The present invention relates to microbiocidal oxadiazole 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 oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogen ic microorganisms, preferably fungi.

EP 0 276 432 and WO 2015/185485 describe the use of substituted oxadiazoles for combating phytopathogen ic fungi.

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

wherein

A is A-1 or A-2;

(A-1 ) (A-2)

wherein A-1 and A-2 are optionally substituted by one or two groups independently selected from halogen and methyl;

R ¹ is hydroxyl, amino, thiol, halogen, Ci-3alkoxy, Ci-3haloalkyl, Ci-3haloalkoxy, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, Ci-3alkylamino, Ci-3alkoxyamino, Ci-3haloalkoxyamino, Ci-3alkylcarbonyloxy, C3- ₄ alkenyloxyamino, C3- ₄ alkynyloxyamino, N-Ci-3alkyl-N-Ci-3alkoxyamino, N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl, or C3-6cycloalkylCi-3alkoxyamino;

R ² is hydrogen, Ci-3alkyl, Ci-3haloalkyl, C3-6cycloalkyl, phenyl, C2-6alkenyl, or C2-6alkynyl; or R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) or =NOR ^a group, wherein R ^a is Ci-salkyl, Ci-3haloalkyl, C3-6cycloalkyl, or C3-6cycloalkylCi- ₂ alkyl;

R ³ and R ⁴ are the same and are selected from halogen and Ci-C6alkyl; or

R ³ and R ⁴ , together with the carbon to which they are bonded, form a 3-, 4-, 5-, or 6-membered cycloalkyl group;

Y is O or S;

Z is Z ¹ or Z ² ;

Z ¹ represents -OR ⁵ , wherein:

R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl, Ci-3haloalkyl, cyanoC- _M alkyl, hydroxyC _2-4 alkyl, C-i- 3alkoxyCi-3alkyl, Ci-3haloalkoxyC _2-4 alkyl, aminoC _2-4 alkyl, N-Ci- ₄ alkylaminoC _2-4 alkyl, N,N-diCi- ₄ alkylaminoC ₂ - ₄ alkyl, Ci-3alkylcarbonylCi-3alkyl, Ci- ₄ alkoxycarbonylCi-3alkyl, or Ci-3alkylcarbonyloxyC _2-4 alkyl; or

R ⁵ is C3-6cycloalkyl, C3-6cycloalkylCi- ₂ alkyl, phenyl, phenylCi-2alkyl, heteroaryl, heteroarylCi-2alkyl, heterocyclyl, or heterocyclylCi-2alkyl, wherein the cycloalkyl and heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁶ ;

R ⁶ is cyano, fluoro, chloro, bromo, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;

Z ² represents -NR ⁷ R ⁸ , wherein:

R ⁷ is hydrogen, amino, hydroxyl, cyano, Ci-6alkyl, Ci- ₄ alkoxy, C3-salkenyl, C3-salkynyl, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, cyanoCi- ₄ alkyl, Ci- ₄ haloalkyl, C3-5haloalkenyl, Ci- ₄ haloalkoxy, hydroxyC _2-4 alkyl, C-i- ₂ alkoxyC _2-4 alkyl, Ci- ₂ haloalkoxyC _2-4 alkyl, Ci- ₂ alkoxyC _2-4 alkoxyC _2-4 alkyl, N-Ci- ₄ alkylamino, N,N-diCi- ₄ alkylamino, N-Ci- ₄ alkylcarbonyl-N-Ci- ₄ alkylamino, aminoC _2-4 alkyl, N-Ci-3alkylaminoC _2-4 alkyl, N,N-diCi- 3alkylaminoC _2-4 alkyl, N-Ci-3alkyl-N-Ci-3alkoxyaminoC _2-4 alkyl, Ci-3alkylcarbonylaminoC _2-4 alkyl, N-Ci- 3alkylcarbonyl-(N-Ci-3alkyl)aminoC ₂ -3alkyl, Ci-3alkylcarbonylCi-3alkyl, Ci-3alkoxycarbonylCi-3alkyl, or Ci- 3alkylcarbonyloxyC2-4alkyl; or

R ⁷ is C3-6cycloalkyl, C3-6cycloalkylCi- ₂ alkyl, phenyl, phenylCi-2alkyl, or 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, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S; and wherein the cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁹ ;

R ⁸ is hydrogen, methyl, ethyl, propyl, isopropyl, prop-2-enyl, prop-2-ynyl, methoxy, 2-methoxyethyl, or cyclopropyl; or

R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6-membered cycle optionally containing an additional heteroatom or group selected from O, S, S(0) ₂ , and NR ¹⁰ ;

R ⁹ is hydroxyl, Ci-3alkyl, halogen, Ci-3alkoxy, or Ci-3haloalkyl; and

R ¹⁰ is hydrogen, methyl, methoxy, fluoromethoxy, difluoromethoxy, formyl or acyl; or a salt or N-oxide thereof.

Surprisingly, it has been found that the novel compounds of formula (I) have, for practical purposes, 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). Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.

According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogen ic microorganisms, 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, the term“hydroxyl” or“hydroxy” means an -OH group.

As used herein, amino means an -IMH2 group. As used herein, acyl means a -C(0)CH3 group.

As used herein, formyl means a -C(0)H group.

As used herein, the term "Ci-6alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-salkyl, Ci- ₄ alkyl, Ci-3alkyl and Ci-2alkyl are to be construed accordingly. Examples of Ci-6alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1 -methylethyl (isopropyl), /7-butyl, and 1 -dimethylethyl (f-butyl). A“Ci-2alkylene” group refers to the corresponding definition of Ci-2alkyl, except that such radical is attached to the rest of the molecule by two single bonds. Examples of Ci-2alkylene, are -CH2- and -CH2CH2-.

As used herein, the term "Ci- ₄ alkoxy" refers to a radical of the formula R _a O- where R _a is a Ci- ₄ alkyl radical as generally defined above. Ci-3alkoxy is to be construed accordingly. Examples of Ci- ₄ alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and f-butoxy.

As used herein, the term "Ci- ₄ haloalkyl" refers to a Ci- ₄ alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. The terms Ci-3haloalkyl and Ci-2haloalkyl are to be construed accordingly. Examples of Ci- ₄ haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl.

As used herein, the term "C2-6alkenyl" refers to a straight or branched hydrocarbon chain radical group 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 six carbon atoms, which is attached to the rest of the molecule by a single bond. The terms C3-salkenyl and C3- ₄ alkenyl are to be construed accordingly. Examples of C2-6alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl), and but-1 -enyl.

As used herein, the term "C3- ₄ alkenyloxy" refers to a radical of the formula R _a O-, where R _a is a C3- ₄ alkenyl radical as generally defined above.

As used herein, the term "C3- ₄ alkenyloxyamino" refers to a radical of the formula R _a ONH-, where R _a is a C3- ₄ alkenyl radical as generally defined above

As used herein, the term "C3-5haloalkenyl" refers to a straight or branched hydrocarbon chain radical group 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 three to five carbon atoms, which is attached to the rest of the molecule by a single bond, substituted by one or more of the same or different halogen atoms.

As used herein, the term "C2-6alkynyl" 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 six carbon atoms, and which is attached to the rest of the molecule by a single bond. The terms C3-salkynyl and C3-4alkynyl are to be construed accordingly. Examples of C2-6alkynyl include, but are not limited to, prop-1- ynyl, propargyl (prop-2-ynyl), and but-1 -ynyl.

As used herein, the term "C3- ₄ alkynyloxy" refers to a radical of the formula R _a O-, where R _a is a C3- ₄ alkynyl radical as generally defined above.

As used herein, the term "C3- ₄ alkynyloxyamino" refers to a radical of the formula R _a ONH-, where R _a is a C3- ₄ alkynyl radical as generally defined above. As used herein, the term "Ci-3alkoxyCi- ₄ alkyl" refers to radical of the formula Rb-0-R _a - where Rb is a Ci-3alkyl radical as generally defined above, and R _a is a Ci- ₄ alkylene radical as generally defined above. The terms Ci- ₂ alkoxyCi- ₄ alkyl, Ci-3alkoxyCi-3alkyl and Ci- ₂ alkoxyC _2-4 alkyl are to be construed accordingly.

As used herein, the term "Ci- ₄ haloalkoxy" refers to a Ci- ₄ alkoxy group as defined above substituted by one or more of the same or different halogen atoms. The terms Ci-3haloalkoxy and Ci-2haloalkoxy are to be construed accordingly. Examples of Ci- ₄ haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

As used herein, the term "Ci- ₂ haloalkoxyC _2-4 alkyl" refers to a radical of the formula Rb-0-R _a - where Rb is a Ci-2alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms, and R _a is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“hydroxyC _2-4 alkyl” refers to a C _2-4 alkyl radical as generally defined above substituted by one or more hydroxy groups.

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

As used herein, the term "Ci- ₄ alkylcarbonylaminoC _2-4 alkyl" refers to a radical of the formula R _a C(0)NHRb-, where R _a is a Ci- ₄ alkyl radical as generally defined above and Rb is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“Ci- ₂ alkoxyC _2-4 alkoxyC _2-4 alkyl” refers to a radical of the formula R _c ORbOR _a - , where R _a and Rb are C _2-4 alkylene radicals as generally defined above, and R _c is a Ci-2alkyl radical as generally defined above.

As used herein, the term“Ci-4alkoxycarbonylCi-3alkyl” refers to a radical of the formula R _a OC(0)Rb-, where R _a is a Ci- ₄ alkyl radical as generally defined above and Rb is a Ci-3alkylene radical as generally defined above.

As used herein, the term“N-Ci- ₄ alkylamino” refers to a radical of the formula R _a NH- where R _a is a C-i- ₄ alkyl radical as generally defined above. The term N-Ci-3alkylamino is to be construed accordingly.

As used herein, the term“N-Ci- ₄ alkylaminoC _2-4 alkyl” refers to a radical of the formula R _a NHRb - where R _a is a Ci- ₄ alkyl radical as generally defined above and Rb is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“N,N-diCi- ₄ alkylamino” refers to a radical of the formula R _a (Rb)N- where R _a and Rb are Ci- ₄ alkyl radicals as generally defined above.

