula (I-H), wherein:

[0193] n = 1-3 and more preferably n = 1. According to any of the above embodiments of the present invention, the compound of formula (I) or formula (I-A) to formula (I-H), wherein:

[0194] R1is selected from halogen, cyano or Ci-Ce-alkyl;

[0195] R2is selected from hydrogen, Ci-Ce-alkyl, or Ci-Ce-haloalkyl;

[0196] R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkcnyl. C2-C6-alkynyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, or Ci-Ce-alkylthio;

[0197] R4aand R4bare each independently selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl or together with the carbon atom to which they are attached, may form an oxo group (=0) or a 3- to 6-membered carbocyclic ring;

[0198] R5is selected from hydrogen or Ci-Ce-alkyl; B is preferably selected from a phenyl or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, and said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6;

[0199] D is selected from a direct bond, cyclohexyl, phenyl, pyridyl or thiophenyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with one or two of the same or different substituents selected from R1band / or R1c;

[0200] E is selected from a non-aromatic nitrogen containing 5 -membered saturated or partially saturated heterocyclic ring, which is selected from dihydroisoxazolyl, dihydroisothiazolyl, 2-oxopyrrolidinyl, or 4H-pyrazolyl, wherein said each ring is unsubstituted or substituted at the ring nifrogen(s) with substituent selected from RNand at the ring carbon atoms with 1 to 3 identical or different substituents selected from R9; W is O;

[0201] R1ais selected from hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, Ci-Ce-haloalkcnyl. Ci-Ce-alkynyl. Ci-Ce-haloalkynyl. C3-Cs-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkcnyloxy. Ci-Ce-haloalkcnyloxy. Ci-Ce-alkynyloxy, Ci-Ce-haloalkynyloxy. C3-C6-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, C3-Ce-cycloalkylthio, Ci-Ce-alkylsulphinyl, Ci-Ce-haloalkylsulphinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfonyl, -N(R7)2, -P(O)(R8)2, -CO-N(R9)2, -S(O)(R8)=NR9, -N=S(O)(R8)2, Si(R8)3, or phenyl which is unsubstituted or substituted with one or more of the same or different substituents selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C8-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0202] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0203] R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl; Rlaand Rlboptionally together along with the phenyl ring may form an 9- to 10-membered bicyclic carbocyclic or heterocyclic ring system that can be optionally substituted with one or more of the same or different substituents selected from R1baand / or R1ca, wherein the bicyclic heterocyclic ring system comprises one or more heteroatoms / groups independently selected from nitrogen, oxygen, S, S(O) or S(O)2;

[0204] R6is selected from hydrogen, halogen, cyano, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-C8-cycloalkyl, or -N(R7)2; R7is selected from hydrogen, Ci-Ce-alkyl, C3-Cs-cycloalkyl, Ci-Ce-alkylcarbonyl, or C3-C6-cycloalkylcarbonyl;

[0205] R8is selected from hydrogen, halogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0206] R9is selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl;

[0207] RNis selected from the group consisting of hydrogen, Ci-Ce-alkyl, C3-C6-cycloalkyl, Ci-Ce-alkoxy, C(O)Rn, and S(O)2Rn, wherein said Ci-Ce-alkyl or Ci-Ce-alkoxy are each unsubstituted or substituted by one to three halogen;

[0208] R11is selected from hydrogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy or -N(R7)2;

[0209] R1bais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy;

[0210] R1cais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Cs-cycloalkyl; and

[0211] n is 1-3, preferably n = 1-2 and more preferably n = 1.

[0212] In yet another preferred embodiment of the present invention, the compound of formula (I), or formula (I-A) to formula (I-H), wherein:

[0213] R1is preferably Ci-Ce-alkyl, more preferably R1is methyl;

[0214] R2is hydrogen;

[0215] R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, or Ci-Ce-alkylthio, preferably hydrogen, chloro, bromo, cyano, methyl, CH2CI, or -SMe;

[0216] R4ais selected from hydrogen or Ci-Ce-alkyl, preferably R4ais selected from hydrogen or methyl; R4bis selected from hydrogen or Ci-Ce-alkyl, more preferably R4bis hydrogen;

[0217] or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;

[0218] R5is selected from hydrogen or Ci-Ce-alkyl, more preferably R5is selected from hydrogen or methyl; B is preferably selected from a phenyl or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, and said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6; D is selected from a direct bond, cyclohexyl, phenyl, pyridyl or thiophenyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with one or two of the same or different substituents selected from R1band / or R1c;

[0219] E is dihydroisoxazolyl, dihydroisothiazolyl, 2-oxo-pyrrolidinyl or 4H-pyrrolyl, wherein said ring is attached to the C=O through a carbon atom or nitrogen and said each ring is unsubstituted or substituted with one to two of the same or different substituents selected from R9;

[0220] W = O;

[0221] Rlais preferably selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C6-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-C6-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce-alkylsulfonyl, more preferably hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, tert-butyl, frifluoromethyl, OMe, OCF3, or cyclopropyl;

[0222] Rlbis preferably selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6-cycloalkyl, more preferably hydrogen, fluoro, chloro, bromo, cyano, methyl, frifluoromethyl or cyclopropyl;

[0223] Rlcis preferably selected from hydrogen, halogen, cyano, Ci-Ce-alkyl or Ci-Ce-haloalkyl, more preferably hydrogen, halogen such as fluoro, chloro or bromo or cyano;

[0224] R6is selected from hydrogen, halogen, methyl, or cyano, more preferably R6is selected from hydrogen, fluoro, chloro or cyano;

[0225] R9is preferably selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl, more preferably R9is selected from hydrogen, methyl or trifluoromethyl; and

[0226] n is 1-3, preferably n = 1.

[0227] In another preferred embodiment of the present invention, the compound of formula (I), wherein: R1is Ci-Cg-alkyl;

[0228] R2is hydrogen;

[0229] R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, or Ci-Ce-haloalkyl;

[0230] R4aand R4bare independently selected from hydrogen or Ci-Ce-alkyl;

[0231] or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;

[0232] R5is selected from hydrogen or Ci-Ce-alkyl; B is selected from a phenyl ring or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, wherein said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6;

[0233] D is selected from a direct bond, cyclohexyl, phenyl, pyridyl or thiophenyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with one or two of the same or different substituents selected from R1band / or R1c;

[0234] E is selected from:

[0235]

[0236] W = O;

[0237] R1ais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Ce-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce-alkylsulfonyl;

[0238] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6-cycloalkyl; R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl or Ci-Ce-haloalkyl;

[0239] R6is selected from hydrogen, halogen, methyl or cyano; and

[0240] R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

[0241] In yet another preferred embodiment of the present invention, the compound of formula (I-A) to formula (I-H), wherein:

[0242] R1is Ci-Cg-alkyl;

[0243] R2is hydrogen;

[0244] R3is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, or Ci-Ce-haloalkyl;

[0245] R4aand R4bare independently selected from hydrogen or Ci-Ce-alkyl;

[0246] or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;

[0247] R5is selected from hydrogen or Ci-Ce-alkyl; B is selected from a phenyl ring or thiophenyl ring, which is fused at C3, C4-carbons of piperidine ring C, wherein said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6;

[0248]

[0249] E is selected from

[0250]

[0251] ;

[0252] R1ais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Ce-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce-alkylsulfonyl;

[0253] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6-cycloalkyl; R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl or Ci-Ce-haloalkyl;

[0254] R6is selected from hydrogen, halogen, methyl or cyano; and

[0255] R9is preferably selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

[0256] In a more preferred embodiment, the compound of formula (I -A) to formula (I-H), wherein, R1is Ci-Ce-alkyl, preferably methyl;

[0257] R2is hydrogen;

[0258] R3is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl, preferably hydrogen, methyl or -CH2CI;

[0259] R4ais selected from hydrogen or Ci-Ce-alkyl, preferably hydrogen or methyl;

[0260] R4bis selected from hydrogen or Ci-Ce-alkyl, preferably hydrogen;

[0261] or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;

[0262] R5is selected from hydrogen or Ci-Ce-alkyl, preferably hydrogen or methyl;

[0263] E is selected from any one of the following rings E-l to E-4:

[0264]

[0265] R1ais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-Ce-cycloalkyl, Ci- Ce-alkoxy, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce- alkylsulfonyl, preferably hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, tert-butyl, trifluoromethyl, methoxy, trifluoromethoxy, or cyclopropyl;

[0266] R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-Ce-cycloalkyl, preferably hydrogen, fluoro, chloro, bromo, cyano, methyl, trifluoromethyl or cyclopropyl;

[0267] R1cis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl or Ci-Ce-haloalkyl, preferably hydrogen, halogen such as fluoro, chloro or bromo or cyano;

[0268] R6is selected from hydrogen, halogen or cyano, preferably hydrogen, fluoro, chloro or cyano; R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl, preferably hydrogen, methyl or trifluoromethyl; and

[0269] n is 1-3, preferably n = 1-2 and more preferably n = 1.

[0270] In one preferred embodiment of the present invention,

[0271]

[0272] formula (I) or formula (I-A) to formula (I-H) is selected from:

[0273]

[0274]

[0275] In another preferred embodiment, the present invention provided the compound of formula (I-A) to

[0276] formula (I-H), wherein

[0277]

[0278] particularly described in the below table: Table A describes the variables Rla, Rlband Rlcof the compounds of formula (I-A) to formula (I- H).

[0279] Table A:

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288] * CyPr =cyclopropyl

[0289] The agriculturally acceptable salts of the compounds of formula (I), or formula (I -A) to formula (I-H) encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds of formula (I), or formula (I-A) to formula (I-H). The salts obtainable in this way likewise have fungicidal properties.

[0290] Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula (I) or any of formulas (I-A) to (I-H), with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid. The compounds of the present invention may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers e.g. a racemate, individual stereoisomers, or constitutional isomers or as an optically active form. The various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixtures of these isomers fall within the scope of the claims of the present disclosure. One skilled in the art will appreciate that one stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s). Additionally, the person skilled in the art knows processes or methods or technologies to separate, enrich, and / or to selectively prepare said isomers.

[0291] The compounds of formula (I) or formula (I-A) to formula (I-H) can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention. The compounds of formula (I) or formula (I-A) to formula (I-H) can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.

[0292] The compounds selected from formula (I), or formula (I-A) to formula (I-H) (including all stereoisomers, N-oxides, and salts thereof), may typically exist in more than one form. The compounds of formula (I), or formula (I-A) to formula (I-H) thus include all crystalline and non-crystalline forms of the compound that formula (I), or formula (I-A) to formula (I-H). Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The following schemes illustrate approaches for preparing compounds of formula (I), or formula (I-A) to formula (I-H). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns. Further, the mentioned reagents, solvents and reaction conditions are intended for the purpose of exemplification only and should not be construed as limiting.

[0293] In one embodiment, the present invention provides a process for the synthesis of compounds of formula (I), or formula (I-A) to formula (I-H).

[0294] The compounds of the present invention as defined by formula (I), or formula (I-A) to formula (I-H) and / or in table 1 are prepared, in a known manner, in a variety of ways as described in the schemes 1 -6. The definitions of B, Rla-Rlc, R1, R2, R3, R4a, R4b, R5and E in the compounds of formulae (I), (I-A to I-H), are as defined above in the detailed description of the invention unless otherwise stated specifically.

[0295] Scheme- 1:

[0296]

[0297] In one of the preferred embodiments, compounds of the general formula (I-A) of the present invention, can be prepared by amidation reactions between an amine compound of formula 1 (or it’s hydrochloric acid salt) and a compound of the general formula 2 wherein X represents -OH or -halo group in the presence or absence of coupling reagents such as 1-propanephosphonic acid cyclic anhydride, hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, etc. or alkyl chloroformates such as ethyl chloroformate, isobutylchloroformate, etc. and a solvent such as dichloromethane, tetrahydrofuran, N,N-dimethyl formamide etc. These transformations are typically run at 0 °C to 25 °C.

