The present invention relates to microbiocidal benzothiophene derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular, fungicidal activity. The invention also relates to agrochemical compositions which comprise at least one of the benzothiophene derivatives, to processes of preparation of these compounds and to uses of the benzothiophene derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.

EP0243014 and EP0433233 describe the use of thiophene derivatives for combating phytopathogenic fungi.

According to the present invention, there is provided a compound of formula (I): wherein

T is selected from the group consisting of a group of formula T ₁ , T ₂ and T ₃ below wherein the jagged line defines the point of attachment to the remaining part of a compound of formula (I), A ¹ , A ² and A ³ are each independently O or NH; and

R ¹ is selected from the group consisting of hydrogen, halogen, methyl, methoxy and cyclopropyl;

R ² is selected from the group consisting of hydrogen, halogen, cyano and methyl; R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, halogen, C ₁ -C ₄ alkyl, C ₂ - C ₄ alkynyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10-membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heterocyclyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different;

R ⁴ is selected from the group consisting of hydrogen, halogen, methyl, cyano and heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and the heteroaryl moiety is optionally substituted by 1 or 2 R ^5a substituents, which may be the same or different; each R ⁵ is independently selected from the group consisting of halogen, cyano, hydroxy, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, cyanoC ₁ -C ₄ alkyl-, C ₃ -C ₆ cycloalkyl, C ₃ - C6cycloalkenyl, -S(O) ₂ C ₁ -C ₄ alkyl, -C(O)NR ⁷ R ⁸ , phenyl, phenoxy, heterocyclyl, wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, heteroaryloxy, wherein the heteroaryl moiety is a 5- or 6- membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heterocyclyl, or heteroaryl moieties are optionally substituted by 1 or 2 R ⁶ substituents, which may be the same or different; each R ^5a is independently selected from the group consisting of halogen, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy; each R ⁶ is independently selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, cyano, difluoromethyl, difluoromethoxy and trifluoromethyl;

R ⁷ and R ⁸ are independently selected from the group consisting of hydrogen, methyl and ethyl; or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form an azetidine, pyrrolidine or piperidine ring; and

L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl- , C ₂ -C ₄ -alkenyl, C ₂ -C ₄ alkynyl, -(C=O)-, -C(O)O-, -O-, -S-, -S(O)-, -S(O) ₂ -, -C(R ⁹ )=NO- and - CH ₂ C(R ¹⁰ )=NO-;

R ⁹ is selected from the group consisting of hydrogen, methyl and ethyl; R ¹⁰ is selected from hydrogen or methyl; or an agronomically acceptable salt thereof; or an N-oxide thereof.

It has been found that the novel compounds of formula (I) have, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) and an agrochemically- acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient.

According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms (such as Phakopsora pachyrhizi ), wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the invention, the use may exclude methods for the treatment of the human or animal body by surgery or therapy.

As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

As used herein, cyano means a -CN group.

As used herein, hydroxy means a -OH group.

As used herein, the term "C ₁ -C ₄ alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and which is attached to the rest of the molecule by a single bond. C ₁ -C ₂ alkyl is to be construed accordingly. Examples of C ₁ -C ₄ alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1- methylethyl (iso-propyl), n-butyl, and 1-dimethylethyl (t-butyl).

As used herein, the term “cyanoC ₁ -C ₄ alkyl-” refers to a C ₁ -C ₄ alkyl radical as generally defined above substituted by one or more cyano groups.

As used herein, the term "C ₁ -C ₄ alkoxy" refers to a radical of the formula -OR _a where R _a is a C ₁ -C ₄ alkyl radical as generally defined above. Examples of C ₁ -C ₄ alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and t-butoxy. As used herein, the term " C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl-" refers to radical of the formula R _a -O-R _b - where R _a is a C ₁ -C ₄ alkyl radical as generally defined above, and R _b is a C ₁ -C ₄ alkylene radical as generally defined above.

As used herein, the term "C ₁ -C ₄ haloalkyl" refers to a C ₁ -C ₄ alkyl radical, as generally defined above, substituted by one or more of the same or different halogen atoms. Examples of C ₁ -C ₄ haloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2- trifluoroethyl.

As used herein, the term "C ₁ -C ₄ haloalkoxy" refers to a C ₁ -C ₄ alkoxy group, as defined above, substituted by one or more of the same or different halogen atoms. Examples of C ₁ -C ₄ haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

As used herein, the term "C ₂ -C ₄ alkenyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configuration, having from two to four carbon atoms, which is attached to the rest of the molecule by a single bond. C ₂ -C ₃ alkenyl is to be construed accordingly. Examples of C ₂ -C ₄ alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl) and but-1-enyl.

As used herein, the term "C ₂ -C ₄ alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C ₂ - C ₄ alkynyl include, but are not limited to, prop-1-ynyl and propargyl (prop-2-ynyl).

As used herein, the term "C ₁ -C ₄ alkylcarbonyl" refers to a radical of the formula -C(O)R _a where R _a is a C ₁ -C ₄ alkyl radical as generally defined above. C ₁ -C ₃ alkylcarbonyl is to be construed accordingly.

As used herein, unless explicitly stated otherwise, the term "C ₃ -C ₆ cycloalkyl" refers to a stable, monocyclic ring radical which is fully saturated and contains 3 to 6 carbon atoms. C ₃ -C ₄ cycloalkyl is to be construed accordingly. Examples of C ₃ -C ₆ cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, unless explicitly stated otherwise, the term "C ₃ -C ₆ cycloalkenyl" refers to a stable, monocyclic ring radical which is partially unsaturated and contains 3 to 6 carbon atoms. C ₃ -C ₄ cycloalkyl is to be construed accordingly. Examples of C ₃ -C ₆ cycloalkyl include, but are not limited to, cyclopentenyl and cyclohexenyl.

As used herein, the term "phenoxy" refers to a phenyl ring attached to the rest of the molecule via an oxygen atom. As used herein, unless explicitly stated otherwise, the term "heterocyclyl" or "heterocyclic" refers to a stable 4- to 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or d-lactamyl.

As used herein, unless explicitly stated otherwise, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heteroaryl include, furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.

As used herein, the term "heteroaryloxy" refers to a heteroaryl ring as defined above attached to the rest of the molecule via an oxygen atom.

As used herein, the term “heterodiaryl” refers to a 9 or 10-membered aromatic fused bicyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterodiaryl include, indolyl, indazolyl, benzimidazolyl, pyrrolopyridinyl or triazolopyridinyl.

The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of formula (I).

In each case, the compounds of formula (I) according to the invention are in free form, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

Compounds of formula (I) wherein R ³ is -L-R ^w and L is -C(R ⁹ )=NO- may be represented by a compound of formula (l-l) as shown below: wherein T, R ¹ , R ² , R ⁴ , R ⁹ and R ^w are as defined for compounds of formula (I).

Compounds of formula (I) wherein R ³ is -L-R ^w and L is -CH ₂ C(R ¹⁰ )=NO- may be represented by a compound of formula (l-ll) as shown below: wherein T, R ¹ , R ² , R ⁴ , R ¹⁰ and R ^w are as defined for compounds of formula (I).

Compounds of formula (I) wherein R ³ is -L-R ^w and L is -C(O)O- may be represented by a compound of formula (l-llI) as shown below: wherein T, R ¹ , R ² , R ⁴ and R ^w are as defined for compounds of formula (I).

The following lists provide definitions, including preferred definitions, for substituents T, A ¹ , A ² , A ³ R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^5a , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^w and L with reference to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

T is selected from the group consisting of a group of formula T ₁ , T ₂ and T ₃ below

wherein the jagged line defines the point of attachment to the remaining part of a compound of formula

(I)·

Preferably, T is selected from a group of formula T ₁ or T ₂ . More preferably, T is a group of formula T ₁ .

In a preferred embodiment, T is selected from the group consisting of formula T _1a , T _2a and T _3a (preferably T _1a or T _2a , more preferably T _1a ) below wherein the jagged line defines the point of attachment to the remaining part of a compound of formula

(I)·

A ¹ , A ² and A ³ are each independently O or NH. Preferably A ² is NH and A ¹ and A ³ are O.

R ¹ is selected from the group consisting of hydrogen, halogen, methyl, methoxy and cyclopropyl. Preferably, R ¹ is selected from the group consisting of hydrogen, chloro, fluoro, methyl, methoxy and cyclopropyl. More preferably, R ¹ is selected from the group consisting of hydrogen, chloro, fluoro and methyl. Even more preferably, R ¹ is selected from the group consisting of hydrogen, fluoro and methyl. Even more preferably still, R ¹ is selected from hydrogen or methyl. Most preferably, R ¹ is hydrogen.

R ² is selected from the group consisting of hydrogen, halogen, cyano and methyl. Preferably, R ² is selected from the group consisting of hydrogen, chloro, fluoro, cyano and methyl. More preferably, R ² is hydrogen or methyl. Most preferably, R ² is hydrogen. R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, halogen, C ₁ -C ₄ alkyl, C ₂ - C ₄ alkynyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10-membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heterocyclyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different.

Preferably, R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, halogen, C ₁ - C ₄ alkyl, C ₂ -C ₄ alkynyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10-membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heterocyclyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different.

More preferably, R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, chloro, bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10-membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different.

Even more preferably, R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10- membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different. Even more preferably still, R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, cyclopropyl, cyclohexyl, cyclohexenyl, phenyl, pyrazolyl, thiazolyl, isoxazolyl, pyridyl, benzodioxolyl, benzodioxinyl and indazolyl, and wherein any of said phenyl, pyrazolyl, thiazolyl, isoxazolyl, pyridyl, benzodioxolyl, benzodioxinyl or indazolyl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different.

Yet even more preferably still, R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, cyclopropyl, cyclohexyl, cyclohexenyl, phenyl, pyrazolyl, thiazolyl, pyridyl, benzodioxolyl, benzodioxinyl and indazolyl, and wherein any of said phenyl, pyrazolyl, thiazolyl, pyridyl, benzodioxolyl, benzodioxinyl or indazolyl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different.

In one embodiment, R ³ is selected from the group consisting of hydrogen, bromo, n-butyl, acetyl, 3- prop-1-ynyl, 3-methoxyprop-1-ynyl, 2-cyclopropylethynyl, prop-2-ynoxymethyl, n-propoxy, methoxymethyl, ethoxymethyl, 2,2-difluoroethoxy, 2,2-difluoroethoxymethyl, cyclopropyl, cyclohexyl, cyclopentoxy, cyclohexen-1-yl, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4- difluorophenyl, 3,5-difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-cyanophenyl, 3- (cyanomethyl)phenyl, 4-(cyanomethyl)phenyl, 3-(trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 3- (trifluoromethoxy)phenyl, 4-(trifluoromethoxy)phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 4-ethylphenyl, 4-propylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 3-isopropoxyphenyl, 4-cyclopropylphenyl, 4-methylsulfonylphenyl, 3- (methylcarbamoyl)phenyl, 3-(pyrrolidine-1 -carbonyl)phenyl, 4-morpholinophenyl, 4-pyrazol-1 -ylphenyl, benzyl, 3-thiazol-4-yl, 2-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 3-cyclopropylpyrazol-1-yl, 2,4- dimethylpyrazol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2-fluoro-3- pyridyl, 2-fluoro-4-pyridyl, 6-phenoxy-2-pyridyl, 1 ,3-benzodioxol-5-yl, 2,3-dihydro-1 ,4-benzodioxin-6-yl, 1-methylindazol-6-yl, methoxyiminomethyl, ethoxyiminomethyl, N-methoxy-C-methyl-carbonimidoyl andN -ethoxy-C-methyl-carbonimidoyl. Preferably, R ³ is selected from the group consisting of hydrogen, bromo, acetyl, 3-prop-1-ynyl, 3-methoxyprop-1-ynyl, 2-cyclopropylethynyl, n-propoxy, 2,2- difluoroethoxy, cyclohexyl, cyclohexen-1-yl, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4- difluorophenyl, 3,5-difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-cyanophenyl, 3- (cyanomethyl)phenyl, 4-(cyanomethyl)phenyl, 3-(trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 3- (trifluoromethoxy)phenyl, 4-(trifluoromethoxy)phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 4-ethylphenyl, 4-propylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 3-isopropoxyphenyl, 4-cyclopropylphenyl, 4-methylsulfonylphenyl, 3- (methylcarbamoyl)phenyl, 3-(pyrrolidine-1 -carbonyl)phenyl, 4-morpholinophenyl, 4-pyrazol-1 -ylphenyl, benzyl, 3-thiazol-4-yl, 2-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 3-cyclopropylpyrazol-1-yl, 2,4- dimethylpyrazol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2-fluoro-3- pyridyl, 2-fluoro-4-pyridyl, 6-phenoxy-2-pyridyl, 1 ,3-benzodioxol-5-yl, 2,3-dihydro-1 ,4-benzodioxin-6-yl, 1-methylindazol-6-yl, methoxyiminomethyl, ethoxyiminomethyl, N-methoxy-C-methyl-carbonimidoyl and N-ethoxy-C-methyl-carbonimidoyl. More preferably, R ³ is selected from the group consisting of 3-prop- 1-ynyl, 3-methoxyprop-1-ynyl, 2-cyclopropylethynyl, n-propoxy, 2,2-difluoroethoxy, phenyl, 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3-chlorophenyl, 4- chlorophenyl, 4-cyanophenyl, 3-(cyanomethyl)phenyl, 4-(cyanomethyl)phenyl, 3- (trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 3-(trifluoromethoxy)phenyl, 4-

(trifluoromethoxy)phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 4- ethylphenyl, 4-propylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4- dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 3-isopropoxyphenyl, 4-cyclopropylphenyl, 4-methylsulfonylphenyl, 3- (methylcarbamoyl)phenyl, 3-(pyrrolidine-1 -carbonyl)phenyl, 4-morpholinophenyl, 4-pyrazol-1 -ylphenyl, benzyl, 3-thiazol-4-yl, 2-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 3-cyclopropylpyrazol-1-yl, 2,4- dimethylpyrazol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2-fluoro-3- pyridyl, 2-fluoro-4-pyridyl, 6-phenoxy-2-pyridyl, methoxyiminomethyl, ethoxyiminomethyl, N -methoxy-C- methyl-carbonimidoyl and N -ethoxy-C-methyl-carbonimidoyl. Even more preferably, R ³ is selected from the group consisting of 3-prop-1-ynyl, 3-methoxyprop-1-ynyl, 2-cyclopropylethynyl, n-propoxy, 2,2- difluoroethoxy, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3- ethylphenyl, 4-ethylphenyl, 4-propylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 3-isopropoxyphenyl, 4-cyclopropylphenyl, 2-pyridyl, 3-pyridyl, 4- pyridyl, 6-fluoro-2-pyridyl, 6-fluoro-3-pyridyl, 2-fluoro-3-pyridyl, 2-fluoro-4-pyridyl, 6-phenoxy-2-pyridyl, methoxyiminomethyl, ethoxyiminomethyl, N-methoxy-C-methyl-carbonimidoyl and N -ethoxy-C-methyl- carbonimidoyl.