As used herein, the term“N,N-diCi- ₄ alkylaminoC _2-4 alkyl” refers to a radical of the formula R _a (Rb)NR _c - where R _a and Rb are Ci^alkyl radicals as generally defined above, and R _c is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“aminoC _2-4 alkyl” refers to a radical of the formula H2NR _a - where R _a is a C2- ₄ alkylene radical as generally defined above.

As used herein, the term“Ci- ₄ alkylamino” refers to a radical of the R _a NH- where R _a is a Ci- ₄ alkyl radical as generally defined above. The term Ci-3alkylamino is to be construed accordingly. As used herein, the term "Ci-3haloalkoxyamino" refers to a radical of the R _a ONH- where R _a is a C-i- 3alkyl group as defined above substituted by one or more of the same or different halogen atoms.

As used herein, the term“Ci-3alkylcarbonylCi-3alkyl” refers to a radical of the formula RbC(0)R _a - where Rb is a Ci-3alkyl as generally defined above and R _a is a Ci-3alkylene radical as generally defined above.

As used herein, the term“Ci- ₄ alkoxycarbonylCi-3alkyl” refers to a radical of the formula RbOC(0)R _a - where Rb is a Ci- ₄ alkyl as generally defined above and R _a is a Ci-3alkylene radical as generally defined above.

As used herein, the term“Ci-3alkylcarbonyloxyC2-4alkyl” refers to a radical of the formula RbC(0)OR _a - where Rb is a Ci-3alkyl as generally defined above and R _a is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“Ci- ₄ alkoxyamino” refers to a radical of the formula R _a ONH-, wherein R _a is a Ci- ₄ alkyl radical as generally defined above. The term Ci-3alkoxyamino is to be construed accordingly.

As used herein, the term “N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl” refers to a radical of the formula (R _a O)(RbC(0))N-, wherein R _a and Rb are Ci-3alkyl radicals as generally defined above.

As used herein, the term “N-Ci-3alkyl-N-Ci-3alkoxyamino” refers to a radical of the formula (R _a )(RbO)N-, wherein R _a and Rb are Ci-3alkyl radicals as generally defined above.

As used herein, the term“N-Ci-3alkyl-N-Ci-3alkoxyaminoC _2-4 alkyl” refers to a radical of the formula (R _a )(RbO)NR _c -, wherein R _a and Rb are Ci-3alkyl radicals as generally defined above, and R _c is a C _2-4 alkylene radical as generally defined above.

As used herein, the term“N-Ci-4alkylcarbonyl-N-Ci-4alkylamino” refers to a radical of the formula (RbC(0))(R _a )N-, wherein R _a and Rb are Ci^alkyl radicals as generally defined above.

As used herein, the term“N,N-diCi- ₄ alkylamino” refers to a radical of the formula (R _a )(Rb)N-, wherein R _a and Rb are each Ci- ₄ alkyl radicals as generally defined above.

As used herein, the term“N,N-diCi- ₄ alkylaminoC _2-4 alkyl” refers to a radical of the formula (R _c )(Rb)NR _a - , wherein Rb and R _c are each independently Ci- ₄ alkyl radicals as generally defined above, and R _a is a C2- ₄ alkylene radical as generally defined above.

As used herein, the term“N-Ci-3alkylcarbonyl-(N-Ci-3alkyl)aminoC ₂ -3alkyl” refers to a radical of the formula (R _c C(0))(Rb)NR _a -, wherein Rb and R _c are each independently Ci-3alkyl radicals as generally defined above, and R _a is a C ₂ -3alkylene radical as generally defined above.

As used herein, the term "C3-6cycloalkyl" refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-5cycloalkyl and C3- ₄ cycloalkyl are to be construed accordingly. Examples of C3-6cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.

As used herein, the term "C3-6cycloalkylCi- ₂ alkyl" refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-2alkylene radical as defined above. Examples of C3-6cycloalkylCi- 2alkyl include, but are not limited to cyclopropyl-methyl and cyclobutyl-ethyl. As used herein, the term "C3-6cycloalkylCi-3alkoxyamino" refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a -R _a ONH- radical, where R _a is a Ci-3alkylene radical as generally defined above.

As used herein, the term "phenylCi-2alkyl" refers to a phenyl ring attached to the rest of the molecule by a Ci-2alkylene radical as defined above. Examples of phenylCi-2alkyl include, but are not limited to, benzyl.

As used herein, the term "heteroaryl" generally refers to a 5- or 6-membered monocyclic aromatic ring radical which comprises 1 or 2 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 but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, iso azolyl, pyrazinyl, pyridazinyl, pyrimidyl and pyridyl.

As used herein, the term "heterocyclyl" or "heterocyclic" generally refers to a stable, saturated or partially saturated, 4- to 6-membered, non-aromatic monocyclic ring, 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, azetidinyl, oxetanyl, pyrrolidyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholino.

As used herein, the term "heterocyclylCi-2alkyl" refers to a heterocyclic ring as defined above which is attached to the rest of the molecule by a Ci-2alkylene radical as defined above.

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 oxidized form as an N-oxide, 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 .

The designations of A (A-1 , A-2), Z (Z ¹ , Z ² ), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ with reference to the compounds of formula (I) of the present invention apply generally to the compounds of formula (l-l) and formula (l-ll), as well as to the specific disclosures of combinations of A (A-1 , A-2), Z (Z ¹ , Z ² ), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ , as represented for compounds of formula (I) in Tables 1 .1 to 1 .12 (below), or in Tables 3.1 to 3.6 (below), the compounds 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below).

A is A-1 or A-2;

(A-1 ) (A-2) wherein A-1 and A-2 are each optionally substituted by one or two groups selected from halogen and methyl.

Preferably, A is A-1 or A-2, wherein A-1 and A-2 are each optionally substituted by one or two groups selected from halogen and methyl, more preferably chloro, fluoro and methyl. Even more preferably, A is 1 ,4-phenylene or 2,5-thienylene.

R ¹ is hydroxyl, amino, thiol, halogen, Ci-3alkoxy, Ci-3haloalkyl, Ci-3haloalkoxy, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, Ci-3alkylamino, Ci-3alkoxyamino, Ci-3haloalkoxyamino, Ci-3alkylcarbonyloxy, C3- ₄ alkenyloxyamino, C3- ₄ alkynyloxyamino, N-Ci-3alkyl-N-Ci-3alkoxyamino, N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl, or C3-6cycloalkylCi-3alkoxyamino.

Preferably, R ¹ is hydroxyl, amino, thiol, halogen, Ci-3alkoxy, Ci-2haloalkyl, Ci-2haloalkoxy, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, Ci-2alkylamino, Ci-3alkoxyamino, Ci-2haloalkoxyamino, Ci-3alkylcarbonyloxy, N- Ci-3alkyl-N-Ci-3alkoxyamino, or N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl.

More preferably, R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy, N-Ci-3alkyl- N-Ci-3alkoxyamino, or N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl. Even more preferably, R ¹ is hydroxyl, thiol, methoxy, methoxyamino, methylcarbonyloxy, N-methyl-N-methoxyamino, or N-methoxy-N’-methylcarbonyl.

R ² is hydrogen, Ci-3alkyl, Ci-3haloalkyl, C3-6cycloalkyl, phenyl, C2-6alkenyl, or C2-6alkynyl. Preferably, R ² is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, cyclobutyl, phenyl, prop-2-enyl, or prop-2-ynyl. More preferably, R ² is hydrogen, methyl, ethyl, cyclopropyl, prop-2-enyl, or prop-2-ynyl. Even more preferably, R ² is hydrogen or methyl.

Or, R ¹ and R ² can, together with the carbon to which they are bonded, form an oxy (=0) or =NOR ^a group, wherein R ^a is Ci-salkyl, Ci-3haloalkyl, C3-6cycloalkyl, or C3-6cycloalkylCi- ₂ alkyl. Preferably, R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) or =NOR ^a group, wherein R ^a is C1- 3alkyl, Ci-3haloalkyl, C3- ₄ cycloalkyl, or C3- ₄ cycloalkylCi- ₂ alkyl. More preferably, R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group.

In one set of embodiments, R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy, N-Ci-3alkyl-N-Ci-3alkoxyamino, or N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl, and R ² is hydrogen or methyl; or R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group.

In a further set of embodiments, R ¹ is hydroxyl, thiol, methoxy, methoxyamino, methylcarbonyloxy, N-methyl-N-methoxyamino, or N-methoxy-N’-methylcarbonyl, and R ² is hydrogen or methyl; or R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group.

R ³ and R ⁴ are both the same and are selected from halogen and Ci-C6alkyl; or

R ³ and R ⁴ , together with the carbon to which they are bonded, form a 3-, 4-, 5-, or 6-membered cycloalkyl group. Preferably, R ³ and R ⁴ are both the same and are selected from halogen and Ci-C ₄ alkyl, more preferably, fluoro, bromo, chloro and Ci-C3alkyl, even more preferably, fluoro, bromo, chloro, methyl and ethyl, and more preferably still R ³ and R ⁴ are both the same and are selected from fluoro and methyl; or R ³ and R ⁴ , together with the carbon to which they are bonded, form a 3-, 4-, or 5-membered cycloalkyl group, preferably, a 3- or 4-membered cycloalkyl group, and more preferably a cyclopropyl group.

In one set of embodiments, R ³ and R ⁴ are both the same and are selected from fluoro and methyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl group.

Y is O or S. In some embodiments Y is O, in other embodiments Y is S.

Z is Z ¹ or Z ² ;

Z ¹ represents -OR ⁵ , wherein:

R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl, Ci-3haloalkyl, cyanoC- _M alkyl, hydroxyC _2-4 alkyl, C-i- 3alkoxyCi-3alkyl, Ci-3haloalkoxyC _2-4 alkyl, aminoC _2-4 alkyl, N-Ci- ₄ alkylaminoC _2-4 alkyl, N,N-diCi- ₄ alkylaminoC ₂ - ₄ alkyl, Ci-3alkylcarbonylCi-3alkyl, Ci- ₄ alkoxycarbonylCi-3alkyl, or Ci-3alkylcarbonyloxyC _2-4 alkyl; or

R ⁵ is C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, phenyl, phenylCi-2alkyl, heteroaryl, heteroarylCi-2alkyl, heterocyclyl, or heterocyclylCi-2alkyl, wherein the cycloalkyl and heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁶ ;

R ⁶ is cyano, fluoro, chloro, bromo, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. Preferably, R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl, Ci-3haloalkyl, cyanoCi-2alkyl, hydroxyC _2-4 alkyl, Ci-3alkoxyCi-3alkyl, Ci-3haloalkoxyC _2-4 alkyl, aminoC _2-4 alkyl, Ci-3alkylcarbonylCi- ₂ alkyl, or Ci-3alkoxycarbonylCi- ₂ alkyl; or

R ⁵ is C3-6cycloalkyl, C3-6cycloalkylCi- ₂ alkyl, phenyl, phenylCi-2alkyl, heteroaryl or heterocyclyl, wherein the cycloalkyl and heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁶ .

