NZ745282B2 - Microbiocidal quinoline (thio)carboxamide derivatives - Google Patents

Abstract

Compounds of the formula (I) wherein the subsitiuents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi. rticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

Description

W0 2017/153380 MICROBIOCIDAL QUINOLINE (THIOICARBOXAMIDE DERIVATIVES The present invention relates to microbiocidal quinoline (thio)carboxamide derivatives, e.g. as active ingredients, which have microbiocidal ty, in particular fungicidal activity. The invention also relates to preparation of these quinoline (thio)carboxamide derivatives, to intermediates useful in the preparation of these quinoline (thio)carboxamide derivatives, to the ation of these intermediates, to agrochemical compositions which comprise at least one of the quinoline (thio)carboxamide derivatives, to preparation of these compositions and to the use of the quinoline (thio)carboxamide derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or ving materials by athogenic microorganisms, in particularfungi.

Certain fungicidal quinoline carboxamide compounds are described in WOO4039783.

It has now singly been found that certain novel quinoline (thio)carboxamide derivatives have favourable fungicidal properties.

The present invention therefore provides compounds of formula (I) R10In R13 R2 X \ N | H R7 R11 N R3 R5 R5 n XisOorS; R1 is hydrogen, halogen, methyl, methoxy or cyano; R2 and R3 are each independently hydrogen, n or methyl; R4 is hydrogen, cyano, C1-C4 alkyl, or Cs-C4 cycloalkyl, wherein the alkyl and cycloalkyl, may be optionally substituted with 1 to 3 substituents independently ed from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio; R5 and Rs are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1- C4 alkoxy and C1—C4 alkylthio; or R5 and R3 together with the carbon atom to which they are ed represent C=O, C=NORC , C3-C5 cycloalkyl or C2-C5 alkenyl, wherein the cycloalkyl and alkenyl may be optionally tuted with 1 to 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio; R7 is hydrogen, C1-C5 alkyl, C3-C5 cycloalkyl, C2-C5 l, C3-C5 cycloalkenyl, or C2- C5 alkynyl, n the alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 4 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, hydroxyl and C1-C3 alkylthio; R3 and R9 are each independently ed from hydrogen, halogen, C1-C4 alkyl and C1-C4 alkoxy; or R3 and R9 together with the carbon atom to which they are attached represent C3-C5 lkyl, wherein the cycloalkyl may be optionally tuted with 1 to 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio; each R10 independently represents halogen, nitro, cyano, formyl, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-Cs cycloalkyl, C1-C5 alkoxy, C3-C5 alkenyloxy, C3-C5 alkynyloxy, C1- C5 alkylthio, -C(=NORc)C1-C5alkyl, or C1-C5 alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy and alkylthio may be optionally substituted with 1 to 5 substituents independently selected from halogen, C1-C3 alkyl, C1-C3 alkoxy, cyano and C1-C3 alkylthio; n is 0, 1, 2, 3, 4 or 5; each Rcis independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C3-C4 alkynyl, C3-C4 cycloalkyl(C1-C2)alkyl and C3-C4 cycloalkyl, n the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents ndently selected from halogen and cyano; R11 is hydrogen, halogen, , methoxy or cyano; R12 and R13 are each independently selected from hydrogen, halogen, methyl, methoxy or hydroxyl; and salts and/or N-oxides f; provided that the compound is not one of the following compounds: / O___O ”-NHd'CIII-I—CH2-UeM , or a nd wherein R1 is hydrogen, R2 is hydrogen, R3 is methyl, R4 is hydrogen, R5 is hydrogen, R6 is hydrogen, R7 is hydrogen, R8 is en, R9 is hydrogen, n is 1, R10 is 2- methyl, R11 is fluoro, R12 is hydrogen, R13 is hydrogen, and X is O.

In a second aspect the present invention provides an agrochemical composition comprising a compound of formula (I).

Compounds of a (I) may be used to control phytopathogenic microorganisms.

Thus, in order to control a phytopathogen a compound of formula (I), or a composition comprising a compound of a (I), according to the invention may be applied directly to the athogen, or to the locus of a phytopathogen, in particular to a plant susceptible to attack by athogens.