[0298] Scheme-2:

[0299]

[0300] As shown in scheme 2, compounds of the general formula (I-A) of the present invention, can also be prepared by ester-amine coupling reaction between an amine compound of formula 1 (or it’s hydrochloric acid salt) and a compound of the general formula 3, wherein R is alkyl or aryl group in the presence or absence of a base such as LiHMDS, KOt-Bu, etc. and in the presence or absence of activating reagents such as Lewis acids. These reactions are carried out in various solvents such as toluene, tetrahydrofuran, methanol etc. and typically at a temperature ranging from 0 °C to 120 °C. Scheme-3:

[0301]

[0302] According to scheme 3, compounds represented by the general formula (I-A) of the present invention, can also be prepared by a metal catalyzed C-N coupling of an amine of formula 4a and an aryl halide compound of formula 5a. The compounds of formula 5a with required substitution pattern can either be purchased from commercial sources or can be prepared using literature protocols. The requisite coupling partner of the general formula 4a can be constructed via an amidation reaction between an acid or acyl halide of formula 10 and an amine of the general formula 1 (or it’s hydrochloric acid salt). The C-N coupling reactions are usually carried out in the presence of solvents, while the solvents which can be used for this reaction are not particularly limited as long as they do not adversely affect the reaction. For example, ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol, dimethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; N-amides such as N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, butanol, 2-propanol and 2-methyl-2-propanol; nitriles such as acetonitrile; or water or a mixture thereof may serve this purpose. Preferable solvents include aromatic hydrocarbons such as toluene and xylene; and ethers such as 1,4-dioxane, tetrahydrofuran; out of which toluene and 1,4-dioxane are the most preferable ones.

[0303] The C-N coupling reaction is carried out in the presence of a base selected from, but not limited to, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, caesium carbonate, sodium phosphate, tribasic potassium phosphate, potassium hydrogenphosphate, and potassium hydride; organic bases such as triethylamine, N, N-diisopropylethylamine and pyridine. Preferred bases include metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide and inorganic bases such as caesium carbonate and tribasic potassium phosphate.

[0304] The palladium catalysts that can be used for this C-N coupling reaction include, but are not limited to, inorganic palladium salts such as palladium chloride; organic palladium complexes such as palladium acetate; tetrakis(triphenylphosphine)palladium(0), bis (triphenylphosphine )palladium(II) chloride, 1,1'-bis (diphenylphosphino) phenylpalladium (II) chloride, and tris(dibenzylidene acetone)dipalladium(O). Palladium catalysts such as palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, 1,1'- bis (diphenylphosphino) phenylpalladium (II) chloride and tris (dibenzylidene acetone) dipalladium (0) are more preferable. The C-N coupling reaction can also be carried out using further ligands in combination with the above-mentioned catalysts for a successful transformation. A list of possible ligands for this transformation include, but is not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphonium tetrafluoroborate, (oxydi -2, 1 -phenylene )bis[dicyclohexyl] phosphine, 4,5 -bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-l, 1 '-biphenyl, (2-biphenylyl) di-tert-butylphosphine; 2-(di-tert-butylphosphino)biphenyl, 2-di-tert- butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-l, T-biphenyl, l,l'-ferrocenediyl-bis(diphenylphosphine), 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-methyl-2'-dicyclohexylphosphinobiphenyl and [l,l'-biphenyl]-3-sulfonic acid, 2'-(dicyclohexylphosphino)-2,6-dimethoxy- sodium salt. The preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl (Oxydi-2,1-phenylene)bis[dicyclohexyl] phosphine, 1,1'-ferrocenediyl-bis(diphenylphosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

[0305] Pre-catalysts can also be utilized for such transformations. A list of possible pre-catalysts include, but is not limited to, (SP-4-3)-[dicyclohexyl[3,6-dimethoxy-2',4',6'-tris(l-methylethyl)[l, T-biphenyl]-2-yl]phosphine-KP](methanesulfonato-KO)[2'-(methylamino-KN)[l, T-biphenyl]-2-yl-KC], [(2-di-cyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl- 1, 1 '-biphenyl)-2-(2'-amino- 1, T -biphenyl)]palladium(II) methanesulfonate, [(2-di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-l, T-biphenyl)-2-(2'-amino-l, T-biphenyl)]palladium(II) methanesulfonate, [2-(di-l-adamantylphosphino)-2',4',6'-triisopropyl-3,6-dimethoxybiphenyl] [2-(2'-amino- 1, 1 '-biphenyl)]palladium(II) methanesulfonate, [2'-(amino-κN)[1,1'-biphenyl]-2-yl-κC][2'-[(1,1-dimethylethyl)phenylphosphino-κP]-N2,N'2,N6,N'''-tetramethyl[1,1'-biphenyl]-2,6-diamine](methanesulfonato-κO)palladium, [dicyclohexyl[3-(l-methylethoxy)-2',4',6'-tris( 1 -methylethyl) [1,1 '-biphenyl] -2-yl]phosphine-KP] (methanesulfonato-KO) [2'-(methylamino-KN) [1,1 '-biphenyl] -2-yl-KC] palladium.

[0306] Halogens, such as, chloro-, bromo-, and iodo-, are the trivial leaving groups (LG) that are used in this transformation. However, it is also possible to use tosylates, mesylates, and triflates, in somewhat similar manner, as leaving groups allowing successful transformations.

[0307] The reactions can be performed at a temperature range of 0-200 °C, preferably at a temperature range of 50-150 °C for a duration of time between 30 minutes to 24 hours.

[0308] Scheme-4:

[0309]

[0310] According to scheme 4, compounds represented by the general formula (I-A) of the present invention can also be prepared by Suzuki or Suzuki -Miyaura type Csp2-Csp2bond formation reaction between the compound of formula 4b, wherein Y is Cl, Br or I and an aryl boronic compound of formula 5b. The requisite coupling partner of the general formula 4b can be constructed via amidation reaction between an acid or acid halide of formula 11 and an amine compound of formula 1 (or its hydrochloric acid salt). The Suzuki or Suzuki -Miyaura type Csp2-Csp2bond formation reactions according to Scheme-4 are usually carried out in the presence of appropriate solvent(s) for instance, 1,4-dioxane, tetrahydrofuran, ethylene glycol, dimethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; N-amides such as N,N-dimethylformamide, N-dimethylacetamide and 1-methyl -2 -pyrrolidone; nitriles such as acetonitrile; or water or a mixture thereof may serve this purpose. Preferable solvents include dimethylformamide, tetrahydrofuran, water, 1,4-dioxane or in their binary mixture.

[0311] The Suzuki or Suzuki -Miyaura type Csp2-Csp2bond formation reactions according to Scheme-4 are carried out in the presence of a base selected from, but not limited to, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, tribasic potassium phosphate, potassium hydrogenphosphate, and potassium hydride; organic bases such as triethylamine, N,N-diisopropylethylamine and pyridine. Preferred bases include metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide and inorganic bases such as potassium carbonate, sodium carbonate, caesium carbonate and tribasic potassium phosphate. The palladium catalysts that can be used for this Suzuki or Suzuki-Miyaura type Csp2-Csp2bond formation reactions according to Scheme-4, include, but are not limited to, inorganic palladium salts such as palladium chloride; organic palladium complexes such as palladium acetate; tetrakis(triphenylphosphine)palladium(0), bis (triphenylphosphine)palladium(II) chloride, l,l'-bis (diphenylphosphino) phenylpalladium (II) chloride, and tris(dibenzylidene acetone)dipalladium(O). Palladium catalysts such as palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, 1'- bis (diphenylphosphino) phenylpalladium (II) chloride, dichlorofl, l'-bis(diphenylphosphino)ferrocene]palladium(II), and tris (dibenzylidene acetone) dipalladium (0) are more preferable.

[0312] The Suzuki or Suzuki-Miyaura type Csp2-Csp2bond formation reactions according to Scheme-4 can also be carried out using further ligands in combination with the above-mentioned catalysts for a successful transformation. A list of possible ligands for this transformation includes, but is not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphonium tetrafluoroborate, (oxydi-2,1-phenylene)bis [dicyclohexyl] phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-l,l'-biphenyl, (2 -biphenylyl) di-tert- butylphosphine; 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, 1,1 '-ferrocenediyl -bis(diphenylphosphine), 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-methyl-2'-dicyclohexylphosphinobiphenyl and [ 1,1 '-biphenyl] -3-sulfonic acid, 2'-(dicyclohexylphosphino)-2,6-dimethoxy- sodium salt. The preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-l,l'-biphenyl (Oxydi-2,1-phenylene)bis [dicyclohexyl] phosphine, 1,1 '-ferrocenediyl -bis(diphenylphosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

[0313] It is also possible to use Y = tosylates, mesylates, and triflates in the compound of formula 4b, in somewhat similar manner, as leaving groups to achieve the Suzuki-Miyaura type Csp2-Csp2bond formation reactions according to Scheme -4.

[0314] The Suzuki or Suzuki-Miyaura type Csp2-Csp2bond formation reactions according to scheme-4, can be performed at a temperature ranging between 70 °C-140 °C.

[0315] Scheme-5:

[0316]

[0317] As shown in scheme 5, compounds denoted by the general formula (I- A) can also be synthesized through oxidation of an active methylene group (for instance benzylic -CH2-), as present in compounds of formula 7, in the presence or absence of metal oxides such as iron oxide, manganese oxide, selenium dioxide etc or under an oxygen atmosphere. These types of transformations are typically carried out in solvents such as water, ethyl acetate, acetonitrile, dimethyl sulfoxide etc and in a range of temperature such as 25 °C to 100 °C.

[0318] Scheme-6:

[0319]

[0320] Formula 8 Formula 2 Formula (l-C)

[0321] In one of the preferred embodiments of the present invention, compound represented by formula (I-C) of the present invention, can be prepared via an amidation coupling reaction of an amine (or it’s Hydrochloric acid salt) of formula 8 and an acid or acyl halide denoted by the general formula 2 in the presence of commonly used amidation reaction conditions as shown in Scheme-1 and Scheme-6. Scheme-7:

[0322]

[0323] Formula (l-D)

[0324] In another preferred embodiment, the compound represented by formula (I-D) of the present invention, can also be prepared via an amide coupling reaction of an amine (or it’s hydrochloric acid salt) of formula 9 and an acid or acyl halide denoted by the general formula 2 under commonly used coupling reaction conditions as shown in Scheme-1 and Scheme-7.

[0325] Scheme-8:

[0326]

[0327] In another embodiment of the present invention, the compound of formula 2, wherin X = OH can be prepared via acid or base mediated hydrolysis of corresponding ester compound of formula 3. The carboxylic acid thus obtained can be converted to acid halides of formula 2, wherein X = halogen (preferably Cl) by treatment with oxalyl chloride or thionyl chloride under suitable moisture free condition. Such transformation can be carried out at temperature ranging from 0 °C to reflux according to scheme-8.

[0328] Scheme-9:

[0329]

[0330] Formula 8-a

[0331] In one embodiment of the present invention, a bicyclic amine intermediate of formula 8-a can be prepared by hydrogenation of the quinoline compound of formula 11 using a combination of sodium borohydride and iodine in a suitable solvent, preferably in tetrahydrofuran (THF) according to Scheme-9. The quinoline compounds of formula 11 can also be obtained by adopting known literature methods described in WO 2022253645. In one embodiment, the present invention provides a method for combating phytopathogenic fungi, comprising treating plants, soil, seeds or materials to be protected with the compound of formula (I), or any of formulas (I-A) to (I-H), stereo-isomers, tautomers, polymorphs or agriculturally acceptable salts, a composition or combination thereof.

