WO2023094304A1

WO2023094304A1 - Microbiocidal heterobiaryl amide derivatives

Info

Publication number: WO2023094304A1
Application number: PCT/EP2022/082567
Authority: WO
Inventors: Andrew Edmunds; Nicolas Germain; Thomas James Hoffman
Original assignee: Syngenta Crop Protection Ag
Priority date: 2021-11-25
Filing date: 2022-11-21
Publication date: 2023-06-01

Abstract

Compounds of Formula (I), wherein the substituents are as defined in claim 1, useful as pesticides, especially as fungicides.

Description

MICROBIOCIDAL HETEROBIARYL AMIDE DERIVATIVES

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

WO 2021/233861 discloses the use of azabicyclic(thio)amides derivatives as fungicidal compounds. WO 2021/249995 discloses the use of azabicyclyl-oxadiazole derivatives as fungicidal compounds. WO 2021/224220 A1 discloses the use of pyridine (thio)amide derivatives as fungicidal compounds. WO 2020/127780 discloses the use of pyridazine-oxadiazole derivatives as fungicidal compounds. WO 2020/109391 discloses the use of pyridazine (thio)amide derivatives for controlling phytopathogenic microorganisms.

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

wherein:

R¹ is phenyl or a 5- or 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S, wherein the phenyl or heteroaryl ring is optionally substituted by 1 , 2 or 3 substituents each independently selected from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci- C4-alkoxy, Ci-Cs-alkylsulfanyl, Ci-Cs-alkylsulfinyl Ci-C3-alkylsulfonyl, Ci-C2-haloalkoxy, C2-C3-alkenyl, C2-C3-haloalkenyl, C2-C3-alkynyl, Cs-Ce-cycloalkyl, Cs-Ce-cycloalkyloxy, hydroxyl, halogen, mercapto, amino, cyano and -NH(COCH3);

R² and R³ are each independently selected from hydrogen, and Ci-C4-alkyl; or

R² and R³ together with the carbon atom to which they are attached, form a cyclopropyl or cyclobutyl group;

R⁴ and R⁵ are each independently selected from hydrogen, halogen, cyano, hydroxy, mercapto, Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-Cs-haloalkoxy, C1-C4- alkylsulfanyl, Ci-C4-alkylsulfinyl, and Ci-C4-alkylsulfonyl; or

R⁴ and R⁵ together with the carbon atom to which they are attached, form a cyclopropyl or cyclobutyl group;

L¹ is -O- or -CH2- or a bond;

R⁶ is phenyl or a 5- or 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S, wherein the phenyl or heteroaryl ring is optionally substituted by 1 , 2 or 3 substituents each independently selected from Ci-C4-alkyl, Ci-C2-haloalkyl, C1- C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C2-haloalkoxy, C2-C3-alkenyl, C2-C3-haloalkenyl, C2-C3-alkynyl, Cs-Ce-cycloalkyl, Cs-Ce-cycloalkyloxy, hydroxyl, halogen, mercapto, amino, cyano or -NH(COCH3);

Y¹, Y², Y³ and Y⁴ form, together with the two carbon atoms to which Y¹ and Y⁴ are attached, an aromatic, partially saturated or fully saturated carbocyclic or heterocyclic ring; wherein: a) Y¹ is selected from NR^7a, S, SO2, oxygen, carbon substituted with one or two R⁸ substituents, and a direct bond; b) Y² is carbon substituted with one or two R⁸ substituents, or CR⁸-CHR^8aR^8b; c) Y³ is carbon substituted with one or two R⁸ substituents or CR⁸-CHR^8aR^8b; d) Y⁴ is selected from NR^7b, S, SO2, oxygen, carbon substituted with one or two R⁸ substituents, and a direct bond; and wherein R^7a and R^7b are each independently selected from hydrogen and Ci-C4alkyl; and R⁸, R^8a and R^8b are each independently selected from hydrogen, Ci-C4alkyl, and Cs-Cecycloalkyl;

Z¹ is N or CR⁹, wherein R⁹ is selected from hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkyl, and Cs-Ce-cycloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, and N-oxide of the compound of formula (I).

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 phytopathogenic 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 “hydroxyl” or “hydroxy” means an -OH group.

As used herein, the term “mercapto” means an -SH group.

As used herein, the term “cyano” means a -CN group.

As used herein, amino means an -NH2 group.

As used herein, nitro means an -NO2 group.

As used herein, oxo means an =O group (eg, as in a carbonyl (C=O) group).

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, the term "Ci-4alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Ci-salkyl should be construed accordingly. Examples of Ci-4alkyl include, but are not limited to, methyl, ethyl, /so-propyl.

As used herein, the term "C2-3alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that may be of either the (E) or (Z) configuration, having two or three carbon atoms, which is attached to the rest of the molecule by a single bond. Examples of C2-3alkenyl include, but are not limited to, vinyl (ethenyl), prop-1 -enyl and allyl (prop-2-enyl).

As used herein, the term "C2-3haloalkenyl" refers to a C2-3alkenyl group as defined above substituted by one or more of the same or different halogen atoms.

As used herein, the term "C2-3alkynyl" 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 or three carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2-3alkynyl include, but are not limited to, ethynyl, prop-1-ynyl and propargyl (prop-2-ynyl).

As used herein, the term "Ci-3alkoxy" refers to a radical of the formula R_aO- where R_a is a Cisalkyl radical as generally defined above. Examples of Ci-3alkoxy include, but are not limited to, methoxy, ethoxy and /so-propoxy.

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

As used herein, the term "Ci-3fluoroalkyl" refers to a Ci-3alkyl radical as generally defined above substituted by one or more fluorine atoms. Examples of Ci-3fluoroalkyl include, but are not limited to difluoromethyl and trifluoromethyl.

As used herein, the term "Ci-3fluoroalkoxy" refers to a Ci-3alkoxy radical as generally defined above substituted by one or more fluorine atoms. Examples of Ci-3fluoroalkoxy include, but are not limited to trifluoromethoxy.

As used herein, the term "C3-4cycloalkyl" refers to a stable, monocyclic ring radical which is saturated and contains 3 or 4 carbon atoms.

As used herein, the term “Ci-3alkylsulfanyl” refers to a radical of the formula -SR_a wherein R_a is a Ci-3alkyl radical as generally defined above.

As used herein, the term “Ci-3alkylsulfonyl” refers to a radical of the formula -S(O)2R_a wherein R_a is a Ci-3alkyl radical as generally defined above.

The term “heteroaryl” as used herein refers to a 5- or 6-membered aromatic monocyclic ring having 1 , 2 or 3 heteroatoms independently selected from N, O and S. Examples are heteroaryls J-1 to J-31 shown in Table J below.

Table J: Heteroaryl J-1 to J-31 :

As used herein, the expression “a group optionally substituted by 1 , 2 or 3 substituents” means that the group may be unsusbstituted, or that one, two or three hydrogen atoms of the group are replaced with a susbstituent.

As used herein, the expression “1 , 2 or 3 substituents each independently selected from” or “1 , 2 or 3 heteroatoms each independently selected from” means that the substituents or heteroatoms, as the case may be, may be all the same, all different from each other, or, when 3 substituents or heteroatoms are considered, that two of them are the same and the third is different from the former two. For instance, in a 5- or 6-membered monocyclic heteroaryl ring comprising 2 or 3 heteroatoms each independently selected from N, O and S, the heteroatoms may be all the same, for example only nitrogen atoms, or different, for instance one or two nitrogen atoms and one oxgen atom, or one or two nitrogen atom and one sulfur atom. Examples of heteroaryl rings are shown in Table J above, with heteroaryls J-1 to J-31 .

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 ketoenol 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 following lists provide definitions, including preferred definitions, for Y¹, Y², Y³, Y⁴, Z¹, L¹, R¹, R², R³, R⁴, R⁵, R⁶, R^7a, R^7b, R⁸ R^8a, and R^8b, with reference to the compounds of Formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

In an embodiment, R¹ is selected from:

A. phenyl or a 5- or 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S, wherein the phenyl or heteroaryl ring is optionally substituted by 1 , 2 or 3 substituents each independently selected from methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, trifluoromethoxy, difluoromethoxy, vinyl, allyl, 2,2-difluorovinyl, ethynyl, prop-1 -ynyl, propargyl, C3-C4-cycloalkyl, C3- C4-cycloalkyloxy, hydroxyl, chloro, fluoro, bromine, mercapto, amino, cyano and -NH(COCH3); or

B. phenyl or a 5- or 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S, wherein the phenyl or heteroaryl ring is optionally substituted by 1 , 2 or 3 substituents each independently selected from methyl, trifluoromethyl, methoxy, ethoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethynyl, prop-1 -ynyl, propargyl, cyclopropyl, cyclobutyl, cyclopropyloxy, chloro, fluoro, cyano and -NH(COCH3); or

C. phenyl or pyridyl, wherein the phenyl or pyridyl is optionally substituted by a single substituent selected from methyl, trifluoromethyl, methoxy, methylsulfonyl, ethynyl, prop-1 -ynyl, propargyl, cyclopropyl, cyclobutyl, cyclopropyloxy, chloro, fluoro, cyano and -NH(COCH3); or

D. phenyl or pyridyl, wherein the phenyl or pyridyl is optionally substituted by a single substituent selected from methyl, trifluoromethyl, methylsulfonyl, ethynyl, cyclopropyl, cyclopropyloxy, chloro, cyano and fluoro; or

E. phenyl, 3-methylphenyl, 3-chlorophenyl, 3-cyclopropylphenyl, 3-ethynylphenyl, 3- trifluoromethylphenyl, 3-cyclopropyl-2-fluorophenyl, 3-pyridyl, 5-chloro-3-pyridyl, 5-fluoro-3-pyridyl, 5-methyl-3-pyridyl, and 5-cyano-3-pyridyl; or

F. 3-methylphenyl, 3-chlorophenyl, 3-cyclopropylphenyl, 3-trifluoromethylphenyl, and 3-cyclopropyl-2- fluorophenyl; or

G. 3-cyclopropylphenyl. In an embodiment, R² and R³ are as follows:

A. R² and R³ are each independently selected from hydrogen and Ci-Cs-alkyl; or R² and R³, together with the carbon atom to which they are attached, form a cyclopropyl or cyclobutyl group; or

B. R² is Ci-Cs-alkyl, and R³ is hydrogen or Ci-Cs-alkyl different from R²; or

C. R² and R³ are each independently selected from hydrogen, methyl, ethyl, propyl, and methylethyl; R² and R³, together with the carbon atom to which they are attached, form a cyclopropyl group; or

D. R² is methyl, ethyl, propyl, and methylethyl, and R³ is hydrogen; or

E. R² is methyl or ethyl, and R³ is hydrogen; or

F. R² is methyl, and R³ is hydrogen; or

G. R² and R³, together with the carbon atom to which they are attached, form a cyclopropyl group; or

H. R² and R³ are each independently selected from hydrogen and methyl; or

I. hydrogen.

Preferably, R² and R³ are hydrogen.