More preferably, R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl, C3-6cycloalkyl, C3-6cycloalkylCi- 2alkyl, phenyl, phenylCi-2alkyl.

In a particular set of embodiments, R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl or C3- 6cycloalkyl, preferably, hydrogen, Ci-salkyl, C3- ₄ alkenyl, C3- ₄ alkynyl or C3- ₄ cycloalkyl, more preferably, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, prop-2 -enyl, prop-2 -ynyl or cyclopropyl, and most preferably, R ⁵ is hydrogen, methyl or ethyl.

Z ² represents -NR ⁷ R ⁸ , wherein:

R ⁷ is hydrogen, amino, hydroxyl, cyano, Ci-6alkyl, Ci- ₄ alkoxy, C3-salkenyl, C3-salkynyl, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, cyanoCi- ₄ alkyl, Ci- ₄ haloalkyl, C3-shaloalkenyl, Ci- ₄ haloalkoxy, hydroxyC _2-4 alkyl, Ci-2alkoxyC2-4alkyl, Ci-2haloalkoxyC2-4alkyl, Ci-2alkoxyC2-4alkoxyC2-4alkyl, N-Ci-4alkylamino, N,N-diCi- ₄ alkylamino, N-Ci- ₄ alkylcarbonyl-N-Ci- ₄ alkylamino, aminoC _2-4 alkyl, N-Ci-3alkylaminoC _2-4 alkyl, N,N-diCi- 3alkylaminoC _2-4 alkyl, N-Ci-3alkyl-N-Ci-3alkoxyaminoC _2-4 alkyl, Ci-3alkylcarbonylaminoC _2-4 alkyl, N-C1- 3alkylcarbonyl-(N-Ci-3alkyl)aminoC ₂ -3alkyl, Ci-3alkylcarbonylCi-3alkyl, Ci-3alkoxycarbonylCi-3alkyl, or C1- 3alkylcarbonyloxyC _2-4 alkyl; or

R ⁷ is C3-6cycloalkyl, C3-6cycloalkylCi- ₂ alkyl, phenyl, phenylCi-2alkyl, or 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, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S; and wherein the cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁹ ;

Preferably, R ⁷ is hydrogen, amino, cyano, Ci-salkyl, Ci- ₄ alkoxy, C3-salkenyl, C3-salkynyl, C3- ₄ alkenyloxy, C3- ₄ alkynyloxy, cyanoCi- ₄ alkyl, Ci- ₄ haloalkyl, C3-shaloalkenyl, Ci- ₄ haloalkoxy, hydroxyC _2-4 alkyl, Ci- ₂ alkoxyC _2-4 alkyl, Ci- ₂ haloalkoxyC _2-4 alkyl, Ci- ₂ alkoxyC _2-4 alkoxyC _2-4 alkyl, N-Ci- ₄ alkylamino, or N,N-diCi- ₄ alkylamino; or R ⁷ is C3-6cycloalkyl, C3-6cycloalkylCi- ₂ alkyl, phenyl, phenylCi-2alkyl, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N and O, heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O; and wherein the cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R ⁹ .

More preferably, R ⁷ is hydrogen, amino, Ci- ₄ alkyl, Ci- ₄ alkoxy, C3- ₄ alkenyl, C3- ₄ alkynyl, C3- 4alkenyloxy, C3-4alkynyloxy, Ci-4haloalkyl, C3-shaloalkenyl, Ci-4haloalkoxy, hydroxyC2-4alkyl, Ci-2alkoxyC2- ₄ alkyl, Ci- ₂ haloalkoxyC _2-4 alkyl, N-Ci-2alkylamino, N,N-diCi-2alkylamino, C3-6cycloalkyl, C3-6cycloalkylCi- 2alkyl, phenyl, phenylCi-2alkyl, or heteroaryl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, or heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O.

Even more preferably, R ⁷ is hydrogen, Ci- ₄ alkyl, C3- ₄ alkenyl, C3- ₄ alkynyl, C3-6cycloalkyl, or C3- 6cycloalkylCi-2alkyl, more preferably still, hydrogen, Ci- ₄ alkyl, C3- ₄ alkenyl, C3- ₄ alkynyl, C3- ₄ cycloalkyl, or C3- ₄ cycloalkylCi- ₂ alkyl.

In a particularly preferred set of embodiments, R ⁷ is hydrogen, methyl, ethyl, n-propyl, isopropyl, prop-2-enyl, prop-2 -ynyl, cyclopropyl or cyclopropylmethyl, more preferably, hydrogen, methyl, ethyl, n- propyl, isopropyl, or cyclopropyl.

R ⁸ is hydrogen, methyl, ethyl, propyl, isopropyl, prop-2-enyl, prop-2-ynyl, methoxy, 2-methoxyethyl, or cyclopropyl. Preferably, R ⁸ is hydrogen, methyl, ethyl, propyl, isopropyl, prop-2-enyl, prop-2 -ynyl or cyclopropyl. More preferably hydrogen, methyl, or prop-2-enyl, and more preferably still, R ⁸ is hydrogen or methyl.

Or R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6-membered cycle optionally containing an additional heteroatom or group selected from O, S, S(0) ₂ , and NR ¹⁰ . Preferably, R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6- membered cycle optionally containing an additional heteroatom or group selected from O and NR ¹⁰ . More preferably, R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6-membered cycle optionally containing an additional heteroatom or group selected from O, even more preferably a 5- or 6-membered cycle containing an additional oxygen atom, and most preferably R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a morpholino group. R ⁹ is hydroxyl, Ci-3alkyl, halogen, Ci-3alkoxy, or Ci-3haloalkyl. Preferably, R ⁹ is hydroxyl, methyl, ethyl, isopropyl, chloro, fluoro, methoxy, difluoromethyl or trifluoromethyl. More preferably, R ⁹ is methyl, chloro, fluoro, methoxy or trifluoromethyl.

R ¹⁰ is hydrogen, methyl, methoxy, fluoromethoxy, difluoromethoxy, formyl or acyl. Preferably, R ¹⁰ is hydrogen, methyl, formyl or acyl. More preferably, R ¹⁰ is hydrogen or methyl, and most preferably, R ¹⁰ is hydrogen.

In one set of embodiments, when R ⁷ is hydrogen, methyl, ethyl, n-propyl, isopropyl, prop-2-enyl, prop- 2-ynyl, cyclopropyl or cyclopropylmethyl, R ⁸ is hydrogen, methyl or prop-2-enyl, or R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a morpholino group.

In another set of embodiments, when R ⁷ is hydrogen, methyl, ethyl, n-propyl, isopropyl or cyclopropyl, R ⁸ is hydrogen or methyl, or R ⁷ and R ⁸ , together with the nitrogen atom to which they are bonded, form a morpholino group.

In a compound of formula (I) according to the present invention, preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy or N-Ci-3alkoxy-N’-Ci-

3alkylcarbonyl;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci-6alkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O;

Z is Z ¹ ;

R ⁵ is hydrogen, Ci-salkyl, C3-salkenyl, C3-salkynyl or C3-6cycloalkyl.

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

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy or N-Ci-3alkoxy-N’-Ci-

3alkylcarbonyl;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci-6alkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O;

Z is Z ¹ ; and R ⁵ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, allyl, prop-2-ynyl, or cyclopropyl.

In a further compound of formula (I) according to the present invention, preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, Ci-3alkoxy, Ci-3alkoxyamino or N-Ci-3alkoxy-N’-Ci-3alkylcarbonyl;

R ² is hydrogen; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci ealkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O;

Z is Z ¹ ; and

R ⁵ is hydrogen or Ci-6alkyl.

In a further compound of formula (I) according to the present invention, more preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, methoxy, methoxyamino or N-methoxy-N’-methylcarbonyl;

R ² is hydrogen; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from fluoro and methyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O;

Z is Z ¹ ; and

R ⁵ is hydrogen, methyl or ethyl.

In a further still compound of formula (I) according to the present invention, preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy or N-Ci-3alkoxy-N’-Ci- 3alkylcarbonyl;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci-6alkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O or S;

Z is Z ² ;

R ⁷ is hydrogen, Ci-6alkyl, C3-salkenyl, C3-salkynyl, C3-6cycloalkyl or C3-6cycloalkylCi- ₂ alkyl; and R ⁸ is hydrogen, methyl or propen-2 -yl. More preferably, in a further still compound of formula (I) according to the present invention, more preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, Ci-3alkoxy, Ci-3alkoxyamino, Ci-3alkylcarbonyloxy or N-Ci-3alkoxy-N’-Ci- 3alkylcarbonyl;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci-6alkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O or S;

Z is Z ² ;

R ⁷ is hydrogen, methyl, ethyl, n-propyl, isopropyl, prop-2 -enyl, prop-2 -ynyl, cyclopropyl or cyclopropylmethyl; and

R ⁸ is hydrogen, methyl or propen-2 -yl.

In another compound of formula (I) according to the present invention, preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, Ci-3alkoxy or Ci-3alkylcarbonyloxy;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from halogen and Ci ealkyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O or S;

Z is Z ² ;

R ⁷ is hydrogen, Ci-6alkyl or C3-6cycloalkyl;

R ⁸ is hydrogen; or

R ⁷ and R ⁸ , together with the nitrogen to which they are bonded, form a 4-, 5- or 6-membered cycle optionally containing an additional heteroatom or group selected from O and NR ¹⁰ ; and

R ¹⁰ is hydrogen, methyl, methoxy, fluoromethoxy, difluoromethoxy, formyl or acyl.