[0332] Examples of application methods for the compounds of the invention and compositions thereof, that are common methods of controlling pests in agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring which are to be selected to suit the intended aims of the prevailing circumstances.

[0333] One method of application in agriculture is application to the foliage of the plants (foliar application), thereby being possible to select frequency and rate of application to match the danger of infestation with the pest or fungi in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application). In the case of paddy rice plants, such granules can be metered into the flooded paddy-field.

[0334] Typical rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha, such as 50 to 300 g / ha.

[0335] The compounds of the present disclosure may be applied by a variety of known techniques, either as the compounds themselves or as formulations comprising these compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates.

[0336] Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising the compounds of formula (I), or any of formulas (I-A) to (I-H) together with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.

[0337] The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.

[0338] In one embodiment, the present invention provides an agrochemical composition comprising a compound of formula (I), or any of formulas (I-A) to (I-H), agriculturally acceptable salts, constitutional isomers, stereo-isomers, diastereoisomers, enantiomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, geometric isomers, or N-oxides thereof, optionally with one or more additional active ingredient(s), and optionally together with an auxiliary such as an inert carrier or any other essential ingredient(s) such as surfactants, additives, solid diluents and liquid diluents.

[0339] An agrochemical composition comprises a fungicidally effective amount of a compound of formula (I), or any of formulas (I-A) to (I-H). The term "effective amount" denotes an amount of the composition or of the compound of formula (I), or any of formulas (I-A) to (I-H), which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions, and the specific compound of formula (I), or any of formulas (I-A) to (I-H) being used.

[0340] In another embodiment, the present invention provides a composition comprising at least one compound of formula (I), or any of formulas (I-A) to (I-H) and seeds. The amount of the compound of formula (I), or any of formulas (I-A) to (I-H) in the composition ranges from 0.1 g ai (gram per active ingredient) to 1 kg ai (kilogram per active ingredient) per 100 kg of seeds.

[0341] The compounds of formula (I), or any of formulas (I-A) to (I-H), their N-oxides, isomers, polymorphs or the agriculturally acceptable salts thereof can be converted into customary types of agrochemical compositions, e. g. into solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for such composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF).

[0342] Examples for suitable auxiliaries for formulations and / or agrochemical compositions according to the invention are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti -foaming agents, colorants, tackifiers and binders.

[0343] Suitable solvents and liquid carriers in this context are for instance water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil, oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; dimethyl sulfoxide; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof. Suitable solid carriers or fillers are for instance mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulphate, magnesium sulphate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

[0344] Suitable surfactants are surface -active compounds, for instance such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Suitable anionic surfactants are for instance alkali, alkaline earth or ammonium salts of sulfonates, sulphates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl-and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulphates are sulphates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0345] Suitable nonionic surfactants are for instance alkoxylates, '-substitutcd fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.

[0346] Examples of '-substitutcd fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar -based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.

[0347] Suitable cationic surfactants are for instance quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are for instance alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are for instance alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.

[0348] Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound of Formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries.

[0349] The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active ingredient (ai). The active ingredients (ai) are employed in a purity from 90% to 100%, preferably from 95% to 100% (according to the NMR spectrum).

[0350] For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active substance concentrations from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready -to-use preparations.

[0351] When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 1.0 kg per ha, and in particular from 0.1 to 0.5 kg per ha.

[0352] In the treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, the generally required amounts of active substance are ranging from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds).

[0353] When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are ranging from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0354] Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be mixed with the composition according to the invention in a weight ratio of 1: 100 to 100: 1.

[0355] A pesticide is generally a chemical or biological agent (such as pesticidally active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for diseases.

[0356] The term "pesticide" includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.

[0357] The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, a drone, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and / or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

[0358] In one embodiment, the present invention provides a combination comprising the compounds of formula (I), or any of formulas (I-A) to (I-H) and at least one further pesticidally active substance selected from the group consisting of fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients.

[0359] The compounds of formula (I), or any of formulas (I-A) to (I-H), the combinations and the compositions thereof comprising them in the use as fungicides with other fungicides may result in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, extraordinary and unexpected effects are obtained. The present invention also relates to agrochemical combinations comprising at least one compound of formula (I), or any of formulas (I-A) to (I-H), and at least one further pesticidally active substance selected from the group of fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients.

[0360] The present invention furthermore relates to agrochemical mixtures comprising at least one compound of formula (I), or any of formulas (I-A) to (I-H) (component 1) and at least one further active substance useful for plant protection.

[0361] By applying the compounds of formula (I), or any of formulas (I-A) to (I-H) together with at least one pesticidally active compound, an additional effect can be obtained.

[0362] This can be obtained by applying the compounds of formula (I), or any of formulas (I-A) to (I-H) and at least one further pesticidally active substance simultaneously, either jointly (e. g. as tank -mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further pesticidally active substance(s). The order of application is not essential for working of the present invention.

[0363] When applying the compounds of formula (I), or any of formulas (I-A) to (I-H) and a pesticidally active substance sequentially the time between both applications may vary e. g. between 2 hours to 7 days, preferably from 2 hours to 1 day. In the binary mixtures and the composition according to the invention the weight ratio of component 1) and component 2) generally depends on the properties of the active components used, usually it is in the range of 1: 1000 to 1000: 1, often in the range of 1:500 to 500: 1, regularly in the range of 1: 100 to 100: 1..

[0364] According to a further embodiment of the binary mixtures and the composition thereof, the weight ratio of component 1) and component 2) usually is in the range of 1000:1 to 1:1000, often in the range of 100:1 to 1:100.

[0365] These ratios are also suitable for inventive mixtures applied by seed treatment.

[0366] According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer). Further auxiliaries may be added, if appropriate.

[0367] Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein. Application of the compounds of formula (I), the combinations and the compositions thereof can be carried out before or during sowing. Methods for applying the compounds of formula (I), the combinations and the compositions thereof, respectively, are application onto plant propagation material, especially seeds, including dressing, coating, pelleting, dusting, and soaking as well as infurrow application methods.

[0368] Preferably, the compounds of formula (I) or any of formulas (I-A) to (I-H), the combinations and the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

[0369] In one embodiment, the present invention provides a method for controlling or preventing infestation of plants by phytopathogenic microorganisms such as phytopathogenic fungi, in agricultural crops and / or horticultural crops wherein an effective amount of at least one compound of formula (I) or any of formulas (I-A) to (I-H) or the combinations or the composition, is applied to the plants, plant parts or locus thereof, soil or materials to be protected against fungal attack.

[0370] In another embodiment, the present invention provides a method for controlling or preventing infestation of plants by phytopathogenic microorganisms such as phytopathogenic fungi in agricultural crops and or horticultural crops wherein an effective amount of at least one compound of formula (I) or any of formulas (I-A) to (I-H) or the combination or the composition, is applied to the seeds of plants. The compounds of formula (I), or any of formulas (I-A) to (I-H) and the compositions according to the invention, respectively, are suitable for use as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomyceles). Chylridiomyceles. Zygomycetes. Ascomyceies. Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically active and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

[0371] The compounds of formula (I), or any of formulas (I-A) to (I-H) and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as com, soybean, rape, sugar cane or oil palm; com; tobacco; nuts; coffee; tea; bananas; vines (table grapes, grape juice and grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Particularly, the compounds of formula (I), or any of formulas (I-A) to (I-H) and the composition according to the invention are important in the control of phytopathogenic fungi on cereals (e. g. wheat, rye, barley, triticale, oats or rice) and soybeans and on the plant propagation material, such as seeds, and the crop material of cereals and soybeans.

[0372] Preferably, the compounds of formula (I), or any of formulas (I-A) to (I-H) and composition thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, com, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

[0373] The term "plant propagation material" is to be understood to denote all the generative or reproductive parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts, twigs, flowers, and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.

[0374] These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

[0375] Preferably, treatment of plant propagation materials with the compounds of formula (I), or any of formulas (I-A) to (I-H), the combinations and or the compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, com, cotton and soybeans as well as legumes, fruits and grapevines.

[0376] The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development. Genetically modified plants are plants, which genetic material has been so modified by recombinant DNA techniques that otherwise cannot readily be obtained by cross breeding under natural circumstances, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo-or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or famesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4 -D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Bayer CropScience), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, BASF, Germany).

[0377] Furthermore, plants capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus (Bacillus), by use of recombinant DNA techniques are within the scope of the present invention. The Bacillus are particularly from Bacillus thuringiensis, such as δ-endotoxins. e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl -transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e.g. W002 / 015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e.g., in EP374753, WO93 / 007278, WO95 / 34656, EP427529, EP451878, W003 / 18810 und W003 / 52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants, producing these proteins, tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (com cultivars producing the CrylAb toxin), YieldGard® Plus (com cultivars producing CrylAb and Cry3Bbl toxins), Starlink® (com cultivars producing the Cry9c toxin), Herculex® RW (com cultivars producing Cry34Abl, Cry35Abl and the enzyme phosphinothricin-A-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the Cryl Ac toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf®(potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Btl 1 (e. g. Agrisure® CB) and Btl76 from Syngenta Seeds SAS, France, (com cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (com cultivars producing a modified version of the Cry3A toxin, c.f. WO 03 / 018810), MON 863 from Monsanto Europe S. A., Belgium (com cultivars producing the Cry3Bbl toxin), IPC 531 from Monsanto Europe S. A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (com cultivars producing the Cryl F toxin and PAT enzyme).

[0378] Furthermore, plants capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens by the use of recombinant DNA techniques are also within the scope of the present invention. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g. EP392225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above.

[0379] Furthermore, plants capable to synthesize one or more proteins, by use of recombinant DNA techniques, to increase the productivity (e. g. biomass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants are within the scope of the present invention. Furthermore, plants that contain a modified quantity of substances of content or new substances of content, by the use of recombinant DNA techniques, to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada) are also within the scope of the present invention. Furthermore, plants that contain a modified quantity of substances of content or new substances of content, by the use of recombinant DNA techniques, to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany) are also within the scope of the present invention.

[0380] The compounds of formula (I), or any of formulas (I-A) to (I-H) may be, for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:

[0381] Absidia corymbifera, Alternaria spp. Aphanomyces spp. Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nididans. A. niger. A. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea. Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Colletotrichum capsid, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Parastagonospora nodorum, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infe stans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including. S'. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including. S'. nodorum, S. tritici, Septoria lycopersici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp., including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp., and Xanthomonas spp, Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, Cerotelium fci, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacahata, Puccinia graminis, Puccinia sorghi, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, or Uredinales such as Cronartium rihicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fahae, Cryptococcus spp., Exohasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries, Blastocladiomycetes, such as Physoderma maydis, Mucoromycetes, such as Choanephora cucurhitarum.

[0382] Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include diseases caused by rust pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae,' Hemileia species, for example Hemileia vastatrix,' Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae,' Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis,' Uromyces species, for example Uromyces appendiculatus. In particular, Cronartium ribicola (White pine blister rust); Gymnosporangium juniperi-virginianae (Cedar-apple rust); Hemileia vastatrix (Coffee rust); Phakopsora meibomiae and P. pachyrhizi (Soybean rust); Puccinia coronata (Crown Rust of Oats and Ryegrass); Puccinia graminis (Stem rust of wheat and Kentucky bluegrass, or black rust of cereals); Puccinia hemerocallidis (Daylily rust); Puccinia persistens subsp. triticina (wheat rust or 'brown or red rust'); Puccinia sorghi (rust in com); Puccinia striiformis ('Yellow rust' in cereals); Uromyces appendiculatus (rust of beans); Uromyces phaseoli (Bean rust); Puccinia melanocephala ('Brown rust' in sugarcane); Puccinia kuehnii ('Orange rust' in sugarcane).