In an embodiment, R⁴ and R⁵ are as follows:

A. R⁴ and R⁵ are each independently selected from hydrogen, halogen, cyano, mercapto, Ci-Cs-alkyl, Ci-Cs-haloalkyl, Ci-Cs-alkoxy, and Ci-Cs-haloalkoxy; or R⁴ and R⁵ together with the carbon atom to which they are attached, form an oxo, cyclopropyl, or cyclobutyl group; or

B. R⁴ and R⁵ are each independently selected from hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoro methoxy, difluoromethoxy; or R⁴ and R⁵ together with the carbon atom to which they are attached, form a cyclopropyl group; or

C. R⁴ and R⁵ are each independently selected from hydrogen, fluoro, chloro, cyano, methyl, ethyl, and methoxy; or R⁴ and R⁵ together with the carbon atom to which they are attached, form an oxo or a cyclopropyl group; or

D. R⁴ and R⁵ are each independently selected from hydrogen, fluoro, and methyl; or R⁴ and R⁵ together with the carbon atom to which they are attached, form a cyclopropyl group; or

E. R⁴ and R⁵ are each independently selected from hydrogen and fluoro; or R⁴ and R⁵ together with the carbon atom to which they are attached, form a cyclopropyl group; or

F. R⁴ and R⁵ are each independently selected from hydrogen and fluoro.

In an embodiment, L¹ is -O- or -CH2- or a bond; or L¹ is -O- or a bond. Preferably, L¹ is a bond.

In an embodiment, R⁶ is selected from:

A. phenyl or a 5- or 6-membered monocyclic heteroaryl ring comprising 1 , 2 or 3 heteroatoms each independently selected from N, O and S, wherein the phenyl or heteroaryl ring is optionally substituted by 1 , 2 or 3 substituents each independently selected from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C2-haloalkoxy, C2-C3- alkenyl, C2-C3-haloalkenyl, C2-C3-alkynyl, Cs-Ce-cycloalkyl, Cs-Ce-cycloalkyloxy, hydroxyl, halogen, mercapto, amino, cyano or -NH(COCH3); or B. phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, or thiophene, optionally substituted by 1 or 2 substituents each independently selected from methyl, ethyl, trifluoromethyl, methoxy, methylsulfonyl, difluoromethoxy, vinyl, allyl, ethynyl, chloro, fluoro, cyano and -NH(COCH3); or

C. phenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4-dimethylphenyl, 2-chloro-4- fluoro-phenyl, 4-bromo-2-chloro-phenyl, 2-chloro-4-methyl-phenyl, 2-chlorophenyl, p-tolyl, 2-pyridyl, 4-pyridyl, 5-bromo-2-pyridyl, 4,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3-chloro-2-pyridyl, 3- chloro-5-methyl-2-pyridyl, 6-chloro-3-pyridyl, 4,6-dichloro-3-pyridyl, pyrimidin-4-yl, 4-methoxy- phenyl, 2-chloro-4-methoxy-phenyl, 2-fluoro-4-methoxy-phenyl, 3-chloro-2-thienyl, and 3,5- dichloro-2-thienyl; or

D. 2,4-dichlorophenyl, 2,4-dimethylphenyl, 2-chloro-4-fluoro-phenyl, 2-chloro-4-methyl-phenyl, 5- bromo-2-pyridyl, 4,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl,3 -chloro-5-methyl-2-pyridyl, 6-chloro- 3-pyridyl, 4,6-dichloro-3-pyridyl, 4-methoxy-phenyl, 2-chloro-4-methoxy-phenyl, 2-fluoro-4- methoxy-phenyl, 3-chloro-2-thienyl, and 3,5-dichloro-2-thienyl; or

E. 2,4-dichlorophenyl.

Preferred compounds of formula I are represented by formula la

wherein R¹, R², R³, R⁴, R⁵, L¹, and R⁶ are as defined under formula I and Q1 is laa, lab, lac, lad, lae,

wherein indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; R⁷ is hydrogen or Ci-C4alkyl; R⁸ is hydrogen, Ci-C4alkyl, or Cs-Cecycloalkyl; m is 0,1 , or 2; and Z¹ is N or CH.

Alternatively, preferred compounds of formula I are represented by formula la

wherein indicates the oxygenattachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; R⁷ is hydrogen or Ci-C4alkyl; R⁸ is hydrogen, or Ci-C4alkyl; m is 0,1 , or 2; and Z¹ is N or CH.

Other preferred compounds of formula I are represented by formula la

wherein R¹, R², R³, R⁴, R⁵, L¹, and R⁶ are as defined under formula I and Q1 is laa, lab, lac, lad, lae, laf, lag, lah, lai, laj, lak, lai, lam, and Ian;

wherein ¹ indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; R⁷ is hydrogen or methyl; R⁸ is hydrogen or methyl; m is 0,1 , or 2; and Z¹ is N or CH

Preferred compounds of formula I are represented by formula la

wherein R¹, R², R³, R⁴, R⁵, L¹, and R⁶ are as defined under formula I and Q1 is laa, lab, lae, laf, lag, lah and lai;

wherein indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; R⁸ is hydrogen or methyl; m is 0,1 , or 2; and Z¹ is N or CH.

Preferred compounds of formula I are represented by formula la

wherein R¹, R², R³, R⁴, R⁵, L¹, and R⁶ are as defined under formula I and Q1 is

wherein ¹ indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; and Z¹ is N or CH.

Preferred compounds of formula I are represented by formula la

wherein R¹, R², R³, R⁴, R⁵, L¹, and R⁶ are as defined under formula I and Q1 is :

wherein indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; and Z¹ is N or CH.

Preferred compounds of formula I are represented by formula la

In an embodiment, Z¹ is N or CR⁹, wherein R⁹ is selected from hydrogen, fluoro, chloro , hydroxy, cyano, methyl, methoxy, trifluoromethyl, difluoromethyl and cyclopropyl. Preferably, Z¹ is N or CH. More preferably, Z¹ is CH. A compound of formula (I) is as defined above, provided the compound is not one of the following compounds:

compound 10-06

Preferably, the compound according to Formula (I) are compounds P.1 to P.6 listed in Table P (below).

The compounds of the present invention may be enantiomers of the compound of Formula (I) as represented by Formula (1-1) or Formula (I-2) or Formula (I-3) or Formula (I-4), wherein R² and R³ are different substituents and/or wherein R⁴ and R⁵ are different substituents.

The compounds of formula (I) according to the invention can be made as shown in the following schemes 1 to 5, wherein L¹, R¹, R², R³, R⁴, R⁵, R⁶, Z¹, Y¹, Y², Y³, and Y⁴ are as defined for compounds of formula (I), unless otherwise stated.

The compounds of formula (I) are can be obtained by an amide-coupling transformation with compounds of formula (II), wherein X¹ is OH (namely compounds of formula Ila) and amine compounds of formula (III) by activating the carboxylic acid function of the compounds of formula (II), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group (namely compounds of formula lib) for example by using (COCI)2 or SOCh, prior to treatment with the compounds of formula (III), preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, tetrahydrofuran, 2-methyl-tetrahydrofuran, EtOAc and the like), preferably at temperatures between 25°C and 60°C, and optionally in the presence of a base such as trimethylamine, N,N-diisopropylethylamine or dimethylaminopyridine. For compounds of formula (II) wherein X¹ is iodide (compounds He), the acid chlorides (lib) are treated with potassium iodide, in catalytic in stoichiometric quantities, in an inert solvent such as acetonitrile and these acyl iodides of formula (lie) are then treated with compounds of formula (III) in the absence of a base to give compounds of formula I. Such reactions are well known in the literature (see Org. Lett. 2013, 15, 3, 702- 705). Alternatively such amide couplings can be achieved using compounds of formula II wherein X¹ is OH, namely compounds of formula (Ila), by treating with an activating agent such as 1- propanephosphonic acid cyclic anhydride (T3P) in suitable solvent (e.g., acetonitrile) optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine) in the presence of amines of formula III. For examples, see Chem. Soc. Rev. (2009), 38, 606 and Chem. Sec. Rev. (2011), 40, 5084. A further method of coupling compounds of formula (II) where X¹ is Ci-C4alkoxy, namely compounds of formula (lid), with amines of formula (III) is to treat such compounds with trimethylaluminium, or DABAL- Mes (an adduct of trimethylaluminum and DABCO®) in the presence of compounds of formula (III) in an inert solvent such as toluene at temperatures between 20-90°C. Such amidation reactions of esters with AIMes, or its safer alternative DABAL-Mes, are well known to those skilled in the art and have been reported in Tet. Lett., 1977, 4171-4174 and Tet. Lett., 2006, 5767-5769. These types of reactions are shown in Scheme 1 .

Scheme 1

Compounds of formula (III) are either known or commercially available. Compounds of formula (II), wherein R¹ and Z¹ are as described as in formula (I), X1 is Ci-C4alkoxy, Y¹ is oxygen, Y² is CR⁸R⁸, wherein R⁸ is hydrogen or Ci-C4alkyl, and Y³ and Y⁴ form together a double or single bond, with Y⁴ substituted with a group R⁸, namely compounds of formula (llda);

can be prepared by treatment of compounds of formula (IV)

wherein Z¹ is N or CH, X^2a and X^2b are halogen, and R¹⁰ is Ci-C4alkyl, with a compound of formula R¹- OH, wherein R¹ is as defined as in formula (I), in the presence of a base, such as NaH, CS2CO3, K2CO3, and the like in an inert solvent such as NMP, DMF, CH3CN, at temperatures between 20-120°C to give compounds of formula V);

For such reactions X^2a is chlorine, bromine or fluorine, preferably fluorine, and X^2b is chlorine or bromine. Such SnAr reactions are well known to those skilled in the art and have been reviewed in F. Terrier, Modern Nucleophilic Aromatic Substitution, Wiley-VCH, Weinheim, 2013.

Compounds of formula (V) can be converted to compounds of formula (VI)

wherein R¹, and Z¹ are as described in formula (I), and R¹⁰ is Ci-C4alkyl, by reaction with (E)- benzaldehyde oxime in an aprotic solvent such as acetonitrile or DMF, in the presence of a base, such as CS2CO3 or K2CO3, optionally in the presence of a palladium catalyst such as RockPhos-G3- palladacycle ( [(2-Di-te/Y-butylphosphino-3-methoxy-6-methyl-2',4',6'-triisopropyl-1 ,1 '-biphenyl)-2-(2- aminobiphenyl)]palladium(ll) methanesulfonate) at temperatures between 25-100°C. Such reactions are known in the literature and have been described for example in Ang. Chem. int. Ed. 56, (16) 4478-4482, 2017.

Compounds of formula (VI) so obtained are converted to compounds of formula (VII)

by treatment with as compound of formula (VIII)

wherein X³ is halogen and R⁸ is hydrogen or Ci-C4alkyl, in the presence of a base, such as CS2CO3 or K2CO3, in an inert solvent such as NMP, DMF, acetonitrile and the like, at temperatures between 20°C and 100°C. Such alkylation of phenolic type compounds is well known to those skilled in the art. Compounds of formula (VII) undergo rearrangement (scheme 2) to compounds of formula (lldaa) and/or compounds of (He):

Scheme 2 upon heating, optionally in the presence of a solvent such as 1 ,2-dichlorobenzene, xylene, toluene, NMP, DMF, and A/,/V-Diethylaniline at temperatures between 120°C and 200°C. This type of Claisen reaction is well known in the literature, for example see Chem. Biol., (2000), 7(12), 979-992, Eu. J. Med. Chem., (2010), 45(12), 5833-5847, J. Org. Chem., (2011), 76(10), 3960-3967, Chem. Pharm. Bull., (2019), 67(9), 953-958, Science of Synthesis (2001), 10, 11-86, Tet. Letts., (2012), 53(42), 5695-5698, and references cited therein. The selectivity of the reaction leading to compounds of formula (lldaa) or (lie) will depend on factors such as the nature of substituents, temperature, and additives (see for example Struct. Chem., (2016), 27(5), 1383-1393).