R ⁴ is selected from the group consisting of hydrogen, halogen, methyl, cyano and heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and the heteroaryl moiety is optionally substituted by 1 or 2 R ^5a substituents, which may be the same or different. Preferably, R ⁴ is selected from the group consisting of hydrogen, fluoro, chloro, bromo, methyl, cyano and heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and the heteroaryl moiety is optionally substituted by 1 or 2 R ^5a substituents. More preferably, R ⁴ is selected from the group consisting of hydrogen and heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and the heteroaryl moiety is optionally substituted by 1 R ^5a substituent. Even more preferably, R ⁴ is selected from the group consisting of hydrogen, pyrazolyl and pyridyl, and wherein said pyrazolyl or pyridyl moieties are optionally substituted by 1 R ^5a substituents. Most preferably, R ⁴ is hydrogen. In one embodiment R ⁴ is selected from the group consisting of hydrogen, 1-methylpyrazol-3-yl, 2- methylpyrazol-3-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-fluoro-3-pyridyl, 2-fluoro-4-pyridyl and 6-methoxy-2- pyridyl.

Each R ⁵ is independently selected from the group consisting of halogen, cyano, hydroxy, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, cyanoC ₁ -C ₄ alkyl-, C ₃ -C ₆ cycloalkyl, C ₃ - C ₆ cycloalkenyl, -S(O) ₂ C ₁ -C ₄ alkyl, -C(O)NR ⁷ R ⁸ , phenyl, phenoxy, heterocyclyl, wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, heteroaryloxy, wherein the heteroaryl moiety is a 5- or 6- membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl (including phenoxy), heterocyclyl, or heteroaryl (including heteroaryloxy) moieties are optionally substituted by 1 or 2 R ⁶ substituents, which may be the same or different.

Preferably, each R ⁵ is independently selected from the group consisting of chloro, fluoro, bromo, cyano, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, cyanoC ₁ - C ₄ alkyl-, C ₃ -C ₆ cycloalkyl, -S(O) ₂ Me, -C(O)NR ⁷ R ⁸ , phenyl, phenoxy, heterocyclyl, wherein the heterocyclyl moiety is a 5- or 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heteroaryl, heteroaryloxy, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl (including phenoxy), heterocyclyl, or heteroaryl (including heteroaryloxy) moieties are optionally substituted by 1 or 2 R ⁶ substituents, which may be the same or different.

More preferably, each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, cyanoC ₁ -C ₄ alkyl-, C ₃ - C6cycloalkyl, -S(O) ₂ Me, -C(O)NR ⁷ R ⁸ , phenyl, phenoxy, morpholinyl and pyrazolyl, and wherein any of said phenyl (including phenoxy), morpholinyl, or pyrazolyl moieties are optionally substituted by 1 or 2 R ⁶ substituents, which may be the same or different.

Even more preferably, each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, cyanoC ₁ -C ₄ alkyl-, C ₃ -C ₆ cycloalkyl, - S(O) ₂ Me, -C(O)NR ⁷ R ⁸ , phenoxy, morpholinyl and pyrazolyl.

Even more preferably still, each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, isopropoxy, trifluoromethoxy, cyanomethyl, cyclopropyl, - S(O) ₂ Me, -C(O)NR ⁷ R ⁸ , phenoxy, morpholinyl and pyrazolyl.

Yet even more preferably still, each R ⁵ is independently selected from the group consisting of chloro, fluoro, methyl, methoxy and cyclopropyl. Most preferably, each R ⁵ is independently selected from fluoro and methoxy.

Each R ^5a is independently selected from the group consisting of halogen, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy. Preferably, each R ^5a is independently selected from the group consisting of chloro, fluoro, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy. More preferably, each R ^5a is independently selected from the group consisting of chloro, fluoro, methyl and methoxy. Even more preferably, each R ^5a is independently selected from the group consisting of fluoro and methoxy. each R ⁶ is independently selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, cyano, difluoromethyl, difluoromethoxy and trifluoromethyl. Preferably, each R ⁶ is independently selected from the group consisting of chloro, fluoro, methyl, ethyl, methoxy, cyano, difluoromethyl, difluoromethoxy and trifluoromethyl. More preferably, each R ⁶ is independently selected from the group consisting of chloro, fluoro, methyl and trifluoromethyl. Most preferably each R ⁶ is methyl.

R ⁷ and R ⁸ are independently selected from the group consisting of hydrogen, methyl and ethyl. Preferably, R ⁷ and R ⁸ are independently selected from hydrogen or methyl.

Alternatively, R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form an azetidine, pyrrolidine or piperidine ring. Preferably, R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a pyrrolidine ring.

L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl- , C ₂ -C ₄ -alkenyl, C ₂ -C ₄ alkynyl, -(C=O)-, -C(O)O-, -O-, -S-, -S(O)-, -S(O) ₂ -, -C(R ⁹ )=NO- and - CH ₂ C(R ¹⁰ )=NO-. Preferably, L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl-, C ₂ -C ₄ alkynyl, -(C=O)-, -O-, -S-, -S(O) ₂ -, -C(R ⁹ )=NO- and - CH ₂ C(R ¹⁰ )=NO-. More preferably, L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkynyl, -(C=O)-, -O- and -C(R ⁹ )=NO-. Even more preferably, L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkynyl, -(C=O)- and -C(R ⁹ )=NO-. Even more preferably still, L is selected from the group consisting of a direct bond, C ₁ -C ₂ alkyl, C ₂ -C ₄ alkynyl and - C(R ⁹ )=NO-. Yet even more preferably still, L is selected from the group consisting of a direct bond, C ₂ - C ₄ alkynyl and -C(R ⁹ )=NO-.

In one embodiment L is a direct bond.

In another embodiment L is selected from the group consisting of C ₁ -C ₂ alkyl, C ₂ -C ₄ alkynyl and - C(R ⁹ )=NO-. Preferably, L is C ₂ -C ₄ alkynyl or -C(R ⁹ )=NO-.

R ⁹ is selected from the group consisting of hydrogen, methyl and ethyl. Preferably, R ⁹ is selected from hydrogen or methyl.

R ¹⁰ is selected from hydrogen or methyl. Preferably, in a compound according to formula (I) of the invention;

T is a group of formula T ₁ ;

A ¹ is O;

R ¹ is selected from the group consisting of hydrogen, chloro, fluoro, methyl, methoxy, and cyclopropyl; R ² is hydrogen;

R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, chloro, bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, phenyl, heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and heterodiaryl, wherein the heterodiaryl moiety is a 9- or 10-membered aromatic fused bicyclic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, heteroaryl or heterodiaryl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different;

R ⁴ is hydrogen; each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, cyanoC ₁ -C ₄ alkyl-, C ₃ -C ₆ cycloalkyl, - S(O) ₂ Me, -C(O)NR ⁷ R ⁸ , phenyl, phenoxy, morpholinyl and pyrazolyl, and wherein any of said phenyl, morpholinyl, or pyrazolyl moieties are optionally substituted by 1 or 2 R ⁶ substituents, which may be the same or different; each R ⁶ is independently selected from the group consisting of chloro, fluoro, methyl and trifluoromethyl; L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkynyl, -(C=O)- and - C(R ⁹ )=NO-;

R ⁷ and R ⁸ are independently selected from hydrogen or methyl; or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a pyrrolidine ring; and R ⁹ is selected from hydrogen or methyl.

More preferably, in a compound according to formula (I) of the invention;

T is a group of formula T ₁ ;

A ¹ is O;

R ¹ is selected from the group consisting of hydrogen, fluoro and methyl;

R ² is hydrogen;

R ³ is -L-R ^w , wherein R ^w is selected from the group consisting of hydrogen, bromo, C ₁ -C ₄ alkyl, C ₁ - C ₄ alkoxy, cyclopropyl, cyclohexyl, cyclohexenyl, phenyl, pyrazolyl, thiazolyl, isoxazolyl, pyridyl, benzodioxolyl, benzodioxinyl and indazolyl, and wherein any of said phenyl, pyrazolyl, thiazolyl, isoxazolyl, pyridyl, benzodioxolyl, benzodioxinyl or indazolyl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different;

R ⁴ is hydrogen; each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, isopropoxy, trifluoromethoxy, cyanomethyl, cyclopropyl, -S(O) ₂ Me, - C(O)NR ⁷ R ⁸ , phenoxy, morpholinyl and pyrazolyl; L is selected from the group consisting of a direct bond, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkynyl, -(C=O)- and - C(R ⁹ )=NO-;

R ⁷ and R ⁸ are independently selected from hydrogen or methyl; or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a pyrrolidine ring; and R ⁹ is selected from hydrogen or methyl.

In a preferred embodiment of the invention;

T is a group of formula T ₁ ;

A ¹ is O;

R ¹ is selected from the group consisting of hydrogen, fluoro and methyl;

R ² is hydrogen;

R ³ is selected from the group consisting of phenyl, pyrazolyl, thiazolyl and pyridyl (preferably phenyl or pyridyl), and wherein any of said phenyl, pyrazolyl, thiazolyl or pyridyl moieties are optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different;

R ⁴ is hydrogen; each R ⁵ is independently selected from the group consisting of chloro, fluoro, cyano, C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, isopropoxy, trifluoromethoxy, cyanomethyl, cyclopropyl, -S(O) ₂ Me, - C(O)NR ⁷ R ⁸ , phenoxy, morpholinyl and pyrazolyl (preferably, each R ⁵ is independently selected from the group consisting of chloro, fluoro, methyl, methoxy and cyclopropyl); and

R ⁷ and R ⁸ are independently selected from hydrogen or methyl; or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a pyrrolidine ring.

In another preferred embodiment of the invention;

T is selected from the group consisting of formula T _1a , T2a and T3a (preferably T _1a or T _2a , more preferably T _1a );

R ¹ is selected from the group consisting of hydrogen, fluoro and methyl (preferably, R ¹ is hydrogen or methyl);

R ² is hydrogen;

R ³ is phenyl, wherein said phenyl is optionally substituted by 1 or 2 R ⁵ substituents, which may be the same or different (preferably, R ³ is phenyl);

R ⁴ is hydrogen; each R ⁵ is independently selected from the group consisting of chloro, fluoro, methyl, methoxy and cyclopropyl.

In another preferred embodiment of the invention;

T is a group of formula T ₁ ;

A ¹ is O;

R ¹ is selected from the group consisting of hydrogen, fluoro and methyl;

R ² is hydrogen; R ³ is is -L-R ^w , wherein R ^w is selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and C ₃ - C ₆ cycloalkyl;

R ⁴ is hydrogen;

L is C ₂ -C ₄ alkynyl or -C(R ⁹ )=NO-; and R ⁹ is selected from hydrogen or methyl.

Preferably, the compound according to formula (I) is selected from a compound C-1 to C-78 listed in Table C (below) or a compound D-1 to D-19 listed in Table D (below).

In one embodiment, the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Altemaria alternata, Phakopsora pachyrhizi, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadone).

In a further embodiment, the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Altemaria alternata, Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadone), wherein the mutation is G143A.

In a further embodiment, the compounds of formula (I) according to the invention may be useful for combating phytopathogenic fungi (e.g Phakopsora pachyrhizi ) containing a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin or fenamidone or famoxadone), wherein the mutation is F129L.

In another embodiment, the invention also relates to a method of controlling or preventing infestation by phytopathogenic fungi in a plant (e.g Altemaria alternate, Phakopsora pachyrhizi Plasmopara viticola, Sclerotinia sclerotiorum or Septoria tritici also known as Mycosphaerella graminicola, preferably Phakopsora pachyrhizi), wherein said phytopathogenic fungi contains a mutation in the mitochondrial cytochrome b conferring resistance to Qo inhibitors (e.g strobliurins such as azoxystrobin, pyraclostrobin and trifloxystrobin orfenamidone or famoxadone), said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a compound of formula (I).

The level of resistance and therefore the impact on the performance of the fungicide can be measured by the use of a 'Resistance Factor' (RF). The resistance factor can be calculated by dividing the concentration of a fungicide that provides a set level of disease control (i.e. 50 percent) for the 'resistant' fungal strain with the concentration of the same fungicide that provides the same level of disease control for the 'susceptible' strain of the same fungal species (RF = EC50 value of the resistant strain/EC50 value of the sensitive strain). Although there are no set rules, three categories can be defined: 1) RF ≥ 50 = resistant strain, 2) 5 ≤ RF < 50 = less sensitive strain (shift in sensitivity), and 3) RF < 5 = sensitive strain.

In order to obtain resistant fungal strains, a researcher is to locate a host crop and geographical region where the relevant resistance had been reported in literature. Leaf samples infected by the target disease are then collected from the locations/host crops and sent to a laboratory, where pure cultures would be isolated. The resistant phenotype of the fungal cultures is determined either by conducting a full dose response bioassay and comparing the bioassay results to similar bioassay results for a known susceptible strain of the same species. Alternatively the resistance genotype of the fungal strain can be determined by molecular techniques (e.g. qPCR) if the resistance mechanism for the relevant species is known.

Compounds of the present invention can be made as shown in the following schemes 1 to 15, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

The compounds of formula (la), wherein R ¹ , R ² , R ³ , and R ⁴ are as previously described in formula (I) can be obtained from compounds of formula (lla), wherein R ^a is defined as in scheme 1 below, and W is hydrogen via C-H functionalization with an appropriate arene coupling partner or alternatively when W is a halogen or pseudo halogen, compounds of formula (I) may be prepared via cross coupling transformation using a suitable palladium catalyst complex in the presence of a suitable halo-arene system. For related examples, see: Chem. Eur. J. 2012, 18, 8448 or Angew. Chem., Int. Ed. 2011 , 50, 2387. This is shown in scheme 1 .