In another compound of formula (I) according to the present invention, more preferably:

A is A-1 or A-2;

R ¹ is hydroxyl, thiol, methoxy or acetoxy;

R ² is hydrogen or methyl; or

R ¹ and R ² , together with the carbon to which they are bonded, form an oxy (=0) group;

R ³ and R ⁴ are the same and are selected from fluoro and methyl, or R ³ and R ⁴ , together with the carbon to which they are bonded, form a cyclopropyl ring;

Y is O or S; Z is Z ² ;

R ⁷ is methyl, ethyl, n-propyl, isopropyl or cyclopropyl;

R ⁸ is hydrogen or methyl; or

R ⁷ and R ⁸ , together with the nitrogen to which they are bonded, form a morpholino group.

Preferably, the compound according to formula (I) is selected from a compound 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below). The compounds of the present invention may be enantiomers of the compound of formula (I) as represented by a formula (la) or a formula (lb), wherein R ¹ and R ² are different substituents and R ³ and R ⁴ are the same and are selected from halogen and Ci-6alkyl, or R ³ and R ⁴ together with the carbon to which they are attached form a 3-, 4-, 5-, or 6-membered cycloalkyl group:

It is understood that, when in aqueous media, the compounds of formula (I) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (i.e., the compounds of formula (l-la) and formula ( I- 1 la ) as shown below, which may exist in tautomeric form as the compounds of formula (l-lb) and formula (l-llb)) at the CF3-oxadiazole motif. This dynamic equilibrium may be important for the biological activity of the compounds of formula (I).

Compounds of the present invention can be made as shown in the following schemes 1 to 10, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

The compounds of formula (l-a) wherein Y is O, can be obtained by a coupling transformation with compounds of formula (II), wherein Z represents -OR ⁵ or -NR ⁷ R ⁸ and compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (III), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI)2 or SOCI2, prior to treatment with the compounds of formula (II), preferably in a suitable solvent (e.g., dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or N,N- diisopropylethylamine, or under conditions described in the literature for an amide coupling. For examples, see Valeur, E.; Bradley, M. Chem. Soc. Rev. 2009, 38, 606 and Chinchilla, R., Najera, C. Chem. Soc. Rev. 2011 , 40, 5084. Compounds of formula (II) are either known or commercially available. This is shown in Scheme 1 below.

Scheme 1

The compounds of formula (l-a), can also be obtained from compounds of formula (l-c), wherein R ^5A is methyl or ethyl (preferably ethyl), and compounds of formula (IV), wherein Z represents -NR ⁷ R ⁸ either by activating the amine function of the compounds of formula (IV), a process that usually takes place by reacting amines with aluminium reagents such AIMes or DABAL-Me3, prior to treatment with the compounds of formula (l-c), preferably in a suitable solvent (e.g., dimethylformamide, tetrahydrofuran or 2- methyltetrahydrofuran), preferably at a temperature of between 25°C and 100°C, or by activating esters, compounds of formula (l-c) using catalyst such as lanthanum triflate or under the conditions described in the literature for an amide coupling. For examples of reaction by activating amines, the compounds of formula (IV) see Novak, A. et al. Tetrahedron Letters 2006, 47, 5767-5769 and for examples of reaction by activating esters using lanthanum trifluoromethanesulfonate, see Morimoto H. et al., Org. Lett. 2014, 16, 2018-2021 . Compounds of formula (IV) are either known or commercially available. This is shown in Scheme 2 below.

Scheme 2

Alternatively, compounds of formula (l-a), can be prepared from compounds of formula (V) by treatment with trifluoroacetic anhydride, trifluoroacetic chloride, or trifluoroacetic fluoride in the presence of a base (e.g., pyridine or 4-dimethylaminopyridine), in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature of between 25°C and 75°C. For related examples, see: WO 2003/028729 and WO 2010/045251 . This reaction is shown in Scheme 3 below.

Scheme 3

Compounds of formula (V) can be prepared from compounds of formula (VI) by treatment with a hydroxylamine hydrochloride in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature of between 0°C and 100°C. For related examples, see Kitamura, S. et al Chem. Pharm. Bull. 2001 , 49, 268 and WO 2013/066838. This reaction is shown in Scheme 4 below.

Scheme 4

Compounds of formula (l-a) can be obtained through a coupling transformation with compounds of formula (II) and compounds of formula (l-c), wherein R ^5A is hydrogen, methyl or ethyl (preferably methyl), in a suitable solvent (e.g., methanol), optionally in the presence of a base (e.g., triethylamine), at a temperature of between 25°C and 65°C. Compounds of formula (II) are either known or commercially available. This reaction is shown in Scheme 5 below.

Compounds of formula (l-c) wherein R ³ is F, R ⁴ is F, R ¹ is OH, R ^5A is ethyl and A and R ² are as defined for a compound of formula (I) can be prepared by reacting compounds of formula (VII) with ethyl-2, 2-difluoro- 2-trimethylsilylacetate (formula (VIII)), in a suitable solvent (e.g., dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C in the presence of fluorine anion donors such as tris(dimethy!amino)sulfonium difluorotrimethylsilicate (TASF), tetrabutylammonium fluoride (TBAF), potassium fluoride, cesium fluoride or the like; in analogy to the conditions reported in Tetrahedron Letters 2000, 41, 8763-8767 or JP10101614A. This reaction is shown in Scheme 6 below.

Scheme 6

Compounds of formula (l-c) wherein R ¹ is OFI, R ^5A is ethyl and A, Z, R ² , R ³ and R ⁴ are as defined for a compound of formula (I) can be prepared by reacting compounds of formula (VII) with O-silyl ketene acetals of formula (X) in a suitable solvent (e.g., dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C in the presence of lewis acid such as TiCU or SnCh or fluorine anion donors such as tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF), tetrabutylammonium fluoride (TBAF), potassium fluoride, cesium fluoride or the like. O-silyl ketene acetal of formula (X) can be prepared by the conditions known in literature such as Tetrahedron Letters 2000, 41, 8763-8767; Journal of Organic Chemistry, 2007, 72, 7125-7134; and Synthesis, 1989, 3, 163-6. This reaction is shown in Scheme 7 below.

Scheme 7

Additionally, compounds of formula (l-c) wherein R ¹ is OH and A, Z, R ² , R ³ and R ⁴ are as defined for a compound of formula (I) can be prepared by reacting compounds of formula (III) with ester enolates of formula (XII) in a suitable solvent (e.g., methyltetrahydrofuran or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C. Ester enolates of formula (XII) can be prepared by treatment of compounds of formula (XIII) with a base such as lithium diisopropylamide, in suitable solvent such as tetrahydrofuran using the conditions known in literature for example Journal of Organic Chemistry, 1971 , 36, 1 149. This reaction is shown in Scheme 8 below.

Scheme 8

Additionally, compounds of formula (l-a) wherein R ¹ is OH and A, Z, R ² , R ³ and R ⁴ are as defined for a compound of formula (I) can also be prepared from carbonyl compounds of formula (XVI), in a suitable solvent, (e.g., tetrahydrofuran), at a temperature of between 60°C and 75°C, and followed by the addition of a nucleophile, such as an alkyl Grignard reagent (e.g., Ci- ₄ alkylMgBr) in a suitable solvent, (e.g., tetrahydrofuran or ethanol), at a temperature of between 0°C and 25°C. For related examples, see Cogan, D., Ellman J. A. J. Am. Chem. Soc. 1999, 121 , 268. This reaction is shown in Scheme 9.

Scheme 9

Compounds of formula (l-b) wherein Y is S, can be prepared from compounds of formula (l-a), via reactions with a suitable sulfur source [e.g., elemental sulfur (Ss), Lawesson’s reagent, or P2S5], in an acceptable solvent (e.g., toluene, CH2CI2, CHCI3, tetrahydrofuran, f-butylmethyl ether), at a temperature of between 0°C to 100°C. For related examples, see Flermant, F. et al Organometallics, 2014, 33, 5643; Fleyde, C. et al E. J. Org. Chem. 2000, 19, 3273. This reaction is shown in Scheme 10.

Scheme 10

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 phytopathogen ic 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 a 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 dev/ation 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 gram inis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Flelminthosporium spp, Flemileia spp, Flistoplasma spp. including FI. 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 Liberty Link®.

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 CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) 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 CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 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 d- endotoxins, e.g. CrylAb, CrylAc, 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. or Xenorhabdus 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; ribosome-inactivating 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 CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative 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 CrylAb, 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).

T ransgenic 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 CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a Cry1 Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1 Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 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 ( Osthnia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb 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 CrylAb 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-1 150 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-1 150 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-1 150 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 ^c 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 CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

The compounds of formula (I) according to the present invention (including any one of compounds 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below)) may be used in controlling or preventing phytopathogen ic diseases, especially phytopathogen ic 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. Cry1 Ac (Cry1 Ac 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 201 1/022470, WO 201 1/022471 , 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.

Under certain circumstances, compounds of formula (I) according to the present invention when used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above), may display a synergistic interaction between the active ingredients. Additionally, to date, no cross-resistance has been observed between the compounds of formula (I) (including any one of compounds 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below)) and the current fungicidal solutions used to control Phakopsora pachyrhizi.

Indeed, 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’ Simoes 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: 121 1-1215.

Thus, in a preferred embodiment, the compounds of formula (I) (including any one of compounds 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below)), 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 compounds of formula (I) (including any one of compounds 1 .1 to 1 .33 described in Table T 1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below)) or fungicidal compositions according to the present invention comprising a compound of formula (I) may be used in controlling or preventing phytopathogen ic diseases, especially phytopathogen ic 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 Rusf, 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, 93M1 1 , 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, S1 1 -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 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below)), orfungicidal 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 above) 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.

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 or tackifiers 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, nonionic 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 sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; 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, anti-foaming 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 of 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-1 H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1 -methyl-indan-4-yl)-amide (1072957-71 -1 ), 1 -methyl-3-difluoromethyl-1 H- 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-ethylj-amide, (5-Chloro-2,4-dimethyl-pyridin- 3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, (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)-methoxyimino]-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, o[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-(1 H-1 ,2,4-triazol-1 -yl)-cycloheptanol, 2-(1 -ferf-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-metho xyacrylate, 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-methoxyacrylate, methyl (E)-2-[2-[6-(2,6- difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 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-methoxyacr ylate, methyl

(E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacry late, 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-methoxyacrylat e, methyl (E)-2-(2-(3- (1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl (E)-2-(2-[3-(alpha- hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, 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-fert- 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-methoxya crylate, methyl (E)- 2-[2-[6-(2-methyl-phenoxy)pyrimidin-4-yloxy]phenyl]-3-methox yacrylate, methyl (E)-2-[2-(5-bromo-pyridin- 2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]pheny l]-3-methoxyacrylate, methyl (E),(E)-2-[2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)ph enyl]-3-methoxyacrylate, methyl (E)- 2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3 -methoxy-acrylate, 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-methoxyacrylate, methyl (E),(E)-2-{2-[(4-chlorophenyl)- methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5-triazin-4- yloxy]phenyl}-3-methoxyacrylate, 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-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] th io )- b-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, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanylbutyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054, LY21 1795, 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, 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 96/1 1945, 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, esfen valerate, 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-1 1 11 , 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.