[0383] The present invention further relates to the use of the compounds of formula (I) or any of formulas (I- A) to (I-H), the combinations or the compositions thereof for controlling or preventing against phytopathogenic fungi such as Septoria spp., Blumeria spp., Podosphaera spp., Sphaerotheca spp., Uncinula spp., Erysiphe spp., Erysiphe spp., Microsphaera diffusa spp., Botrytis spp., Phytophthora spp, Plasmopara spp., Colletotrichum spp, Altemaria spp., Venturia inaequalis spp., and Monilinia spp., Corynespora spp., Cercospora spp., of agricultural crops and or horticultural crops.

[0384] The present invention further relates to the use of the compounds of formula (I), the combinations or the compositions thereof for controlling or preventing against phytopathogenic fungi such as Septoria spp., Blumeria spp., Podosphaera spp., Sphaerotheca spp., Uncinula spp., Erysiphe spp., Erysiphe spp., Microsphaera diffusa spp., Botrytis spp., Phytophthora spp, Plasmopara spp., Colletotrichum spp, Alternaria spp., Venturia inaequalis spp., and Monilinia spp., Corynespora spp., Cercospora spp., in cereals, soybeans, grapevines, fruits, nuts and vegetables.

[0385] Plants which can be treated in accordance with the invention include the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp (for example pome fruits such as apples, pears, apricots, cherries, almonds and peaches), Rihesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Ruhiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges and grapefruit); Vitaceae sp. (for example grapes); Solanaceae sp. (for example tomatoes, peppers), Liliaceae sp., Asteraceae sp. (for example lettuce), Umhelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurhitaceae sp. (for example cucumber), Alliaceae sp. (for example leek, onion), Papilionaceae sp. (for example peas); major crop plants, such as Poaceae / Gramineae sp. (for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress), Fabacae sp. (for example bean, peanuts), Papilionaceae sp. (for example soya bean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, swiss chard, beetroot); Malvaceae (for example cotton); useful plants and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.

[0386] More preference is given to controlling the following diseases of soya beans: Fungal diseases on leaves, stems, pods and seeds caused, for example, by Altemaria leaf spot (Altemaria spec, atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines ), cercospora leaf spot and blight ( Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn. ), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani). rust (Phakopsora pachyrhizi. Phakopsora meibomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicolci).

[0387] Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectiia crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseoloruni), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidennatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimuni), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani, sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

[0388] The present invention also relates to the use of the compounds of formula (I) or any of formulas (I-A) to (I-H), the combinations or the compositions thereof for controlling or preventing the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondi ta (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye and Phakopsoraceae spp. on various plants, in particular Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans, Hemileia vastatrix (Coffee rust), Uromyces appendiculatus, Uromyces fabae and Uromyces phaseoli (rust of beans).

[0389] The compounds, the combinations and the compositions of the present invention can be used for controlling or preventing plant diseases. The compounds of formula (I), or any of formulas (I-A) to (I-H), the combinations and / or the compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:

[0390] Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis),' Altemaria spp. (Altemaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on com, e. g. spot blotch (C. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana'. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on com (e. g. Gray leaf spot: C. zeae-maydis). rice, sugar beets (e. g. C. beticola). sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on com (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae)'. Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), com (e. g. C. graminicola. Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes'. black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides),' Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri. teleomorph: Neonectria liriodendri'. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on com, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa,' Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium spp. on com (e. g. E. turd cum),' Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on com; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and com; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi'. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on com, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf mst) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicolci (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae). rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica),' Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola'. can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum),' Physoderma maydis (brown spots) on com; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), soybeans, potatoes and tomatoes (e. g. P. infestans'. late blight) and broad-leaved trees (e. g. P. ramonim: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or.rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici- repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, com, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum),' Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, com, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and. S', attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g.. S', sclerotiorum) and soybeans (e. g.. S', rolfsii or. S', sclerotiorum),' Septoria spp. on various plants, e. g.. S', glycines (brown spot) on soybeans,. S', tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodomm (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on com (e. g.. S'. iurcicum. syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on com, (e. g.. S', reiliancr. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g.. S', nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria) nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (mst) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae),' Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), com (e. g. U. maydis'. com smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.

[0391] In one embodiment, the compounds of formula (I) or any of formulas (I-A) to (I-H) have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Zymoseptoria tritici), wheat brown mst (Puccinia triticina), wheat stripe mst (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), downy mildew of grapevine (Plasmopara viticola), late blight of potatoes and tomatoes (Phythophtora infestans), barley scald (Rhynchosporium secalis), blast of rice (Pyricularia oryzae), mst of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), blotch of wheat (Septoria nodorum), powdery mildew of wheat (Blumeria graminis f. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), downy mildew of cucumber (Pseudoperonospora cubensis), anthracnose of cucurbits (Colletotrichum lagenarium, Colletotrichum capsid), leaf spot of tomato, beet and soybean (Cercospora beticola, Cercospora kikuchi, Corynespora cassiicola), early blight of tomato (Alternaria solani), spot blotch of barley (Cochliobolus sativus), grey mold on fruits, tomato and berries (Botrytis cinerea), stem rot or white mold on vegetables and field crops such as soybean (Sclerotinia sclerotiorum), sheath blight on rice (Rhizoctonia solani) and Foot rot / Head blight of cereals such as wheat(Fusarium culmorum).

[0392] The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the parts of the plant or other products to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.

[0393] The compounds of formula (I), or any of formulas (I -A) to (I-H), the combinations and the compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fibre or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.

[0394] As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans. Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Pora spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Altemaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.

[0395] In one embodiment, the present invention provides a method for controlling or preventing phytopathogenic fungi. The method comprises treating the fungi or the materials, plants, plant parts, locus thereof, soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula (I), or any of formulas (I-A) to (I-H), or a combination or a composition comprising at least one compound of formula (I), or any of formulas (I-A) to (I-H).

[0396] The method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leaves, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according to the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.

[0397] It is also possible to use the compounds of formula (I), or any of formulas (I-A) to (I-H) as a fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi.

[0398] The compounds of formula (I), or any of formulas (I-A) to (I-H), the combinations and the compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and / or the locus where the plant is growing or is to grow with an effective amount of compound of formula (I), or any of formulas (I-A) to (I-H) and the composition thereof, respectively.

[0399] The term "plant health" is to be understood to denote a condition of the plant and / or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and / or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and / or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and / or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

[0400] The compounds of formula (I), or any of formulas (I-A) to (I-H) are employed as such or in the form of a composition for treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials, or rooms by the fungi.

[0401] Plant propagation material may be treated with the compounds of formula (I) or any of formulas (I-A) to (I-H), the combinations and the compositions thereof protectively either at or before planting or transplanting.

[0402] The compounds of the invention can be used in combination with models e.g. embedded in computer programs for site specific crop management, satellite farming, precision farming or precision agriculture. Such models support the site specific management of agricultural sites with data from various sources such as soils, weather, crops (e.g. type, growth stage, plant health), weeds (e.g. type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment. In particular, such models can help to optimize agronomical decisions, control the precision of pesticide applications and record the work performed. As an example, the compounds of the invention can be applied to a crop plant according to an appropriate dose regime if a model models the development of a pest and calculates that a threshold has been reached for which it is recommendable to apply the compound of the invention to the crop plant. Commercially available systems which include agronomic models are e.g. FieldScripts™ from The Climate Corporation, Xarvio™ from BASF, AGLogic™ from John Deere, etc.

[0403] The compounds of the invention can also be used in combination with smart spraying equipment such as e.g. spot spraying or precision spraying equipment attached to or housed within a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc. Such an equipment usually includes input sensors (such as e.g. a camera) and a processing unit configured to analyze the input data and configured to provide a decision based on the analysis of the input data to apply the compound of the invention to the crop plants (respectively the weeds) in a specific and precise manner. The use of such smart spraying equipment usually also requires positions systems (e.g. GPS receivers) to localize recorded data and to guide or to control farm vehicles; geographic information systems (GIS) to represent the information on intelligible maps, and appropriate farm vehicles to perform the required farm action such as the spraying.

[0404] In an example, pests can be detected from imagery acquired by a camera. In an example the pests can be identified and / or classified based on that imagery. Such identification and / classification can make use of image processing algorithms. Such image processing algorithms can utilize machine learning algorithms, such as trained neutral networks, decision trees and utilize artificial intelligence algorithms. In this manner, the compounds described herein can be applied only where needed.

[0405] Positive crop response:

[0406] The compounds of the present invention not only control microorganisms effectively but also show positive crop response such as plant growth enhancement effects like enhanced root growth, enhanced tolerance to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality plant products, higher number of productive tillers, enhanced resistance to insect pests and the like, which results in higher yields.

[0407] Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.

[0408] The invention disclosed in the present disclosure shall now be elaborated with the help of non-limiting examples.

[0409] CHEMISTRY EXAMPLES:

[0410] Example 1: Synthesis of 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline

[0411]

[0412] A solution of 4-(l-methyl-lH-pyrazol-4-yl)isoquinoline (14 g, 67 mmol) in tetrahydrofuran (130 mL) was treated with iodine (10.2 g, 40 mmol) followed by sodium borohydride (NaBH4)(10.1 g, 268 mmol) at 0 °C. The resulting reaction mixture was stirred at 60 °C for 16 h and then treated with methanol at 0 °C. Volatiles were removed under reduced pressure and the residue obtained was dissolved in water: dioxane (1:2; 150 mL) and treated with sodium hydroxide(NaOH) (13.4 g, 335 mmol) at 90 °C for 5 h. The reaction mixture was extracted with ethyl acetate (3 x 80 mL), the combined organic layers were washed with water (80 mL) and brine solution (60 mL), dried over anhydrous Na2SO4, and evaporated under reduced pressure. The residue obtained was further treated with dioxane HC1 solution to obtain 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (10 g, 40.0 mmol, 60 % yield).

[0413] In a similar way, other bicyclic amine compounds of formula 8-a were prepared and optionally converted to its salt, preferably hydrochloride salt by known procedures and used in the preparation of the compounds of formula I.

[0414] Example 2: Synthesis of 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylic acid (Formula 2A)

[0415]

[0416] Step 1: Synthesis of 2,4-difluoro-l-(prop-l-en-2-yl)benzene

[0417] A solution of methyltriphenylphosphonium bromide (10.3 g, 29 mmol) in anhydrous tetrahydrofuran (30 mL) was treated with potassium tert-butoxide (3.2 g, 29 mmol) at 0 °C under nitrogen atmosphere and stirred for 1 h. The resulting reaction mass was further treated with l-(2,4-difluorophenyl)ethan-l-one (2.5 g, 16 mmol) at 0 °C and stirred at 25 °C for 12 h. After completion of the reaction, the solvent was removed under reduced pressure. The obtained residue was diluted with water (200 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to isolate crude 2,4-difluoro-l-(prop-l-en-2-yl)benzene which was used for next step without any purification.

[0418] Step 2: Synthesis of ethyl 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylate (Formula 3A) A solution of 2,4-difluoro-l-(prop-l-en-2-yl)benzene (2 g, 13 mmol) in ethyl acetate (40 mL) was treated with sodium bicarbonate (1.64 g, 19.5 mmol) and ethyl (Z)-2-chloro-2-(hydroxyimino)acetate (2.56 g, 16.9 mmol) at 25 °C, heated to 50 °C and stirred for 16 h. After completion of the reaction, the reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (2 x 80 mL). The combined organic layers were washed with sat. NaCl solution (30 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to isolate crude material which was then purified by CombiFlash® chromatography on silica gel (0-20% ethyl acetate in hexane) to obtain ethyl 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylate (Formula 3A, 800 mg, 2.97 mmol, 23 % yield) as a colorless oil.