Alternatively, compounds of formula (lldaa) can be obtained from compounds of formula (VII) by treatment of compounds of formula (VII) in an inert solvent such as dichloromethane the presence of a Au(l) catalyst such as [(2-biphenyl)-di-tert-butylphosphine]gold(l) hexafluoroantimonate (Echavarren’s catalyst). Such reactions have been reported for example in J. Org. Chem., (2021) 86 (1), 178-198 and are also known to give preferentially compounds of formula (lldaa) rather than (He) (see /ACS Catal. (2017), 7, 7146-7155).

Compounds of formula (lldaa) can be reduced by catalytic hydrogenation to give compounds of formula (lldab)

(lldab) using methods well known to those skilled in the art. Compounds of formula (lie) may also be reduced to compounds of formula (Ilf)

by reduction with a trialkyl silane, such as triethy silane, in the presence of strong acid such as trifluoroacetic acid in an inert solvent such as methylene chloride. Such reactions have also been reported in for example Organic Reactions (Hoboken, NJ, United States) (2008), 71 , 1-737.

Compounds of formula (II) wherein R¹, Z¹ are as defined in formula (I), R¹⁰ is Ci-C4alkyl, Y¹ is oxygen, Y² is CR⁸CHR⁸R⁸ , wherein R⁸ is hydrogen or Ci-C4alkyl, Y³ is CR⁸R⁸, and Y⁴ is a direct bond, namely compounds of formula (llg)

can be prepared by treating compounds of formula (X)

wherein R⁸ is as previously defined and X⁴ is halogen, with compounds of formula (VI)

in the presence of a base, such as CS2CO3 or K2CO3, in an inert solvent as described vide supra for the synthesis of compounds of formula (VII), to give compounds of formula (XI).

Compounds of formula (XI), wherein R¹, Z¹ are as defined in formula (I), R¹⁰ is Ci-C4alkyl, R⁸ is hydrogen or Ci-C4alkyl, can be converted to compounds of formula (llg)

by a Claisen rearrangement, for example by heating compounds of formula (XI) optionally in the presence of a solvent, for example N-methylpyrrolidone or dichlorobenzene, optionally in the presence of an inorganic acid, such as formic or acetic acid, or an organic acid such as p-toluene sulfonic acid, at temperatures between 180-250°C.

Such Claisen rearrangements are well known in the literature (see for example C. Ferri, "Reaktionen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff Chemistry in Britain’, 5, p:111-116, WO2018/215304, or WO2017/174449. The reaction can be performed under such conditions that is possible to isolate intermediates of formula (XII), which can then be converted to compounds of formula (llg) by heating, optionally in an acid such as formic or acetic acid at temperatures between 60-200°C.

Compounds of formula (II) wherein Y¹ is S, SO, or SO2, Y² is CR⁸CHR⁸R⁸, Y³ is CR⁸R⁸, wherein R⁸ is hydrogen or Ci-C4alkyl, Y⁴ is a direct bond, R¹⁰ is Ci-C4alkyl, and R¹ and Z¹ are as described under formula (I), namely compounds of formula (llh), (Hi), and (llj)

can be prepared from compounds of formula (XII)

by acylation with a compound of formula (XIII)

wherein X⁵ halogen, preferably chlorine, bromine or iodine, and R¹¹ is Ci-C4alkyl, to yield compounds of formula (XIV):

which is then subjected to a rearrangement yielding compounds of formula (XV):

Compounds of formula (XV) are then hydrolyzed then and subsequently cyclized to form compounds of formula (llh)

wherein R¹ Z¹, R¹⁰, and R⁸ are as previously described. Compounds of formula (llh) can be oxidized to compounds of formula (Hi) or (llj) where those skilled in the art will recognize that the oxidation leading selectively to (Hi) or (llj) will depend upon the number of equivalents of oxidizing agent used. The synthesis is summarized in scheme 3.

Scheme 3

In accordance with Scheme 3, the resulting phenol derivative of formula (XII) is acylated, for example with a thiocarbamoyl halide of formula (XIII), e.g. N,N-dimethylthioformyl chloride, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g, acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or cesium carbonate, or a metal hydride, e.g. sodium hydride. The acylation is advantageously carried out at temperatures of from 0°C to 110°C.

The rearrangement of the thiocarbamate of formula (XIV) in scheme 3 is effected, for example, thermally in an inert solvent, for example an ether, e.g. diphenyl ether, at temperatures of from 100°C to 300°C and yields the thiocarbamate of formula (XV) which is then hydrolyzed and cyclized using base or acid catalysis to form compounds of formula (llh). This is effected advantageously either with a metal hydroxide, e.g. sodium hydroxide, or with a mineral acid, e.g. hydrochloric acid or sulfuric acid, at temperatures of from 0°C to 110°C. Suitable solvents are, for example, water, ethers, e.g. tetrahydrofuran, halogenated hydrocarbons, e.g. dichloromethane, and aromatic hydrocarbons, e.g. toluene.

The resulting benzothiophene derivative of formula (llh) can then be oxidized in accordance with various standard methods known to those skilled in the art. Advantageously, the oxidation is carried out, for example, with hydrogen peroxide in an acidic solvent, for example an organic acid, e.g. acetic acid, or with an organic peracid, for example meta-chloroperbenzoic acid (m-CPBA), in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene. The reaction temperatures for the oxidation are generally in the range of from 0°C to 110°C. The degree of oxidation at the sulfur atom to give compounds of formula (Hi) or (llj) can be controlled by the amount of oxidizing agent.

The above reaction sequence via acylation of the phenol derivative of formula (XII) to form a thiocarbamate of formula (XIV), rearrangement of the latter compound to form a thiolcarbamate of formula (XV) and hydrolysis and cyclisation to form a compound of formula (llh) is carried out, for example, analogously to Org. Synth. 51 , 139 (1971) or W09909023, and the oxidation to form a compound of formula (Hi) or (llj) is carried out, for example, as described in H. O. House, "Modern Synthetic Reactions" W. A. Benjamin, Inc., Menlo Park, California, 1972, pages 334-335 and 353-354.

Those skilled in the art will recognize that compounds of formula (II) wherein R¹ and Z¹ are as described as in formula (I), Y⁴ is oxygen, Y³ is CR⁸CHR⁸R⁸ , Y² is CR⁸R⁸, and Y¹ is a direct bond, namely compounds of formula (Ilk) can be prepared by the same chemistry discussed vide supra, and shown in scheme 4:

Compounds of formula (XVI) can be prepared from compounds of formula (XVIII)

wherein R¹⁰, Z¹ and R¹ are as previously described and X⁶ is halogen, preferably bromine, by treatment with compounds of formula R¹-OH, wherein R¹ is as defined as in formula (I),

In the presence of a base such as an alkyl lithium, e.g. n-butyl lithium, or an earth metal hydride such as NaH, in an inert solvent, such as tetrahydrofuran, 2-methyl tetrahydrofuran, or hexane with compounds of formula (XX):

wherein R¹⁰ is Ci-C4-alkoxy, X⁶ is halogen, preferably chlorine or bromine and X⁷ is halogen, preferably fluorine, with compounds of formula R¹-OH, wherein R¹ is as defined as in formula (I), in the presence of a base, such as NaH, CS2CO3, K2CO3, and the like in an inert solvent such as NMP, DMSO, DMF, CH3CN, at temperatures between 20-120°C. Compounds of formula (XX) are known in the literature or are commercially available.

Compounds of formula (XVII) may be converted to compounds of formula (III), (llm) and (lln)

by analogous chemistry described in scheme 3.

Compounds of formula (II), wherein R¹, Z¹ and R¹⁰ are as described previously, Y¹ is NR^7a, wherein R^7a is hydrogen or Ci-C4alkyl, Y² is CR⁸R⁸ , wherein R⁸ is hydrogen or Ci-C4alkyl, and Y³ and Y⁴ form together a double or single bond, with Y⁴ substituted with a group R⁸, namely compounds of formula (Ho);

can be prepared by treating compounds of formula (V)

wherein R¹, Z¹, and R¹⁰ are as previously described, and X² is halogen, preferably chlorine or bromine, with a nitrogen source, such as ammonium hydroxide, in the presence of a catalyst, such as copper(l)iodide in the presence of a proline ligand, in water, or DMSO, at temperatures between 20- 120°C. Such reactions have been described in for example J. Org. Chem., (2012), 77(16), 6908-6916 and CN102146008 and yield compounds of formula (XXI)

Similar reactions for converting compounds of formula (V) to compounds of formula (XXI) are also known using palladium catalysts and amides and then hydrolyzing the amide compounds (see for example Tetrahedron (2009), 65(10), 1951-1956). Compounds of formula (XXI) can be reacted with compounds of formula (VIII)

wherein R⁸ and X³ are as described under formula (VIII), in the presence of a catalyst, such as Cu(l)CI in a solvent or mixture of solvents such as THF and water to give compounds of formula (XXII):

wherein R¹, Z¹, R¹⁰ and R⁸ are as previously described and R^7a is hydrogen. Similar transformations are known in the literature, for example see Aust. J. Chem., (2005), 58(5), 368-374. Refluxing compounds of formula (XXII) in an inert solvent such as toluene, in the presence of a copper catalyst (analogously to conditions described in Aust. J. Chem., (2005), 58(5), 368-374 or Tetrahedron (2005), 61 (1), 155- 165) leads to compounds of formula (lloa)

Compounds of formula (lloa) can be reduced with catalytic hydrogenation by methods know well to those skilled in the art to give compounds of formula (Hob).

Compounds of formula (lip)

wherein R¹, R¹⁰, R⁸, Z¹ are as previously described, and R^7a is hydrogen, can be prepared as shown in scheme 5.

As shown in scheme 5, alkylation of compounds of formula (XXI) with compounds of formula

(X) optionally in the presence of a base such as triethyl amine, or K2CO3, in an inert solvent leads to compounds of formula (XXIII). Compounds of formula (XXIII) can be rearranged to compounds of formula (XXIV) by heating, optionally in the presence of an acid catalyst. Such reactions are known and described for example in Chimia (1977), 31 (2), 46-9 and Chemistry - A European Journal (2012), 18(6), 1711-1726. Compounds of formula (XXIV) undergo cyclisation to compounds of formula (llo) using typically zirconium catalytic methods described, for example, in RSC Advances (2016), 6(13), 10541- 10548 and J. Amer. Chem. Soc., (2013), 135(19), 7235-7250. Those skilled in the art will further recognize that compounds of formula (llq)

can be prepared from compounds of formula (XVIII)

using the methods described above.