The following mixtures of the compounds of formula (I) with active ingredients are preferred. The abbreviation “TX” means one compound selected from the group consisting of the compounds as represented in Tables 1 .1 to 1 .12 (below), or in Tables 3.1 to 3.6 (below), or the compounds 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below):

a compound selected from the group of substances consisting of petroleum oils + TX, 1 ,1 -bis(4- chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1- naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, abamectin + TX, acequinocyl + TX, acetoprole + TX, acrinathrin + TX, aldicarb + TX, aldoxycarb + TX, alpha-cypermethrin + TX, amidithion + TX, amidoflumet + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azinphos-ethyl + TX, azinphos-methyl + TX, azobenzene + TX, azocyclotin + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzoximate + TX, benzyl benzoate + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromophos-ethyl + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbaryl + TX, carbofuran + TX, carbophenothion + TX, cymiazole + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenapyr + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorfenvinphos + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorpyrifos + TX, chlorpyrifos-methyl + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, clofentezine + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, cyflumetofen + TX, cyhalothrin + TX, cyhexatin + TX, cypermethrin + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-0 + TX, demephion-S + TX, demeton + TX, demeton-methyl + TX, demeton-0 + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, diafenthiuron + TX, dialifos + TX, diazinon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dicofol + TX, dicrotophos + TX, dienochlor + TX, dimefox + TX, dimethoate + TX, dinactin + TX, dinex + TX, dinex-diclexine + TX, dinobuton + TX, dinocap + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, disulfoton + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endosulfan + TX, endothion + TX, EPN + TX, eprinomectin + TX, ethion + TX, ethoate- methyl + TX, etoxazole + TX, etrimfos + TX, fenazaflor + TX, fenazaquin + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, fenvalerate + TX, fipronil + TX, fluacrypyrim + TX, fluazuron + TX, flubenzimine + TX, flucycloxuron + TX, flucythrinate + TX, fluenetil + TX, flufenoxuron + TX, flumethrin + TX, fluorbenside + TX, fluvalinate + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formothion + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, heptenophos + TX, hexadecyl cyclopropanecarboxylate + TX, hexythiazox + TX, iodomethane + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, lufenuron + TX, malathion + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos + TX, methamidophos + TX, methidathion + TX, methiocarb + TX, methomyl + TX, methyl bromide + TX, metolcarb + TX, mevinphos + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3- pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilacarb + TX, nitrilacarb 1 :1 zinc chloride complex + TXomethoate + TX, oxamyl + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phenthoate + TX, phorate + TX, phosalone + TX, phosfolan + TX, phosmet + TX, phosphamidon + TX, phoxim + TX, pirimiphos-methyl + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, profenofos + TX, promacyl + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaben + TX, pyridaphenthion + TX, pyrimidifen + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, spirodiclofen + TX, spiromesifen + TX, SSI-121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau-fluvalinate + TX, tebufenpyrad + TX, TEPP + TX, terbam + TX, tetrachlorvinphos + TX, tetradifon + TX, tetranactin + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trichlorfon + TX, trifenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichlone + TX, dichlorophen + TX, endothal + TX, fentin + TX, hydrated lime + TX, nabam + TX, quinoclamine + TX, quinonamid + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, emamectin + TX, emamectin benzoate + TX, piperazine + TX, spinosad + TX, thiophanate + TX, chloralose + TX, endrin + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1 -hydroxy-1 H- pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicin + TX, fenaminosulf + TX, formaldehyde + TX, hydrargaphen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus firmus + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. aizawai + TX, Bacillus thuringiensis subsp. israelensis + TX, Bacillus thuringiensis subsp. japonensis + TX, Bacillus thuringiensis subsp. kurstaki + TX, Bacillus thuringiensis subsp. tenebrionis + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Helicoverpa zea NPV + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholate + TX, bisazir + TX, busulfan + TX, diflubenzuron + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1 -yl acetate with (E)-dec-5-en-1 -ol + TX, (E)-tridec-4-en-1 -yl acetate + TX, (E)-6- methylhept-2-en-4-ol + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1 -yl acetate + TX, (Z)-hexadec-11 -enal + TX, (Z)-hexadec-l 1 -en-1 -yl acetate + TX, (Z)-hexadec-13-en-11 -yn-1 -yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1 -al + TX, (Z)-tetradec-9-en-1 -ol + TX, (Z)-tetradec-9-en- 1 -yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1 -yl acetate + TX, (9Z,1 1 E)-tetradeca-9,11 -dien-1 -yl acetate + TX, (9Z,12E)-tetradeca-9, 12-dien-1 -yl acetate + TX, 14-methyloctadec-1 -ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodec-8-en-1 -yl acetate + TX, dodec-9-en-1 -yl acetate + TX, dodeca-8 + TX, 10-dien-1 -yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, frontalin + TX, gossyplure + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyl eugenol + TX, muscalure + TX, octadeca-2,13-dien-1 -yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11 -en-1 -yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure Bi + TX, trimedlure B2 + TX, trimedlure C, trunc-call + TX, 2-(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX, oxamate + TX, picaridin + TX, 1 - dichloro-1 -nitroethane + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1 ,2-dichloropropane + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene + TX, 1 -bromo-2-chloroethane + TX, 2,2,2-trichloro-1 -(3,4- dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1 ,3- dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl- 1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1 ,3-dione + TX, 2-methyl(prop-2- ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1 -chloroprop-1-ene + TX, 3-methyl-1 -phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1 -enyl dimethylcarbamate + TX, acephate + TX, acetamiprid + TX, acethion + TX, acrylonitrile + TX, alanycarb + TX, aldrin + TX, allethrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azadirachtin + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, bendiocarb + TX, benfuracarb + TX, bensultap + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioallethrin + TX, bioallethrin S-cyclopentenyl isomer + TX, bioethanomethrin + TX, biopermethrin + TX, bioresmethrin + TX, bis(2-chloroethyl) ether + TX, bistrifluron + TX, borax + TX, bromfenvinfos + TX, bromo- DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, cadusafos + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbosulfan + TX, cartap + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlorethoxyfos + TX, chlorfluazuron + TX, chlormephos + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, chromafenozide + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, cloethocarb + TX, clothianidin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cycloprothrin + TX, cyfluthrin + TX, cyphenothrin + TX, cyromazine + TX, cythioate + TX, d-limonene + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, deltamethrin + TX, diamidafos + TX, dicapthon + TX, dichlofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilor + TX, dimefluthrin + TX, dimetan + TX, dimethrin + TX, dimethylvinphos + TX, dimetilan + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinotefuran + TX, diofenolan + TX, dioxabenzofos + TX, dioxacarb + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, El 1642 + TX, EMPC + TX, empenthrin + TX, EPBP + TX, epofenonane + TX, esfenvalerate + TX, etaphos + TX, ethiofencarb + TX, ethiprole + TX, ethoprophos + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etofenprox + TX, EXD + TX, famphur + TX, fenamiphos + TX, fenchlorphos + TX, fenethacarb + TX, fenfluthrin + TX, fenitrothion + TX, fenobucarb + TX, fenoxacrim + TX, fenoxycarb + TX, fenpirithrin + TX, fensulfothion + TX, fenth ion-ethyl + TX, flonicamid + TX, flubendiamide + TX, flucofuron + TX, flufenerim + TX, flufenprox + TX, fonofos + TX, fosmethilan + TX, fospirate + TX, fosthiazate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, gamma-cyhalothrin + TX, guazatine + TX, guazatine acetates + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, halofenozide + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, hexaflumuron + TX, HHDN + TX, hydramethylnon + TX, hydrogen cyanide + TX, hydroprene + TX, hyquincarb + TX, imidacloprid + TX, imiprothrin + TX, indoxacarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprocarb + TX, isoprothiolane + TX, isothioate + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lambda- cyhalothrin + TX, lead arsenate + TX, lepimectin + TX, leptophos + TX, lirimfos + TX, lythidathion + TX, m- cumenyl methylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mecarphon + TX, menazon + TX, mercurous chloride + TX, mesulfenfos + TX, metaflumizone + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methoxyfenozide + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, metofluthrin + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nitenpyram + TX, nithiazine + TX, nornicotine + TX, novaluron + TX, noviflumuron + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, 0,0- diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, oxydemeton-methyl + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, permethrin + TX, PH 60- 38 + TX, phenkapton + TX, phenothrin + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pirimetaphos + TX, pirimicarb + TX, pirimiphos-ethyl + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, prallethrin + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, propaphos + TX, prothiofos + TX, protrifenbute + TX, pymetrozine + TX, pyraclofos + TX, pyrazophos + TX, pyresmethrin + TX, pyridalyl + TX, pyriproxyfen + TX, quassia + TX, quinalphos-methyl + TX, quinothion + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadilla) + TX, schradan + TX, sebufos + TX, selamectin + TX, SI-0009 + TX, silafluofen + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, spirotetramat + TX, sulcofuron + TX, sulcofuron- sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebufenozide + TX, tebupirimfos + TX, teflubenzuron + TX, tefluthrin + TX, temephos + TX, terallethrin + TX, terbufos + TX, tetrachloroethane + TX, tetramethrin + TX, theta-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodicarb + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tolfenpyrad + TX, tralomethrin + TX, transfluthrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, triflumuron + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, xylylcarb + TX, zeta-cypermethrin + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, and brofluthrinate + TX, cyantraniliprole + TX, chlorantraniliprole + TX, cyenopyrafen + TX, pyrifluquinazon + TX, spinetoram + TX, sulfoxaflor + TX, flufiprole + TX, meperfluthrin + TX, tetramethylfluthrin + TX, triflu mezopyrim + TX,bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, metaldehyde + TX, niclosamide + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + TX, pyriprole + TX, imicyafos + TX, 1 ,2-dibromo-3-chloropropane + TX, 1 ,3-dichloropropene + TX, 3,4- dichlorotetrahydrothiophene 1 ,1 -dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, phosphocarb + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, fluensulfone + TX, potassium ethylxanthate + TX.acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, alpha-chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride) + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene) + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, mercuric oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazole + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidine + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, ofurace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole+ TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, iprodione + TX, myclozoline + TX, procymidone + TX, vinclozoline+ TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, f fenaminstrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid+ TX, bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal- isopropyl + TX, edifenphos + TX, iprobenphos + TX, phosdiphen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfo- carb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-d ifluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, afidopyropen + TX.pyflubumide + TX, isoflucypram + TX, isotianil + TX, dipymetitrone + TX, 6-ethyl-5,7- dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1 ,1 - dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3- carbonitrile + TX, (R)-3-(difluoromethyl)-1 -methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5 -dimethyl-pyrazol-3-amine + TX, 4-(2- Bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1 ,3-dimethyl-1 H-pyrazol-5-amine + TX, fluindapyr + TX, jiaxiangjunzhi + TX, Ivbenmixianan + TX, dichlobentiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4- dihydro-3,3-dimethylisoquinolin-1 -yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiprolin + TX, tert-butyl N-[6-[[[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, mefentrifluconazole+ TX, ipfentrifluconazole+ TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1 -dimethyl- indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-e thyl-N-methyl-formamidine + TX, [2-[3-[2-[1 -[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl ]thiazol-4-yl]-4,5-dihydroisoxazol-5- yl]-3-chloro-phenyl] methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2- methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazi ne + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1 -methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4- methyl-tetrazol-5-one + TX, 1 - methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1 -yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctradin + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1 -(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pe nt-3-enamide + TX, (florylpicoxamid + TX, and fenpicoxamid+ TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamid + TX, N-[2-[2,4- dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4- (trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, phenamacril + TX, 5-amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2:1 ) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3- ethyl-1 ,1 -dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1 ,1 ,3- trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1 -difluoro-2-hydroxy-3- (1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(Difluoromethyi)-N-((3R)- 1 ,1 ,3-trimethyl indan-4-yl )pyrid ine-3-carboxam ide + TX, a-(1 ,1 -dimethylethyl)-a-[4'-(trifluoromethoxy)[1 ,T- biphenyl]-4-yl]-5-pyrimidinemethanol + TX.