[0419] Step 3: Synthesis of 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylic acid (Formula 2A)

[0420] A stirred solution of ethyl 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylate (0.8 g, 3 mmol) in tetrahydrofuran (8 mL) and water (4 mL) was treated with lithium hydroxide hydrate (0.25 g, 6 mmol) at 25 °C and stirred for 18 h. After completion of the reaction, the solvent was evaporated under reduced pressure, and the residue was acidified with IN aq. HC1 solution. The solid precipitated was filtered and dried under reduced pressure to obtain 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole -3 -carboxylic acid (Formula 2A, 650 mg, 2.7 mmol, 91 % yield) as an off white solid.

[0421] Example 3: Synthesis of (5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazol-3-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone (Compound 11)

[0422]

[0423] A solution of 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (220 mg, 0.9 mmol) and 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylic acid (212 mg, 0.9 mmol) in dichloromethane (8 mL) was treated with triethyl amine (0.4 mL, 2.6 mmol) and 1-propanephosphonic acid cyclic anhydride (1 mL, 1.9 mmol) at 0 °C and stirred at 25 °C for 18 h. After completion of the reaction, the reaction mixture was diluted with water (60 mL) and extracted with dichloromethane (3 x 80 mL). The combined organic layers were washed with sat. brine solution (20 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude material which was purified by reverse phase preparative HPLC to obtain (5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazol-3-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone (compound 11, 185 mg, 0.42 mmol, 48 % yield) as a white solid. Example 4: Synthesis of 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylic acid (Formula 2B)

[0424]

[0425] Step 1: Synthesis of ethyl 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylate (Formula 3B)

[0426] A solution of 2,4-difluoro-l-vinylbenzene (2 g, 14.3 mmol) in ethyl acetate (40 mL) was treated with sodium bicarbonate (1. 8 g, 21.4 mmol) and ethyl (Z)-2-chloro-2-(hydroxyimino)acetate (2.81 g, 18.6 mmol) at 25 °C, heated to 50 °C, and stirred for 16 h. After completion of the reaction, the reaction mixture was poured into water (80 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic layers were washed with sat. brine solution (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to isolate a crude material which was purified by CombiFlash® chromatography on silica gel (0-30% ethyl acetate in hexane) to obtain ethyl 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylate (Formula 3B, 2 g, 7.84 mmol, 55 % yield) as a colorless oil.

[0427] Step 2: Synthesis of 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylic acid (Formula 2B) A solution of ethyl 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylate (2 g, 7.84 mmol) in tetrahydrofuran (20 mL) and water (10 mL) was treated with lithium hydroxide hydrate (658 mg, 15.7 mmol) at 25 °C and stirred for 18 h. After completion of the reaction, the solvent was evaporated under reduced pressure. The residue obtained was acidified with 1 N aq. HC1 to obtain a precipitate which was filtered and dried under reduced pressure to obtain 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylic acid (Formula 2B, 1.7 g, 7.48 mmol, 95 % yield) as an off white solid.

[0428] Example 5: Synthesis of (5-(2,4-difluorophenyl)-4,5-dihydroisoxazol-3-yl)(4-(l-methyl-lH-pyrazol- 4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone (Compound

[0429]

[0430]

[0431] A solution of 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (230 mg, 0.92 mmol) and 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylic acid (209 mg, 0.92 mmol) in dichloromethane (6 mL) was treated with triethyl amine (0.4 mL, 2.76 mmol) and 1-propanephosphonic acid cyclic anhydride (1.1 mL, 1.84 mmol) at 0 °C and stirred at 25 °C for 18 h. After completion of the reaction, the reaction mixture was diluted with water (60 mL) and extracted with dichloromethane (3 x 80 mL). The combined organic layers were washed with sat. brine solution (20 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude material which was then purified by preparative HPLC to obtain (5-(2,4-difluorophenyl)-4,5-dihydroisoxazol-3-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone (Compound 12, 325 mg, 0.77 mmol, 84 % yield) as an off white solid.

[0432] Example 6: Synthesis of (5-(2,4-difluorophenyl)-4,5-dihydroisoxazol-3-yl)(4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone (compound 130)

[0433]

[0434] A suspension of 4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (0.25 g, 1.1 mmol) and 5-(2,4-difluorophenyl)-4,5-dihydroisoxazole-3-carboxylic acid (0.243 g, 1.1 mmol) in dichloromethane (8 mL), was treated with triethyl amine (0.3 mL, 2.14 mmol) followed by propane phosphonic acid anhydride (0.7 mL, 1.18 mmol) at 0 °C and stirred at 25 °C for 6 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were washed with water (30 mL), brine (30 mL), dried over sodium sulphate and evaporated. The crude material thus obtained was purified by preparative HPLC to afford (5-(2,4-difluorophenyl)-4,5-dihydroisoxazol-3-yl)(4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone 130 (0.31 g, 0.7 mmol, 65% yield) as an off white solid.

[0435] Example 7: Synthesis of (5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazol-3-yl)(7-methyl-4- (l-methyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone (Compound 139)

[0436]

[0437] A suspension of 7-methyl-4-(l-methyl-lH-pyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (0.2 g, 0.86 mmol) and 5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazole-3-carboxylic acid (0.207 g, 0.86 mmol) in dichloromethane (8 mL), was treated with triethyl amine (0.24 mL, 1.71 mmol) followed by propane phosphonic acid anhydride (0.6 mL, 0.94 mmol) at 0 °C and then stirred at 25 °C 6 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were washed with water (30 mL), brine (30 mL), dried over sodium sulphate and evaporated to get a crude material, which was then purified by preparative HPLC to obtain (5-(2,4-difluorophenyl)-5-methyl-4,5-dihydroisoxazol-3-yl)(7-methyl-4- (l-methyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone 139 (0.195 g, 0.427 mmol, 49.8 % yield) as an off white solid.

[0438] Example 8: Synthesis of (4-(l,5-dimethyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone (Compound 133)

[0439]

[0440] Step-1: Synthesis of l-fhioro-4-(3,3,3-trifluoroprop-l-en-2-yl)benzene

[0441] A suspension of potassium tert-butoxide (8.76 g, 78 mmol) in tetrahydrofuran (120 mL) was treated with triphenylmethyl phosphonium iodide (31.6 g, 78 mmol) at -20 °C and stirred for 1 h. To this, a solution 2,2,2-trifhioro-l-(4-fluorophenyl)ethan-l-one (10 g, 52.1 mmol) in 10 ml of THF was added slowly and stirred for 3 h. After completion of the reaction, the reaction mixture was filtered and the filtrate was evaporated to obtain 1-fluoro-4-(3,3,3-trifluoroprop-1-en-2-yl)benzene (9 g, 47.3 mmol, 91% yield). The crude product was used in the next step without any purification.

[0442] Step-2: Synthesis of ethyl 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate A solution of 1-fluoro-4-(3,3,3-trifluoroprop-1-en-2-yl)benzene (10 g, 52.6 mmol) in ethyl acetate (100 mL) was treated with sodium bicarbonate (8.84 g, 105 mmol) and ethyl 2-chloro-2-(hydroxyimino)acetate (7.97 g, 52.6 mmol) at 25 °C and stirred at 60 °C for 16 h. After completion of the reaction, the reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated under reduced pressure to isolate a crude product, which was then purified by a column chromatography to obtain ethyl 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate (7.5 g, 24.57 mmol, 47% yield).

[0443] Step-3: Synthesis of 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid A solution of ethyl 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate (7 g, 22.93 mmol) in tetrahydrofuran (30 mL), methanol (5 mL) and water (1 mL), was treated with lithium hydroxide (1.1 g, 46 mmol) at 25 °C and stirred for 18 h. After completion of the reaction, solvents were evaporated and the resulting residue was acidified with aq. HC1. The precipitated solid was filtered and dried to obtain 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid (5 g, 18 mmol, 79% yield) as an off white solid.

[0444] Step-4: Synthesis of(4-(l,5-dimethyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone

[0445] A suspension of 4-(l,5-dimethyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (250 mg, 0.95 mmol) and 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid (263 mg, 0.95 mmol) in dichloromethane (5 mL), was treated with triethyl amine (264 pL, 1.9 mmol) followed by propane phosphonic acid anhydride (452 mg, 1.4 mmol) at 0 °C and then stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was poured into water (30 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were washed with water (30 mL), brine (30 mL), dried over sodium sulphate and evaporated to obtain a crude product, which was then purified by preparative HPLC to obtain (4-(l,5-dimethyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone 133 (200 mg, 0.41 mmol, 44% yield).

[0446] Example 9: Preparation of (3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone (Compound 56)

[0447]

[0448] Step-1: Synthesis of 2-chloro-6-(trifluoromethyl)benzaldehyde oxime

[0449] A solution of 2-chloro-6-(trifluoromethyl)benzaldehyde (4.92 ml, 33.6 mmol) in methanol (50 mL), was treated with hydroxylamine Hydrochloride (4.66 g, 67.1 mmol) followed by sodium acetate (5.51 g, 67.1 mmol) at 25 °C and stirred for 5 h. After completion of the reaction, the solvent was evaporated and the resulting residue was diluted with water. The precipitated solid was filtered to obtain 2-chloro-6-(trifluoromethyl)benzaldehyde oxime (5 g, 22.36 mmol, 67% yield) as white solid.

[0450] Step-2: Synthesis of methyl 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate

[0451] A solution of 2-chloro-6-(trifluoromethyl)benzaldehyde oxime (6 g, 26.8 mmol) in N, N-dimethylformamide (60 mL), was treated with NCS (4.30 g, 32.2 mmol) at 25 °C. The resulting mixture was stirred for 1 h at the same temperature and then diluted with water (100 mL) and dichloromethane (100 mL). The organic layers were separated, dried over Na2SO4and cooled to 5 °C. This cold solution was further treated with methyl methacrylate (3.16 mL, 29.5 mmol) and triethyl amine (4.1 mL, 29.5 mmol). After stirring at 25 °C for 18 h, the reaction mixture was washed with water (2 x 50 mL). The separated organic layer was dried over Na2SO4, and evaporated to obtain a crude material, which was then purified by a column chromatography to obtain methyl 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate (8.5 g, 26.4 mmol, 98% yield) as a pale-yellow oil.

[0452] Step-3: Synthesis of 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid

[0453] A solution of methyl 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate (8.5 g, 26.4 mmol) in tetrahydrofuran (40 mL) and water (20 mL), was treated with lithium hydroxide hydrate (2.22 g, 52.8 mmol) at 25 °C for 18 h. After completion of the reaction, solvents were evaporated and the obtained residue was diluted with IN HC1 solution. The precipitated solid material was filtered and dried under high vacuum to obtain 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid (6.3 g, 20.48 mmol, 77 % yield) as an off white solid. Step-4: Synthesis of (3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-yl) (4-( 1 -methyl- lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2( lH)-yl)methanone

[0454] A solution of 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (250 mg, 1 mmol) and 3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid (308 mg, 1 mmol) in dichloromethane (10 mL) was treated with triethyl amine (0.28 mL, 2 mmol) and propane phosphonic acid anhydride (0.661 ml, 1.101 mmol) at 0 °C. The resulting reaction mixture was stirred at 25 °C for 18 h. The reaction mixture was then diluted with water (10 mL) and extracted with dichloromethane (2x 50 mL). The combined organic layers were dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain a crude compound, which was purified by preparative HPLC to obtain (3-(2-chloro-6-(trifluoromethyl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone 56 (246 mg, 0.489 mmol, 49% yield) as a white solid.