All of the compounds of formula (II), namely (lldaa), (lldab), (He), (Ilf), (llg), (llh), (Hi), (llj), (Ilk), (III), (llm), (lln), (lloa), (llob), (lip), and (llq) can be converted to compounds of formula (I) by amidation with compounds of formula (III) as described under scheme 1 . Some of the intermediates shown above may also be new and are also embodiments of the invention.

As already indicated, surprisingly, it has now been found that the compounds of Formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

The compounds of Formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The compounds of Formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.

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

It is also possible to use compounds of Formula (I) as 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 deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

It may also be possible to use compounds of Formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, forthe 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. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp.Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi- virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.

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

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

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

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

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a 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 (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

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

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 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; ribosomeinactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to be understood by d-endotoxins, for example 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, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a 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 CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 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-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

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

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

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, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of 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 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.

Specific examples of suitable additional active ingredients also include a compound selected from the group of substances consisting of petroleum oils, 1 ,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1 -naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxafos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carbophenothion, cymiazole, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorfenethol, chlorfenson, chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cufraneb, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos, dienochlor, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethoate-methyl, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, formetanate, formetanate hydrochloride, formparanate, gamma-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin l. jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro- 2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilacarb, nitrilacarb 1 :1 zinc chloride complex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, proclonol, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin, rotenone, schradan, sebufos, selamectin, sophamide, SSI-121 , sulfiram, sulfluramid, sulfotep, sulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox, thiometon, thioquinox, thuringiensin, triamiphos, triarathene, triazophos, triazuron, trifenofos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichlone, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1 -hydroxy-1 H-pyridine-2-thione, 4-(quinoxalin-2- ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicin, fenaminosulf, formaldehyde, hydrargaphen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brong niartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)- tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradeca-4,10-dien-1-yl acetate, (Z)-dodec- 7-en-1-yl acetate, (Z)-hexadec-l 1-enal, (Z)-hexadec-l 1-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11 E)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)- tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan-5- one, alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8, 10-dien-1 -yl acetate, dominicalure, ethyl 4- methyloctanoate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid, methyl eugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradec-11-en-1 -yl acetate, trimedlure, trimedlure A, trimedlure Bi, trimedlure B2, trimedlure C, trunc-call, 2-(octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1 -nitroethane, 1 ,1-dichloro-2,2-bis(4- ethylphenyl)ethane, 1 ,2-dichloropropane with 1 ,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2- trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2- (1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl- 1 ,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindan-1 ,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1 -chloroprop-1 -ene, 3-methyl-1-phenylpyrazol- 5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate, acethion, acrylonitrile, aldrin, allosamidin, allyxycarb, alphaecdysone, aluminium phosphide, aminocarb, anabasine, athidathion, azamethiphos, Bacillus thuringiensis delta endotoxins, barium hexafluorosilicate, barium polysulfide, barthrin, Bayer 22/190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenvinfos, bromo-DDT, bufencarb, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis- resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, dicapthon, dichlofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5- methylpyrazol-3-yl phosphate, dilor, dimefluthrin, dimetan, dimethrin, dimethylvinphos, dimetilan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzofos, dithicrofos, DSP, ecdysterone, El 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenethacarb, fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion- ethyl, flucofuron, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, guazatine, guazatine acetates, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hyquincarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lead arsenate, leptophos, lirimfos, lythidathion, m-cumenyl methylcarbamate, magnesium phosphide, mazidox, mecarphon, menazon, mercurous chloride, mesulfenfos, metam, metam-potassium, metam- sodium, methanesulfonyl fluoride, methocrotophos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methylchloroform, methylene chloride, metoxadiazone, mirex, naftalofos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, 0,0,0',0'-tetrapropyl dithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60- 38, phenkapton, phosnichlor, phosphine, phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quassia, quinalphos- methyl, quinothion, rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadilla, schradan, sebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar oils, tazimcarb, TDE, tebupirimfos, temephos, terallethrin, tetrachloroethane, thicrofos, thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronat, trimethacarb, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, trifenmorph, 1 ,2-dibromo-3- chloropropane, 1 ,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1 ,1-dioxide, 3-(4-chlorophenyl)- 5-methylrhodanine, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anisiflu purin, benclothiaz, cytokinins, DCIP, furfural, isamidofos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenols, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbormide, phosacetim, phosphorus, pindone, pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2- butoxyethoxyjethyl piperonylate, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomer, S421 , sesamex, sesasmolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibencon- azole, ipconazole, metconazole, myclobutanil, paclobutrazole, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, edifenphos, iprobenphos, phosdiphen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucypram, isotianil, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3- carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6- difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3- trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)- 2,5-dimethyl-pyrazol-3-amine, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1 , 3- dimethyl- 1 H- pyrazol- 5- amine, fluindapyr, coumethoxystrobin (jiaxiangjunzhi), Ivbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2- [2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N-[6-[[[(1- methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl- 1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [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, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2- methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1- [2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3- methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, ametoctradin, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid, ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3- carboxylate (may be prepared from the methods described in WO 2020/056090), methyl N-[[4-[1-(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl- phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2- difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2- fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro- ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4- carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole- 4-carboxamide, benzothiostrobin, phenamacril, 5-amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N- (3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4-yl) pyridine- 3- carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3- (1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, metyltetraprole, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide, a- (1 , 1- dimethylethyl) - a- [4‘- (trifluoromethoxy) [1, 1 '- biphenyl] - 4- yl] -5- pyrimidinemethanol, fluoxapiprolin, enoxastrobin, methyl (Z)-3-methoxy-2-[2- methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(4- propyltriazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]- 3-methoxy-prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2- enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in W02020/079111), methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020/193387), 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy] benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4-triazol-

1-yl)propyl]-3-pyridyl]oxy] benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo- 4H-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, coumoxystrobin, zhongshengmycin, thiodiazole copper, zinc thiazole, amectotractin, iprodione, seboctylamine, N'-[5-bromo-2-methyl-6- [(1 S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6- [(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1- methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-

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

2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019/1 10427); N-[(1 R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8- fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3- carboxamide, N-[(1 R)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N- [(1 S)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 R)-1 -benzyl- 1 ,3- dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide,

N-[(1 S)-1 -benzyl- 1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1 R)-1 - [(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1 S)-1 -[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]- 8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl- 1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide,

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

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

3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide, 1 -methoxy-3-methyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethy I- 1 -methoxy-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1 -[[4-[5-(trifluoromethyl)-

1 .2.4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-

1 .2.4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine (these compounds may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy- propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4- carbonitrile (this compound may be prepared from the methods described in WO 2016/156290); (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO 2014/006945); 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']d ipyrrole-1 ,3,5,7(2H,6H)-tetrone (this compound may be prepared from the methods described in WO 2011/138281) N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide; N- methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N- [(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methanone (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018/202428).

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 B1 to B17, Tables C1 to C17, Tables D1 to D27, Tables E1 to E4, Tables F1 , F2, H1 and H2(below), or a compound listed in Table P (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, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbophenothion + TX, cymiazole + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S- methyl + TX, demeton-S-methylsulfon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexine + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fenpyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flucycloxuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + 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 + TX, omethoate + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phosalone + TX, phosfolan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, promacyl + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, SSI-121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau-fluvalinate + TX, TEPP + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trifenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole + TX, 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, piperazine + TX, thiophanate + TX, chloralose + 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, 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 sphaericus Neide + 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, 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, 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, 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,11 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, 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 B1 + TX, trimedlure B2 + TX, trimedlure C + TX, 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 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, acethion + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + 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, diofenolan + TX, dioxabenzofos + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, El 1642 + TX, EMPC + TX, EPBP + TX, etaphos + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenchlorphos + TX, fenethacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpirithrin + TX, fensulfothion + TX, fenthion-ethyl + TX, flucofuron + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, guazatine + TX, guazatine acetates + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hyquincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lead arsenate + 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, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl O- 4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4- yl phosphorothioate + TX, 0,0,0',0'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, paradichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, phenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + 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, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebupirimfos + TX, temephos + TX, terallethrin + TX, tetrachloroethane + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + 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, anisiflupurin + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + 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, chloroinconazide + 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, fenpropidin + 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, 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, 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, cyclobutrifluram + 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, flumetylsulforim + TX, fluopicolide + TX, fluoxytioconazole + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + 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, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide + 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, coumethoxystrobin (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-ethyl-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)pyridazine + 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-pent-3-enamide + TX, florylpicoxamid + TX, fenpicoxamid + TX, metarylpicoxamid + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamid + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (may be prepared from the methods described in WO 2020/056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3- trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (may be prepared from the methods described in WO 2020/056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2- methyl-phenyl]methyl]carbamate + TX (may be prepared from the methods described in WO 2020/097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl- phenyl]methyl]carbamate + TX (may be prepared from the methods described in WO 2020/097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl- pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5- methyl-pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro- ethyl]-5-methyl-pyridazine-4-carboxamide + TX (may be prepared from the methods described in WO 2020/109391), 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, flufenoxadiazam + 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- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, a- (1 , 1- dimethylethyl) - a- [4'- (trifluoro methoxy) [1 , 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl (Z)-3- methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-2-[5-(3- isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2- methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3- (trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate + TX (these compounds may be prepared from the methods described in W02020/079111), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate + TX (these compounds may be prepared from the methods described in W02020/193387), 4- [[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1 ,2,4- triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, coumoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl- N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N- ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1 -methyl-2-propoxy-ethoxy)-3-pyridyl]-N- ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N- ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N- isopropyl-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N- methyl-formamidine + TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4-(2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl- ethyl)phenyl]-N-methyl-formamidine+ TX, N’-[4-(1 -cyclopropyl-2,2,2-trifluoro-1 -hydroxy-ethyl)-5- methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2- trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2019/110427); N-[(1 R)-1-benzyl-3-chloro-1-methyl-but-3- enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro- quinoline-3-carboxamide + TX, N-[(1 R)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3- carboxamide + TX, N-[(1 S)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1- benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1 R)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1 S)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1 R)-1-benzyl-1 ,3-dimethyl- butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline- 3-carboxamide + TX, N-((1 R)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1 S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds may be prepared from the methods described in WO2017/153380); 1-(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3- dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3-yl)-

4.4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds may be prepared from the methods described in WO2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6- chloro-4,4-difluoro-3,3-dimethyl-1 -(4-methylbenzimidazol-1 -y I) isoq u i n ol in e + TX, 4,4-difluoro-1 -(5- fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1- isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-

1 .2.4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-

1 .2.4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-

1 .2.4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N- dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine + TX. The compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1 - yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290); 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290); (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound may be prepared from the methods described in WO 2014/006945); 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3- c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone + TX (this compound may be prepared from the methods described in WO 2011/138281); N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound may be prepared from the methods described in WO 2018/153707); N'-(2-chloro-5- methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5- methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4- yl]pyridine-3-carboxamide + TX (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]pyrazole-4-carboxylate + TX (this compound may be prepared from the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX (these compounds may be prepared from the methods described in WO 2018/202428).