The active ingredient mixture of the compounds of formula (I) selected from one compound as represented in Tables 1 .1 to 1 .12 (below), or in Tables 3.1 to 3.6 (below), or a compound 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below), is 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 as represented in Tables 1 .1 to 1 .12 (below), or in Tables 3.1 to 3.6 (below), or a compound 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below), 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 a compound as represented in Tables 1 .1 to 1 .12 (below), or in Tables 3.1 to 3.6 (below), or a compound 1 .1 to 1 .33 described in Table T1 (below), the compounds 2.1 to 2.18 described in Table T2 (below), or the compounds 3.1 and 3.2 described in Table T3 (below), and the active ingredient(s) 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 (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 granular form (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 1 g 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 condensation 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.

Table 1 .1 : This table discloses 104 specific compounds of formula (T-1 ):

wherein A is A-1 , R ³ is F, R ⁴ is F, R ¹ and R ² are as defined in Table 2 and -NR ⁷ R ⁸ is as defined below in Table 1 and Y=0.

Each of Tables 1 .2 to 1 .12 (which follow Table 1 .1 ) make available 104 individual compounds of the formula (T-1 ) in which A, R ¹ , R ² , R ³ , R ⁴ and Y are specifically defined below in Tables 1 .2 to 1 .12, which refer to Table 1 wherein -NR ⁷ R ⁸ is specifically defined, and Table 2 wherein R ¹ and R ² are specifically defined.

Table 1

Table 2

Table 1 .2: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-1 , R ³ is F, R ⁴ is F, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 1 .3: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ is F, R ⁴ is F, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=0.

Table 1 .4: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ is F, R ⁴ is F, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 1 .5: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-1 , R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=0.

Table 1.6: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-1 , R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 1.7: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=0.

Table 1.8: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 1 .9: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-1 , R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=0.

Table 1.10: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-1 , R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 1.11 : This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=0. Table 1.12: This table discloses 104 specific compounds of formula (T-1 ) wherein A is A-2, R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined in Table 2, -NR ⁷ R ⁸ is as defined in Table 1 , and Y=S.

Table 3.1 : This table discloses 88 specific compounds of formula (T-3):

wherein A is A-1 , R ³ is F, R ⁴ is F, and R ¹ , R ² are as defined above in Table 2, and R ⁵ is as defined below in Table 3.

Each of Tables 3.2 to 3.6 (which follow Table 3.1 ) make available 88 individual compounds of the formula (T-3) in which A, R ¹ , R ² , R ³ and R ⁴ are specifically defined in Tables 3.2 to 3.6, which refer to Table 3 wherein R ⁵ is specifically defined, and Table 2 wherein R ¹ and R ² are specifically defined. Table 3

Table 3.2: This table discloses 88 specific compounds of formula (T-3) wherein A is A-1 , R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined above in Table 2, and R ⁵ is as defined above in Table 3. Table 3.3: This table discloses 88 specific compounds of formula (T-3) wherein A is A-1 , R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined above in Table 2, and R ⁵ is as defined above in Table 3.

Table 3.4: This table discloses 88 specific compounds of formula (T-3) wherein A is A-2, R ³ is F, R ⁴ is F, R ¹ and R ² are as defined in Table 2, and R ⁵ is as defined above in Table 3. Table 3.5: This table discloses 88 specific compounds of formula (T-3) wherein A is A-2, R ³ is Me, R ⁴ is Me, R ¹ and R ² are as defined above in Table 2, and R ⁵ is as defined above in Table 3.

Table 3.6: This table discloses 88 specific compounds of formula (T-3) wherein A is A-2, R ³ and R ⁴ together form a cyclopropyl ring, R ¹ and R ² are as defined above in Table 2, and R ⁵ is as defined above in Table 3.

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 method A is as follows:

The description of the LC/MS apparatus and the method A is:

SQ Detector 2 from Waters

Ionisation method: Electrospray

Polarity: positive and negative ions

Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 150, Desolvation

Temperature (°C) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650

Mass range: 100 to 900 Da

DAD Wavelength range (nm): 210 to 500

Method Waters ACQUITY UPLC with the following HPLC gradient conditions:

(Solvent A: Water/Methanol 20:1 + 0.05% formic acid and Solvent B: Acetonitrile+ 0.05% formic acid)

Time (minutes) A (%) Flow rate (ml/m in)

0 100 0 0.85 1 .2 0 100 0.85

1 .5 0 100 0.85

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.

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, e.g., 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 water to 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.

AIBN = azobisisobutyronitrile

DIBAL-H = diisobutylaluminium hydride

DIPEA = N,N-di-isopropylethylamine

EtOAc = ethyl acetate

HCI = hydrochloric acid

mp = melting point

°C = degrees Celsius

N = normal

NBS = A/-bromosuccinimide

M = molar

TFAA = trifluoroacetic acid anhydride

THF = tetrahydrofuran

Rt = retention time (in minutes)

LC/MS = Liquid Chromatography Mass Spectrometry (description of the apparatus and the

methods used for LC/MS analysis are given above)

Preparation Examples

Example 1 : This example illustrates the preparation of ethyl 2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl) -1 ,2,4-oxadiazol-3-yl]phenyl]propanoate (Compound 2.11 of Table T2)

Step 1 : Preparation of N'-hvdroxy-4-methyl-benzamidine

To a suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water (440 mL) was added at room temperature hydroxylamine hydrochloride (41.1 g, 0.58 mol), potassium carbonate (65.4 g, 0.47 mol) and 8-hydroxyquinoline (0.22 g, 1 .5 mmol). The reaction mixture was heated at 80°C for 4 hours. The mixture was then cooled to room temperature and diluted with 2N HCI to pH 8. The volatiles were removed under reduced pressure and the reaction contents were filtered, washed with water, and dried under vacuum to afford 39.1 g of the title compound. LC/MS (Method A) retention time = 0.23 minutes, 151 .0 (M+H).

Step 2: Preparation of 3-(p-tolvn-5-(trifluoromethvn-1 ,2.4-oxadiazole

To a solution of N'-hydroxy-4-methyl-benzamidine (38.7 g, 0.25 mol) in 2-methyltetrahydrofuran (750 mL) was added TFAA at 0°C. The reaction mixture was stirred at 15°C for two hours then diluted with water. The organic layer was separated, washed successively with a saturated aqueous sodium bicarbonate solution, a saturated aqueous ammonium chloride solution, and water, then dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (heptane/EtOAc eluent gradient 99:1 to 90:10) to afford 54.1 g of the title compound as clear oil, which solidified after storage. LC/MS (Method A) retention time = 1 .15 minutes, mass not detected.

¹ H NMR (400 MHz, CDCb) d ppm: 8.00 (d, 2H), 7.32 (d, 2H), 2.45 (s, 3H).

¹⁹ F NMR (400 MHz, CDCb) d ppm: -65.41 (s).

Step 3a: Preparation of 3-[4-(bromomethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole

A mixture of 3-(p-tolyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (56.0 g, 0.24 mol) and NBS (45.4 g, 0.25 mol) in tetrachloromethane (480 mL) under argon was heated to 70°C. AIBN (4.0 g, 24 mmol) was added and the reaction mixture was stirred at 65°C for 18 hours. The mixture was cooled to room temperature and diluted with dichloromethane and water. The layers were separated and the organic layer was washed with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 100:0 to 95:5) to afford 44.7 g of the title compound as a white solid mp: 58-63°C.

¹ H NMR (400 MHz, CDCb) d ppm: 8.1 1 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

¹⁹ F NMR (400 MHz, CDCb) d ppm: -65.32 (s). By-product, 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole was isolated as a white solid mp: 61 -66°C.

¹ H NMR (400 MHz, CDCb) d ppm: 8.15 (d, 2H), 7.73 (d, 2H), 6.68 (s, 1 H).

1 ⁹ F NMR (400 MHz, CDCb) d ppm: -65.34 (s).