Scheme 1 As shown in scheme 2, compounds of formula (laa) wherein R ^b is halogen can be converted into compounds of formula (lab) wherein T ^a is T ₄ or T ₅ by treatment with a metalating agent (e.g. bis- pinacolatodiboron) optionally in the presence of a suitable catalyst (e.g. Pd(dppf)Cl ₂ ) and base (e.g. potassium phosphate) in solvents such as 1 ,4-dioxane, dimethylformamide or toluene at a temperature between 20°C - 150°C. Compounds of formula (lab) can subsequently be converted into compounds of formula (lac), wherein Z is CH or N, by coupling with a compound of formula (IlIa) wherein A ¹ is as described for formula (I), Z is CH or N, and Xa is a halogen or pseudohalogen, in the presence of a suitable catalyst such as palladium diacetate and optionally a supporting ligand (e.g. CatCXiumA®) and base (e.g. potassium phosphate) in a suitable solvent such as 1 ,4-dioxane, dimethylformamide or toluene at temperatures between 20°C - 150°C. This is shown in scheme 2 and related examples of such transformations are described in Tetrahedron, 2011 , 67, 624-635 and Advanced Synthesis and Catalysis, 2017, 359, 3865 - 3879.

Alternatively, compounds of formula (la), wherein R ^a is described as in scheme 1 above, and R ¹ , R ² , R ³ , and R ⁴ are as previously described in formula (I), can be obtained via electrophilic aromatic substitution reactions from carbonyl compounds of formula (III), wherein R ¹ , R ² , R ³ , and R ⁴ are as previously described in formula (I), optionally in the presence of a suitable acid reagent. For related examples, see: Bioorg. Med. Chem. Lett. 2003, 13, 1277 or Org. Lett. 2016, 18, 3034. This is shown in scheme 3.

Compounds of formula (III) wherein R ^a is described as scheme 1 , and R ¹ , R ² , R ³ , and R ⁴ are as previously described in formula (I), can be obtained via nucleophilic substitution reaction with compounds of formula (V), wherein R ⁴ and R ³ are as defined as in formula (I) and Xa is a suitable leaving group such as a halogen or pseudo-halogen, and compounds of formula (VI), using base promoted reaction conditions. For related examples, see: J. Med. Chem. 2007, 50, 2682. This is shown in scheme 4.

Scheme 4

Compounds of formula (II), wherein R ^a is defined as in scheme 1 , and R ¹ , R ² , R ³ , and R ⁴ are as defined previously, and W is a halogen or pseudo-halogen, such as -OSO ₂ CF ₃ , can be prepared from carbonyl compounds of formula (VII) using a suitable activing agent, such as POCI ₃ or O(SO ₂ CF ₃ ) ₂ . For related examples, see: Chem. Eur. J. 2012, 18, 8448. This is shown in scheme 5

Scheme 5

Compounds of formula (VII) can be prepared according to scheme 6.

As shown in scheme 6, compounds of formula (VI) can be treated with compounds of formula (VIII), wherein Xa is as previously defined, and R ^z is hydrogen or C ₁ -C ₆ alkyl, under basic or acidic conditions to give compounds of formula (IX). Compounds of formula (IX) wherein R ¹ , R ² , and R ⁴ , are as described in formula (I) and R ^a is as described in scheme 1 , are activated to compounds of formula (X), wherein Xb is halogen, preferably chlorine or bromine, by methods known to those skilled in the art and described for example in Tetrahedron, 61 (46) , 10827-10852, 2005. For example, compounds where Xb is halogen are formed by treatment of compounds of formula (IX), wherein R ^z is hydrogen, with for example, oxalyl chloride or thionyl chloride in the presence of catalytic quantities of DMF in inert solvents such as methylene dichloride or THF at temperatures between 20 °C to 100 °C, preferably 25 °C. Compounds of formula (X) are then converted to compounds of formula (VII) by an intramolecular Friedel-Crafts acylation in the presence of a Lewis acid, such as FeCI ₃ , BF ₃ or AlCI ₃ in an inert solvent such as methylene chloride. Such sequences are well known to those skilled in the art and have been reported for example in J. Chem. Pharm. Res., 2016, 8(11), 75-82 and Chemistry-A European Journal, (2017), 23(26), 6237-6243. Acid catalysis cyclizations are also know, for example see J. Amer. Chem. Soc., (2017), 139(32), 10956-10959 (trifluoromethanesulfonic acid in methylene chloride).

Alternatively compounds of formula (lb) wherein W is a halogen can be prepared from compounds of formula (XI) by treatment with a formylating agent such as methyl formate, optionally in the presence of a base (e.g. K ₂ CO ₃ ) in a suitable solvent (e.g. DMF) at temperatures between 20°C and 160 °C followed by methylation with a methylating agent (e.g. (MeO) ₂ SO ₂ or Mel) in the presence of a base (e.g. K ₂ CO ₃ or NaH) in a solvent such as DMF or THF at a temperature between 0°C and 100°C. This is illustrated in scheme 7.

Compounds of formula (XI) can be prepared from compounds of formula (XII) wherein R ^c is C ₁ -C ₄ alkyl by decarboxylation with a reagent such as LiCI or NaCN in solvents such as dimethyl sulfoxide or water at temperatures between 20°C and 200°C, as shown in Scheme 8. Such Krapcho decarboxylations are well known in the literature, see for example J. Org. Chem, 1978, 43 (1): 138— 147, and references cited therein.

Compounds of formula (XII) can be prepared from compounds of formula (XIII), wherein Xc is halogen or psuedohalogen, by coupling with a suitable nucleophile of formula (XIV) wherein A ¹ is as defined in formula (I) and R ^c is C ₁ -C ₄ alkyl, in the presence of a suitable catalyst such as Pd ₂ dba ₃ and optionally a supporting ligand such as P(tBu) ₃ and base (e.g. Cs ₂ CO ₃ ) in a solvent such as dimethoxyethane or dioxane at temperatures between 20°C and 100°C to form a compound of formula (XV). Compounds of formula (XV) can be treated with a halogenating agent such as N-bromosuccinimide optionally in the presence of an acid such as acetic acid ortrifluoroacetic acid and optionally in a solvent such as chloroform at a temperature between 0°C and 80°C to form compounds of formula (XII). This is shown in scheme 9.

Compounds of formula (lc) can be prepared from compounds of formula (XVI) wherein R ¹ , R ² , R ⁴ , R ⁹ are as described in formula (I) and R ^a is as described in scheme 1 by treatment with a hydroxylamine of formula (XVII) optionally under acidic or basic conditions, as shown in scheme 10. Related examples are described in US6130187 and Heterocycles, 1988, 27, 423 (Scheme 10).

Scheme 10

Compounds of formula (XVI) can be prepared from compounds of formula (lla) wherein W is hydrogen and R ¹ , R ² , and R ⁴ are as described for formula (I) and R ^a is as described in scheme 1 , by treatment with an electrophile such as N,N-dimethylformamide or 1 ,1-dichloromethyl ether and an activating agent e.g. phosphorus oxychloride or tin(IV) chloride. This is shown in scheme 11 and related examples are given in Bioorg. Med. Chem. Lett. 2017, 25, 1341 or Org. Lett. 2018, 20, 5835.

Compounds of formula (XVI) can be obtained by reacting a compound of formula (XVIa), wherein R ⁹ is H, with an organometallic reagent (XVIII) (or a reducing agent when R ⁹ is H) to form compounds of formula (XVII) which can be converted into compounds of formula (XVI) upon treatment with an oxidizing agent such as, for example, Dess-Martin periodinane. This is shown in scheme 12 and related examples are described in Chem. Lett. 2013, 42, 1170, Org. Lett. 2019, 21, 5101 and J. Org. Chem, 2008, 73, 4101.

Compounds of formula (XVI) wherein R ⁹ is methyl, namely compounds of formula (XVIb), may also be prepared by the chemistry shown in scheme 13. Thus, treatment of compounds of formula (II), wherein W is a halogen or pseudo halogen and R ¹ , R ² , R ^a and R ⁴ are as previously described, with tri- butyl(1-methoxyvinyl)stannane (XIX) in the presence of a palladium catalyst, such as dichlorobis(triphenylphosphine)palladium, in an inert solvent such as toluene at temperatures from 20 °C to 110 °C , followed by hydrolysis of the intermediate vinyl ether (XX), leads to compounds of formula (XVIb).

Such reactions have been described in the literature, for example WO2014/142322 or Bio. Med.

Chem. Letts., (2019), 29(11), 1419-142.

Compounds of formula (XXI), wherein R ¹ , R ² , R ³ , and R ⁴ are as defined for compounds of formula (I), can be prepared from compounds of formula (la), wherein Ra is bromo or iodo, via cross-coupling with methyl N-methoxycarbamate in the presence of a suitable catalyst complex, such as [tBuXPhos Pd(allyl)]OTf , and a base (e.g. cesium carbonate), in a solvent such as toluene at temperatures between 25°C and 60°C. This is shown in scheme 14 Compounds of formula (XXII), wherein A ² is O or NH, can be prepared from compounds of formula (la), wherein Ra is bromo or iodo, optionally by treatment with methylamine or methanol, in the presence of a suitable catalyst such as PEPPSI™ -IPr and a base such as potassium carbonate, in an appropriate solvent (e.g. 1 ,4-dioxane or dimethylformamide) under an atmosphere of carbon monoxide at pressures between 0 and 20 bar and temperatures between 20°C and 120°C. Related examples are described in RSC Advances, 2014, 4, 48177-48190 and Organic Leters, 2009, 11, 1321-1324. Compounds of formula (XXIII), wherein A ² is O or NH, can be prepared from compounds of formula (XXII) by treatment with N-methyl hydroxylamine or a salt thereof, optionally in the presence of a base such as sodium acetate or an acid such as acetic acid and in solvents such as ethanol, methanol or water at temperatures between 20°C and 100°C. Related examples are described in US5856573 and Journal of Medicinal Chemistry, 2000, 43, 560-568. This is shown in scheme 15.

For preparing all further compounds of the formula (I) functionalized according to the definitions of R ₁ , R ₂ , R ₃ , R ₄ and T, there are a large number of suitable known standard methods, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, and palladium catalyzed C-C- bond couplings such as Stille (Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction; John Wiley & Sons: New York, 1998), Sonagashira (J. Org. Chem., 2006, 71 , 379-381), Heck (J. Org. Chem., 1972, 37(14), 2320-2322), Suzuki ( Nachrichten aus der Chemie. Band 50,

2002, S. 1122-1127), and Negishi (Chem. Comm. 1977, 683;) reactions, as well as metal catalyzed C-X type coupling such as Buchwald-Hartwig (J. Am. Chem. Soc., 1994, 116(13), 5969-5970 and 1994, 116(17), 7901-7902) and Chan-Lam ( Tetrahedron , 2012, 68, 7735-7754) reactions. The choice of the preparation methods which are suitable depending on the properties (reactivity) of the substituents in the intermediates.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required because in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

As already indicated, surprisingly, it has now been found that the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi. The compounds of formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.

The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) is applied to the plants, to parts thereof or the locus thereof.

It is also possible to use compounds of formula (I) as fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

It may also be possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.

Furthermore, the compounds of formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.

The compounds of formula (I) are 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: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, 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, 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, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, 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, 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.

The compounds of formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.

Within the scope of present invention, target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

The term "useful plants" is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl- shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

The term "useful plants" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a Cryll IB(b1 ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryll IB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a Cryll IA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®. The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ- endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. orXenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosomeinactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to be understood by d-endotoxins, for example Cry1Ab, Cry1Ac, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, orvegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651. The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

The compounds of formula (I) (including any one of compounds C-1 to C-78 or D-1 to D-19) orfungicidal compositions according to the present invention comprising a compound of formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi ) on soy bean plants.

In particular, transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g. Cry1Ac (Cry1Ac Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (see U.S. Patent No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (eg, see paragraph [008] reference to Intacta RR2 PRO™ soybean)), event MON87751 (US. Patent Application Publication No. 2014/0373191) or event DAS- 81419 (U.S. Patent No. 8632978 and related applications and patents).

Other transgenic soybean plants may comprise event SYHT0H2 - HPPD tolerance (U.S. Patent Application Publication No. 2014/0201860 and related applications and patents), event MON89788 - glyphosate tolerance (U.S. Pat. No. 7,632,985 and related applications and patents), event MON87708 - dicamba tolerance (U.S. Patent Application Publication No. US 2011/0067134 and related applications and patents), event DP-356043-5 - glyphosate and ALS tolerance (U.S. Patent Application Publication No. US 2010/0184079 and related applications and patents), event A2704-12 - glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0320616 and related applications and patents), event DP-305423-1 - ALS tolerance (U.S. Patent Application Publication No. US 2008/0312082 and related applications and patents), event A5547-127 - glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0196127 and related applications and patents), event DAS-40278-9 - tolerance to 2,4- dichlorophenoxyacetic acid and aryloxyphenoxypropionate (see WO 2011/022469, WO 2011/022470, WO 2011/022471 , and related applications and patents), event 127 - ALS tolerance (WO 2010/080829 and related applications and patents), event GTS 40-3-2 - glyphosate tolerance, event DAS-68416-4- 2,4-dichlorophenoxyacetic acid and glufosinate tolerance, event FG72 - glyphosate and isoxaflutole tolerance, event BPS-CV127-9 - ALS tolerance and GU262 - glufosinate tolerance or event SYHT04R - HPPD tolerance.

The compounds of formula (I) (including any one of compounds C-1 to C-78 or D-1 to D-19) orfungicidal compositions according to the present invention comprising a compound of formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi ) on soy bean plants. In particular, there are known in the scientific literature certain Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome, see for example: “Fighting Asian Soybean Rust, Langenbach C, et al, Front Plant Science 7(797) 2016).