Thus, in a third aspect the present invention provides the use of a compound of a (I), or a composition sing a compound of formula (I), as described herein to control a phytopathogen.

In a further aspect the present invention provides a method of controlling phytopathogens, comprising applying a compound of formula (I), or a composition comprising a nd of formula (I), as described herein to said phytopathogen, or to the locus of said phytopathogen, in particular to a plant susceptible to attack by a phytopathogen.

Compounds of formula (I) are ularly effective in the control of phytopathogenic fungi.

Thus, in a yet r aspect the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control phytopathogenic fungi.

In a further aspect the present invention provides a method of controlling phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogenic fungi, or W0 2017/153380 to the locus of said phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi.

Where substituents are indicated as being ally substituted, this means that they may or may not carry one or more cal or different substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time. Where a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.

The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably ne, chlorine or bromine.

Alkyl substituents (either alone or as part of a larger group, such as alkoxy-, alkylthio-) may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, npropyl , n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert—butyl or iso-amyl.

Alkenyl substituents (either alone or as part of a larger group, eg. alkenyloxy) can be in the form of straight or ed chains, and the alkenyl moieties, where appropriate, can be of either the (E)— or (;)-configuration. Examples are vinyl and allyl. The alkenyl groups are preferably C2-C6, more preferably 02-04 and most ably C2-C3 l groups.

Alkynyl substituents (either alone or as part of a larger group, eg. loxy) can be in the form of straight or branched chains. Examples are ethynyl and gyl. The alkynyl groups are preferably Cz-Cs, more preferably C2-C4 and most preferably C2-C3 alkynyl groups.

Cycloalkyl substituents may be saturated or lly unsaturated, preferably fully saturated, and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Haloalkyl groups (either alone or as part of a larger group, eg. haloalkyloxy) may contain one or more identical or different halogen atoms and, for e, may stand for CHzcl, CHCI2, CCls, CH2F, CHF2, CF3, CFsCHz, CHsCFz, CFsCFz or CCI300I2.

Haloalkenyl groups (either alone or as part of a larger group, eg. haloalkenyloxy) are alkenyl groups, tively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2—difluorovinyl or 1,2-dichlorofluoro-vinyl.

Haloalkynyl groups (either alone or as part of a larger group, eg. haloalkynyloxy) are alkynyl groups, respectively, which are substituted with one or more of the same or ent halogen atoms and are, for example, ro-propynyl.

Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above. Alkoxy groups include, but are not limited to, y, ethoxy, 1-methylethoxy, propoxy, butoxy, 1- methylpropoxy and 2—methylpropoxy.

W0 2017/153380 Cyano means a —CN group.

Amino means an -NH2 group.

Hydroxyl or hydroxy stands for a —OH group.

Aryl groups (either alone or as part of a larger group, such as e.g. aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, yl, anthracenyl, indenyl or threnyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is preferably substituted by one to four substituents, most ably by one to three tuents.

Heteroaryl groups (either alone or as part of a larger group, such as e.g. heteroaryloxy, heteroaryl-alkyl) are aromatic ring systems containing at least one atom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three atoms and bicyclic systems up to four heteroatoms which will preferably be chosen from en, oxygen and sulfur. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g. [1,2,4] triazolyl), furanyl, thiophenyl, oxazolyl, olyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples of bicyclic groups include purinyl, inyl, cinnolinyl, quinoxalinyl, indolyl, lyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.

Monocyclic heteroaryl groups are preferred, pyridyl being most preferred. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is preferably substituted by one to four substituents, most ably by one to three substituents.

Heterocyclyl groups or heterocyclic rings (either alone or as part of a larger group, such as heterocyclyl-alkyl) are non-aromatic ring structures containing up to 10 atoms including one or more (preferably one, two or three) heteroatoms selected from O, S and N.