Step 3b: Preparation of 3-[4-(bromomethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole

To a 1 :9 ratio mixture of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole and 3-[4- (dibromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (10.2 g) in acetonitrile (95 mL), water (1.9 mL) and DIPEA (6.20 mL, 35.7 mmol) was added diethylphosphite (4.7 mL, 35.7 mmol) at 5°C. The mixture was stirred at 5-10°C for two hours, 1 M HCI was added, and volatiles were removed under reduced pressure. The resultant white slurry was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 9:1 ) to afford 7.10 g of the title compound as a white solid mp: 58-63 °C.

¹ H NMR (400 MHz, CDCb) d ppm: 8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).

¹⁹ F NMR (400 MHz, CDCb) d ppm: -65.32 (s).

Step 4: Preparation of 4-[5-(trifluoromethvn-1.2.4-oxadiazol-3-vHbenzaldehvde

In a 75 mL multineck flask equipped with stirrer, at -78°C under argon, DIBAL-H, 1.0M in toluene (16 mL, 16.0 mmol) was added drop-wise to a solution of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzamide (4.1 g, 13.3 mmol) in 2-methyltetrahydrofuran (90 mL). The mixture was stirred for two hours at -78°C, and for one hour at 0°C. Complete conversion observed by LC/MS. The mixture was quenched by drop-wise addition of saturated aqueous ammonium chloride solution. Precipitation of a white solid occurred, and 4 M HCI was added until full solubilisation. The mixture was extracted with ethyl acetate, the combined organics dried over magnesium sulfate and reduced under pressure to afford the crude product as beige solid. The crude was subject to flash chromatography over silica gel (heptane/EtOAc eluent gradient 99: 1 to 90:10) to afford 2.9 g of the title compound as a white solid mp: 40-50°C.

¹ H NMR (400 MHz, CDCb) d ppm: 10.12 (s, 1 H), 8.31 (d, 2H), 8.05 (d, 2H).

¹⁹ F N MR (400 MHz, CDCb) d ppm : -65.29 (s).

Step 5: Preparation of ethyl 2.2-difluoro-3-hvdroxy-3-[4-[5-(trifluoromethyl)-1 .2.4-oxadiazol-3-yllphenyll propanoate (Compound 2.1 1 in Table T2)

To a stirred solution of ethyl 2,2-difluoro-2-trimethylsilylacetate (1 .8 g, 9.09 mmol) and 4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzaldehyde (2.0 g, 8.26 mmol) in dry THF (30 mL) was added tetrabutylammonium difluorotriphenylsilicate (0.5 g, 0.83 mmol) at 0°C. The reaction mass was stirred for 12 hours at room temperature. The reaction mass was diluted with 45 mL water and the mixture was extracted with ethyl acetate. Combined organics were dried over magnesium sulfate and reduced under pressure to afford the crude product. The crude was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99: 1 to 70:30) to afford 0.6 g of the title compound as a white solid.

¹ H NMR (400 MHz, DMSO-c/6) d ppm: 8.10 (d , J=8.44 Hz, 2H) 7.70 (d, J=8.19 Hz, 2H ) 6.87 (d,

J= 5.75 Hz, 1 H) 5.24 (br d, J=1 7.73 Hz, 1 H) 4.32 (q, J=7.1 1 , 1 .65 Hz, 2H) 1 .26 (t, J= 7.09 Hz, 3H).

¹⁹ F N MR (377 MHz, DMSO-c/6) d ppm: -64.71 (s, 1 F) -109.98 (d, 1 F) -120.61 (d, 1 F).

Example 2: This example illustrates the preparation of 2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]propanoic acid (Compound 2.10 in Table T2)

To a stirred solution of ethyl 2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]propanoate (2.4 g, 6.6 mmol) in THF (10 mL/g), a solution of LiOH (0.3 g, 13 mmol) in water (10 mL/g) was added at ambient temperature. The resulting mixture was stirred at ambient temperature for 6 hours. The reaction mass was then acidified with 1 N HCI. Precipitation of a white solid occurred, which was collected by filtration. The white solid obtained was washed with water and dried under vacuum to afford 1 .5 g of 2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]propanoic acid as white solid.

¹ H NMR (400 MHz, DMSO -c/6) d ppm: 8.08 (d, J=8.31 Hz, 2H) 7.68 (d, J=8.19 Hz, 2H) 5.15 - 5.24

(m, 1 H).

¹⁹ F NMR (proton decoupled, 377 MHz, DMSO-c/6) d ppm: -59.95 (s, 1 F) -106.3 (d, 1 F), -1 16.14 (d, 1 F).

LCMS: M+H: 338.9 (RT 1.28 min).

Example 3: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]phenyl]propanamide (Compound 1 .22 in Table T1 )

To a stirred solution of 2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]propanoic acid (135 mg, 0.40 mmol) in dichloromethane (10 mL/g) were added ethylamine hydrochloride (35.8 mg, 0.44 mmol), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (102 mg, 0.52 mmol) and 1 -hydro xybenzotriazole hydrate (30 mg, 0.20 mmol), followed by triethylamine (0.17 mL, 1 .20 mmol) and allowed to stir for 16 hours. The reaction mass was diluted with 15 mL water and the mixture was extracted with dichloromethane. The combined organics were dried over magnesium sulfate and evaporated to afford the crude product. The crude product was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 90:10 to 50:50) to afford 60 mg of the title compound as a white solid.

¹ H NMR (400 MHz, DMSO-c/6) d ppm: 8.69 (br s, 1 H) 8.08 (d, J=8.44 Hz, 2H) 7.66 (d, J=8.31 Hz,

2H) 6.63 (d, J=5.75 Hz, 1 H) 5.25(m, 1 H) 3.15 (m, 2H) 1 .02 (t, J=7.21 Hz, 3H).

¹⁹ F NMR (proton decoupled, 377 MHz, DMSO-c/6) d ppm: -64.71 (s, 1 F), -1 12.04 (d, 1 F), -121.9 (d,

1 F).

MS: M+H: 366 (RT 1 .482 min). Example 4: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-methoxy-3-[4-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]phenyl]propanamide (Compound 1 .14 in Table T1 )

To a stirred solution of N-ethyl-2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]propanamide (90 mg, 0.25 mmol) in acetonitrile (10 mL/g) were added potassium carbonate potassium carbonate (85 mg, 0.62 mmol) and dimethyl sulfate (47 mg, 0.37 mmol). The resulting reaction mixture was allowed to stir at 60 °C for 16 hours. The mixture was quenched by drop-wise addition of saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate, and the combined organics were dried over magnesium sulfate and evaporated to afford the crude as beige solid. The crude product was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 50: 50) to afford 16 mg of the title compound as a white solid.

¹ H NMR (400 MHz, CDCb) d ppm: 8.15 - 8.19 (d, J=8.2, 2H) 7.61 (m, J=8.19 Hz, 2H) 6.34 (s, 1 H) 4.92 (dd, J=18.71 , 6.24 Hz, 1 H) 3.35 -3.44 (q, 2H) 3.40 (s, 3H) 1 .20 (t, J=7.34 Hz, 3H).

¹⁹ F NMR (377 MHz, CDCb) d ppm: -65.34 (s, 1 F) -1 11 .4 (d, 1 F) -124.7 (d, 1 F).

LCMS: M+H: 380.1 (R _t : 1 .507 min).

Example 5: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-oxo-3-[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]propanamide (Compound 1 .17 in Table T 1 )

To stirred solution of N-ethyl-2,2-difluoro-3-hydroxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yljphenyljpropanamide (100 mg, 0.27 mmol) in dichloromethane (3 mL, 30 mL/g) was added Dess-Martin periodinane (144 mg, 0.33 mmol) at ambient temperature. The resulting mixture was stirred at ambient temperature for 12 hours. The mixture was quenched by drop-wise addition of saturated aqueous sodium bicarbonate solution. The mixture was extracted with dichloromethane, and the combined organics were washed with copious amounts of water. The organic layer was then dried over magnesium sulfate and evaporated to afford the crude mass. The crude product was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 50: 50) to afford 22 mg of the title compound as a white solid.

Ή NMR (400 MHz, CDCb) d ppm: 8.26 - 8.34 (m, 4H) 6.51 (br s, 1 H) 3.44 (q, 2H) 1 .25 (t, 3H).

1 ⁹ F NMR (proton decoupled, 377 MHz, CDCb) d ppm: -65.27 (s, 1 F) -108.46 (s, 2F).

LCMS: M+H: 363.9 (RT: 1 .507 min).

Example 6: This example illustrates the preparation of ethyl 2,2-difluoro-3-hydroxy-3-[5-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]propanoate (Compound 2.3 in Table T2)

Step 1 : Preparation of N'-hvdroxy-5-methyl-thiophene-2-carboxamidine

To a suspension of 5-methylthiophene-2-carbonitrile (9.0 g, 73 mmol) in ethanol (365 mL) stirring at room temperature was added triethylamine (20.6 mL, 146 mmol) followed by the portion-wise introduction of hydroxylamine hydrochloride (10.3 g, 146 mmol). The reaction contents were heated at reflux for 3.5 hours, cooled to 25°C, and concentrated under reduced pressure to provide 32.0 g of the title compound as a crude residue which was used in the next transformations without further purification. LC/MS (Method A) retention time = 0.24 minutes, 156 (M+H).

Step 2: Preparation of 3-(5-methyl-2-thienvn-5-(trifluoromethvn-1 ,2.4-oxadiazole

To a suspension of crude N'-hydroxy-5-methyl-thiophene-2-carboxamidine (32.0 g) in tetrahydrofuran (1000 mL) was introduced pyridine (24 mL, 292 mmol) and the contents cooled to 10°C. T o this suspension, trifluoroacetic anhydride (30.9 mL, 219 mL) was introduced drop-wise. The reaction mixture was allowed to warm to 25°C overnight, and then concentrated under reduced pressure. The resultant residue was dissolved in ethyl acetate, washed with an aqueous 1 M HCI solution, water, and a saturated aqueous Na ₂ CC>3 solution. The organic layer was dried over sodium sulfate, filtered, and the volatiles were removed under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a cyclohexane/EtOAc eluent gradient to afford 13.1 g of the title compound as a clear oil. LC/MS (Method A) retention time = 1 .13 minutes, mass not detected.

¹ H NMR (400 MHz, CDCb) d ppm: 7.68 (d, 1 H), 6.84 (d, 1 H), 2.57 (s, 3H).