The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html. Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula (I) selected from one compound as represented in Tables B1 to B17, Tables C1 to C17, Tables D1 to D27, Tables E1 to E4, Tables F1 , F2, H1 and H2(below), or a compound listed in Table P (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 B1 to B17, Tables C1 to C17, Tables D1 to D27, Tables E1 to E4, Tables F1 , F2, H1 and H2(below), or a compound listed in Table P (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 B1 to B17, Tables C1 to C17, Tables D1 to D27, Tables E1 to E4, Tables F1 , F2, H1 and H2(below), or a compound listed in Table P (below) and the active ingredient(s) as described above, is not essential for working the present invention.

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, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin. Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

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

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

Bactericides: chlortetracycline, oxytetracycline, streptomycin.

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

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) forthe preparation ofthese compositions are also a subject ofthe 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 1g of active substance per kg of seeds.

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

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

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

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly Formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the 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 ofthe invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of Formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

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

The compounds according to the following Tables B1 to B17, Tables C1 to C17, Tables D1 to D27, Tables E1 to E4, Tables F1 , F2, H1 and H2below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I).

Table A: This table denotes G substituents for specific compounds in tables B1 to B17, C1 to C17, D1 to D27, E1 to E4, F1 , F2, H1 , and H2

The following tables B1 to B17, C1 to C17, D1 to D27, E1 to E4, F1 , F2, H1 , and H2 show specific compounds of formula (l-A) to (l-F) wherein G substituents in compounds of formulae (l-A) to (l-F) are as defined in Table A. In formulae (l-A) to (l-F), Q corresponds to R¹ in formula (I).

Table B1 : This table provides 54 compounds B1-1 to B1-54 of formula (l-A) wherein R^8a and R^8b are methyl, Q is ph

defined in Table A. For example, compound B1-2 has the following structure:

Table B2: This table provides 54 compounds B2-1 to B2-54 of formula (l-A) wherein R^8a and R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table B3: This table provides 54 compounds B3-1 to B3-54 of formula (l-A) wherein R^8a and R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is CH, and G is as defined in Table A. Table B4: This table provides 54 compounds B4-1 to B4-54 of formula (l-A) wherein R^8a and R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is CH, and G is as defined in Table A. Table B5: This table provides 54 compounds B5-1 to B5-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-ethynyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table B6: This table provides 54 compounds B6-1 to B6-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table B7: This table provides 54compounds B7-1 to B7-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table B8: This table provides 54 compounds B8-1 to B8-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table B9: This table provides 54 compounds B9-1 to B9-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 5-chloro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table B10: This table provides 54 compounds B10-1 to B10-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 5-fluoro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table B11 : This table provides 54 compounds B11-1 to B11-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 5-methyl-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table B12: This table provides 54 compounds B12-1 to B12-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 5-cyano-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table B13: This table provides 54 compounds B13-1 to B13-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table B14: This table provides 54 compounds B14-1 to B14-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is N, and G is as defined in Table A.

Table B15: This table provides 54 compounds B15-1 to B15-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table B16: This table provides 54 compounds B16-1 to B16-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table B17: This table provides 54 compounds B29-1 to B29-54 of formula (l-A) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is N, and G is as defined in Table A.

Table C1 : This table provides 54 compounds C1-54 to C1-54 of formula (l-B)

wherein R^8a, R^8b are methyl, Q is phenyl, Z¹ is CH, and G is as defined in Table A. For example, compound C1-8 has the following structure:

Compound C1-8

Table C2: This table provides 54 compounds C2-1 to C2-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C3: This table provides 54 compounds C3-1 to C3-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C4: This table provides 54 compounds C4-1 to C4-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C5: This table provides 54 compounds C5-1 to C5-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-ethynyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C6: This table provides 54 compounds C6-1 to C6-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C7: This table provides 54 compounds C7-1 to C7-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table C8: This table provides 54 compounds C8-1 to C8-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table C9: This table provides 54 compounds C9-1 to C9-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 5-chloro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table C10: This table provides 54 compounds C10-1 to C10-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 5-fluoro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table C11 : This table provides 54 compounds C11-1 to C11-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 5-methyl-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table C12: This table provides 54 compounds C12-1 to C12-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 5-cyano-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table C13: This table provides 54 compounds C13-1 to C13-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table C14: This table provides 54 compounds C14-1 to C14-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is N, and G is as defined in Table A.

Table C15: This table provides 54 compounds C15-1 to C15-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table C16: This table provides 54 compounds C16-1 to C16-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table C17: This table provides 54 compounds C17-1 to C17-54 of formula (l-B) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is N, and G is as defined in Table A.

Table D1 : This table provides 54 compounds D1-1 to D1-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is pheny

defined in Table A. For example, compound D1-14 has the following structure:

Compound D1-14

Table D2: This table provides 54 compounds D2-1 to D2-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D3: This table provides 54 compounds D3-1 to D3-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D4: This table provides 54 compounds D4-1 to D4-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D5: This table provides 54 compounds D5-1 to D5-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-ethynyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D6: This table provides 54 compounds D6-1 to D6-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D7: This table provides 54 compounds D7-1 to D7-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D8: This table provides 54compounds D8-1 to D8-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table D9: This table provides 54 compounds D9-1 to D9-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 5-chloro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table D10: This table provides 54 compounds D10-1 to D10-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 5-fluoro-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table D11 : This table provides 54 compounds D11-1 to D11-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 5-methyl-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table D12: This table provides 54 compounds D12-1 to D12-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 5-cyano-3-pyridyl, Z¹ is CH, and G is as defined in Table A.

Table D13: This table provides 54 compounds D13-1 to D13-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is N, and G is as defined in Table A. Table D14: This table provides 54 compounds D14-1 to D14-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-chloro-phenyl, Z¹ is N, and G is as defined in Table A.

Table D15: This table provides 54 compounds D15-1 to D15-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table D16: This table provides 54 compounds D16-1 to D16-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table D17: This table provides 54 compounds D17-1 to D17-54 of formula (l-C) wherein R^8a, R^8b are methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is N, and G is as defined in Table A.

Table D18: This table provides 54 compounds D18-1 to D18-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D19: This table provides 54 compounds D19-1 to D19-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is Q is 3-chloro-phenyl, Z¹ is CH, and G is as defined in Table A

Table D20: This table provides 54 compounds D20-1 to D20-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-cyclopropyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D21 : This table provides 54 compounds D21-1 to D21-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D22: This table provides 54 compounds D22-1 to D22-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is CH, and G is as defined in Table A.

Table D23: This table provides 54 compounds D23-1 to D23-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-methyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table D24: This table provides 54 compounds D24-1 to D24-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is Q is 3-chloro-phenyl, Z¹ is N, and G is as defined in Table A

Table D25: This table provides 54 compounds D25-1 to D25-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-cyclopropyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table D26: This table provides 54 compounds D26-1 to D26-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-trifluoromethyl-phenyl, Z¹ is N, and G is as defined in Table A.

Table D27: This table provides 54 compounds D27-1 to D27-54 of formula (l-C) wherein R^8a is H, R^8b is methyl, Q is 3-cyclopropyl-2-fluoro-phenyl, Z¹ is N, and G is as defined in Table A.

Table E1 : This table provides 54 compounds E1-1 to E1-54 of formula (l-D)

wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is CH, X is S, and G is as defined in Table A. For example, compound E1-17 has the following structure:

Compound E1-17

Table E2: This table provides 54 compounds E1-1 to E1-54 of formula (l-D) wherein R^8a, R^8b are methyl, Q is 3-methyl-phenyl, Z¹ is CH, X is SO2, and G is as defined in Table A.

Table E3: This table provides 54 compounds E3-1 to E3-54 of formula (l-D) wherein R^8a, R^8b are methyl, Q is 3-cylopropyl-phenyl, Z¹ is CH, X is S, and G is as defined in Table A.

Table E4: This table provides 54 compounds E4-1 to E4-54 of formula (l-D) wherein R^8a, R^8b are methyl, Q is 3-cylopropyl-phenyl, Z¹ is CH, X is SO2, and G is as defined in Table A.

Table F1 : This table provides 54 compounds F1-1 to F1-54 of formula (l-E)

wherein Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A. For example, compound F1-12 has the following structure:

Compound F1-12

Table F2: This table provides 54 compounds F2-1 to F2-54 of formula (l-E) wherein Q is 3-cylopropyl- phenyl, Z¹ is CH, and G is as defined in Table A.

Table H1 : This table provides 54 compounds H1-1 to H1-54 of formula (l-F)

wherein Q is 3-methyl-phenyl, Z¹ is CH, and G is as defined in Table A. For example, compound H1-35 has the following structure:

Compound H1-35

Table H2: This table provides 54 compounds H2-1 to H2-54 of formula (l-F) wherein Q is 3-cylopropyl- phenyl, Z¹ is CH, and G is as defined in Table A.

EXAMPLES

The Examples which follow serve to illustrate the invention.

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

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

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

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

Formulation Examples

Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 %

Kaolin 62 % 27 %

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

Extruded 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 %

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

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

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

List of abbreviations aq. = aqueous

°C = degrees Celsius

DCM = dichloromethane

DMF = dimethylformamide

DMSO = dimethyl sulfoxide

DMSO-cfe = deuterated dimethyl sulfoxide EtOAc = ethyl acetate equiv. = equivalent hr = hour(s)

M = molar min = minutes mp = melting point ppm = parts per million

RT = room temperature

Rt = retention time

LC/MS = Liquid Chromatography Mass Spectrometry

Preparation Examples

The following examples further illustrate, but do not limit, the invention. Those skilled in the art will promptly recognize appropriate variations from the procedures both as to reactants and as to reaction conditions and techniques.

¹ H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)⁺ or (M-H)-. The following abbreviations are used: s = singlet; br s = broad singlet; d = doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, quin = quintuplet, sept = septet; m = multiplet. Method A:

Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1 .8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 1.5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1.0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10% B isocratic for 0.05 min.

Method B:

Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1 .8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 3.0 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 2.5 min, 100% B isocratic for 0.3min.

Method C:

Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 100 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment, diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 3.0 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow: 0-2.5 min: 0.85, then 1 ml/min, Gradient: 0% B isocratic for 0.2 min, then 0-10% B in 2.3 min, 10-100%B in 0.05min Flow 1 ml/min, 100% B isocratic for 0.2 min, 100-0% B in 0.05min, 0% B isocratic for 0.2 min.

Method D:

Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1 % formic acid, B= Acetonitrile + 0.1 % formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.

Example 1 : Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2- dimethyl-3H-furo[3,2-blpyridine-7-carboxamide (compound P-1 , table P)

(compound P-1 , table P)

Step A: Preparation of methyl 3-bromo-5-(3-cyclopropylphenoxy)pyridine-4-carboxylate

To a stirring solution of methyl 3-bromo-5-fluoro-pyridine-4-carboxylate (1.47 g, 5.97 mmol, CAS: 1214325-21-9) and 3-cyclopropylphenol (1.10 g, 7.76 mmol, CAS: 28857-88-7)) in DMSO (15 mL) was added cesium carbonate (3.07 g, 8.95 mmol). The resulting suspension was stirred at room temperature for one night. The reaction mixture was quenched by the slow addition of water (exothermic) and the aqueous layer was extracted with ethylacetate. The combined organic layers was washed with water, dried over magnesium sulfate, filtered and evaporated. The crude obtained was purified by chromatography over silica gel to afford methyl 3-bromo-5-(3-cyclopropylphenoxy)pyridine-4- carboxylate (1 .5 g, 4.1 mmol).