[0455] Example 10: Preparation of (3-(4-fluorophenyl)-5-methyl-4,5-dihydroisoxazol-5-yl)(7-methyl-4- (l-methyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone (42)

[0456]

[0457] A solution of 7-methyl-4-(l-methyl-lH-pyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (0.3 g, 1.29 mmol) in dichloromethane (8 mL), was treated with triethyl amine (0.36 mL, 2.58 mmol), 3-(4-fluorophenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid (0.287 g, 1.29 mmol) and propane phosphonic acid anhydride (0.85 mL, 1.42 mmol) at 0 °C. The resulting mixture was stirred at 25 °C for 8 h. After completion of the reaction, the reaction mixture was diluted with water (40 mL) and extracted with dichloromethane (3 x 10 mL). The combined organic layers were washed with brine solution (30 mL), dried over sodium sulphate and evaporated. The crude material thus obtained was purified by preparative HPLC to isolate (3-(4-fluorophenyl)-5-methyl-4,5-dihydroisoxazol-5-yl)(7-methyl-4-(l-methyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)methanone 42 (0.17 g, 0.39 mmol, 30% yield).

[0458] Example 11: Preparation of (4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin- 6(5H)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone (Compound 131)

[0459]

[0460] Step-1: Synthesis of l-fluoro-4-(3,3,3-trifluoroprop-l-en-2-yl)benzene A suspension of potassium tert-butoxide (8.76 g, 78 mmol) in tetrahydrofuran (120 mL) was portion wise treated with Triphenylmethyl phosphonium iodide (31.6 g, 78 mmol) at -10 °C and stirred for 1 h. To this, a solution of 2,2,2-trifluoro-l-(4-fluorophenyl)ethan-l-one (10 g, 52.1 mmol) in 10 ml of tetrahydrofuran was added slowly and stirred for 3 h. After completion of the reaction, the reaction mass was diluted with water (100 mL) and extracted with ethyl acetate (3 x 80 mL). The combined organic layers were dried over Na2SO4and evaporated to obtain l-fluoro-4-(3,3,3-trifluoroprop-l-en-2-yl)benzene (9 g, 47.3 mmol, 91% yield). The crude product was used for next step without any purification.

[0461] Step-2: Synthesis of ethyl 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate A solution of l-fluoro-4-(3,3,3-trifluoroprop-l-en-2-yl)benzene (10 g, 52.6 mmol) in ethyl acetate (100 mL), was treated with sodium bicarbonate (8.84 g, 105 mmol) and ethyl 2-chloro-2-(hydroxyimino)acetate (7.97 g, 52.6 mmol) at 25 °C. The resulting reaction mixture was stirred at 60 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed brine solution (100 mL), dried over Na2SO4, filtered and concentrated under reduced pressure to obtain a crude compound, which was purified by a column chromatography to obtain ethyl 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate (7.5 g, 24.6 mmol, 47% yield).

[0462] Step-3: Synthesis of 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid A solution of ethyl 5-(4-fhiorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylate (7 g, 22.93 mmol) in tetrahydrofiiran (30 mL), methanol (5 mL) and water (1 ml), was treated with lithium hydroxide hydrate (1.1 g, 46 mmol) at 25 °C for 18 h. After completion of the reaction, solvents were evaporated, and the residue was diluted with water (50 mL) and acidified with 1 N aq. HC1 solution. The precipitated solid was filtered and dried to obtain 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole -3 -carboxylic acid (5 g, 18 mmol, 79% yield) as an off white solid.

[0463] Step-4: Synthesis of (4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone

[0464] A suspension of 4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (0.2 g, 0.86 mmol) and 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid (0.238 g, 0.86 mmol) in dichloromethane (8 mL), was treated with triethylamine (0.239 mL, 1.71 mmol) followed by propane phosphonic acid anhydride (0.566 ml, 0.943 mmol) at 0 °C. The resulting reaction mixture was stirred at 25 °C for 6 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were washed with brine solution (30 mL), dried over sodium sulphate and evaporated to obtain a crude material, which was purified by preparative HPLC to obtain (4-(l,5-dimethyl-lH-pyrazol-4-yl)-4,7-dihydrothieno[2,3-c]pyridin-6(5H)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone 131 (0.2 g, 0.41 mmol, 47% yield) as an off white solid. Example 12: Preparation of (4-(l,5-dimethyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone (Compound 133)

[0465]

[0466] A suspension of 4-(l,5-dimethyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (250 mg, 0.948 mmol) and 5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole-3-carboxylic acid (263 mg, 0.948 mmol) in dichloromethane (6 mL) was treated with triethylamine (264 μl, 1.9 mmol) followed by propane phosphonic acid anhydride (452 mg, 1.422 mmol) at 0 °C and stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were washed with brine solution (30 mL), dried over sodium sulphate and evaporated to obtain a crude material, which was purified by preparative HPLC to obtain (4-(l,5-dimethyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)(5-(4-fluorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)methanone 133 (200 mg, 0.41 mmol, 43% yield).

[0467] Example 13: Preparation of (5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazol-3-yl)(4-(l-methyl-lH-

[0468]

[0469] Step-1: Synthesis of ethyl 4-(4-fluorophenyl)-4-hydroxy-2-oxobut-3-enoate

[0470] A solution of potassium tert-butoxide (8.94 g, 80 mmol) in tetrahydrofuran (80 mL) was treated with a solution of l-(4-fluorophenyl)ethan-l-one (10 g, 72.4 mmol) in tetrahydrofuran (20 mL) at 0 °C and stirred at 25 °C for 1 h. To this, diethyl oxalate (10.8 mL, 80 mmol) was added slowly at 0 °C and stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was poured into icewater (300 mL), acidified with aqueous HC1 (3 M) till pH ~3 and extracted with ethyl acetate (2 x 500 mL). The combined organic layers were dried over sodium sulphate and evaporated under reduced pressure to obtain a crude product, which was purified by column chromatography to obtain ethyl 4-(4-fluorophenyl)-4-hydroxy-2-oxobut-3-enoate (10.3 g, 43.2 mmol, 60% yield) as a pale-yellow semi solid.

[0471] Step-2: Synthesis of ethyl 4-(4-fluorophenyl)-3,3-dimethyl-2,4-dioxobutanoate

[0472] A solution of ethyl 4-(4-fluorophenyl)-4-hydroxy-2-oxobut-3-enoate (10 g, 42.0 mmol) in acetone (100 mL), was treated with methyl iodide (15.75 ml, 252 mmol) and potassium carbonate (11.60 g, 84 mmol) at 25 °C and stirred at 50 °C for 3 h. After completion of the reaction, the reaction mixture was diluted with water (200 mL) and extracted with ethyl acetate (2 x 300 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and evaporated under reduced pressure to obtain a crude product, which was purified by column chromatography to obtain ethyl 4-(4-fhiorophenyl)-3,3-dimethyl-2,4-dioxobutanoate (3.5 g, 13.14 mmol, 31% yield) as apale-yellow liquid.

[0473] Step-3: Synthesis of ethyl 5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazole-3-carboxylate

[0474] A solution of ethyl 4-(4-fluorophenyl)-3,3-dimethyl-2,4-dioxobutanoate (3.5 g, 13.14 mmol) in dichloromethane (30 mL), was treated with hydrazine hydrate (0.9 mL, 13.1 mmol) at 0 °C and stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude material, which was purified by column chromatography to obtain ethyl 5-(4-fhiorophenyl)-4,4-dimethyl-4H-pyrazole-3-carboxylate (2 g, 7.63 mmol, 58% yield) as a paleyellow semi solid.

[0475] Step-4: Synthesis of lithium 5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazole-3-carboxylate

[0476] A solution of ethyl 5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazole-3-carboxylate (2 g, 7.63 mmol) in THF (tetrahydrofuran, 10 mL) and water (10 mL), was treated with lithium hydroxide (0.183 g, 7.63 mmol) at 0 °C and stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the resulting residual material was triturated with methyl tertiary-butyl ether (MTBE, 2 x 30 mL). The precipitated solid was filtered and dried under reduced pressure to obtain lithium 5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazole-3-carboxylate (1.7 g, 7.1 mmol, 93% yield) as a white solid.

[0477] Step-5: Synthesis of (5-(4-fhiorophenyl)-4,4-dimethyl-4H-pyrazol-3-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone

[0478] A solution of 4-(l-methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline hydrochloride (286 mg, 1.145 mmol), triethylamine (0.6 mL, 4.16 mmol) and propane phosphonic acid anhydride (0.93 mL, 1.56 mmol) in dichloromethane (5 mL), was treated with lithium 5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazole-3 -carboxylate (250 mg, 1.04 mmol) at 0 °C and stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was diluted with chilled water (20 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and evaporated under reduced pressure to obtain a crude material, which was purified by column chromatography to obtain (5-(4-fluorophenyl)-4,4-dimethyl-4H-pyrazol-3-yl)(4-(l-methyl-lH-pyrazol-4-yl)-3,4-dihydroisoquinolin-2(lH)-yl)methanone 147 (250 mg, 0.582 mmol, 56 % yield) as a white solid.

[0479] Example 13: Preparation of l-(2,4-difluorophenyl)-4-(4-(l-methyl-lH-pyrazol-4-yl)-l, 2,3,4-tetrahydroisoquinoline-2-carbonyl)pyrrolidin-2-one (Compound 63)

[0480]

[0481] Step-1: Synthesis of l-(2,4-difluorophenyl)-5-oxopyrrolidine-3-carboxylic acid A solution of 2,4-difluoroaniline (5 g, 38.7 mmol) in water (30 mL) was treated with 2- methylenesuccinic acid (5.04 g, 38.7 mmol) at 25 °C and the resulting mixture was stirred at 100 °C for 10 h. After completion of the reaction, the reaction mixture was diluted with water 50 mL and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine solution (10 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude solid, which was washed with hexane to obtain l-(2,4-difluorophenyl)-5 -oxopyrrolidine-3 -carboxylic acid (3.5 g, 14.51 mmol, 38% yield).

[0482] Step-2: Synthesis of 1 -(2, 4-difluorophenyl)-4-(4-(l -methyl- lH-pyrazol-4-yl)-l, 2,3,4- tetrahydroisoquinoline-2-carbonyl)pyrrolidin-2-one

[0483] A solution of l-(2,4-difluorophenyl)-5-oxopyrrolidine-3-carboxylic acid (0.22 g, 0.91 mmol) and 4-(l- methyl-lH-pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline (0.195 g, 0.912 mmol) in dichloromethane (4 mL), was treated with triethylamine (0.25 mL, 1.82 mmol) followed by propane phosphonic acid anhydride (0.6 mL, 1 mmol) at 0 °C and stirred at 25 °C for 8 h. After completion of the reaction, the reaction mixture was poured into water (20 mL) and extracted with dichloromethane (DCM, 3 x 10 mL). The combined organic layers were dried over sodium sulphate and evaporated to obtain a crude material, which was purified by preparative HPLC to obtain l-(2,4-difluorophenyl)-4-(4-(l -methyl- 1H- pyrazol-4-yl)-l,2,3,4-tetrahydroisoquinoline-2-carbonyl)pyrrolidin-2-one 63 (186 mg, 0.43 mmol, 47% Table 1: Representative compounds of the present disclosure are prepared according to the methods as described above by employing the suitable starting materials:

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504] BIOLOGY EXAMPLES:

[0505] As described herein the compounds of the general formula (I) show fungicidal activity which is exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops. The compounds of the present invention were assessed fortheir activity as described in the following tests:

[0506] Example 1: Pyricularia oryzae (Rice blast):

[0507] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri -plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Pyricularia oryzae. The plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated inoculated control.