¹⁹ F NMR (400 MHz, CDCb) d ppm: -65.44 (s).

Step 3a: Preparation of 3-f5-(bromomethvn-2-thienyll-5-(trifluoromethvn-1 .2.4-oxadiazole

To a solution of 3-(5-methyl-2-thienyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (13.1 g, 55.7 mmol) and tetrachloromethane (11 1 mL) under argon was added AIBN (0.93 g, 5.6 mmol) then NBS (1 1 .02 g, 61 .3 mmol). The contents were heated at 70°C for 18 hours. The mixture was cooled to 25°C then diluted with dichloromethane and water. The layers were separated, the organic phase was dried over sodium sulfate, and the volatiles were removed under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a cyclohexane/EtOAc eluent gradient to afford 3.86 g of the title compound as a yellow oil. LC/MS (Method A) retention time = 1.14 minutes, mass not detected.

¹ H NMR (400 MHz, CDCh) d ppm: 8.1 1 (d, 1 H), 7.55 (d, 1 H), 4.53 (s, 2H).

¹⁹ F NMR (400 MHz, CDC ) d ppm: -65.31 (s).

By-product, 3-[5-(dibromomethyl)-2-thienyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole was as a yellow amorphous solid (13.0 g).

¹ H NMR (400 MHz, CDCb) d ppm: 7.73 (d, 1 H), 7.32 (d, 1 H), 6.91 (s, 1 H).

Step 4: Preparation of 5-[5-(trifluoromethvn-1 ,2.4-oxadiazol-3-vHthiophene-2-carbaldehvde

To a stirred solution of 4-methylmorpholine-N-oxide (7.33 g, 60.68 mmol) and activated 4A molecular sieves (50 g) in acetonitrile (8 mL/mmol), was added 3-[5-(bromomethyl)-2-thienyl]-5- (trifluoromethyl)-l ,2,4-oxadiazole (5 g, 15.1 mmol) as a solution in 10 ml acetonitrile at a temperature of 0°C. The reaction was continued to stir at 10°C for 3 hours. The solids were filtered then dried under vacuum. The resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 : 0.1 ) to afford 2.4 g of the title compound as a pale yellow solid.

¹ H NMR (400 MHz, CDCb) d ppm: 10.02 (s, 1 H) 7.97 (d, J=3.91 Hz, 1 H) 7.84 (d, J=3.91 Hz, 1 H).

Step 5: Preparation of ethyl 2,2-difluoro-3-hydroxy-3-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl] propanoate (Compound 2.3 in Table T2)

To a stirred solution of ethyl 2,2-difluoro-2-trimethylsilyl-acetate (261 mg 1.33 mmol) and 5-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]thiophene-2-carbaldehyde (300 mg, 1 .21 mmol) in dry tetrahydrofuran (3 mL, 37 mmol), was added tetrabutylammonium difluorotriphenylsilicate (67 mg 0.12 mmol) at 0°C. The reaction mass was then allowed to stir for 12 hours at ambient temperature and diluted with water. The contents were extracted with ethyl acetate and the total combined organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 :1 ) to afford 1 10 mg of the title compound as a white solid.

¹ H NMR (400 MHz, CDCb) d ppm: 1.35 (t, 3H) 4.38 (m, 2H) 5.50 (dd, 114) 7.24 (d, 1 H) 7.81 (d, 1 H).

¹⁹ F NMR (proton decoupled, 377 MHz, CDCb) d ppm: -65.32 (s, 1 F) -112.26 (d, 1 F) -120.15 (d, 1 F).

Example 7: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-hydroxy-3-[5-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]propanamide (Compound 1 .4 in Table T 1 )

To a stirred solution of ethyl 2,2-difluoro-3-hydroxy-3-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]propanoate (400 mg, 1 .07 mmol) in toluene (10 ml/g) were added ethylamine (2.0 mol/l) in tetrahydrofuran (2.7 ml, 5.37 mmol) followed by bis(trimethylaluminum)-1 ,4-diazabicyclo[2.2.2]octane adduct (421 mg, 1 .61 mmol) at 0°C. The resulting mixture was stirred at 70°C for overnight. The reaction mixture was quenched with by slow addition of water (40 mL). The contents were extracted with ethyl acetate and the total combined organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 90:1 to 60:40) to afford 320 mg of the title compound as a white solid; mp 141 -143 °C.

¹ H NMR (400 MHz, DMSO-c/6) d ppm: 8.82 (t, J= 5.82 Hz, 1 H) 7.85 (d, J= 3.76 Hz, 1 H) 7.27 (d,

J= 3.76 Hz, 1 H) 7.20 (d, J=6.02 Hz, 1 H) 5.51 (m, 1 H) 3.12 - 3.23 (m, 2H) 1 .04 (t, J= 7.28 Hz, 3H). 1 ⁹ F NMR (proton decoupled, 376 MHz, DMSO-c/6) d ppm: -64.74 (s, 1 F) -1 1 1.76 (s, 1 F) -122.61 (s, 1 F).

Example 8: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-oxo-3-[5-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]-2-thienyl]propanamide (Compound 1 .3 in Table T 1 )

To stirred solution of N-ethyl-2,2-difluoro-3-hydroxy-3-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]propanamide (130 mg, 0.35 mmol) in dichloromethane (3 mL/mmol) was added Dess-Martin periodinane (225 mg, 0.53 mmol) at ambient temperature. The resulting mixture was stirred at ambient temperature for 12 hours. The mixture was quenched by drop-wise addition of saturated aqueous sodium bicarbonate solution, extracted with dichloromethane, and the combined organics were washed with copious amounts of water before being dried over magnesium sulfate and evaporated to afford the crude mass. The crude product was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 80: 20) to afford 65 mg of the title compound as a white solid.

¹ H NMR (400 MHz, CDCh) d ppm: 8.21 (d, J=4.68 Hz, 1 H) 7.94 (d, J=4.16 Hz, 1 H) 6.38 - 6.59 (m, 1 H) 3.42 (quin J=6.85 Hz, 2H) 1.24 (t, J= 7.27 Hz, 3H). ¹⁹ F NMR (377 MHz, CDC ) d ppm: -65.21 (s, 1 F) -109.88 (s, 1 F).

LCMS: M+H: 369.9 (Rt: 1 .50 min).

Example 9: This example illustrates the preparation of N-ethyl-2,2-difluoro-3-hydroxy-3-[5-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]-2-thienyl]butanamide (Compound 1 .1 of Table T 1 )

To a solution of N-ethyl-2,2-difluoro-3-oxo-3-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]propanamide (40 mg, 0.10 mmol) in tetrahydrofuran (10 mL/mmol, 0.309 mmol) was added dropwise methylmagnesium chloride solution (1 M) in THF (0.15 ml_, 0.15 mmol) at -78°C. The resulting reaction mass was stirred at -78°C for 2 hours. The mixture was quenched by drop-wise addition of saturated aqueous ammonium chloride solution. The resulting mixture was extracted with ethyl acetate, the combined organics were dried over magnesium sulfate and evaporated to afford the crude mass. The crude product was subject to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99:1 to 70: 30) to afford 12 mg of the title compound as colorless gummy mass.

¹ H NMR (400 MHz, DMSO-c/6) d ppm: 7.75 (d, J=3.91 Hz, 1 H) 7.13 (d, J=3.91 Hz, 1 H) 6.41 (brs,

1 H) 5.38 (s, 1 H) 3.23 - 3.35 (m , 2H) 1 .77 (s, 3H) 1 .08 (t, J=7.27 Hz, 3H).

¹⁹ F NMR (proton decoupled, 377 MHz, DMSO-c/6) d ppm: -64.74 (s, 1 F) -1 14.9 (d, 1 F). Table T 1 : Melting point (mp) data and/or retention times (R) for compounds according to formula (D:

Table T2: Melting point (mp) data and/or retention times (RO for compounds according to formula (D:

Table T3: Melting point (mp) data and/or retention times (RO for compounds according to formula (D:

BIOLOGICAL EXAMPLES

General examples of leaf disk tests in well plates:

Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse. The cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar. The leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.

General examples of liquid culture tests in well plates:

Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 pi of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/m ycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated in the dark at 24°C and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check is calculated.

Example 1 : Fungicidal activity against Puccinia recondita f. so. tritici / wheat / leaf disc preventative (Brown rust)

Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 ^° C and 75% relative humidity (rh) under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).

The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Compounds (from Table T1 ) 1 .1 , 1 .2, 1 .3, 1 .4, 1 .5, 1 .6, 1 .7, 1 .8, 1 .9, 1 .10, 1 .1 1 , 1 .12, 1 .13, 1 .14, 1 .15, 1.16, 1 .17, 1.18, 1 .19, 1 .20, 1.21 , 1 .22, 1.23, 1 .24, 1.25, 1 .26, 1.27, 1 .28, 1 .29, 1 .30, 1 .31 .

Compounds (from Table T2) 2.4, 2.13.

Compounds (from Table T3) 3.1 .

Example 2: Fungicidal activity against Puccinia recondita f. so. 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 then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).

The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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 to 14 days after application).

The following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Compounds (from Table T1 ) 1 .5, 1 .9, 1.13, 1 .16, 1 .17, 1.23, 1 .24, 1.27, 1 .28, 1.29, 1 .30, and 1.31 . Compounds (from Table T2) 2.6.

Example 4: Fungicidal activity against Glomerella laaenarium (Colletotrichum laaenarium) liquid culture / cucumber / preventative (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 to 4 days after application.

The following compounds at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

Compounds (from Table T1 ) 1 .1 , 1 .2, 1.3, 1 .4, 1 .5, 1 .6, 1.7, 1 .8, 1 .9, 1 .10, 1 .1 1 , 1 .12, 1 .13, 1 .14, 1 .15, 1.16, 1 .17, 1 .20, 1.22, 1 .23, 1.24, 1 .25, 1 .26, 1.27, 1 .28, 1.29, 1 .30, 1 .31 .

Compounds (from Table T2) 2.2, 2.4, 2.5, 2.6, 2.7, 2.13, 2.14, 2.16, 2.17, 2.18.

Compounds (from Table T3) 3.1 . Example 5: Fungicidal activity against Mvcosphaerella qraminicola (Septoria triticO / 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 at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development

Compounds (from Table T1 ) 1.14.