Examples of monocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, thietanyl, pyrrolidinyl, ydrofuranyl, [1,3]dioxolanyl, piperidinyl, piperazinyl, ioxany|, imidazolidinyl, [1,3,5]oxadiazinanyl, hexahydro-pyrimidinyl, [1,3,5]triazinanyl and morpholinyl or their oxidised versions such as 1-oxo-thietanyl and 1,1-dioxo-thietanyl. Examples of bicyclic groups include 2,3-dihydro-benzofuranyl, benzo[1,4]dioxolanyl, benzo[1,3]dioxolanyl, chromenyl, and 2,3-dihydro-benzo[1,4]dioxinyl. Where a heterocyclyl moiety is said to be substituted, the heterocyclyl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.

The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of cted rotation about a single bond. Formula (I) is intended to include all those possible ic forms and mixtures thereof. The present invention es all those possible isomeric forms W0 2017/153380 and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include all possible ers. The present invention includes all possible tautomeric forms for a compound of formula (I).

In each case, the nds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form. es 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.

Preferred values of X, R1, R2, R3, R4, R5, R6, R7, R3, R9, R10, R11, R12, R13, n and RC are, in any combination thereof, as set out below: Preferably X is O.

Preferably R1 is hydrogen, fluoro, , methyl, or cyano.

More preferably R1 is en, fluoro, methyl, or cyano.

Most preferably R1 is hydrogen or fluoro.

Preferably R2 and R3 are each independently hydrogen or methyl.

More preferably R2 is hydrogen and R3 is hydrogen or methyl; or R2 is hydrogen or methyl and R3 is hydrogen.

Most preferably R2 and R3 are both hydrogen.

Preferably R4 is hydrogen, cyano, C1-C3 alkyl, or ropyl, wherein the alkyl and cycloalkyl, may be optionally substituted with 1 to 3 substituents independently selected from , chloro, cyano, methyl, y and methylthio.

More preferably R4 is hydrogen, cyano, methyl or ethyl, wherein the methyl and ethyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro and methoxy.

Most preferably R4 is methyl or ethyl (wherein the methyl and ethyl may be ally substituted with 1 to 3 fluoro substituents or methoxy).

Preferably R5 and Rs are each independently selected from hydrogen, fluoro, C1-C2 alkyl, C1-C2 alkoxy and C1-C2 hio; or R5 and Rs together with the carbon atom to which they are attached represent C=O or cyclopropyl, wherein the cyclopropyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, methyl and cyano.

More preferably R5 and Rs are each independently selected from en, fluoro, methyl, methoxy and methylthio; or R5 and R5 together with the carbon atom to which they are attached ent cyclopropyl.

Most ably R5 and Rs are each independently selected from hydrogen and fluoro.

W0 53380 ably R7 is C1-C4 alkyl, C3-C4 lkyl, C2-C4 alkenyl, or C2-C3 alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, hydroxyl and methylthio.

More preferably R7 is C1-C4 alkyl, Cs-C4 cycloalkyl, or C2-C4 alkenyl, wherein the alkyl, lkyl and alkenyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, , hydroxyl, cyano and methyl.

Most ably R7 is methyl, ethyl, n-propyl, opyl, tyl, tert—butyl, Cs-C4 cycloalkyl, or C2-C4 alkenyl, wherein the methyl, ethyl, n-propyl, opyl, sec-butyl, tert- butyl, cycloalkyl and alkenyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro and methyl.

Preferably R9 and R9 are each independently selected from hydrogen, , C1-C2 alkyl and C1-C2 alkoxy; or R9 and R9 together with the carbon atom to which they are attached ent cyclopropyl, wherein the cyclopropyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, cyano, and methyl.

More preferably R8 and R9 are each independently selected from hydrogen, fluoro and methyl; or R9 and R9 together with the carbon atom to which they are attached represent cyclopropyl.

Most ably R9 and R9 are each independently selected from en or fluoro.

Preferably each R10 independently represents halogen, cyano, C1-Cs alkyl, C2-C3 alkenyl, Cz-Cs alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C1-C2 alkylthio, wherein the alkyl, cyclopropyl, alkenyl, alkynyl, methoxy, allyloxy, propargyloxy and alkylthio may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, methyl, and cyano; n is 0, 1, 2 or 3.