[0508] Compounds 1 7 8 12 13 14 16 17 18 21 24 25 27 32 33 40 41 42 43 44 45 46 47 74 77 78 79 80 81 86 90 94 96 100 106 117 121 124 125 127 129 130 133 134 145 148 149 150 151 153 154 155 156 157 158 162 163 164 165 166 168 172 176 177 178 179 181 182 183 184 185 186 187 188 189 190 191 192 193 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0509] Example 2: Alternaria solani (early blight of tomato / potato): The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri -plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Alternaria solani. The plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated inoculated control.

[0510] Compounds 8 12 14 16 17 21 26 27 32 40 41 43 44 47 75 116 117 121 124 130 134 140 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 172 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0511] Example 3: Colletotrichum capsici (anthracnose):

[0512] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri -plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Colletotrichum capsici. The plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated inoculated control.

[0513] Compounds 1 2 7 8 10 11 12 13 14 15 16 17 18 21 22 23 24 25 26 27 28 31 32 33 34 37 41 43 44 47 106 107 110 112 115 116 117 119 120 121 122 123 124 125 126 129 130 131 132 133 134 136 137 138 139 140 141 142 150 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 175 176 177 178 179 180 181 182 184 185 186 187 188 189 190 191 192 193 at 300 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0514] Example 4: Corynespora cassiicola (Leaf spot of tomato): The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri -plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Corynespora cassiicola. The plates were incubated in growth chambers at 25 °C temperature and 70% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated inoculated control.

[0515] Compounds 8 14 17 33 36 41 43 44 45 116 117 130 at 300 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0516] Example 5: Phytophthora infestans (Late blight of potato & tomato):

[0517] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Rye Agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri-plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Phytophthora infestans. The plates were incubated in growth chambers at 18 °C temperature and 95% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated inoculated control.

[0518] Compounds 29 75 134 159 at 300 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0519] Example 6: Botrytis cinerea (Gray mold)

[0520] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium, with the compound in the desired test concentration, was dispensed into a 60 mm sterile petri-plate. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Botrytis cinerea. The plates were incubated in growth chambers at 22 °C temperature and 70% relative humidity for four days and the radial growth was measured and compared to the one of the untreated control.

[0521] Compounds 14 16 40 41 43 44 45 116 130 134 153 163 164 172 173 184 186 189 193 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0522] Example 7: Botrytis cinerea (Gray mold): (Liquid testing) Yeast, bacterial peptone and sodium acetate (YBA) liquid medium containing a BOTRCI (104spores / mL) spore suspension was prepared. For the inhibition assay, each test compound was solved in dimethyl sulfoxide and 100 µl of the respective test solution was given into a well of a 96-well microtiter plate, consequently, the same volume (100 µl) of the media and spore suspension was added to each well to obtain the final test concentration. The plates were incubated at 22 °C for 15-18 days. The growth inhibition was evaluated by measuring the OD600. Percent inhibition was calculated with the below formula:

[0523] 1= (C-B)-(T-B) / (C-B)*100

[0524] Where T=treatment, C=control, and B=blank

[0525] Compounds 1 2 8 10 12 13 14 15 17 19 22 26 27 28 29 32 33 36 37 38 44 45 47 48 64 69 72 97 99 100 101 103 104 106 107 108 109 110 111 115 116 117 119 120 121 122 123 124 127 129 132 133 134 135 141 143 144 145 148 149 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated inoculated check which showed extensive pathogen growth.

[0526] Example 8: Sclerotinia sclerotiorum (White mold):

[0527] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired test concentration was dispensed into 60 mm sterile petri -plates. After solidification, each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate of Sclerotinia sclerotiorum. The plates were incubated in growth chambers at 20 °C temperature and 70% relative humidity for four days and the radial growth was measured and compared to the one of the inoculated, untreated control.

[0528] Compounds 1 7 8 10 11 12 13 14 15 16 17 18 21 22 27 32 33 34 36 40 41 42 43 44 45 47 57 58 73 74 80 83 94 96 106 107 116 117 120 121 122 123 124 125 126 130 131 132 133 134 136 139 140 146 147 148 152 153 154 155 156 157 159 160 161 163 164 165 166 167 168 170 172 173 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive pathogen growth. Example 9: Fusarium culmorum (Foot rot / Head blight of cereals):

[0529] The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into petri dishes. 5ml medium with compound in the desired test concentration was dispensed into 60mm sterile petri-plates. After solidification each plate was seeded with a 5mm size mycelial disc taken from the periphery of actively growing virulent culture plates of Fusarium culmorum. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for four days and the radial growth was measured and compared to the one of the untreated control.

[0530] Compounds 116 117 at 300 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive pathogen growth.

[0531] Example 10: Septoria nodorum (Leaf blotch)

[0532] Yeast, bacterial peptone and sodium acetate (YBA) liquid medium containing a Septoria nodorum (104spores / mL) spore suspension was prepared. For the inhibition assay, each test compound was dissolved in dimethyl sulfoxide and 100 pL of the respective test solution was dispensed into a 96-well microtiter plate, consequently, the same volume (100 pL) of the media and spore suspension were added to each well to obtain the final test concentration. The plates were incubated at 22 °C for 15-18 days. The growth inhibition was evaluated by measuring the OD600. Percent inhibition was calculated with the below formula:

[0533] 1= (C-B)-(T-B) / (C-B)*100

[0534] where T=treatment, C=control, and B=blank.

[0535] Compounds 8 10 12 13 14 17 26 27 28 32 33 36 37 44 45 47 106 107 108 110 111 116 117 121 124 129 132 133 134 135 148 at 300 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive disease development.

[0536] Example 11: Septoria tritici

[0537] Potato dextrose (PDB) liquid medium (Difco) containing a Septoria tritici (105spores / mL) spore suspension was prepared. For the inhibition assay, each test compound was dissolved in dimethyl sulfoxide. 100 pL of the test media-solution was added to a 96-well microtiter plate, consequently, the same volume (100 pL) of spore suspension was added to the well making the final test concentrations and the plate was incubated at 18 °C for 15 to 18 days. After the period of incubation, the length of pycnidiospores were measured under a microscope using software for image acquisition and analysis. Then, for each condition of the test, a mean length of pycnidiospores was calculated by averaging the size of pycnidiospores. From this mean length of pycnidiospores, the efficacy (E) of the product for each condition can be calculated by comparison to the mean length of pycnidiospores obtained in the control condition (untreated) according to the formula:

[0538] E = 100 x [(C-T) / C]

[0539] C is the mean length of pycnidiospores obtained for the control condition (untreated) and T is the mean length of pycnidiospores for conditions treated with the specific concentration (c) of the fungicide. Compounds 1 2 3 4 7 8 10 11 12 13 14 15 16 17 18 21 22 23 24 26 27 28 29 31 32 33 34 37 40 41 42 45 47 80 96 106 107 110 116 117 119 120 121 122 123 124 125 129 130 131 132 133 134 136 139 140 141 142 at 100 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive disease development.

[0540] Green House tests on plants:

[0541] Example A: Phakopsora pachyrhizi test on soybean plants

[0542] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to the calibrated spray volume of 30 mL. Each spray solution was poured into a spray bottle for further application.

[0543] To test the preventive activity of the compounds, healthy young soybean plants, raised in the greenhouse, were sprayed with the active compound preparation at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a conidial suspension containing 2 x105Phakopsora pachyrhizi inoculum. The inoculated plants were then kept in a greenhouse chamber at 22-24 °C temperature and 80-90% relative humidity for disease expression.

[0544] A visual assessment of the compounds performance was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compound was calculated by comparing the disease rating in the treatment with the one of the untreated control. The treated plants were also assessed for plant damage by recording symptoms like necrosis, chlorosis and stunting.

[0545] Compounds 3 11 22 24 30 34 40 65 94 117 118 123 124 132 136 146 at 500 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive disease development.

[0546] Example B: Corynespora cassiicola test on soybean plants

[0547] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing an emulsifier to the calibrated spray volume of 30 mL. Each spray solution was poured into a spray bottle for further application.

[0548] To test the preventive activity of the compounds, healthy young soybean plants, raised in the greenhouse, were sprayed with the active compound preparation at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 0.5 x 106Corynespora cassiicola inoculum. The inoculated plants were then kept in a greenhouse chamber at 22-24 °C temperature and 90-95 % relative humidity for disease expression.

[0549] A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated, inoculated control plants. The treated plants were also assessed for plant damage by recording symptoms like necrosis, chlorosis and stunting.

[0550] Compounds 100 127 146 149 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development. Example C: Pyricularia oryzae test in rice

[0551] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to a calibrated spray volume of 30 mL. The test solutions were poured into spray bottles for further applications.

[0552] To test the preventive activity of the compounds, healthy young rice plants, raised in the greenhouse, were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 1.4 x 106Pyricularia oryzae inoculum. The inoculated plants were then kept in a greenhouse chamber at 24 °C temperature and 95 % relative humidity for disease expression.

[0553] A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds were calculated by comparing the disease rating in the treatment with the one of the untreated, inoculated control plants. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis and stunting.

[0554] Compounds 5 6 15 30 76 85 127 132 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development.

[0555] Example D: Alternaria solani test in tomato

[0556] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to a calibrated spray volume of 30 mL. The test solutions were poured into spray bottles for further applications. To test the preventive activity of the compounds, healthy young tomato plants, raised in the greenhouse, were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 0.24 x106Alternaria solani inoculum and 2% malt. The inoculated plants were then kept in a greenhouse chamber at 22-24 °C temperature and 90-95 % relative humidity for disease expression. A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated, inoculated control plants. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis and stunting.

[0557] Compounds 43 106 107 130 140 147 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development.

[0558] Example E: Phytophthora infestans test on tomato plants

[0559] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to the desired test concentration in a calibrated spray volume of 30 mL. The test solutions were poured into spray bottles for further applications.

[0560] To test the preventive activity of the compounds, healthy young tomato plants raised in the greenhouse were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a sporangial suspension (cold sterile water containing 0.3x106Phytophthora infestans inoculum). After inoculation, the plants were kept in darkness at 15°C during 24 h, and then moved to a greenhouse chamber with 18 °C temperature and 95-100 % relative humidity for disease expression.

[0561] A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated control. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis and stunting.

[0562] Compounds 3 7 9 11 29 32 65 76 77 78 92 93 96 120 123 124 132 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development. Example F: Septoria nodorum test in wheat

[0563] The compounds were dissolved in 2% DMSO / Acetone and then mixed with water containing an emulsifier to a calibrated spray volume of 30 mb. The spray solutions were poured into spray bottles for further applications. To test the preventive activity of the compounds, healthy young wheat plants, raised in the greenhouse, were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a suspension containing 2.8x 10 Septoria nodorum inoculum. The inoculated plants were then kept in a greenhouse chamber at 22-25 °C temperature and 90-100 % relative humidity for disease expression.

[0564] A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated, inoculated control plants. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis & stunting.

[0565] Compounds 27 28 119 at 500 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive disease development.

[0566] Example G: Fusarium culmorum test in Wheat

[0567] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to a calibrated spray volume of 30 mL. The test solutions were poured into spray bottles for further applications.

[0568] To test the preventive activity of the compounds, healthy young wheat plants, raised in the greenhouse, were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 2x106Fusarium culmorum inoculum with 2% malt. The inoculated plants were then kept in a greenhouse chamber at 24 °C temperature and 80-90 % relative humidity for disease expression. A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated control. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis and stunting.

[0569] Compounds 81 86 149 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development.