An elite plant is any plant from an elite line, such that an elite plant is a representative plant from an elite variety. Non-limiting examples of elite soybean varieties that are commercially available to farmers or soybean breeders include: AG00802, A0868, AG0902, A1923, AG2403, A2824, A3704, A4324, A5404, AG5903, AG6202 AG0934; AG1435; AG2031 ; AG2035; AG2433; AG2733; AG2933; AG3334; AG3832; AG4135; AG4632; AG4934; AG5831 ; AG6534; and AG7231 (Asgrow Seeds, Des Moines, Iowa, USA); BPR0144RR, BPR 4077NRR and BPR 4390NRR (Bio Plant Research, Camp Point, III., USA); DKB17- 51 and DKB37-51 (DeKalb Genetics, DeKalb, III., USA); DP 4546 RR, and DP 7870 RR (Delta & Pine Land Company, Lubbock, Tex., USA); JG 03R501 , JG 32R606C ADD and JG 55R503C (JGL Inc., Greencastle, Ind., USA); NKS 13-K2 (NK Division of Syngenta Seeds, Golden Valley, Minnesota, USA); 90M01 , 91 M30, 92M33, 93M11 , 94M30, 95M30, 97B52, P008T22R2; P16T17R2; P22T69R; P25T51 R; P34T07R2; P35T58R; P39T67R; P47T36R; P46T21 R; and P56T03R2 (Pioneer Hi-Bred International, Johnston, Iowa, USA); SG4771 NRR and SG5161 NRR/STS (Soygenetics, LLC, Lafayette, Ind., USA); S00-K5, S11-L2, S28-Y2, S43-B1 , S53-A1 , S76-L9, S78-G6, S0009-M2; S007-Y4; S04-D3; S14-A6; S20-T6; S21-M7; S26-P3; S28-N6; S30-V6; S35-C3 ; S36-Y6; S39-C4; S47-K5; S48-D9; S52-Y2; S58- Z4; S67-R6; S73-S8; and S78-G6 (Syngenta Seeds, Henderson, Ky., USA); Richer (Northstar Seed Ltd. Alberta, CA); 14RD62 (Stine Seed Co. la., USA); or Armor 4744 (Armor Seed, LLC, Ar., USA).

Thus, in a further preferred embodiment, the compounds of formula (I) (including any one of compounds C-1 to C-78 or D-1 to D-19), or fungicidal compositions according to the present invention comprising a compound of formula (I), are used to control Phakopsora pachyrhizi, (including fungicidally-resistant strains thereof, as outlined herein) on Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome. Numerous benefits may be expected to ensue from said use, e.g. improved biological activity, an advantageous or broader spectrum of activity (inc. sensitive and resistant strains of Phakopsora pachyrhizi ), an increased safety profile, improved crop tolerance, synergistic interactions or potentiating properties, improved onset of action or a longer lasting residual activity, a reduction in the number of applications and/or a reduction in the application rate of the compounds and compositions required for effective control of the phytopathogen (Phakopsora pachyrhizi), thereby enabling beneficial resistance-management practices, reduced environmental impact and reduced operator exposure. Fungicidal-resistant strains of Phakopsora pachyrhizi have been reported in the scientific literature, with strains resistant to one or more fungicides from at least each of the following fungicidal mode of action classes being observed: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI). See for example: “Sensitivity of Phakopsora pachyrhizi towards quinone-outside-inhibitors and demethylation-inhibitors, and corresponding resistance mechanisms.” Schmitz HK et al, Pest Manag Sci (2014) 70: 378-388; “First detection of a SDH variant with reduced SDHI sensitivity in Phakopsora pachyrhizi" Simões K et al, J Plant Dis Prot (2018) 125: 21-2; “Competitive fitness of Phakopsora pachyrhizi isolates with mutations in the CYP51 and CYTB genes.” Klosowski AC et al, Phytopathology (2016) 106: 1278-1284; “Detection of the F129L mutation in the cytochrome b gene in Phakopsora pachyrhizi." Klosowski AC et al, Pest Manag Sci (2016) 72: 1211-1215.

Thus, in a preferred embodiment, the compounds of formula (I) (including any one of compounds C-1 to C-78 or D-1 to D-19), or fungicidal compositions according to the present invention comprising a compound of formula (I), are used to control Phakopsora pachyrhizi which are resistant to one or more fungicides from any of the following fungicidal MoA classes: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI).

The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.

The compounds of formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently Formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders ortackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants, e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular Formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular Formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers. Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosu coin ate salts, such as sodium di(2-ethylhexyl) sulfosu coin ate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

The compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably said composition may comprise at least one or more pesticidally-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula

(I)·

The compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides. Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano-naphthalen-5-yl)- amide , 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6- trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1), 1-methyl-3-difluoromethyl-1H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H- pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4- dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-me thanone, (5-Bromo-4-chloro-2-methoxy- pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1- methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-m ethoxyimino]-N-methyl-acetamide, 3-[5- (4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, (E)-N-methyl-2- [2- (2, 5- dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N, N-dimethyl-6- trifluoromethylbenzimidazole-1 -sulphonamide, a- [N-(3-chloro-2, 6-xylyl)-2-methoxyacetamido]-y- butyrolactone, 4-chloro-2-cyano-N,N - dimethyl-5-p-tolylimidazole-1 -sulfonamide, N-allyl-4, 5,-dimethyl- 2-trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1 , 2-dimethylpropyl)-2- (2, 4-dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl)-cyclopropane carboxamide, ( +-.)-cis-1-(4-chlorophenyl)-2-(1H- 1 ,2,4-triazol-1 -yl)-cycloheptanol, 2-(1 -tert-butyl)-1 -(2-chlorophenyl)-3-(1 ,2,4-triazol-1 -yl)-propan-2-ol, 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl -1 ,3-thiazole- 5-carboxanilide, 1-imidazolyl- 1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl (E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4- yloxy]phenyl]3-methoxyacrylate, methyl (E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3- methoxyacrylate, methyl (E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-met hoxyacrylate, methyl (E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3 -methoxyacryla te, methyl (E)-2-[2- [3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(5-methylpyrimidin-2- yloxy)-phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(phenyl-sulphonyloxy)phenoxy]phenyl-3- methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylat e, methyl (E)-2- [2-phenoxyphenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1 -yl]-3- methoxyacrylate, methyl (E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2[2-(2- phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3- methoxyacrylate, methyl (E)-2-(2-(3-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl (E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyac rylate, methyl (E)-2-(2-(4- phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3- methoxyacrylate, methyl (E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2- [3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-ethoxyphenoxy)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(4 -tert-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (E)-2- [2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[(3-methyl-pyridin-2- yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4- yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxy acrylate, methyl (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]pheny l]-3-methoxyac rylate, methyl (E),(E)-2-[2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-metho x yacrylate, methyl (E)-2-{2-[6-(6- methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-a crylate, methyl (E),(E)-2-{ 2-(3- methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate , methyl (E)-2-{2-(6-(2- azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[6-phenylpyrimidin-4- yl)-methyloximinomethyl]phenyl}-3-methox yacrylate, methyl (E),(E)-2-{2-[(4-chlorophenyl)- methyloximinomethyl]-phenyl}-3-methoxyacryl ate, methyl (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5- triazin-4-yloxy]phenyl}-3-methoxyacr ylate, methyl (E),(E)-2-{2-[(3- nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3- en-5-ine), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propinyl alcohol, 4- chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4- chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2- benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorf, benzohydroxamic acid, benzovindiflupyr, berberine, bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid, di-2- pyridyl disulphide 1 , 1 '-dioxide, dichlofluanid, diclomezine, dichlone, dicloran, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl- S-benzyl thiophosphate, dimefluazole, dimetachlone, dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl (Z)-N-benzyl-N ([methyl (methyl- thioethylideneamino- oxycarbonyl) amino] thio)-β-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexa chlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim- methyl, LY186054, LY211795, LY248908, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mefentrifluconazole, mepanipyrim, mepronil, mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax, milneb, moroxydine, myclobutanil, myclozolin, nabam, natamycin, neoasozin, nickel dimethyldithiocarbamate, nitrostyrene, nitrothal-iso- propyl, nuarimol, octhilinone, ofurace, organomercury compounds, orysastrobin, osthol, oxadixyl, oxasulfuron, oxathiapiprolin, oxine-copper, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol, parinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenamacril, phenazin oxide, phosdiphen, phosetyl-AI, phosphorus acids, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin D, polyoxrim, polyram, probenazole, prochloraz, procymidone, propamidine, propamocarb, propiconazole, propineb, propionic acid, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinacetol, quinazamid, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, santonin, sedaxane, silthiofam, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, urbacide, validamycin, valifenalate, vapam, vinclozolin, zarilamid, zineb, ziram, and zoxamide.

The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP-444964 and EP- 594291 . Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.

The compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.

The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.

The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.

The compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.

Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:

Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.

Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717. Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis-2,2-dimethyl-3-(2- oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta -cyfluthrin, cyfluthrin, a- cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.

Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1111 , R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301.

Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.

Bactericides: chlortetracycline, oxytetracycline, streptomycin.

Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.

Thus, compounds of formula (I) can be used in combination with one or more other active ingeredients to provide various fungicidal mixtures. Specific examples of such mixtures include (wherein “I” represents a compound of formula (I)): a compound selected from the group of substances consisting of petroleum oils + I, 1 ,1-bis(4-chloro-phenyl)-2-ethoxyethanol + I, 2,4-dichlorophenyl benzenesulfonate + I, 2-fluoro-N-methyl-N-1-naphthylacetamide + I, 4-chlorophenyl phenyl sulfone + I, acetoprole + I, aldoxycarb + I, amidithion + I, amidothioate + I, amiton + I, amiton hydrogen oxalate + I, amitraz + I, aramite + I, arsenous oxide + I, azobenzene + I, azothoate + I, benomyl + I, benoxa-fos + I, benzyl benzoate + I, bixafen + I, brofenvalerate + I, bromo-cyclen + I, bromophos + I, bromopropylate + I, buprofezin + I, butocarboxim + I, butoxycarboxim + I, butylpyridaben + I, calcium polysulfide + I, camphechlor + I, carbanolate + I, carbophenothion + I, cymiazole + I, chino-methionat + I, chlorbenside + I, chlordimeform + I, chlordimeform hydrochloride + I, chlorfenethol + I, chlorfenson + I, chlorfensulfide + I, chlorobenzilate + I, chloromebuform + I, chloromethiuron + I, chloropropylate + I, chlorthiophos + I, cinerin I + I, cinerin II + I, cinerins + I, closantel + I, coumaphos + I, crotamiton + I, crotoxyphos + I, cufraneb + I, cyanthoate + I, DCPM + I, DDT + I, demephion + I, demephion-O + I, demephion-S + I, demeton-methyl + I, demeton-O + I, demeton-O-methyl + I, demeton-S + I, demeton-S-methyl + I, demeton-S-methylsulfon + I, dichlofluanid + I, dichlorvos + I, dicliphos + I, dienochlor + I, dimefox + I, dinex + I, dinex-diclexine + I, dinocap-4 + I, dinocap-6 + I, dinocton + I, dino-penton + I, dinosulfon + I, dinoterbon + I, dioxathion + I, diphenyl sulfone + I, disulfiram + I, DNOC + I, dofenapyn + I, doramectin + I, endothion + I, eprinomectin + I, ethoate-methyl + I, etrimfos + I, fenazaflor + I, fenbutatin oxide + I, fenothiocarb + I, fenpyrad + I, fen-pyroximate + I, fenpyrazamine + I, fenson + I, fentrifanil + I, flubenzimine + I, flucycloxuron + I, fluenetil + I, fluorbenside + I, FMC 1137 + I, formetanate + I, formetanate hydrochloride + I, formparanate + I, gamma-HCH + I, glyodin + I, halfenprox + I, hexadecyl cyclopropanecarboxylate + I, isocarbophos + I, jasmolin I + I, jasmolin II + I, jodfenphos + I, lindane + I, malonoben + I, mecarbam + I, mephosfolan + I, mesulfen + I, methacrifos + I, methyl bromide + I, metolcarb + I, mexacarbate + I, milbemycin oxime + I, mipafox + I, monocrotophos + I, morphothion + I, moxidectin + I, naled + I, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)m ethoxy]pyridazin- 3-one + I, nifluridide + I, nikkomycins + I, nitrilacarb + I, nitrilacarb 1 :1 zinc chloride complex + I, omethoate + I, oxydeprofos + I, oxydisulfoton + I, pp'-DDT + I, parathion + I, permethrin + I, phenkapton + I, phosalone + I, phosfolan + I, phosphamidon + I, polychloroterpenes + I, polynactins + I, proclonol + I, promacyl + I, propoxur + I, prothidathion + I, prothoate + I, pyrethrin I + I, pyrethrin II + I, pyrethrins + I, pyridaphenthion + I, pyrimitate + I, quinalphos + I, quintiofos + I, R-1492 + I, phosglycin + I, rotenone + I, schradan + I, sebufos + I, selamectin + I, sophamide + I, SSI-121 + I, sulfiram + I, sulfluramid + I, sulfotep + I, sulfur + I, diflovidazin + I, tau-fluvalinate + I, TEPP + I, terbam + I, tetradifon + I, tetrasul + I, thiafenox + I, thiocarboxime + I, thiofanox + I, thiometon + I, thioquinox + I, thuringiensin + I, triamiphos + I, triarathene + I, triazophos + I, triazuron + I, trifenofos + I, trinactin + I, vamidothion + I, vaniliprole + I, bethoxazin + I, copper dioctanoate + I, copper sulfate + I, cybutryne + I, dichlone + I, dichlorophen + I, endothal + I, fentin + I, hydrated lime + I, nabam + I, quinoclamine + I, quinonamid + I, simazine + I, triphenyltin acetate + I, triphenyltin hydroxide + I, crufomate + I, piperazine + I, thiophanate + I, chloralose + I, fenthion + I, pyridin-4-amine + I, strychnine + I, 1 -hydroxy-1 H-pyridine-2-thione + I, 4- (quinoxalin-2-ylamino)benzenesulfonamide + I, 8-hydroxyquinoline sulfate + I, bronopol + I, copper hydroxide + I, cresol + I, dipyrithione + I, dodicin + I, fenaminosulf + I, formaldehyde + I, hydrargaphen + I, kasugamycin + I, kasugamycin hydrochloride hydrate + I, nickel bis(dimethyldithiocarbamate) + I, nitrapyrin + I, octhilinone + I, oxolinic acid + I, oxytetracycline + I, potassium hydroxyquinoline sulfate + I, probenazole + I, streptomycin + I, streptomycin sesquisulfate + I, tecloftalam + I, thiomersal + I, Adoxophyes orana GV + I, Agrobacterium radiobacter + I, Amblyseius spp. + I, Anagrapha falcifera NPV + I, Anagrus atomus + I, Aphelinus abdominalis + I, Aphidius colemani + I, Aphidoletes aphidimyza + I, Autographa californica NPV + I, Bacillus sphaericus Neide + I, Beauveria brongniartii + I, Chrysoperla carnea + I, Cryptolaemus montrouzieri + I, Cydia pomonella GV + I, Dacnusa sibirica + I, Diglyphus isaea + I, Encarsia formosa + I, Eretmocerus eremicus + I, Heterorhabditis bacteriophora and H. megidis + I, Hippodamia convergens + I, Leptomastix dactylopii + I, Macrolophus caliginosus + I, Mamestra brassicae NPV + I, Metaphycus helvolus + I, Metarhizium anisopliae var. acridum + I, Metarhizium anisopliae var. anisopliae + I, Neodiprion sertifer NPV and N. lecontei NPV + I, Orius spp. + I, Paecilomyces fumosoroseus + I, Phytoseiulus persimilis + I, Steinernema bibionis + I, Steinernema carpocapsae + I, Steinernema feltiae + I, Steinernema glaseri + I, Steinernema riobrave + I, Steinernema riobravis + I, Steinernema scapterisci + I, Steinernema spp. + I, Trichogramma spp. + I, Typhlodromus occidentalis + I , Verticillium lecanii + I, apholate + I, bisazir + I, busulfan + I, dimatif + I, hemel + I, hempa + I, metepa + I, methiotepa + I, methyl apholate + I, morzid + I, penfluron + I, tepa + I, thiohempa + I, thiotepa + I, tretamine + I, uredepa + I, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + I, (E)- tridec-4-en-1-yl acetate + I, (E)-6-methylhept-2-en-4-ol + I, (E,Z)-tetradeca-4,10-dien-1-yl acetate + I, (Z)-dodec-7-en-1-yl acetate + I, (Z)-hexadec-11-enal + I, (Z)-hexadec-11 -en-1 -yl acetate + I, (Z)- hexadec-13-en-11 -yn-1 -yl acetate + I, (Z)-icos-13-en-10-one + I, (Z)-tetradec-7-en-1-al + I, (Z)-tetradec- 9-en-1-ol + I, (Z)-tetradec-9-en-1-yl acetate + I, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + I, (9Z,11 E)- tetradeca-9,11 -dien-1 -yl acetate + I, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + 1, 14-methyloctadec-1- ene + I, 4-methylnonan-5-ol with 4-methylnonan-5-one + I, alpha-multistriatin + I, brevicomin + I, codlelure + I, codlemone + I, cuelure + I, disparlure + I, dodec-8-en-1-yl acetate + I, dodec-9-en-1-yl acetate + I, dodeca-8 + 1, 10-dien-1 -yl acetate + I, dominicalure + I, ethyl 4-methyloctanoate + I, eugenol + I, frontalin + I, grandlure + I, grandlure I + I, grandlure II + I, grandlure III + I, grandlure IV + I, hexalure + I, ipsdienol + I, ipsenol + I, japonilure + I, lineatin + I, litlure + I, looplure + I, medlure + I, megatomoic acid + I, methyl eugenol + I, muscalure + I, octadeca-2,13-dien-1-yl acetate + I, octadeca-3,13-dien-1- yl acetate + I, orfralure + I, oryctalure + I, ostramone + I, siglure + I, sordidin + I, sulcatol + I, tetradec- 11 -en-1 -yl acetate + I, trimedlure + I, trimedlure A + I, trimedlure B1 + I, trimedlure B2 + I, trimedlure C + I, trunc-call + I, 2-(octylthio)-ethanol + I, butopyronoxyl + I, butoxy(polypropylene glycol) + I, dibutyl adipate + I, dibutyl phthalate + I, dibutyl succinate + I, diethyltoluamide + I, dimethyl carbate + I, dimethyl phthalate + I, ethyl hexanediol + I, hexamide + I, methoquin-butyl + I, methylneodecanamide + I, oxamate + I, picaridin + I, 1-dichloro-1-nitroethane + I, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)-ethane + I,