More preferably each R10 independently represents fluoro, chloro, cyano, methyl, cyclopropyl, methoxy or methylthio, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 substituents independently selected from fluoro and chloro; n is 0,1 or 2.

Most preferably each R10 independently represents fluoro, chloro, cyano or methyl, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 fluoro tuents; n is 0, 1 or 2.

Preferably each Rc is independently selected from hydrogen, methyl, ethyl, allyl, propargyl, and cyclopropylmethyl, wherein the methyl, ethyl, allyl, propargyl, and cyclopropylmethyl groups may be optionally substituted with 1 to 3 substituents independently selected from fluoro and chloro.

Most ably each RC is independently selected from methyl, ethyl, allyl, gyl, and cyclopropylmethyl, wherein the methyl, ethyl, allyl, gyl, and cyclopropylmethyl W0 2017/153380 groups may be optionally substituted with 1 to 3 substituents independently selected from fluoro and chloro.

Preferably R11 is hydrogen, fluoro, chloro, methyl or cyano.

More preferably R11 is hydrogen, fluoro, methyl or .

Most preferably R11 is hydrogen or fluoro.

Preferably R12 and R13 are each independently selected from hydrogen, fluoro, methyl and hydroxyl.

More preferably R12 and R13 are each ndently selected from hydrogen, fluoro and .

Most preferably R12 and R13 are both hydrogen.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula (I), or a salt or N—oxide thereof, as defined above. ment 2 provides compounds according to embodiment 1, or a salt or N-oxide thereof, wherein R1 is en, fluoro, chloro, methyl, or cyano.

Embodiment 3 provides compounds according to ment 1 or 2, or a salt or N- oxide thereof, wherein R2 and R3 are each independently hydrogen or methyl.

Embodiment 4 provides compounds according to any one of embodiments 1, 2 or 3, or a salt or e thereof, n R4 is hydrogen, cyano, C1—C3 alkyl, or cyclopropyl, wherein the alkyl and lkyl, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, and methylthio.

Embodiment 5 provides compounds according to any one of embodiments 1, 2, 3 or 4, or a salt or N-oxide thereof, n R5 and R3 are each independently selected from hydrogen, fluoro, C1-C2 alkyl, C1-C2 alkoxy and C1-C2 alkylthio; or R5 and R3 er with the carbon atom to which they are attached represent C=O or cyclopropyl, wherein the cyclopropyl may be optionally substituted with 1 to 2 substituents independently selected from , methyl and cyano.

Embodiment 6 provides nds according to any one of ments 1, 2, 3, 4, or 5, or a salt or N-oxide thereof, wherein R7 is C1-C4 alkyl, C3-C4 cycloalkyl, C2-C4 alkenyl, or C2-C3 alkynyl, wherein the alkyl, cycloalkyl, alkenyl, l, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, hydroxyl and methylthio.

Embodiment 7 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, or 6, or a salt or N-oxide thereof, wherein R3 and R9 are each independently selected from hydrogen, fluoro, 01-02 alkyl and C1-C2 alkoxy; or R3 and R9 together with the carbon atom to W0 2017/153380 which they are attached represent cyclopropyl, n the cyclopropyl may be optionally substituted with 1 to 2 substituents independently selected from , cyano, and methyl.

Embodiment 8 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, or 7, or a salt or N-oxide thereof, wherein each R10 independently represents halogen, cyano, C1-C3 alkyl, C2-C3 alkenyl, Cz-Cs alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C1—C2 alkylthio, wherein the alkyl, cyclopropyl, l, alkynyl, methoxy, allyloxy, propargyloxy and hio may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, methyl, and cyano; n is O, 1, 2 or 3.

Embodiment 9 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, or 8, or a salt or e thereof, wherein each RC is independently selected from hydrogen, methyl, ethyl, allyl, propargyl, and cyclopropylmethyl, wherein the methyl, ethyl, allyl, propargyl, and cyclopropylmethyl groups may be optionally substituted with 1 to 3 substituents independently selected from fluoro and chloro. ment 10 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, or a salt or N-oxide thereof, wherein R1 is hydrogen, fluoro, methyl, or cyano.