LCMS (Method A): retention time 01.12 min, 350 (M+H)

¹H NMR (CDCb, 400 MHz) 6 8.5-8.6 (m, 1 H), 8.18 (s, 1 H), 7.2-7.3 (m, 2H), 6.93 (d, 1 H, J=7.6 Hz), 6.8-6.9 (m, 1 H), 6.79 (t, 1 H, J=2.0 Hz), 3.95 (s, 3H), 1.90 (tt, 1 H, J=5.1 , 8.4 Hz), 1.0-1.1 (m, 2H), 0.7-0.7 (m, 2H)

Step B: Preparation of methyl 3-(3-cyclopropylphenoxy)-5-hydroxy-pyridine-4-carboxylate

Methyl 3-bromo-5-(3-cyclopropylphenoxy)pyridine-4-carboxylate (6 g, 17.23 mmol), followed by N,N-dimethylformamide ( 35 mL), cesium carbonate (14.04 g, 43.08 mmol), (E)-benzaldehyde oxime (2.296 g, 18.95 mmol) and RockPhos Pd G3 (1 .723 mmol, 1 .445 g) were charged in a three necks flask. The resulting suspension was flushed with argon for 5 minutes and stirred 5 hours at 60°C. The reaction mixture was diluted with ethylacetate and water. The aqueous layer was acidified to pH 1-2 and then extracted 2 times with ethylacetate. The combined organic layer was washed with water, dried over magnesium sulfate, filtered and evaporated to afford crude which was purified by chromatography over silica gel to afford methyl 3-(3-cyclopropylphenoxy)-5-hydroxy-pyridine-4-carboxylate (2.63g, 9.22 mmol)

LCMS (Method A): retention time 0.96min, 286 (M+H)

¹H NMR (CDCb, 400 MHz) 6 10.8-10.9 (m, 1 H), 8.28 (s, 1 H), 7.85 (s, 1 H), 7.25 (t, 1 H, J=7.8 Hz), 6.88 (d, 1 H, J=7.6 Hz), 6.7-6.8 (m, 2H), 3.92 (s, 3H), 1 .90 (tt, 1 H, J=5.0, 8.4 Hz), 1 .0-1 .0 (m, 2H), 0.7- 0.7 (m, 2H)

Step C: Preparation of methyl 3-(3-cyclopropylphenoxy)-5-(2-methylallyloxy)pyridine-4-carboxylate

To a solution of methyl 3-(3-cyclopropylphenoxy)-5-hydroxy-pyridine-4-carboxylate (2.04 g, 7.15 mmol), Triphenylphosphine (2.37 g, 8.94 mmol) and 2-methylprop-2-en-1-ol (0.593 g, 8.22 mmol) in THF (50 mL) was added DIAD (1.80 mL, 8.94 mmol) dropwise at room temperature and the orange solution was stirred 18 hours at room temperature. The mixture was concentrated under vacuum and purified by chromatography over silica gel to afford methyl 3-(3-cyclopropylphenoxy)-5-(2- methylallyloxy)pyridine-4-carboxylate (1 ,66g, 4.89 mmol).

LCMS (Method A): retention time 1.13 min, 340 (M+H) ¹H NMR (CDCh, 400 MHz) 6 8.1-8.2 (m, 1 H), 7.92 (s, 1 H), 7.2-7.3 (m, 1 H), 6.91 (d, 1 H, J=7.6 Hz), 6.8-6.9 (m, 1 H), 6.8-6.8 (m, 1 H), 5.1-5.1 (m, 1 H), 5.0-5.1 (m, 1 H), 4.62 (s, 2H), 3.91 (s, 3H), 1 .89 (s, 1 H), 1.0-1.0 (m, 2H), 0.7-0.7 (m, 2H)

Step D: Preparation of methyl 5-(3-cyclopropylphenoxy)-3-hydroxy-2-(2-methylallyl)pyridine-4- carboxylate

Methyl 3-(3-cyclopropylphenoxy)-5-(2-methylallyloxy)pyridine-4-carboxylate (1.51 g, 4.45 mmol) and 1 ,2-dichlorobenzene (11 mL) were charger in a vial and the resulting mixture was irritated at the microwave for 2 hours at 190°C.The mixture was then directly incorporated on isolute and purified by chromatography over silica gel to afford methyl 5-(3-cyclopropylphenoxy)-3-hydroxy-2-(2- methylallyl)pyridine-4-carboxylate.

LCMS (Method A): retention time 1.20 min, 340 (M+H)

¹H NMR (CDCh, 400 MHz) 6 11.13 (br s, 1 H), 7.85 (s, 1 H), 7.2-7.3 (m, 1 H), 6.84 (d, 1 H, J=7.6 Hz), 6.7-6.7 (m, 2H), 4.89 (s, 1 H), 4.74 (d, 1 H, J=0.7 Hz), 3.90 (s, 3H), 3.64 (s, 2H), 1.89 (m, 1 H), 1.0- 1.0 (m, 2H), 0.7-0.7 (m, 2H)

Step E: Preparation of methyl 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-blpyridine-7- carboxylate

Methyl 5-(3-cyclopropylphenoxy)-3-hydroxy-2-(2-methylallyl)pyridine-4-carboxylate (0,172 mg, 0.507 mmol) and acetic acid ( 2.5 mL) were heated for 2 hours at 180°C and then 2 hr at 200°C under microwave system. Acetic acid was evaporated under vacuum at 60°C. The residue was diluted with water and tBME then pH was set to basic with NaOH 1 M aqueous solution. The organic phase was washed twice with water then with brine, dried over Na2SC>4, filtered and evaporated. The crude was purified by chromatography over silica gel to afford methyl 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H- furo[3,2-b]pyridine-7-carboxylate.

LCMS (Method A): retention time 1.09 min, 340 (M+H)

¹H NMR (CDCb, 400 MHz) 6 7.7-7.7 (m, 1 H), 7.20 (t, 1 H, J=7.8 Hz), 6.8-6.9 (m, 1 H), 6.7-6.8 (m, 2H), 3.82 (s, 3H), 3.13 (s, 2H), 1 .88 (tt, 1 H, J=5.0, 8.5 Hz), 1 .59 (s, 6H), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Step F: Preparation of 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-blpyridine-7-carboxylic acid

Methyl 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-b]pyridine-7-carboxylate (0.032 g, 0.09428 mmol) was stirred in a mixture of THF and water 3:1 (0.8 mL) and LiOH.H2O (0.01009 g, 0.2357 mmol) was added. The resulting mixture was stirred at 50°C for 3hr 30min. Reaction stopped and left over the weekend. The mixture was diluted with ethylacetate and water and then acidified with HCL 1 M aqueous solution. The aqueous layer was extracted twice with ethylacetate. The organic phase was then washed once with brine, dried over Na2SC>4 and evaporated to give 6-(3-cyclopropylphenoxy)- 2,2-dimethyl-3H-furo[3,2-b]pyridine-7-carboxylic acid which was used in the next step without further purification.

LCMS (Method A): retention time 0.90 min, 326 (M+H)

Step G: Preparation of 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-blpyridine-7-carbonyl chloride

In a flask charged with 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-b]pyridine-7- carboxylic acid (0.025 g, 0.07683 mmol), ethyl acetate (0.307 mL, 3.14 mmol) and 1 drop DMF was added oxalyl chloride (0.010 mL, 0.115 mmol) at room temperature and under argon atmosphere. After 40 min stirring at room temperature, the solvents were removed under vacuum at 45°C to get 6-(3- cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-b]pyridine-7-carbonyl chloride which was used in the next step without further purification.

Step H: Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2-dimethyl-

3H-furo[3,2-blpyridine-7-carboxamide

To a mixture of 6-(3-cyclopropylphenoxy)-2,2-dimethyl-3H-furo[3,2-b]pyridine-7-carbonyl chloride (0.026 g, 0.076 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (0.016 g, 0.0768 mmol) in acetonitrile (0.307 mL) was added slowly pyridine (0.015 mL, 0.192 mmol). The resulting mixture was stirred 1 hour at room temperature and then diluted with ethylacetate. The organic layer was washed with NaHCCh sat. solution then with brine, dried over Na2SC>4 and concentrated under reduced pressure to get 60mg crude product. The crude product was purified by reverse phase chromatography to afford

6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2,2-dimethyl-3H-furo[3,2-b]pyridine-

7-carboxamide ( 0.033 mg, 0.064 mmol)

LCMS (Method A): retention time 1.20 min, 515 (M+H)

¹H NMR (DMSO-d6, 400 MHz) 6 8.75 (t, 1 H, J=5.8 Hz), 7.62 (dd, 1 H, J=0.9, 2.0 Hz), 7.5-7.6 (m, 1 H), 7.48 (d, 1 H, J=8.4 Hz), 7.32 (dd, 1 H, J=2.2, 8.4 Hz), 7.2-7.3 (m, 1 H), 6.8-6.9 (m, 1 H), 6.7-6.8 (m, 2H), 5.7-5.9 (m, 1 H), 3.6-3.8 (m, 2H), 3.08 (s, 2H), 1 .90 (tt, 1 H, J=5.0, 8.4 Hz), 1 .49 (s, 6H), 0.9-1 .0 (m, 2H), 0.6-0.7 (m, 2H)

Example 2: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl1-2,2-dimethyl-

carboxylate

Methyl 3-(3-cyclopropylphenoxy)-5-hydroxy-pyridine-4-carboxylate (2 g, 7.010 mmol) and cesium carbonate (4.797 g, 14.72 mmol) were suspended in acetonitrile (55 mL). 3-chloro-3-methyl-1 -butyne (1 .62 mL, 14.02 mmol) and the resulting yellow suspension was stirred for 5 hours at 70°C. The reaction mixture was diluted in ethylacetate and water. The aqueous layer was extracted 3 times with ethylacetate. The combined organic layer was dried with magnesium sulfate, filtered and evaporated. The crude obtained was purified by chromatography to afford methyl 3-(3-cyclopropylphenoxy)-5-(1 ,1- dimethylprop-2-ynoxy)pyridine-4-carboxylate.

LCMS (Method A): retention time 1.14 min, 352 (M+H)

¹H NMR (1-CDCb, 400 MHz) 6 8.7-8.8 (m, 1 H), 7.98 (s, 1 H), 7.24 (s, 1 H), 6.89 (d, 1 H, J=8.0 Hz), 6.8-6.9 (m, 1 H), 6.78 (t, 1 H, J=2.0 Hz), 3.87 (s, 3H), 2.70 (s, 1 H), 1 .8-1 .9 (m, 1 H), 1 .72 (s, 6H), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Step B: Preparation of methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-blpyridine-8- carboxylate

Methyl 3-(3-cyclopropylphenoxy)-5-(1 ,1-dimethylprop-2-ynoxy)pyridine-4-carboxylate (0.13 g, 0.3699 mmol) was dissolved in toluene (1 .850 mL) at room temperature and the resulting mixture was stirred 45 minutes at 150°C in a microwave system. The solvent was evaporated to give the title compound which was used without further purification for the next step.