1 .2-dichloropropane with 1 ,3-dichloropropene + I, 1-bromo-2-chloroethane + I, 2,2,2-trichloro-1-(3,4- dichloro-phenyl)ethyl acetate + I, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + I, 2-(1 ,3- dithiolan-2-yl)phenyl dimethylcarbamate + I, 2-(2-butoxyethoxy)ethyl thiocyanate + I, 2-(4,5-dimethyl-

1 .3-dioxolan-2-yl)phenyl methylcarbamate + I, 2-(4-chloro-3,5-xylyloxy)ethanol + I, 2-chlorovinyl diethyl phosphate + I, 2-imidazolidone + I, 2-isovalerylindan-1 ,3-dione + I, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + I, 2-thiocyanatoethyl laurate + I, 3-bromo-1-chloroprop-1-ene + I, 3-methyl-1- phenylpyrazol-5-yl dimethyl-carbamate + I, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + I, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + I, acethion + I, acrylonitrile + I, aldrin + I, allosamidin + I, allyxycarb + I, alpha-ecdysone + I, aluminium phosphide + I, aminocarb + I, anabasine + I, athidathion + I, azamethiphos + I, Bacillus thuringiensis delta endotoxins + I, barium hexafluorosilicate + I, barium polysulfide + I, barthrin + I, Bayer 22/190 + I, Bayer 22408 + I, beta- cyfluthrin + I, beta-cypermethrin + I, bioethanomethrin + I, biopermethrin + I, bis(2-chloroethyl) ether + I, borax + I, bromfenvinfos + I, bromo-DDT + I, bufencarb + I, butacarb + I, butathiofos + I, butonate + I, calcium arsenate + I, calcium cyanide + I, carbon disulfide + I, carbon tetrachloride + I, cartap hydrochloride + I, cevadine + I, chlorbicyclen + I, chlordane + I, chlordecone + I, chloroform + I, chloropicrin + I, chlorphoxim + I, chlorprazophos + I, cis-resmethrin + I, cismethrin + I, clocythrin + I, copper acetoarsenite + I, copper arsenate + I, copper oleate + I, coumithoate + I, cryolite + I, CS 708 + I, cyanofenphos + I, cyanophos + I, cyclethrin + I, cythioate + I, d-tetramethrin + I, DAEP + I, dazomet + I, decarbofuran + I, diamidafos + I, dicapthon + I, dichlofenthion + I, dicresyl + I, dicyclanil + I, dieldrin + I, diethyl 5-methylpyrazol-3-yl phosphate + I, dilor + I, dimefluthrin + I, dimetan + I, dimethrin + I, dimethylvinphos + I, dimetilan + I, dinoprop + I, dinosam + I, dinoseb + I, diofenolan + I, dioxabenzofos + I, dithicrofos + I, DSP + I, ecdysterone + I, El 1642 + I, EMPC + I, EPBP + I, etaphos + I, ethiofencarb + I, ethyl formate + I, ethylene dibromide + I, ethylene dichloride + I, ethylene oxide + I, EXD + I, fenchlorphos + I, fenethacarb + I, fenitrothion + I, fenoxacrim + I, fenpirithrin + I, fensulfothion + I, tenth ion-ethyl + I, flucofuron + I, fosmethilan + I, fospirate + I, fosthietan + I, furathiocarb + I, furethrin + I, guazatine + I, guazatine acetates + I, sodium tetrathiocarbonate + I, halfenprox + I, HCH + I, HEOD + I, heptachlor + I, heterophos + I, HHDN + I, hydrogen cyanide + I, hyquincarb + I, IPSP + I, isazofos + I, isobenzan + I, isodrin + I, isofenphos + I, isolane + I, isoprothiolane + I, isoxathion + I, juvenile hormone I + I, juvenile hormone II + I, juvenile hormone III + I, kelevan + I, kinoprene + I, lead arsenate + I, leptophos + I, lirimfos + I, lythidathion + I, m-cumenyl methylcarbamate + I, magnesium phosphide + I, mazidox + I, mecarphon + I, menazon + I, mercurous chloride + I, mesulfenfos + I, metam + I, metam- potassium + I, metam-sodium + I, methanesulfonyl fluoride + I, methocrotophos + I, methoprene + I, methothrin + I, methoxychlor + I, methyl isothiocyanate + I, methylchloroform + I, methylene chloride + I, metoxadiazone + I, mirex + I, naftalofos + I, naphthalene + I, NC-170 + I, nicotine + I, nicotine sulfate + I, nithiazine + I, nornicotine + I, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + I, O.O- diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + I, O,O-diethyl O-6-methyl-2- propylpyrimidin-4-yl phosphorothioate + I, O,O,O',O'-tetrapropyl dithiopyrophosphate + I, oleic acid + I, para-dichlorobenzene + I, parathion-methyl + I, pentachlorophenol + I, pentachlorophenyl laurate + I, PH 60-38 + I, phenkapton + I, phosnichlor + I, phosphine + I, phoxim-methyl + I, pirimetaphos + I, polychlorodicyclopentadiene isomers + I, potassium arsenite + I, potassium thiocyanate + I, precocene I + I, precocene II + I, precocene III + I, primidophos + I, profluthrin + I, promecarb + I, prothiofos + I, pyrazophos + I, pyresmethrin + I, quassia + I, quinalphos-methyl + I, quinothion + I, rafoxanide + I, resmethrin + I, rotenone + I, kadethrin + I, ryania + I, ryanodine + I, sabadilla) + I, schradan + I, sebufos + I, SI-0009 + I, thiapronil + I, sodium arsenite + I, sodium cyanide + I, sodium fluoride + I, sodium hexafluorosilicate + I, sodium pentachlorophenoxide + I, sodium selenate + I, sodium thiocyanate + I, sulcofuron + I, sulcofuron-sodium + I, sulfuryl fluoride + I, sulprofos + I, tar oils + I, tazimcarb + I, TDE + I, tebupirimfos + I, temephos + I, terallethrin + I, tetrachloroethane + I, thicrofos + I, thiocyclam + I, thiocyclam hydrogen oxalate + I, thionazin + I, thiosultap + I, thiosultap-sodium + I, tralomethrin + I, transpermethrin + I, triazamate + I, trichlormetaphos-3 + I, trichloronat + I, trimethacarb + I, tolprocarb + I, triclopyricarb + I, triprene + I, veratridine + I, veratrine + I, XMC + I, zetamethrin + I, zinc phosphide + I, zolaprofos + I, and meperfluthrin + I, tetramethylfluthrin + I, bis(tributyltin) oxide + I, bromoacetamide + I, ferric phosphate + I, niclosamide-olamine + I, tributyltin oxide + I, pyrimorph + I, trifenmorph + I, 1 ,2- dibromo-3-chloropropane + I, 1 ,3-dichloropropene + I, 3,4-dichlorotetrahydrothio-phene 1 ,1-dioxide + I, 3-(4-chlorophenyl)-5-methylrhodanine + I, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + I, 6- isopentenylaminopurine + I, anisiflupurin + I, benclothiaz + I, cytokinins + I, DCIP + I, furfural + I, isamidofos + I, kinetin + I, Myrothecium verrucaria composition + I, tetrachlorothiophene + I, xylenols + I, zeatin + I, potassium ethylxanthate + I .acibenzolar + I, acibenzolar-S-methyl + I, Reynoutria sachalinensis extract + I, alpha-chlorohydrin + I, antu + I, barium carbonate + I, bisthiosemi + I, brodifacoum + I, bromadiolone + I, bromethalin + I, chlorophacinone + I, cholecalciferol + I, coumachlor + I, coumafuryl + I, coumatetralyl + I, crimidine + I, difenacoum + I, difethialone + I, diphacinone + I, ergocalciferol + I, flocoumafen + I, fluoroacetamide + I, flupropadine + I, flupropadine hydrochloride + I, norbormide + I, phosacetim + I, phosphorus + I, pindone + I, pyrinuron + I, scilliroside + I, -sodium fluoroacetate + I, thallium sulfate + I, warfarin + I, -2-(2-butoxyethoxy)ethyl piperonylate + I, 5-(1 ,3- benzodioxol-5-yl)-3-hexylcyclohex-2-enone + I, farnesol with nerolidol + I, verbutin + I, MGK 264 + I, piperonyl butoxide + I, piprotal + I, propyl isomer + I, S421 + I, sesamex + I, sesasmolin + I, sulfoxide + I, anthraquinone + I, copper naphthenate + I, copper oxychloride + I, dicyclopentadiene + I, thiram + I, zinc naphthenate + I, ziram + I, imanin + I, ribavirin + I, chloroinconazide + I, mercuric oxide + I, thiophanate-methyl + I, azaconazole + I, bitertanol + I, bromuconazole + I, cyproconazole + I, difenoconazole + I, diniconazole -+ I, epoxiconazole + I, fenbuconazole + I, fluquinconazole + I, flusilazole + I, flutriafol + I, furametpyr+ I, hexaconazole + I, imazalil- + I, imiben-conazole + I, ipconazole + I, metconazole + I, myclobutanil + I, paclobutrazole + I, pefurazoate + I, penconazole + I, prothioconazole + I, pyrifenox + I, prochloraz + I, propiconazole + I, pyrisoxazole + I, -simeconazole + I, tebucon-azole + I, tetraconazole + I, triadimefon + I, triadimenol + I, triflumizole + I, triticonazole + I, ancymidol + I, fenarimol + I, nuarimol + I, bupirimate + I, dimethirimol + I, ethirimol + I, dodemorph + I, fenpropidin + I, fenpropimorph + I, spiroxamine + I, tridemorph + I, cyprodinil + I, mepanipyrim + I, pyrimethanil + I, fenpiclonil + I, fludioxonil + I, benalaxyl + I, furalaxyl + I, -metalaxyl -+ I, Rmetalaxyl + I, ofurace + I, oxadixyl + I, carbendazim + I, debacarb + I, fuberidazole -+ I, thiabendazole + I, chlozolinate + I, dichlozoline + I, myclozoline- + I, procymidone + I, vinclozoline + I, boscalid + I, carboxin + I, fenfuram + I, flutolanil + I, mepronil + I, oxycarboxin + I, penthiopyrad + I, thifluzamide + I, dodine + I, iminoctadine + I, azoxystrobin + I, dimoxystrobin + I, enestroburin + I, fenaminstrobin + I, flufenoxystrobin + I, fluoxastrobin + I, kresoxim-methyl + I, metominostrobin + I, trifloxystrobin + I, orysastrobin + I, picoxystrobin + I, pyraclostrobin + I, pyrametostrobin + I, pyraoxystrobin + I, ferbam + I, mancozeb + I, maneb + I, metiram + I, propineb + I, zineb + I, captafol + I, captan + I, fluoroimide + I, folpet + I, tolylfluanid + I, bordeaux mixture + I, copper oxide + I, mancopper + I, oxine-copper + I, nitrothal- isopropyl + I, edifenphos + I, iprobenphos + I, phosdiphen + I, tolclofos-methyl + I, anilazine + I, benthiavalicarb + I, blasticidin-S + I, chloroneb -+ I, chloro-tha-lonil + I, cyflufenamid + I, cymoxanil + I, cyclobutrifluram + I, diclocymet + I, diclomezine -+ I, dicloran + I, diethofencarb + I, dimethomorph -+ I, flumorph + I, dithianon + I, ethaboxam + I, etridiazole + I, famoxadone + I, fenamidone + I, fenoxanil + I, ferimzone + I, fluazinam + I, flumetylsulforim + I, fluopicolide + I, fluoxytioconazole + I, flusulfamide + I, fluxapyroxad + I, fenhexamid + I, fosetyl-aluminium -+ I, hymexazol + I, iprovalicarb + I, cyazofamid + I, methasulfocarb + I, metrafenone + I, pencycuron + I, phthalide + I, polyoxins + I, propamocarb + I, pyribencarb + I, proquinazid + I, pyroquilon + I, pyriofenone + I, quinoxyfen + I, quintozene + I, tiadinil + I, triazoxide + I, tricyclazole + I, triforine + I, validamycin + I, valifenalate + I, zoxamide + I, mandipropamid + I, flubeneteram + I, isopyrazam + I, sedaxane + I, benzovindiflupyr + I, pydiflumetofen + I, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + I, isoflucypram + I, isotianil + I, dipymetitrone + I, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2- c]isothiazole-3-carbonitrile + I, 2-(difluoromethyl)-N-[3-ethyl-1 , 1 -dimethyl-indan-4-yl]pyrid ine-3- carboxamide + I, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbon itrile + I, (R)-3- (difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + I, 4-(2-bromo-4-fluoro- phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3- amine + I, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1 , 3- dimethyl- 1 H- pyrazol- 5- amine + I, fluindapyr + I, coumethoxystrobin (jiaxiangjunzhi) + I, Ivbenmixianan + I, dichlobentiazox + I, mandestrobin + I, 3-(4,4- difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + I, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol + I, oxathiapiprolin + I, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + I, pyraziflumid + I, inpyrfluxam + I, trolprocarb + I, mefentrifluconazole + I, ipfentrifluconazole+ I, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4- yl]pyridine-3-carboxamide + I, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamid ine + I, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-e thyl-N-methyl-formamidine + I, [2-[3-[2-[1-[2- [3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thi azol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro- phenyl] methanesulfonate + I, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + I, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-