Embodiment 11 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9 or 10, or a salt or N-oxide thereof, wherein R2 is hydrogen and R3 is hydrogen or methyl; or R2 is en or methyl and R3 is hydrogen.

Embodiment 12 provides nds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt or N-oxide thereof, wherein R4 is en, cyano, methyl or ethyl, wherein the methyl and ethyl may be optionally tuted with 1 t0 3 substituents independently selected from fluoro and methoxy.

Embodiment 13 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11 or 12, or a salt or N-oxide thereof, wherein R5 and Rs are each independently selected from hydrogen, , methyl, methoxy and methylthio; or R5 and R5 together with the carbon atom to which they are attached represent cyclopropyl. ment 14 es nds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12 or 13, or a salt or e thereof, wherein R7 is C1-C4 alkyl, Cs-C4 cycloalkyl, or 02-04 alkenyl, wherein the alkyl, cycloalkyl and l may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, hydroxyl, cyano and methyl.

Embodiment 15 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt or N-oxide thereof, wherein R3 and R9 are each independently selected from hydrogen, fluoro and methyl; or R3 and R9 together with the carbon atom to which they are attached represent cyclopropyl.

Embodiment 16 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, or a salt or N-oxide thereof, wherein each R10 W0 2017/153380 2017/055273 independently represents fluoro, chloro, cyano, methyl, cyclopropyl, methoxy or thio, n the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 substituents independently selected from fluoro and ; n is 0, 1 or 2.

Embodiment 17 provides nds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11,12, 13, 14, 15 or 16, or a salt or N—oxide thereof, wherein each Rois independently selected from methyl, ethyl, allyl, propargyl, and cyclopropylmethyl, wherein the methyl, ethyl, allyl, propargyl, and cyclopropylmethyl groups may be optionally tuted with 1 to 3 substituents independently selected from fluoro and chloro.

Embodiment 18 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15,16 or 17, or a salt or e thereof, wherein R1 is hydrogen or fluoro.

Embodiment 19 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17 or 18, or a salt or N-oxide thereof, wherein R2 and R3 are both hydrogen.

Embodiment 20 es compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, or a salt or N-oxide thereof, wherein R4 is methyl or ethyl (wherein the methyl and ethyl may be optionally substituted with 1 to 3 fluoro substituents).

Embodiment 21 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or a salt or N—oxide thereof, wherein R5 and Rs are each independently selected from hydrogen and fluoro.

Embodiment 22 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20 or 21, or a salt or N—oxide thereof, wherein R7 is methyl, ethyl, n-propyl, iso-propyl, tyl, tert-butyl, Cs-C4 lkyl, or Cz- C4 alkenyl, wherein the methyl, ethyl, n-propyl, iso—propyl, sec-butyl, tert-butyl, cycloalkyl and alkenyl may be optionally substituted with 1 to 3 tuents independently selected from fluoro, chloro and methyl.

Embodiment 23 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, ora salt or e thereof, wherein R3 and R9 are each independently selected from hydrogen or fluoro.

Embodiment 24 provides compounds ing to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or23, ora salt or N—oxide thereof, wherein each R10 independently represents fluoro, chloro, cyano or methyl, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 fluoro substituents; n is 0, 1 or 2.

Embodiment 25 es compounds according to any one of ments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24, ora salt or N-oxide W0 2017/153380 thereof, wherein R11 is hydrogen, fluoro, chloro, methyl or Embodiment 26 provides compounds according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, , 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, or a salt or N-oxide thereof, wherein R12 and R13 are each independently selected from hydrogen, fluoro, methyl and hydroxyl. ment 27 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 or26, ora salt or N- oxide thereof, wherein R11 is hydrogen, fluoro, methyl or .

Embodiment 28 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22,23,24, 25,26 or27, ora salt or N-oxide thereof, wherein R12 and R13 are each independently selected from hydrogen, fluoro and methyl.