LCMS (Method A): retention time 1.16 min, 352 (M+H)

¹H NMR (1-CDCb, 400 MHz) 6 7.7-7.8 (m, 1 H), 7.2-7.3 (m, 1 H), 6.8-6.9 (m, 2H), 6.78 (br s, 1 H), 6.51 (d, 1 H, J=10.2 Hz), 5.8-5.9 (m, 1 H), 3.8-3.9 (m, 3H), 1.8-2.0 (m, 1 H), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H) Step C: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyDethyl1-2,2-dimethyl- pyrano[3,2-blpyridine-8-carboxamide

A suspension of 2-(2,4-dichlorophenyl)ethanamine (0.0278 mL, 0.184 mmol) in toluene (0.73 mL) was purged with argon. Methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine-8- carboxylate (0.129 g, 0.368mmol) was added followed by 1 ,4- diazabicyclo[2.2.2]octane;trimethylalumane (0.094 g, 0.368 mmol). The resulting mixture was stirred one night at 90°C. The solution obtained was diluted with ethylacetate and water carefully. Then the aqueous layer was extracted 2 times with ethylacetate. The organic layer was dried over sodium sulfate, filtered and evaporated. The crude obtained was purified by chromatography over silica gel to afford 7- (3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2,2-dimethyl-pyrano[3,2-b]pyridine-8- carboxamide.

LCMS (Method A): retention time 1.24 min, 509 (M+H)

¹H NMR (CDCb, 400 MHz) 6 7.71 (s, 1 H), 7.36 (d, 1 H, J=2.2 Hz), 7.24 (t, 1 H, J=7.8 Hz), 7.19 (d, 1 H, J=8.0 Hz), 7.05 (dd, 1 H, J=2.0, 8.2 Hz), 6.88 (d, 1 H, J=8.0 Hz), 6.7-6.8 (m, 2H), 6.50 (d, 1 H, J=10.2 Hz), 5.9-6.0 (m, 1 H), 5.86 (d, 1 H), 3.70 (q, 2H, J=6.9 Hz), 3.00 (t, 2H, J=6.9 Hz), 1.89 (tt, 1 H, J=5.1 , 8.4 Hz), 1 .50 (s, 6H), 1 .0-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Example 3: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2- dimethyl-pyrano[3,2-blpyridine-8-carboxamide (compound P-5, table P)

Compound P-5, table P

Step A: Preparation of 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-blpyridine-8-carboxylic acid

Methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine-8-carboxylate (0.2 g, 0.5692 mmol) was dissolved in tetrahydrofuran (5 mL) and hydroxylithium;hydrate (0.047 g, 1.138 mmol) was added. The resulting mixture was stirred one night at 70°C then the solvent was evaporated under vacuum. A 1 M HCI aqueous solution was added to the residue (pH 2 obtained) and then the aqueous layer was extracted two times with ethylacetate. The combined organic layer were dried over magnesium sulfate, filtered and evaporated to afford 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2- b]pyridine-8-carboxylic acid.

LCMS (Method A): retention time 0.95 min, 338 (M+H)

¹H NMR (2-DMSO, 400 MHz) 6 13.4-13.8 (m, 1 H), 7.68 (s, 1 H), 7.24 (t, 1 H, J=7.8 Hz), 6.86 (d, 1 H, J=8.0 Hz), 6.7-6.8 (m, 2H), 6.48 (d, 1 H, J=10.2 Hz), 6.09 (d, 1 H, J=10.2 Hz), 1.9-2.0 (m, 1 H), 0.9- 1.0 (m, 2H), 0.6-0.7 (m, 2H)

Step B: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2-dimethyl- pyrano[3,2-blpyridine-8-carboxamide (Compound P-5, table P)

Compound P-5, table P

7-(3-Cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine-8-carboxylic acid (184 mg, 0.545 mmol, then was dissolved in Ethyl acetate (2 mL). 1 drop of DMF was added followed by the slow addition of oxalyl chloride (0.072 mL., 0.8180 mmol) at room temperature and under argon atmosphere. After one night at room temperature, the reaction mixture was evaporated under vaccum and to get 7- (3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine-8-carbonyl chloride.

To a mixture of 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine-8-carbonyl chloride (0.05 g, 0.1405 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (29 mg, 0.140 mmol) in Ethyl acetate (1.5 mL) under argon atmosphere, was added DMAP (0.03468 g, 0.2811 mmol) at room temperature. The reaction mixture was stirred 1 hour at room temperature and then was diluted with water. The aqueous layer was extracted 2 times with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude obtained was purified by chromatography over silica gel to afford 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro- ethyl]-2,2-dimethyl-pyrano[3,2-b]pyridine-8-carboxamide.

LCMS (Method A): retention time 1.24 min, 527 (M+H)

¹H NMR (CDCb, 400 MHz) 6 7.7-7.8 (m, 1 H), 7.4-7.5 (m, 2H), 72-7. (m, 2H), 6.87 (d, 1 H, J=8.0 Hz), 6.7-6.8 (m, 2H), 6.52 (d, 1 H, J=10.2 Hz), 6.3-6.4 (m, 1 H), 5.89 (d, 1 H, J=10.2 Hz), 5.8-6.0 (m, 1 H), 4.1-4.3 (m, 1 H), 3.5-3.7 (m, 1 H), 1.8-2.0 (m, 1 H), 1.54 (d, 6H, J=7.6 Hz), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Example 4: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2- dimethyl-3,4-dihydropyrano[3,2-blpyridine-8-carboxamide (Compound P-4, table P)

Compound P-4, table P

Step A: Preparation of methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4-dihydropyrano[3,2-blpyridine-

8-carboxylate

A three neck flask, under argon atmosphere, was charged with palladium 10 % on carbon (0.01514 g, 0.1423 mmol). Then methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-pyrano[3,2-b]pyridine- 8-carboxylate (0.25 g, 0.71 14 mmol) was dissolved in ethylacetate (7.5 mL) and added in the previous flask. The flask was washed three times with vacuum and argon then hydrogen was added. The flask was washed 2 times with vacuum and hydrogen and the reaction mixture was stirred at room temperature under hydrogen atmosphere. After one night, the flask was washed with vacuum and argon. The reaction mixture was filtered over celite, filter cake was washed with ethylacetate several times and the filtrate was evaporated to afford methyl 7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4- dihydropyrano[3,2-b]pyridine-8-carboxylate

LCMS (Method A): retention time 1.14 min, 354 (M+H) ¹H NMR (1-CDCh, 400 MHz) 6 7.8-7.8 (m, 1 H), 7.21 (t, 1 H, J=7.8 Hz), 6.85 (d, 1 H, J=7.6 Hz), 6.8-6.8 (m, 1 H), 6.8-6.8 (m, 1 H), 3.86 (s, 3H), 2.96 (t, 2H, J=6.7 Hz), 1.98 (t, 2H, J=6.9 Hz), 1 .8-1 .9 (m, 1 H), 1.41 (s, 6H), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Step B: Preparation of 7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4-dihydropyrano[3,2-blpyridine-8- carboxylic acid

7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4-dihydropyrano[3,2-b]pyridine-8-carboxylate (0.24 g, 0.679 mmol) was dissolved in tetrahydrofuran (5 mL) and water (1 .6 mL) and lithium hydroxide-hydrate (0.056 g, 1.35 mmol) was added. The resulting mixture was stirred 3 days at 70°C. The solvent was evaporated under vacuum. 1 M HCI was added to the residue (pH 2 obtained) and then it was extracted two times with ethyl acetate. The combined organic layer were dried over magnesium sulfate, filtered and evaporated to afford 7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4-dihydropyrano[3,2-b]pyridine-8- carboxylic acid.

LCMS (Method A): retention time 0.86 min, 340 (M+H)

¹H NMR (DMSO-d6, 400 MHz) 6 13.2-13.7 (m, 1 H), 7.75 (s, 1 H), 7.22 (t, 1 H, J=8.0 Hz), 6.83 (d, 1 H, J=8.0 Hz), 6.7-6.8 (m, 1 H), 6.71 (ddd, 1 H, J=0.9, 2.5, 8.2 Hz), 2.86 (t, 2H, J=6.7 Hz), 1.8-2.0 (m, 3H), 1.33 (s, 6H), 0.9-1 .0 (m, 2H), 0.6-0.7 (m, 2H)

Step C: Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2,2-dimethyl- 3,4-dihydropyrano[3,2-blpyridine-8-carboxamide

The desired compound was prepared by reaction of 7-(3-cyclopropylphenoxy)-2,2-dimethyl-3,4- dihydropyrano[3,2-b]pyridine-8-carboxylic acid and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine as described for Example 3 step B, to afford 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro- ethyl]-2,2-dimethyl-3,4-dihydropyrano[3,2-b]pyridine-8-carboxamide. LCMS (Method A): retention time 1.22 min, 529 (M+H)

¹H NMR (1-CDCb, 400 MHz) 6 7.84 (s, 1 H), 7.4-7.5 (m, 2H), 7.2-7.3 (m, 2H), 6.7-6.9 (m, 3H), 6.30 (br dd, 1 H, J=5.1 , 6.5 Hz), 5.8-6.0 (m, 1 H), 4.1-4.3 (m, 1 H), 3.54 (dddd, 1 H, J=4.7, 7.7, 14.8, 19.7 Hz), 2.97 (t, 2H, J=6.9 Hz), 1 .99 (t, 2H, J=6.9 Hz), 1 .8-1 .9 (m, 1 H), 1 .42 (d, 6H, J=4.0 Hz), 0.9-1 .0 (m, 2H), 0.6-0.7 (m, 2H)

Example 5: Preparation 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyDethyl1-2,2-dimethyl-3,4- dihydropyrano[3,2-blpyridine-8-carboxamide (compound P-3, table P)

(compound P-3 table P)

The desired compound was prepared as described for Example 3 step B using 2-(2,4- dichlorophenyl)ethanamine as amine to afford 7-(3-cyclopropylphenoxy)-N-[2-(2,4- dichlorophenyl)ethyl]-2,2-dimethyl-3,4-dihydropyrano[3,2-b]pyridine-8-carboxamide (0.035 g, 0.068 mmol)

LCMS (Method A): retention time 1.23 min, 511 (M+H)

¹H NMR (CDCb, 400 MHz) 6 7.80 (s, 1 H), 7.36 (d, 1 H, J=2.2 Hz), 7.18 (d, 2H, J=8.4 Hz), 7.05 (dd, 1 H, J=2.2, 8.4 Hz), 6.85 (d, 1 H, J=7.6 Hz), 6.7-6.8 (m, 2H), 5.86 (br t, 1 H, J=6.0 Hz), 3.68 (q, 2H, J=6.9 Hz), 2.97 (td, 4H, J=6.6, 15.8 Hz), 1.96 (t, 2H, J=6.7 Hz), 1.8-1 .9 (m, 1 H), 1.39 (s, 6H), 0.9-1 .0 (m, 2H), 0.7-0.7 (m, 2H)

Example 6: Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2- methyl-furo[3,2-blpyridine-7-carboxamide (Compound P-2, table P)

(Compound P-2, table P)

Step A: Preparation of methyl 3-(3-cyclopropylphenoxy)-5-prop-2-ynoxy-pyridine-4-carboxylate

Methyl 3-(3-cyclopropylphenoxy)-5-hydroxy-pyridine-4-carboxylate (0.566 g, 1.984 mmol) and cesium carbonate (1 .358 g, 4.166 mmol) were suspended in Acetonitrile (15 mL). 3-bromoprop-1-yne (0.264 mL, 2.381 mmol) was added and the resulting yellow suspension was stirred for 30' at 60°C. The reaction mixture was dissolved in ethylacetate and water. The aqueous layer was extracted 3 times with ethylacetate. The combined organic layer was dried with magnesium sulfate, filtered and evaporated.