[0570] Example H: Pseudoperonospora cubensis on cucumber plants

[0571] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to the desired test concentration in a calibrated spray volume of 30 mb. The test solutions were poured into the spray bottles for further applications.

[0572] To test the preventive activity of the compounds, healthy young cucumber plants, raised in the greenhouse were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hallow cone nozzles. One day after treatment, the plants were inoculated with a conidial spore suspension containing 2 x 104Pseudoperonospora cubensis inoculum. The inoculated plants were then kept in a greenhouse chamber at 23 °C temperature & 80-90 % relative humidity for disease expression.

[0573] A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated control. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis and stunting.

[0574] Compounds 140 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development.

[0575] Example I: Botrytis cinerea test in tomato

[0576] The compounds were dissolved in 2% dimethyl sulfoxide / acetone and then mixed with water containing emulsifier to a calibrated spray volume of 30 mL. The test solutions were poured into spray bottles for further applications.

[0577] To test the preventive activity of the compounds, healthy young tomato plants, raised in the greenhouse, were sprayed with the compounds preparations at the stated application rates inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 6xl06Botrytis cinerea inoculum and 2% malt. The inoculated plants were then kept in a greenhouse chamber at 18-20 °C temperature and 90-100 % relative humidity for disease expression. A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one of the untreated, inoculated control plants. The compounds were also assessed for their plant compatibility by recording symptoms like necrosis, chlorosis & stunting.

[0578] Compounds 40 42 43 44 45 69 72 149 at 500 ppm gave more than or equal to 70 % control in these tests when compared to the untreated check which showed extensive disease development.

[0579] Having described the invention with reference to certain preferred embodiments, other embodiments will become apparent to one skilled in the art from the consideration of the specification. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.

Claims

CLAIMS:

1. A compound of formula (I) or an agriculturally acceptable salt, N-oxide, stereoisomer, tautomer or polymorph thereof,wherein,R1is selected from halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, C3-C8- cycloalkyl or Cs-Cs-halocycloalkyl;R2is selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, G-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-Ce-alkoxy, or Ci-Ce-haloalkoxy;R3is selected from hydrogen, halogen, cyano, Ci-Ce -alkyl, Ci-Ce-haloalkyl, C2-C6 -alkenyl, C2- Ce-haloalkenyl, C2-Ce-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce- haloalkoxy, Ci-Ce-alkylthio or C3-C6 -cycloalkylthio;R4aand R4bare each independently selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci- Ce-haloalkyl, CACx-cycloalkyl. Ci-Ce -alkoxy, or Ci-Ce -haloalkoxy; orR4aand R4btogether with the carbon atom to which they are attached, may together form an oxo group (=0), a 3 - to 6-membered carbocyclic ring or a 3 - to 6-membered heterocyclic ring containing at least one heteroatom / group selected from N, O, S, S(0) or S(0)2, wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to two substituents independently selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy or Ci-Ce- haloalkoxy;R5is selected from the group consisting of hydrogen, Ci-Ce-alkyl and C1-C6-haloalkyl;B represents a phenyl ring or a 5 - or 6-membered aromatic heterocyclic ring, which is fused at C3, C4 carbons of the piperidine ring C, wherein said 5- or 6-membered aromatic heterocyclic ring comprises 1 to 3 heteroatoms / groups independently selected from O, N, S, S(0) or S(0)2, wherein said ring B is unsubstituted or substituted with one or more of the same or different substituents selected from R6;D is selected from a direct bond, C3-C6 -cycloalkyl, phenyl or a 5- or 6-membered heteroaryl ring, wherein said 5- or 6-membered heteroaryl ring comprises 1, 2, 3 or 4 heteroatoms / groupseach independently selected from N, O, S, S(O) and S(O) 2, and wherein said phenyl or 5- or 6-membered heteroaryl ring is unsubstituted or substituted with one or more of the same or different substituents selected from R1band / or R1c;ring E is selected from a non -aromatic nitrogen containing 5- or 6-membered saturated or partially saturated heterocyclic ring, wherein the heterocyclic ring may contain 1 to 3 additional heteroatoms / groups independently selected from N, O, S, C(O), S(O) or S(O)2, wherein the heterocyclic ring is unsubstituted or substituted at the ring nitrogen with a substituent selected from RNand at the ring carbon atoms with one to three of the same or different substituents selected from R9, wherein said heterocyclic ring is bound to the C=W group either through a carbon atom or a nitrogen atom;W is selected from O, S or NR10;R1ais selected from hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl, C2-C6-haloalkynyl, O-Cx-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ce -alkoxy, Ci-Ce-haloalkoxy, C2-C6 -alkenyloxy, C2-C6-haloalkenyloxy, C2-Ce-alkynyloxy, C2-C6-haloalkynyloxy, Cs-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, Cs-Ce-cycloalkylthio, Ci-Ce-alkylsulphinyl, Ci-Ce-haloalkylsulphinyl, Ci-Ce-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, -N(R7)2, -P(O)(R8)2, -CO-N(R9)2, -S(O)(R8)=NR9, -N=S(O)(R8)2, Si(R8)s or phenyl which is unsubstituted or substituted with one or more of the same or different substituents selected from halogen, cyano, Ci-Ce -alkyl, Ci-Ce-haloalkyl, C3-Cx-cycloalkyl. Ci-Ce -alkoxy or Ci-Ce-haloalkoxy;Rlbis selected from hydrogen, halogen, cyano, Ci-Ce -alkyl, Ci-Ce-haloalkyl, G-Cx-cycloalkyl. Ci-Ce -alkoxy or Ci-Ce -haloalkoxy;Rlcis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, O-Cx-cycloalkyl. or hydroxyl;R1aand R1b, optionally together along with the phenyl or 5- or 6-membered heteroaryl ring, may form a 8- to 10-membered bicyclic carbocyclic or heterocyclic ring system that is unsubstituted or substituted with one or more of the same or different substituents selected from R1baand / or R1ca, wherein the bicyclic heterocyclic ring system comprises one, two or three heteroatoms / groups independently selected from N, O, S, S(O) or S(O)2, and wherein one or more carbon atom of the bicyclic carbocyclic or heterocyclic ring system may be replaced with C(O);R6is selected from hydrogen, halogen, cyano, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio, G-Cx-cycloalkyl. or -N(R7)2; R7represents hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, G-Cx-cycloalkyl. Ci-Ce-alkylcarbonyl, C3-C6 -cycloalkylcarbonyl, Ci-Ce -alkoxycarbonyl or Ci-Ce -alkylsulfonyl;R8is selected from hydrogen, halogen, hydroxyl, Ci-Ce -alkyl, Ci-Ce-haloalkyl, C2-C6 -alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl, C2-C6-haloalkynyl, O-Cx-cycloalkyl, Ci-Ce-alkoxy or Ci- Ce-haloalkoxy;R9is selected from hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Cx-cycloalkyl:R10is selected from hydrogen, Ci-Ce -alkyl, hydroxy or Ci-Ce-alkoxy;RNis selected from hydrogen, Ci-Ce -alkyl, C2-C6 -alkenyl, Cs-Ce-alkynyl, Cs-Ce-cycloalkyl, Ci- Ce-alkoxy, C(O)Rn, or S(O)2Rn, wherein said Ci-Ce-alkyl, Cs-Ce-alkenyl, G-Ce-alkynyl. C3- Ce -cycloalkyl or Ci-Ce -alkoxy, is each unsubstituted or substituted by halogen or cyano; R11is selected from hydrogen, halogen, hydroxyl, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, O-Cx-cycloalkyl. C-Cx-halocycloalkyl. Cs-Ce-cycloalkyloxy, C3-C6- halocycloalkyloxy or -N(R7)2;R1bais selected from hydrogen, halogen, cyano, Ci-Ce -alkyl, Ci-Ce-haloalkyl, O-Cx-cycloalkyl. Ci-Ce -alkoxy or Ci-Ce -haloalkoxy; andR1cais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, O-Cx-cycloalkyl. or hydroxyl.

2. The compound of formula (I) as claimed in claim 1, wherein B is selected from a phenyl or thiophenyl ring, which is fused at C3, Ocarbons of piperidine ring C, and said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6.

3. The compound of formula (I) as claimed in claim 1, wherein D is selected from a direct bond, phenyl, pyridyl, thiophenyl, or cyclohexyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with R1band / or R1c.

4. The compound of formula (I) as claimed in claim 1, wherein ring E is selected from:E-1 E-2 E-3 E-4wherein R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

5. The compound of formula (I) as claimed in claim 1, wherein W = O.

6. The compound of formula (I) as claimed in claim 1, whereinR1is Ci-Ce-alkyl;R2is hydrogen;R3is selected from hydrogen, halogen, cyano, Ci-Ce -alkyl or Ci-Ce-haloalkyl;R4aand R4bare independently selected from hydrogen or Ci-Ce -alkyl;or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;R5is selected from hydrogen or Ci-Ce -alkyl;B is selected from a phenyl ring or thiophenyl ring, which is fused at C3, C -carbons of piperidine ring C, wherein said phenyl or thiophenyl ring is unsubstituted or substituted with one to two of the same or different substituents selected from R6;D is selected from a direct bond, cyclohexyl, phenyl, pyridyl or thiophenyl, wherein said phenyl or pyridyl ring is unsubstituted or substituted with one or two of the same or different substituents selected from R1band / or R1c;E is selected from:W = O;Rlais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce -alkylsulfonyl;R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6- cycloalkyl;Rlcis selected from hydrogen, halogen, cyano, Ci-Ce -alkyl or Ci-Ce-haloalkyl;R6is selected from hydrogen, halogen, methyl or cyano; andR9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

7. The compound of formula (I) as claimed in claim 1, wherein the compound is selected from formula (I-A),Formula (l-A)wherein n = 1-3; and B, Rla-Rlc, R1, R2, R3, R4a, R4b, R5and E are as defined in claim 1.

8. The compound of formula (I) as claimed in claim 1 or claim 7, wherein the compound is selected from formula (I-C) or formula (I-D),wherein n = 1-3, preferably n = 1; Q is selected from NH, O, or S, preferably S; Rla-Rlc, R1, R2, R3, R4a, R4b, R5and R6, are as defined in claim 1; and E is selected from:wherein R9is selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.

9. The compound of formula (I-C) or formula (I-D) as claimed in claim 8, whereinR1is Ci-Ce-alkyl;R2is hydrogen;R3is selected from hydrogen, halogen, cyano, Ci-Ce -alkyl, or Ci-Ce-haloalkyl;R4aand R4bare independently selected from hydrogen or Ci-Ce -alkyl;or R4aand R4btogether with the carbon atom to which they are attached, may form an oxo group (=0) or cyclopropyl ring;R5is selected from hydrogen or Ci-Ce -alkyl;Rlais selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, or Ci-Ce -alkylsulfonyl;R1bis selected from hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-haloalkyl or C3-C6- cycloalkyl;Rlcis selected from hydrogen, halogen, cyano, Ci-Ce -alkyl or Ci-Ce-haloalkyl; andR6is selected from hydrogen, halogen or cyano.

10. An agrochemical composition comprising the compound of formula (I) as claimed in any one of the claims 1 to 9 and an additional agrochemically acceptable auxiliary.

11. The composition as claimed in claim 10, wherein said composition further comprises an additional active ingredient selected from the group consisting of fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients.

12. A method of controlling or preventing infestation of plants by phytopathogenic fungi in agricultural crops or horticultural crops, wherein an effective amount of the compound of formula (I) as claimed in any one of the claims 1 to 9, or the composition as claimed in claim 10, is applied to the plants, plant parts or locus thereof, soil, seeds or materials to be protected against fungal attack.

13. Use of the compound of formula (I) as claimed in any one of the claims 1 to 9, as a fungicide.

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