Embodiment 29 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, 21,22, 23,24,25,26,27 or28, ora salt or N-oxide thereof, wherein R11 is hydrogen or fluoro.

Embodiment 30 provides compounds according to any one of embodiments 1, 2, 3, 4, , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,26, 27, 28 or29, or a salt or N-oxide f, wherein R12 and R13 are both hydrogen.

One group of compounds according to the invention are those of formula (I’): \ N | H R7 R11 N R3 R5 R6 0‘) n R1, R2, R3, R4, R5, R6, R7, R3, R9, R10, R11, R12, R13, n and R6 are as defined for compounds of formula (I), or a salt or N-oxide thereof. Preferred tions of R1, R2, R3, R4, R5, R6, R7, R3, R9, R10, R11, R12, R13, n and Re are as defined for nds of formula (I).

One group of compounds according to the invention are those of formula (l”): W0 53380 R13 R2 3 \ N | H R7 R11 N R3 R5 R6 wherein R1, R2, R3, R4, R5, R5, R7, R3, R9, R10, R11, R12, R13, n and RC are as defined for compounds of formula (I), or a salt or N-oxide thereof. Preferred definitions of R1, R2, R3, R4, R5, R3, R7, R3, R9, R10, R11, R12, R13, n and Re are as defined for compounds of formula (I).

A preferred group of compounds according to the invention are those of formula (M) which are compounds of formula (I) wherein X is O or 8; R1 is hydrogen, fluoro, chloro, methyl, or cyano; R2 and R3 are each independently hydrogen or methyl; R4is hydrogen, cyano, C1—C3 alkyl, or cyclopropyl, wherein the alkyl and cycloalkyl, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, and methylthio; R5 and R3 are each independently selected from hydrogen, fluoro, C1—C2 alkyl, C1—C2 alkoxy and C1-C2 alkylthio; or R5 and R5 together with the carbon atom to which they are attached represent C=O or cyclopropyl, wherein the ropyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, methyl and cyano; R7 is C1—C4 alkyl, C3-C4 cycloalkyl, C2-C4 alkenyl, or C2—C3 alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, may be optionally substituted with 1 to 3 tuents independently selected from , chloro, cyano, methyl, hydroxyl and methylthio; R3 and R9 are each independently selected from hydrogen, fluoro, C1-C2 alkyl and C1-C2 alkoxy; or R3 and R9 together with the carbon atom to which they are attached represent ropyl, wherein the ropyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, cyano, and methyl; each R10 independently represents n, cyano, C1-C3 alkyl, C2-Cs alkenyl, C2-C3 alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C1- C2 alkylthio, n the alkyl, cyclopropyl, l, alkynyl, methoxy, xy, propargyloxy and alkylthio may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, methyl, and cyano; n is 0, 1, 2 or 3; R11 is en, fluoro, chloro, methyl or cyano; and R12 and R13 are each independently selected from hydrogen, fluoro, methyl and hydroxyl; or a salt or e thereof.

One group of compounds according to this embodiment are compounds of formula (I- 1a) which are nds of formula (l-1) wherein X is O.

W0 2017/153380 Another group of compounds according to this embodiment are compounds of formula (H b) which are compounds of formula (l-1) n X is S.

A further preferred group of compounds according to the invention are those of a (l-2) which are compounds of formula (I) wherein X is O or 8; R1 is hydrogen, fluoro, , or cyano; R2 is en and R3 is hydrogen or methyl; or R2 is hydrogen or methyl and R3 is hydrogen; R4 is hydrogen, cyano, methyl or ethyl, wherein the methyl and ethyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro and methoxy; R5 and R5 are each ndently selected from hydrogen, fluoro, methyl, methoxy and methylthio; or R5 and R5 together with the carbon atom to which they are attached represent cyclopropyl; R7 is C1-C4 alkyl, Cs-C4 cycloalkyl, or C2-C4 alkenyl, wherein the alkyl, cycloalkyl and alkenyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, hydroxyl, cyano and methyl; R9 and R9 are each independently selected from hydrogen, fluoro and methyl; or R9 and R9 together with the carbon atom to which they are attached ent cyclopropyl; each R10 independently represents fluoro, chloro, cyano, methyl, cyclopropyl, methoxy or methylthio, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 substituents independently selected from fluoro and chloro; n is O, 1 or 2; R11 is hydrogen, , methyl or chloro; and R12 and R13 are each independently selected from hydrogen, fluoro and methyl; or a salt or N-oxide thereof.