2-methyl-phenyl]methyl]carbamate + I, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazi ne + I, pyridachlometyl + I, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + I, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-ph enyl]-4-methyl-tetrazol-5-one + I, 1- methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one + I, aminopyrifen + I, ametoctradin + I, amisulbrom + I, penflufen + I, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-

3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + I, florylpicoxamid + I, fenpicoxamid + I, metarylpicoxamid + I, tebufloquin + I, ipflufenoquin + I, quinofumelin + I, isofetamid + I, N-[2-[2,4- dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazol e-4-carboxamide + I, N-[2-[2-chloro-4- (trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl -pyrazole-4-carboxamide + I, benzothiostrobin + I, phenamacril + I, 5-amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2:1) + I, fluopyram + I, flufenoxadiazam + I, flutianil + I, fluopimomide + I, pyrapropoyne + I, picarbutrazox + I, 2- (difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + I, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + I, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1- difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + I, metyltetraprole + I, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + I, a- (1 , 1- dimethylethyl) - a- [4'- (trifluoromethoxy) [1 , 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + I, fluoxapiprolin + I, enoxastrobin + I, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy] benzonitrile + I, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4- triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + I, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3- (5-thioxo-4H-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + I, trinexapac + I, coumoxystrobin + I, zhongshengmycin + I, thiodiazole copper + I, zinc thiazole + I, amectotractin + I, iprodione + I, seboctylamine + I; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-py ridyl]-N-ethyl-N- methyl-formamidine + I, N'-[5-bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N- methyl-formamidine + I, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl ]-N-ethyl-N- methyl-formamidine + I, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridy l]-N-ethyl-N- methyl-formamidine + I, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl ]-N-isopropyl-N- methyl-formamidine + I (these compounds may be prepared from the methods described in

WO2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl -N-methyl- formamidine + I (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4-(2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl- formamidine+ I, N’-[4-(1 -cyclopropyl-2, 2, 2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N- isopropyl-N-methyl-formamidine + I (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxeta n-2-yl]phenyl]-N-methyl- formamidine + I, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifuoromethyl)tetrah ydrofuran-2-yl]phenyl]-N- methyl-formamidine + I (these compounds may be prepared from the methods described in

WO2019/110427); N-[(1 R)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + I, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quin oline-3-carboxamide + I, N-[(1 R)-1- benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide + I , N-[(1 S)-1 -benzyl-3, 3,3- trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + I, N-[(1 R)-1 -benzyl-1 ,3-dimethyl-butyl]- 7,8-difluoro-quinoline-3-carboxamide + I, N-[(1S)-1 -benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3- carboxamide + I, 8-fluoro-N-[(1 R)-1-[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3- carboxamide + I, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3- carboxamide + I, N-[(1 R)-1 -benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + I, N-[(1S)-1- benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + I, N-((1 R)-1-benzyl-3-chloro-1-methyl- but-3-enyl)-8-fluoro-quinoline-3-carboxamide + I , N-((1 S)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl)-8- fluoro-quinoline-3-carboxamide + I (these compounds may be prepared from the methods described in WO2017/153380); 1-(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4, 4, 5-trifluoro-3, 3-dimethyl-isoquinoline + I, 1-(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4, 4, 6-trifluoro-3, 3-dimethyl-isoquinoline + I, 4,4-difluoro-

3.3-dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + I, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + I, 1-(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3-yl)-4,4- difluoro-3, 3-dimethyl-isoquinoline + I (these compounds may be prepared from the methods described in WO2017/025510); 1 -(4, 5-dimethylbenzimidazol-1-yl)-4, 4, 5-trifluoro-3, 3-dimethyl-isoquinoline + 1, 1- (4, 5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3, 3-dimethyl-isoquinoline + I, 6-chloro-4,4-difluoro-3,3- dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline + 1 , 4,4-difluoro-1 -(5-fluoro-4-methyl-benzimidazol- 1 -yl)-3, 3-dimethyl-isoquinoline + I, 3-(4,4-difluoro-3,3-dimethyl-1 -isoquinolyl)-7,8-dihydro-6H- cyclopenta[e]benzimidazole + I (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + I, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + I, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + I, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea + I, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + I, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + I, N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + I,

4.4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + I, 5,5- dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + I, ethyl 1-[[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + I, N,N-dimethyl-1-[[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine + I. The compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4- triazol-1-yl)propan-2-ol + I (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol + I (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1- chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imida zole-4-carbonitrile + I (this compound may be prepared from the methods described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-

2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitril e + I (this compound may be prepared from the methods described in WO 2016/156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate + I (this compound may be prepared from the methods described in WO 2014/006945); 2,6- Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone + I (this compound may be prepared from the methods described in WO 2011/138281); N-methyl-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzenecarbothioamide + I; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yljbenzamide + I; (Z,2E)-5-[1 -(2, 4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N, 3-dimethyl-pent-

3-enamide + I (this compound may be prepared from the methods described in WO 2018/153707); N'-

(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-for mamidine + I; N'-[2-chloro-4-(2- fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + I (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl- indan-4-yl]pyridine-3-carboxamide + I (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + I, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + I (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide + I (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]pyrazole-4-carboxylate + I (this compound may be prepared from the methods described in WO 2018/158365) ; 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]acetamide + I, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yljbenzamide + I, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + I, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]benzamide + I (these compounds may be prepared from the methods described in WO 2018/202428)..

The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names. Copyright © 1995- 2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula (I) and an active ingredient as described above are preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 : 1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula (I) and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients) as described above, is not essential for working the present invention.

The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds of formula (I) for the preparation of these compositions are also a subject of the invention.

Another aspect of the invention is related to the use of a compound of formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.

A further aspect of the invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.

Controlling or preventing means reducing infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.

A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation, e.g. a composition containing the compound of formula (I), and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants). Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.

When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of formula I per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.

Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the ondensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The compounds according to the following Tables B-1 to B-12 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I).

Table A: This table discloses 165 substituent definitions of the formula (Id): wherein the R ³ substituents are as defined below:

Table A: Substituent definitions of R ³ :

The following compounds are thus specifically described:

Table B-1 : This table provides 165 compounds B-1.001 to B-1.165 of formula (Id) wherein R ¹ is hydrogen, R ² is hydrogen, A ¹ is O and R ³ are as defined in table A.

For example, compound B-1.036 has the following structure;

Table B-2: This table provides 165 compounds B-2.001 to B-2.165 of formula (Id) wherein R ¹ is CH ₃ , R ² is hydrogen, A ¹ is O and R ³ are as defined in table A. Table B-3: This table provides 165 compounds B-3.001 to B-3.165 of formula (Id) wherein R ¹ is F, R ² is hydrogen, A ¹ is O and R ³ are as defined in table A.

Table B-4: This table provides 165 compounds B-4.001 to B-4.165 of formula (le); wherein R ¹ is hydrogen, R ² is hydrogen, A ² is O and R ³ are as defined in table A. For example, compound B-4.036 has the following structure;

B-4.036

Table B-5: This table provides 165 compounds B-5.001 to B-5.165 of formula (le) wherein R ¹ is hydrogen, R ² is hydrogen, A ² is NH and R ³ are as defined in table A.

Table B-6: This table provides 165 compounds B-6.001 to B-6.165 of formula (le) wherein R ¹ is CH ₃ , R ² is hydrogen, A ² is O and R ³ are as defined in table A.

Table B-7: This table provides 165 compounds B-7.001 to B-7.165 of formula (le) wherein R ¹ is CH ₃ , R ² is hydrogen, A ² is NH and R ³ are as defined in table A.

Table B-8: This table provides 165 compounds B-8.001 to B-8.165 of formula (le) wherein R ¹ is F, R ² is hydrogen, A ² is O and R ³ are as defined in table A.

Table B-9: This table provides 165 compounds B-9.001 to B-9.165 of formula (le) wherein R ¹ is F, R ² is hydrogen, A ² is NH and R ³ are as defined in table A.

Table B-10: This table provides 165 compounds B-10.001 to B-10.165 of formula (If) wherein R ¹ is hydrogen, R ² is hydrogen, A ³ is O and R ³ are as defined in table A. For example, compound B-10.036 has the following structure;

Table B-11 : This table provides 165 compounds B-11.001 to B-11.165 of formula (If) wherein R ¹ is CH ₃ , R ² is hydrogen, A ³ is O and R ³ are as defined in table A.

Table B-12: provides 165 compounds B-12.001 to B-12.165 of formula (If) wherein R ¹ is F, R ² is hydrogen, A ³ is O and R ³ are as defined in table A.

EXAMPLES

The Examples which follow serve to illustrate the invention.

The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1 .5 ppm, 0.8 ppm or 0.2 ppm.

Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

Throughout this description, temperatures are given in degrees Celsius (°C) and “mp.” means melting point. LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods is as follows: Method A:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 L/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 2.8 μm, 30 x2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 1.2 min; Flow (mL/min) 0.85

Method B:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 2.8 μm, 30 x2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 2.7 min; Flow (ml/min) 0.85

Method C:

Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature:

150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 2.8 μm, 30 x2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1% formic acid, B= Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.

Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.

Formulation Examples

Wettable powders a) b) c) Active ingredient [compound of Formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 %

(7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 %

Kaolin 62 % 27 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions of the desired concentration.

Powders for dry seed treatment a) b) c)

Active ingredient [compound of Formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %

Kaolin 65 % 40 %

Talcum 20 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of Formula (I)] 10 % octylphenol polyethylene glycol ether 3 %

(4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %

Cyclohexanone 30 % xylene mixture 50 %

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts a) b) c)

Active ingredient [compound of Formula (I)] 5 % 6 % 4 %

Talcum 95 %

Kaolin - 94 % mineral filler 96 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder granules

Active ingredient [compound of Formula (I)] 15 % sodium lignosulfonate 2 %

Carboxymethylcellulose 1 %

Kaolin 82 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules

Active ingredient [compound of Formula (I)] 8 % polyethylene glycol (mol. wt. 200) 3 %

Kaolin 89 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate

Active ingredient [compound of Formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

Sodium lignosulfonate 10 %

Carboxymethylcellulose 1 %

Silicone oil (in the form of a 75 % emulsion in water) 1 %

Water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment

Active ingredient [compound of Formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow-Release Capsule Suspension

28 parts of a combination of the compound of Formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension Formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

List of Abbreviations:

Aq. ^; aqueous br s ^; broad singlet °C ^; degrees Celsius

DCM ^; dichloromethane

DME dimethoxyethane

DMF ^; dimethylformamide

DMSO ^; dimethyl sulfoxide

DMSO-d ₆ ^; deuterated dimethyl sulfoxide d ^; doublet dd ^; doublet of doublet

EtOAc ^; ethyl acetate equiv. ^; equivalent h ^; hour(s)

M ^; molar m ^; mulitplet min ^; minutes

MHz ^; mega hertz mp = melting point

Pd ₂ (dba) ₃ = tris(dibenzylideneacetone)dipalladium(0)

Pd(dppf)CI ₂ · DCM = [1 ,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(ll), dichloromethane complex

Pd(PPh ₃ ) ₂ CI ₂ = bis(triphenylphosphine) palladium (II) dichloride S-Phos: Pd(crotyl)CI =chloro(crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxy-1 ,1 biphenyl)palladium(ll)

X-Phos Pd G2 = chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1'-biphenyl)[2-(2'- amino-1 ,1'-biphenyl)]palladium(ll) ppm = parts per million

RT = room temperature

R _t = retention time s = singlet t = triplet

THF = tetrahydrofuran

LC/MS = Liquid Chromatography Mass Spectrometry (description of the apparatus and the methods used for LC/MS analysis are given above)

Preparation Examples

Using the synthetic techniques described both above and below, compounds of formula (I) may be prepared accordingly.