The crude was purified by chromatography to afford methyl 3-(3-cyclopropylphenoxy)-5-prop-2- ynoxy-pyridine-4-carboxylate (0.17 g, 0.499 mmol)

LCMS (Method A): retention time 1.04 min, 324 (M+H)

¹H NMR (400 MHz, CDCb) 6 ppm 8.32 (s, 1 H) 7.99 (s, 1 H) 7.24 (t, J=8.0 Hz, 1 H) 6.90 (d, J=7.6 Hz, 1 H) 6.81 - 6.87 (m, 1 H) 6.77 - 6.80 (m, 1 H) 4.86 (d, J=2.5 Hz, 2 H) 3.90 (s, 3 H) 2.63 (t, J=2.4 Hz, 1 H) 1 .89 (tt, J=8.4, 5.0 Hz, 1 H) 0.96 - 1 .02 (m, 2 H) 0.67 - 0.73 (m, 2 H)

Methyl 3-(3-cyclopropylphenoxy)-5-prop-2-ynoxy-pyridine-4-carboxylate (0.17 g, 0.5258 mmol, 1 .000) was dissolved in 1 ,2-dichlorobenzene (1 mL) at room temperature and the resulting solution was placed in the microwave system for 5h30 at 180°C. The reaction mixture was directly loaded on the chromatography over silica gel column to afford methyl 6-(3-cyclopropylphenoxy)-2-methyl-furo[3,2- b]pyridine-7-carboxylate (0.055 g, 0.1701 mmol)

LCMS (Method A): retention time 1.09 min, 324 (M+H)

¹H NMR (400 MHz, CDCb) 6 ppm 8.24 - 8.31 (m, 1 H) 7.23 (t, J=7.8 Hz, 1 H) 6.86 (br d, J=7.6 Hz, 1 H) 6.71 - 6.79 (m, 3 H) 3.95 (s, 3 H) 2.60 (s, 3 H) 1 .82 - 1 .95 (m, 1 H) 0.92 - 1 .00 (m, 2 H) 0.67 - 0.75 (m, 2 H) i-2-methyl-furo[3,2-b]pyridine-7-carboxylic acid

Methyl 6-(3-cyclopropylphenoxy)-2-methyl-furo[3,2-b]pyridine-7-carboxylate (0.055 g, 0.170 mmol) was dissolved in a mixture of tetrahydrofuran (1.2 mL) and water (0.4 mL) and hydroxylithium;hydrate (0.007 g, 0.170 mmol) was added. The resulting mixture was stirred over night at room temperature. The solvent was evaporated under vacuum. HC1 1 M was added to the aqueous layer (pH 2 obtained) and then it was extracted two times with ethylacetate. The combined organic layer were dried over magnesium sulfate, filtered and evaporated to afford crude 6-(3-cyclopropylphenoxy)- 2-methyl-furo[3,2-b]pyridine-7-carboxylic acid_(0.058 g, 0.1688 mmol) .

LCMS (Method A): retention time 0.86 min, 310 (M+H)

¹H NMR (400 MHz, DMSO) 6 ppm 13.88 - 14.16 (m, 1 H) 8.27 (s, 1 H) 7.20 (t, J=8.0 Hz, 1 H) 6.87 (d, J=0.7 Hz, 1 H) 6.79 (d, J=8.0 Hz, 1 H) 6.72 (t, J=2.0 Hz, 1 H) 6.66 (dd, J=8.0, 2.2 Hz, 1 H) 2.54 (s, 3 H) 1 .83 - 1 .95 (m, 1 H) 0.87 - 0.96 (m, 2 H) 0.59 - 0.68 (m, 2 H)

Step D: Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl1-2-methyl- furo[3,2-blpyridine-7-carboxamide (Compound P-2, table P)

(Compound P-2, table P)

The desired compound was prepared by reaction of 6-(3-cyclopropylphenoxy)-2-methyl-furo[3,2- b]pyridine-7-carboxylic acid and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine as described for Example 3 step B, to afford 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-furo[3,2- b]pyridine-7-carboxamide.

LCMS (Method A): retention time 1.21 min, 498 (M+H)

¹H NMR (CDCb, 400 MHz) 6 ppm 8.23 (s, 1 H) 7.43 (br t, J=5.4 Hz, 1 H) 7.35 - 7.39 (m, 1 H) 7.25 - 7.31 (m, 2H) 7.14 (dd, J=8.4, 1.8 Hz, 1 H) 6.91 (d, J=7.6 Hz, 1 H) 6.76 - 6.81 (m, 1 H) 6.73 - 6.75 (m, 1 H) 6.70 (s, 1 H) 5.82 - 6.00 (m, 1 H) 4.06 - 4.23 (m, 1 H) 3.75 - 3.93 (m, 1 H) 2.61 (d, J=1 .1 Hz, 3H) 1 .89 (tt, J=8.4, 5.1 Hz, 1 H) 0.97 - 1.04 (m, 2H) 0.68 - 0.74 (m, 2 H) Table P: LCMS data and/or retention times (Rt) for compounds according to formula (I):

Biological Examples/Test Methods

Example B-1: Alternaria solani I tomato / leaf disc (early blight)

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

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

P-1 , P-3, and P-4 Example B-2: Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-1 , P-3, P-4, P-5, and P-6

Example B-3: Glomerella lagenarium (Colletotrichum lagenarium) I liquid culture (Anthracnose)

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

The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-1 , P-3, P-4, P-5, and P-6

Example B-4: Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) I wheat I leaf disc preventative (Powdery mildew on wheat)

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

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

P-1 , P-3, P-4, and P-5

Example B-5: Fusarium culmorum / liquid culture (Head blight)

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 3-4 days after application.

The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-1 , P-4, and P-5

Example B-6: Phaeosphaeria nodorum (Septoria nodorum) I wheat I leaf disc preventative (Glume blotch)

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

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

P-3, and P-4

Example B-7: Monoqraphella nivalis (Microdochium nivale) I liquid culture (foot rot cereals)

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

The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-1 , P-3, P-4, P-5, and P-6

Example B-8: Pyrenophora teres I barley I leaf disc preventative (Net blotch)

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

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

P-1 , P-3, P-4, and P-5

Example B-9: Sclerotinia sclerotiorum I liquid culture (cottony rot)

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

The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-1 , P-3, P-4, P-5, and P-6

Example B-10: Mycosphaerella qraminicola (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:

P-3, P-4, P-5, and P-6

Claims

84 CLAIMS

1 . A compound of Formula (I):

wherein:

R² and R³ are each independently selected from hydrogen, and Ci-C4-alkyl; or

L¹ is -O- or -CH2- or a bond;

Y¹, Y², Y³ and Y⁴ form, together with the two carbon atoms to which Y¹ and Y⁴ are attached, an aromatic, partially saturated or fully saturated carbocyclic or heterocyclic ring; wherein: a) Y¹ is selected from NR^7a, S, SO2, oxygen, carbon substituted with one or two R⁸ substituents, and a direct bond; b) Y² is carbon substituted with one or two R⁸ substituents, or CR⁸-CHR^8aR^8b; c) Y³ is carbon substituted with one or two R⁸ substituents or CR⁸-CHR^8aR^8b; d) Y⁴ is selected from NR^7b, S, SO2, oxygen, carbon substituted with one or two R⁸ substituents, and a direct bond; and wherein R^7a and R^7b are each independently selected from hydrogen and Ci-C4alkyl; and R⁸, R^8a and R^8b are each independently selected from hydrogen, Ci-C4alkyl, and Cs-Cecycloalkyl; 85

2. The compound according to claim 1 , of the formula (la)

wherein Q1 is laa, lab, lac, lad, lae, laf, lag, lah, lai, laj, lak, lai, lam, or Ian;

wherein indicates the oxygen attachment to the R¹ group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R²R³)C(CR⁴R⁵)-L¹-R⁶ group; and m is 0,1 , or 2.

The compound according to claim 2, wherein Q1 is

wherein indicates the oxygen attachment to the R1 group and the arrow indicates the carbonyl attachment to the nitrogen of the HNC(R2R3)C(CR4R5)-L1-R6 group; and Z1 is N or CH.

4. The compound according to any one of claims 1 to 3, wherein R¹ is selected from 3- methylphenyl, 3-chlorophenyl, 3-cyclopropylphenyl, 3-trifluoromethylphenyl, and 3-cyclopropyl-2- fluorophenyl 86

5. The compound according to any one of claims 1 to 4, wherein R² and R³ are each independently selected from hydrogen and methyl; R² and R³ together with the carbon atom to which they are attached, form a cyclopropyl group.

6. The compound according to any one of claims 1 to 5, wherein R² and R³ are hydrogen.

7. The compound according to any one of claims 1 to 6, wherein R⁴ and R⁵ are each independently selected from hydrogen and fluoro; or R⁴ and R⁵ together with the carbon atom to which they are attached, form a cyclopropyl group.

8. The compound according to any one of claims 1 to 7, wherein R⁴ and R⁵ are each independently selected from hydrogen and fluoro.

9. The compound according to any one of claims 1 to 8, wherein R⁶ is selected from 2,4- dichlorophenyl, 2,4-dimethylphenyl, 2-chloro-4-fluoro-phenyl, 2-chloro-4-methyl-phenyl, 5-bromo-2- pyridyl, 4,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl,3 -chloro-5-methyl-2-pyridyl, 6-chloro-3-pyridyl, 4,6- dichloro-3-pyridyl, 4-methoxy-phenyl, 2-chloro-4-methoxy-phenyl, 2-fluoro-4-methoxy-phenyl, 3-chloro- 2-thienyl, and 3,5-dichloro-2-thienyl.

10. The compound according to any one of claims 1 to 9, wherein L¹ is -O- or a bond.

11 . The compound according to any one of claims 1 to 10, wherein L¹ is a bond.

12. The compound according to any one of claims 1 to 11 , wherein R^7a and R^7b are hydrogen or Ci-

C4alkyl; R⁸, R^8a and R^8b are independently selected from hydrogen, Ci-C4alkyl, and Cs-Cecycloalkyl.

13. The compound according to any one of claims 1 to 12, wherein Z¹ is N or CH.

14. The compound according to any one of claims 1 to 13, wherein Z¹ is CH.

15. An agrochemical composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 14.

16. The composition according to claim 15, further comprising at least one additional active ingredient and/or at least one agrochemically-acceptable diluent or carrier.

17. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to any of claims 1 to 14, or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof. 87

18. Use of a compound according to any one of claims 1 to 14 as a fungicide.