One group of compounds according to this embodiment are compounds of a (I- 2a) which are compounds of formula (l-2) wherein X is 0.

Another group of compounds according to this embodiment are compounds of a (l—2b) which are compounds of a (l-2) wherein X is S.

A r preferred group of compounds according to the invention are those of formula (l-3) which are compounds of formula (I) wherein X is O or 8; R1 is hydrogen or fluoro; R2 and R3 are both hydrogen; R4 is methyl or ethyl in the methyl and ethyl may be optionally substituted with 1 to 3 fluoro substituents); R5 and Rs are each independently selected from hydrogen and fluoro; R7 is methyl, ethyl, n-propyl, iso-propyl, sec-butyl, tert- butyl, Cs-C4 cycloalkyl, or C2-C4 alkenyl, wherein the methyl, ethyl, n-propyl, iso-propyl, sec- butyl, tert—butyl, cycloalkyl and alkenyl may be optionally tuted with 1 to 3 substituents independently selected from fluoro, chloro and methyl; R8 and R9 are each ndently ed from hydrogen or fluoro; each R10 independently represents , chloro, cyano or methyl, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 fluoro substituents; n is 0, 1 or 2; and R11 is hydrogen or fluoro; R12 and R13 are both hydrogen; or a salt or e thereof.

One group of compounds according to this embodiment are compounds of formula (I- 3a) which are compounds of formula (I-3) wherein X is O.

W0 2017/‘153380 Another group of compounds according to this embodiment are compounds of formula (l-3b) which are compounds of formula (l-3) wherein X is 8.

Compounds according to the ion 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 e, greater ical activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability). ic examples of compounds of formula (I) are illustrated in the Tables A1 to A13 below: Table A1 provides 248 compounds of formula (l-a) R 10 \ N | H R7 R11 N R3 R5 R6 0-8) wherein R1, R2 and R3 are all H and R11, R12, R13 are all H and n the values of R4, R5, R5, R7, R8, R9 and R10 and n (if R10 and n are present) are as defined in Table Z below: Table Z IEI H3 (C|)=CH2 =c<o‘H><CH3)2 xcm» C(3CH3)(CH3)2 CH=C(CH3)2 opyl -methylcyclopropy| -f|uorocyc|opropy| _fl_u,orocyCIObUtyl ,3;difluorocyclobutflm CH2CH2CH3 CW(CH3W)3 ECH=CH2 C(CH3)=CH2 yolopropyl -methylcyC|opropy| yclopropyl ICydopropylm,,,,,,,,,,,,..... M cyclopropyl cyclopropyl ropyl CYCIopropyl cyclopropyi L C(CH3)=CH2 yclopropyl CH(CH3)2 WEWCH(CH3)2 ; CH(CH3)2 F CH5 ,,,,,,,,,,,,,,,,,,,,,,,,,,, “3)2 ECHs E cyclopropyl (CH3)=CH2 (CH3)=CH2 (CH3)=CH2 W0 2017I153380 2017/055273 Table A2 provides 248 compounds of formula (l-a) wherein R11, R12, R13 are all H, R1 is fluoro, R2 and R3 are H and wherein the values of R4, R5, R5, R7, R9, R9 and R19 are as defined in Table Z above.

Table A3 provides 248 compounds of formula (I-a) wherein R11, R12, R13 are all H, R1 is chloro, R2 and R3 are H and wherein the values of R4, R5, R6, R7, R8, R9 and R10 are as defined in Table Z above.

Table A4 provides 248 compounds of formula (I-a) wherein R11, R12, R13 are all H, R1 is bromo, R2 and R3 are H and wherein the values of R4, R5, R6, R7, R3, R9 and R10 are as defined in Table Z above.