Example 1 ; Preparation of Methyl (E)-2-(benzothiophen-5-yl)-3-methoxy-prop-2-enoate

Step A: Preparation of methyl (Z)-2-iodo-3-methoxy-prop-2-enoate To a solution of methyl trans-3-methoxyacrylate (20.0 g, 18.7 mL, 172.2 mmol) in dichloromethane (350 mL ) was added N-iodo succinimide (43.94 g, 189.5 mmol) in small portions. Acetic acid (19.9 mL, 344.5 mmol) was then added dropwise at room temperature and the resulting suspension was stirred for 22 hours at room temperature. Triethyl amine (72.2 mL, 516.7 mmol) was then added dropwise at room temperature while keeping the temperature constant with a water bath. Upon completed addition, the brown solution that was stirred for another 3 hours until LC-MS indicated complete conversion to the desired product. A mixture of Na ₂ S ₂ O ₃ sat. and NaHC O ₃ sat. was added, the layers were separated and the aqueous layer extracted with dichloromethane. The combined organic layers were washed with NaHCO ₃ , Na ₂ S ₂ O ₃ and with brine. Dried over Na ₂ SO ₄ anhydrous, filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel eluting with a gradient of 0% ethyl acetate/cyclohexane to 100% ethyl acetate/cyclohexane to yield methyl (Z)-2-iodo-3-methoxy-prop-2- enoate as a brown solid.

LC/MS (Method A): m/z = 243 [M+H], rt = 0.76 min

NMR: ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.80 (s, 3 H) 4.02 (s, 3 H) 7.67 - 7.75 (m, 1 H).

Step B: Preparation of 2-(Benzothiophen-5-yl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane

To a solution of 5-bromobenzothiophene (3.0 g, 14.1 mmol) in dioxane (70 mL), was added potassium acetate (2.8g, 28.2 mmol) and bis(pinacolato)diboron (5.417 g, 22.11 mmol). The solution was degassed with an argon flux for 5 min then PdCb(dppf) DCM (2.08 g, 2.41 mmol) was added. The resulting reddish mixture was stirred at 100°C for 90 min. After cooling to room temperature, the brown solution was diluted with ethyl acetate and water. The layers were separated, and the organic phase was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% ethyl acetate/cyclohexane to 45% ethyl acetate/cyclohexane to yield 2-(benzothiophen-5-yl)-4, 4, 5, 5-tetramethyl-1 ,3,2-dioxaborolane as an orange solid.

LC/MS (Method A): r.t. 1 .20 (MH+) m/z = 249 [M+H] ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 2.40 (s, 12 H) 7.38 (d, 1 H) 7.44 (d, 1 H) 7.77 (dd, 1 H) 7.91 (d, 1 H) 8.34 (s, 1 H).

Step C: Methyl (E)-2-(benzothiophen-5-yl)-3-methoxy-prop-2-enoate (Compound C-15, Table C)

To a solution of 2-(benzothiophen-5-yl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (4.75 g, 13.0 mmol) and methyl (Z)-2-iodo-3-methoxy-prop-2-enoate (3.76 g, 15.6 mmol) in dioxane (65 mL ) and water (2.6 mL ), was added K ₃ PO ₄ (5.56 g, 25.9 mmol) and Pd(OAc)2 (0.148 g, 0.648 mmol) and butyldi-1- adamantylphosphine (0.474 g, 2.30 mmol). The solution was degassed with an argon flux for 5 min. The resulting brown solution was stirred at 100°C for 2 hours, cooled to room temperature and diluted with ethyl acetate and water. The layers were separated, and the organic phase was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% ethyl acetate/cyclohexane to 25% ethyl acetate/cyclohexane to get methyl (E)-2-(benzothiophen-5-yl)-3-methoxy-prop-2-enoate as a brown solid. LC/MS (Method A): m/z = 249 [M+H], rt= 0.99 min 1H NMR (400 MHz, CDCI ₃ ) δ ppm 3.78 (s, 3 H) 3.89 (s, 3 H) 7.30 - 7.35 (m, 2 H) 7.44 (d, 1 H) 7.64 (s, 1 H) 7.81 (d, 1 H) 7.87 (d, 1 H).

Example 2; Preparation of Methyl (E)-3-methoxy-2-(3-phenylbenzothiophen-5-yl)prop-2-enoate

(Compound C-76, Table C)

To a solution of methyl (E)-2-(benzothiophen-5-yl)-3-methoxy-prop-2-enoate (0.20 g, 0.81 mmol) in 1 ,2- dichloroethane (3 mL ), was added phenylboronic acid (0.40 g, 3.22 mmol), TEMPO (0.51 g, 3.22 mmol) followed by 2,2'-bipyridine (0.013 g, 0.081 mmol) and Pd(OAc) ₂ (0.018 g, 0.081 mmol). The resulting brown solution was stirred at 100°C for 2 hours, cooled to room temperature and quenched with saturated NaHCO ₃ solution. The mixture was then extracted with dichloromethane, the organic phase was washed with Na ₂ S ₂ O ₃ solution and with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% ethyl acetate/cyclohexane to 60% ethyl acetate/cyclohexane to yield a yellow gum which was further purified by reverse-phase chromatography on C ₁₈ -modified silica eluting with a gradient 30% acetonitrile/water to 80% acetonitrile/water. Methyl (E)-3-methoxy-2-(3-phenylbenzothiophen-5-yl)prop-2-enoate was obtained as a colorless gum.

LC/MS (Method A): m/z = 325 [M+H], rt = 1 .17 min 1H NMR (400 MHz, CDCI ₃ ) δ ppm 3.76 (s, 3 H) 3.87 (s, 3 H) 7.37 (dd, 1 H) 7.39 - 7.46 (m, 2 H) 7.47 - 7.54 (m, 2 H) 7.59 - 7.65 (m, 3 H) 7.88 (d, 1 H) 7.90 - 7.94 (m, 1 H).

The following general procedure was used in a combinatorial fashion using appropriate building blocks (compounds (l-la) and (VIla)) to provide the compounds of Formula (l-lla), wherein R ¹¹ is T ¹ and R ¹ , R ² and R ³ are as defined for compound of formula (I). The compounds prepared via the following combinatorial protocol were analyzed using LC/MS Method C.

By way of exemplification, benzothiophene derivatives of formula (l-la) (0.06 mmol in 0.4 mL 1 ,2- dichloroethane) were transferred to aluminum vials containing the variable boronic acid derivatives of formula (Vila) (0.24 mmol) and TEMPO (0.24 mmol) in 0.4 mL 1 ,2-dichloroethane, followed by the addition of a stock solution of palladium (II) acetate (0.006 mmol) and BiPyridine (0.006 mmol) dissolved in 1 ,2- dichloroethane (0.4 mL)). The vials were then sealed and stirred at 75°C for 3 hours to overnight. An extraction with EtOAc/water was done three times and a filtration was carried out. The solvent was removed under a stream of nitrogen. The resultant crude residues were directly submitted for preparative LC/MS purification which provided the compounds of formula (l-lla).

Example 3; Preparation of methyl (E)-3-methoxy-2-[3-(4-pyridyl)benzothiophen-5-yl]prop-2-enoa te (Compound C-43, Table C) Step A; Preparation of dimethyl 2-(benzothiophen-5-yl)propanedioate

To a solution of 5-bromobenzothiophene (5.00 g, 23.0 mmol) in DME (115 mL ) was added CS ₂ CO ₃ (15.0 g, 46.0 mmol), dimethyl malonate (5.36 mL , 46.0 mmol) followed by tBu3P.BF4 (0.27 g, 0.92mmol) and Pd2dba3 (0.27 g, 0.46 mmol). The beige suspension was degassed with an argon flux for 5 min and then stirred at 85°C for 3h. It was cooled to RT and diluted with EtOAc and water, followed by adjustment of pH=2 with HCI (2M). The layers were separated and the organic phase was washed with brine, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% EtOAc/cyclohexane to 30% EtOAc/cyclohexane to yield dimethyl 2-(benzothiophen-5-yl)propanedioate as a yellow liquid.

LC/MS (Method A): m/z = 265 [M+H], rt = 0.97 min ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.77 (s, 6 H) 4.78 (s, 1 H) 7.34 (d, 1 H) 7.39 (dd, 1 H) 7.47 (d, 1 H) 7.77 (br s, 1 H) 7.79 (d, 1 H).

Step B - preparation of dimethyl 2-(3-bromobenzothiophen-5-yl)propanedioate

To a solution of dimethyl 2-(benzothiophen-5-yl)propanedioate (3.00 g, 6.81 mmol) in chloroform (10 mL ) and acetic acid (10 mL ) was added N-bromo succinimide (1.59 g, 8.85 mmol) in small portions at RT. The resulting yellow solution was stirred at 50°C for 2 h. The orange solution was cooled to RT and poured into ice-NaHCO ₃ Aq and extracted twice with DCM. The combined organic layers were washed with NaHCO ₃ , Na ₂ S ₂ O ₃ and with brine. Dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel eluting with a gradient of 0% EtOAc/cyclohexane to 10% EtOAc/cyclohexane to yield dimethyl 2-(3-bromobenzothiophen-5-yl)propanedioate as a white solid. LC/MS (Method A): m/z = 343-345 [M+H], rt = 1 .06 min ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.79 (s, 6 H) 4.83 (s, 1 H) 7.46 (s, 1 H) 7.51 (dd, 1 H) 7.82 (br s, 1 H) 7.86 (d, 1 H).

Step C - Preparation of methyl 2-(3-bromobenzothiophen-5-yl) acetate

To a solution of dimethyl 2-(3-bromobenzothiophen-5-yl)propanedioate (1.80 g, 4.20 mmol) in DMSO (13 mL), was added water (0.076 mL , 4.20 mmol) and LiCI (0.356 g, 8.39 mmol). The yellow suspension was stirred at 110°C for 8h. The orange solution was cooled to RT and diluted with diethyl ether and water. The layers were separated and the organic phase was washed twice with water and once with brine, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% EtOAc/cyclohexane to 10% EtOAc/cyclohexane to yield methyl 2-(3-bromobenzothiophen-5-yl)acetate as a colorless liquid.

LC/MS (Method A): m/z = 283-285 [M+H], rt = 1 .08 min ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.72 (s, 3 H) 3.80 (s, 2 H) 7.36 (dd, 1 H) 7.45 (s, 1 H) 7.74 (br s, 1 H) 7.81 (d, 1 H).

Step D - methyl 2-(3-bromobenzothiophen-5-yl)-3-hvdroxy-prop-2-enoate

To a solution of sodium hydride (60% in oil) (1.42 g, 35.6 mmol) in DMF (15 mL) was added, at RT dropwise, a solution of methyl 2-(3-bromobenzothiophen-5-yl)acetate (2.54 g, 8.91 mmol) and methyl formate (11.1 mL, 178 mmol) in DMF (20 mL). The resulting yellow solution was stirred at RT for 1 h. The crude was slowly quenched with MeOH (5 mL). It was diluted with EA and quenched with water. Acidify to pH=2-3 and extracted with EtOAc. The organic phase was washed twice with water and once with brine, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated to yield a crude methyl 2-(3- bromobenzothiophen-5-yl)-3-hydroxy-prop-2-enoate as a yellow gum (mixture of E and Z isomers). LC/MS (Method A): m/z = 313-315 [M+H], rt = 0.96min and rt = 1 .06 min: 2 isomers ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.83 (s, 3 H) 7.32 (dd, 1 H) 7.38 (d, -OH, 2 isomers) 7.46 (s, 1 H) 7.69 (br s, 1 H) 7.83 (d, 1 H).

Step E: -Preparation of methyl (E)-2-(3-bromobenzothiophen-5-yl)-3-methoxy-prop-2-enoate

To a solution of methyl 2-(3-bromobenzothiophen-5-yl)-3-hydroxy-prop-2-enoate (1.27 g, 3.04 mmol) in DMF (9 mL ) was added K ₂ CO ₃ (1.26 g, 9.12 mmol) followed by dimethyl sulfate (0.70 mL , 7.30mmol) dropwise by keeping temperature under 25°C with ice-bath (exotherm). The resulting yellow solution was stirred at RT for 1 h. The solution was poured into ice-NaHCO ₃ Aq and extracted twice with EtOAc. The combined organic layers were washed twice with water and once with brine. Dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel eluting with a gradient of 0% EtOAc/cyclohexane to 10% EtOAc/cyclohexane to yield methyl (E)-2-(3- bromobenzothiophen-5-yl)-3-methoxy-prop-2-enoate as a white solid.

LC/MS (Method A): m/z = 327-329 [M+H], rt = 1 .09 min mp= 82-84°C 1H NMR (400 MHz, CDCI ₃ ) δ ppm 3.77 (s, 3 H) 3.89 (s, 3 H) 7.37 (dd, 1 H) 7.42 (s, 1 H) 7.65 (s, 1 H) 7.79 (br s, 1 H) 7.83 (d, 1 H).

Step F; Preparation of methyl (E)-3-methoxy-2-[3-(4-pyridyl)benzothiophen-5-yl]prop-2-enoa te (Compound C-43, Table C)

To a solution of methyl (E)-2-(3-bromobenzothiophen-5-yl)-3-methoxy-prop-2-enoate (0.100 g, 0.31 mmol) in dioxane (1.8 mL ) and water (0.46 mL ) was added K ₃ PO ₄ (0.109 g, 0.61 mmol) and pyridine-4- boronic acid (0.116 g, 0.90 mmol). The solution was degassed with an argon flux for 5 min, then S-Phos Pd(crotyl)CI (0.028 g, 0.046mmol) was added and the solution stirred at 100°C for 3h. The brown solution was cooled to RT and diluted with EtOAc and water. The layers were separated and the organic phase was washed with brine, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluting with a gradient of 0% EtOAc/cyclohexane to 90% EtOAc/cyclohexane to yield methyl (E)-3-methoxy-2-[3-(4-pyridyl)benzothiophen-5-yl]prop-2- enoate as a white solid.

LC/MS (Method A): m/z = 326 [M+H], rt = 0.79 min mp= 126-128°C

¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 3.75 (s, 3 H) 3.87 (s, 3 H) 7.40 (dd, 1 H) 7.52 (d, 2 H) 7.54 (s, 1 H) 7.62 (s, 1 H) 7.77 (br s, 1 H) 7.91 (d, 1 H) 8.71 (d, 2 H).

Example 4; Preparation of (2E)-2-methoxyimino-N-methyl-2-(3-phenylbenzothiophen-5-yl) acetamide (Compound D-16, Table D)

Step A; Preparation of 5-bromo-3-phenyl-benzothiophene

Polyphosphoric acid (34 g, 16.6 mL) was placed in a flask and heated to 120°C. To this preheated media was added 2-(4-bromophenyl)sulfanyl-1-phenyl-ethanone (7.66 g) and the resultant brown solution was stirred at 120°C overnight. The heating source was removed and after the contents reached RT the reaction mixture was poured carefully while hot into a stirred 2M K ₂ CO ₃ aq. / ethylacetate solution. The two phases were separated, and the aqueous phase was extracted twice with ethyl acetate. The total combined organic layer was washed with a saturated aqueous NaHCO ₃ solution, brine, dried over MgSO ₄ , filtered and concentrated under reduced pressure. Purification on Combi-Flash (cyclohexane to 9/1 cyclohexane/ EtOAc gradient) afforded 3.5 g (45% yield) of desired product as an amorphous solid. ¹ H NMR (400 MHz, CDCI ₃ δ ppm 8.05 (s, 1 H), 7.76 (d, 1 H), 7.70 - 7.35 (m, 7H)

Step B; Preparation of 5-iodo-3-phenyl-benzothiophene

To a solution of 5-bromo-3-phenyl-benzothiophene (0.50 g, 1.7 mmol) in 1 ,4-dioxane (1.7 mL) was added sodium iodide (0.52 g, 3.5 mmol), copper(l) iodide (0.033 g, 0.17 mmol) and trans-N,N'- dimethylcyclohexane-1 ,2-diamine (0.098 g, 0.69 mmol). After degassing with an argon for 5 min, the contents were heated to 110°C overnight. The reaction was cooled to RT, diluted with EtOAc and water, and a saturated aqueous NH ₄ CI solution. The organic fraction was twice extracted with EtOAc, washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. Purification by Combi- flash (cyclohexane to 9/1 cyclohexane/ EtOAc gradient) to afford 460 mg (79% yield) of desired product as a colorless oil. ¹ H NMR (400 MHz, CDCI ₃ δ ppm 8.25 (s, 1 H), 7.65 (d, 1 H), 7.60 - 7.40 (m, 7H)

Step C Preparation of N-methyl-2-oxo-2-(3-phenylbenzothiophen-5-yl)acetamide

5-iodo-3-phenyl-benzothiophene (0.46 g, 1.37 mmol), potassium carbonate (0.38 g, 2.74 mmol), PEPPSI ⁽ ™ ⁾ -IPR CATALYST (0.046 g, 0.068 mmol), 1 ,4-dioxane (6.8 mL) and methylamine (2M in THF) (1.37 mL, 2.74 mmol) were charged into a high pressure reactor and purged with argon. The reaction mixture was stirred for 17h at 50°C under CO atmosphere (5bars). Water was added and the solution was extracted with EtOAc. The combined organic layers were washed with a 1 M HCI, water, brine, dried over Na ₂ SO ₄ , filtered, and concentrated under vacuum. The crude resisue was purified by combiflash, (DCM to DCM/MeOH 9/1 gradient) to afford 156 mg of the desired compound, (38% yield) as light yellow gum, LC/MS (Method A): m/z = 296 [M+H], rt = 1 .03 min ¹ H NMR (400 MHz, CDCI ₃ δ ppm 9.06 (m, 1 H), 8.33 (m, 1 H), 7.97-8.03 (m, 1 H), 7.60-7.64 (m, 2H), 7.51- 7.57 (m, 2H), 7.48 (s, 1 H), 7.44-7.47 (m, 1 H), 7.15-7.21 (m, 1 H), 2.98 (d, 3H)

Step D; Preparation of (2E)-2-methoxyimino-N-methyl-2-(3-phenylbenzothiophen-5-yl)a cetamide

(Compound D-16, Table D)

To a solution of N-methyl-2-oxo-2-(3-phenylbenzothiophen-5-yl)acetamide (156 mg, 0.53 mmol) in EtOH (0.5 mL) was added NaOAc (0.07 g, 0.79 mmol) and NH ₂ -OMe.HCI (0.07 g, 0.79 mmol). The reaction mixture was then heated at 160°C for 2.5h min in the microwave. The solution was diluted with EtOAc and water. It was then extracted with EtOAc (pH=7-8) and the organic phase was washed with brine, dried over Na ₂ SO ₄ filtered and concentrated under reduced pressure. Purification via Combiflash (cyclohexane to 9/1 cyclohexane/ EtOAc gradient) to afford 65 mg (38% yield) of the desired compound as an amorphous solid. LC/MS (Method A): m/z = 325 [M+H], rt = 1 .01 min ¹ H NMR (400 MHz, CDCI ₃ δ ppm 8.11 (d, 1 H), 7.90 (d, 1 H), 7.72 (d, 1 H), 7.56-7.61 (m, 2H), 7.50 (m, 2H), 7.43 (s, 2H), 6.01 (br d, 1 H), 4.03 (s, 3H), 2.99 (d, 3H).

A by-product, (2Z)-2-methoxyimino-N-methyl-2-(3-phenylbenzothiophen-5-yl)a cetamide (Compound D- 15, Table D) was also isolated as an amorphous solid (62 mg, 38% yield)

LC/MS (Method A): m/z = 325 [M+H], rt = 1 .04 min ¹ H NMR (CDCI ₃ ) d: 7.99 (s, 1 H), 7.95 (d, 1 H), 7.59 (d, 2H), 7.48-7.51 (m, 2H), 7.43-7.48 (m, 2H), 7.42 (s, 1 H), 6.86 (br s, 1 H), 3.98 (s, 3H), 2.95 (d, 3H)

Example 5; Preparation of methyl N-methoxy-N-(3-phenylbenzothiophen-5-yl)carbamate (Compound D-17, Table D)

In a microwave vial, to a solution of 5-iodo-3-phenyl-benzothiophene (0.30 g, 0.89 mmol) and copper(l) oxide (0.033 g, 0.17 mmol) in toluene (2.7 mL ) was added methyl N-methoxycarbamate (0.52 g, 3.5 mmol), N,N'-dimethylethylenediamine (0.031 g, 0.36 mmol) and potassium carbonate (0.25 g, 1.79 mmol). The reaction was heated to 110°C for 2.5h then the contents were cooled to RT and diluted with water. After, the media was extracted with ethylacetate, washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. Purification by Combi-flash (cyclohexane to 9/1 cyclohexane/ EtOAc gradient) afforded 110 mg (39% yield) of the title product as a light yellow oil. LC/MS (Method A): m/z = 314 [M+H], rt = 1 .12 min ¹ H NMR (400 MHz, CDCI ₃ δ ppm 7.96 (d, 1 H), 7.88-7.94 (m, 1 H), 7.57-7.61 (m, 2H), 7.37-7.54 (m, 5H), 3.85 (s, 3H), 3.76 (s, 3H) Table C: Melting point (mp) data and/or retention times (R _t ) for compounds according to formula (I): j !

j j ! j !

j I

I

Table D: Melting point (mp) data and/or retention times (R _t ) for compounds according to formula (I): I

Example B: Biological examples/test methods:

Alternaria solani / tomato / leaf disc preventative (early blight)

Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23 °C / 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).

The following compounds gave at least 80 % control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-3, C-4, C-5, C-11 , C-12, C-14, C-16, C-19, C-21 , C-22, C-25, C-26, C-29, C-33, C-43, C-59, C- 65, C-77

Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.

The following compounds gave at least 80 % control of Botryotinia fuckeliana at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-5, C-25, C-43

Cercospora kikuchii / liquid culture (leaf blight of soybean):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compounds was placed into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24 °C and the inhibition of growth was determined photometrically after 3-4 days at 620 nm.

The following compounds gave at least 80 % control of Cercospora kikuchii at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development: C-1 , C-2, C-3, C-4, C-5, C-7, C-9, C-10, C-11 , C-12, C-13, C-14, C-18, C-19, C-22, C-25, C-33, C-34, C-47, C-48, C-11, C-18

Glomerella lagenarium ( Colletotrichum lagenarium) / liquid culture (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application.

The following compounds gave at least 80 % control of Glomerella lagenarium at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, C-16, C-17, C-18, C- 19, C-20, C-21 , C-22, C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-31 , C-33, C-34, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C-46, C-48, C-51 , C-61 , C-76, C-11, C-18

Blumeria graminis f. so. tritici (Ervsiphe graminis f. sp. tritici) / wheat / leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).

The following compounds gave at least 80 % control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-2, C-4, C-7, C-9, C-10, C-13, C-14, C-29, C-76, C-11, C-18

Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20 °C and 75 % rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

The following compounds gave at least 80 % control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-3, C-10, C-13, C-14, C-18, C-19, C-21 , C-23, C-25, C-76, C-11, C-18 Monographella nivalis ( Microdochium nivale ) / liquid culture (foot rot cereals)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80 % control of Monographella nivalis at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, C-16, C-17, C-18, C- 19, C-20, C-21 , C-22, C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-30, C-31 , C-33, C-34, C-35, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C-46, C-47, C-48, C-49, C-50, C-51 , C-52, C- 53, C-54, C-55, C-56, C-57, C-58, C-60, C-61 , C-62, C-63, C-71 , C-73, C-74, C-75, C-76, C-77, C-78

Mvcosphaerella arachidis (Cercospora arachidicola ) / liquid culture (early leaf spot)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80 % control of Mycosphaerella arachidis at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, C-16, C-17, C-18, C- 19, C-20, C-21 , C-22, C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-30, C-31 , C-33, C-34, C-35, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C-46, C-48, C-49, C-50, C-51 , C-56, C-58, C- 62, C-63, C-76, C-77, C-78

Phakopsora pachyrhizi / soybean / preventative (soybean rust)

Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20 °C and 75 % rh leaf disc are kept at 20 °C with 12 h light/day and 75% rh. The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 - 14 days after application).

The following compounds gave at least 80 % control of Phakopsora pachyrhizi at 67 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-10, C-76, C-77, C-78, D-1 , D-2, D-3, D-4, D-5, D-10, D-11 , D- 12, D-13, D-14, D-15, D-16, D-17, D-18, D-19 Phytophthora infestans / tomato / leaf disc preventative (late blight)

Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 16 °C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

The following compounds gave at least 80 % control of Phytophthora infestans at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-5, C-6, C-7, C-9, C-10, C-11 , C-13, C-16, C-18, C-19, C-21 , C-22, C-23, C-24, C-25, C-27, C-28, C-31 , C-33, C-34, C-35, C-36, C-41 , C-42, C-48, C-49, C-76, C-77, C-78

Plasmopara viticola / grape / leaf disc preventative (late blight)

Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 19 °C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).

The following compounds gave at least 80 % control of Plasmopara viticola at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-4, C-5, C-7, C-9, C-10, C-11 , C-12, C-13, C-14, C-19, C-20, C-21 , C-22, C-27, C-28, C-33, C-34, C-36, C-41 , C-42, C-76, C-77, C-78

Puccinia recondita f. sp. tritici / wheat / leaf disc curative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75 % rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application).

The following compounds gave at least 80 % control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-9, C-10, C-11 , C-13, C-14, C-15, C-16, C-17, C-22, C-33, C-34, C-76, C-77, C-78

Puccinia recondite f. sp. tritici / wheat / leaf disc preventative (Brown rust) Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19 °C and 75 % rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application).

The following compounds gave at least 80 % control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-13, C-14, C-15, C-16, C-17, C-18, C-19, C- 20, C-21 , C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-33, C-34, C-35, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C-46, C-47, C-76, C-11, C-18

Magnaporthe grisea (Pyricularia oryzae) / rice / leaf disc preventative (Rice Blast)

Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22 °C and 80 % rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).

The following compounds gave at least 80 % control of Magnaporthe grisea at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-2, C-3, C-4, C-7, C-8, C-9, C-10, C-11 , C-13, C-14, C-16, C-18, C-19, C-21 , C-22, C-23, C-24, C-25, C-35, C-36, C-38, C-44, C-76, C-11, C-18

Pyrenophora teres / barley / leaf disc preventative (Net blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20 °C and 65 % rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).

The following compounds gave at least 80 % control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-5, C-6, C-7, C-13, C-14, C-15, C-16, C-18, C-19, C-20, C-21 , C-23, C-25, C-29, C-35, C-44, C-76, C-11, C-18

Pythium ultimum I liquid culture (seedling damping off)

Mycelia fragments and oospores of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 2-3 days after application.

The following compounds gave at least 80 % control of Pythium ultimum at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-4, C-5, C-11 , C-34

Thanatephorus cucumeris ( Rhizoctonia solani ) / liquid culture (foot rot, damping-off)

Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80 % control of Thanatephorus cucumeris at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-76

Sclerotinia sclerotiorum / liquid culture (cottony rot)

Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.

The following compounds gave at least 80 % control of Sclerotinia sclerotiorum at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-4, C-11 , C-13, C-19, C-76

Mycosphaerella graminicola (Septoria tritici ) / liquid culture (Septoria blotch)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80 % control of Mycosphaerella graminicola at 6.7 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, C-16, C-17, C-18, C- 19, C-20, C-21 , C-22, C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-30, C-31 , C-33, C-34, C-35, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C-46, C-47, C-48, C-49, C-50, C-51 , C-52, C- 53, C-54, C-55, C-56, C-57, C-58, C-59, C-60, C-61 , C-62, C-76, C-77, C-78 Comparative Data:

The biological activity of compound C-76 and C-78 of the invention are compared to the reference compound X-1. Reference compound X-1 is specifically disclosed on page 15 of EP0243014 as compound no. 57.

The data are presented as the percentage of disease control of each compound for the biological tests and testing rates described below in table H.

Table H - Biological activity against Phakopsora Pachyrhizi (soybean rust):

Soybean leaf disks are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed approx.12 dpi (days after inoculation) as preventive fungicidal activity.