Table A5 provides 248 compounds of formula (I-a) wherein R11, R12, R13 are all H, R1 is , R2 and R3 are H and wherein the values of R4, R5, R6, R7, R3, R9 and R10 are as defined in Table Z above.

W0 2017/153380 Table A6 provides 248 nds of formula (l-a) wherein R11, R12, R13 are all H, R1 is cyano, R2 and R3 are H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A7 provides 248 nds of formula (l-a) wherein R11 is fluoro, R1 is H, R2 and R3 are H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A8 provides 248 compounds of a (l-a) wherein R11, R12, R13 are all H, R2 is methyl, R1 and R3 are H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A9 provides 248 compounds of formula (l-a) wherein R11, R12, R13 are all H, R3 is methyl, R1 and R2 are H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A10 provides 248 compounds of formula (l-a) wherein R11, R12, R13 are all H, R2 is methyl, R1 is fluoro and R3 is H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A11 provides 248 compounds of formula (l-a) wherein R11, R12, R13 are all H, R3 is methyl, R1 is fluoro and R2 is H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A12 provides 248 compounds of formula (l-a) wherein R12, R13 are H, R2 and R3 are H, R1 and R11 are , and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A13 provides 248 compounds of a (l-b) R1o]n R13 R2 S \ N | H R7 R11 N R3 R5 R6 (l-b) wherein R11, R12, R13, R1, R2 and R3 are all H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

Table A14 es 248 compounds of formula (l-b) wherein R1 is fluoro, R11, R12, R13, R2 and R3 are H and wherein the values of R4, R5, R3, R7, R3, R9 and R10 are as defined in Table Z above.

W0 2017/153380 Compounds of the present invention can be made as shown in the following s, in which, unless otherwise stated, the definition of each variable is as defined above for a nd of formula (I).

A shown in scheme 1, compounds of general formula (l—a) wherein R1, R2, R3, R4, R5, R6, R7, R3, R9, R10, R11, R12, R13 and n are as defined for compounds of formula (I) and X is O can be prepared by the reaction of compounds of formula (II) wherein R1, R2, R3, R11, R12 and R13 are as defined for compounds of formula (I) with amines of formula (III) wherein R4, R5, R6, R7, R3, R9, R10 and n are as defined for compounds of formula (I).

R1o] R R H2N R4 _.

R7 R11 (II) (III) (l—a) Scheme 1 Among the various reported methods for this transformation, the most widely applied involve ent of carboxylic acid (II) with an activating agent like thionyl de or an amide coupling reagent like dicyclohexylcarbodiimide in an inert organic solvent like tetrahydrofuran (THF) or dimethylformamide (DMF) and reaction with amine (III) in the presence of a catalyst like dimethylaminopyridine as described in Chem. Soc. Rev., 2009, 1 or Tetrahedron 2005, 10827—10852.

As shown in scheme 2, compounds of general formula (l-a) wherein X is O can also be ed by the reaction of nds of formula (IV) and (V) in the presence of a Bronsted acid like sulphuric acid or trifluoromethane ic acid, in a solvent like dichloromethane or acetic acid at temperatures between -20 °C and +50 °C as described in Eur. J. Org. Chem. 2015, 2727—2732 and Synthesis 2000, 1709—1712.

R1o]n R R R R 13 2 R89 1O]n R13 R2 HO R4 R5 R7 NR5 R67 (IV) (V) (a)" Scheme 2 Alternatively, compounds of general formula (l-a) wherein X is O can also be prepared by the reaction of nds of formula (VI) with amines of formula (III), carbon monoxide, a W0 53380 2017/055273 base like triethylamine or potassium carbonate and a suitably supported transitional metal catalyst like palladium in an inert organic solvent like 1,4-dioxane at a temperature between 20 °C and 110 °C as described in Org. Lett, 2014, 4296—4299 (and nces therein) and shown in scheme 3.

R10] R13 R2 R59 R10] [0'8”] R13 R2 H 2N8 + R4 R7 NR5 R: (VI) (III) (l-a) Scheme 3 Alternatively, compounds of general formula (l-a) wherein X is O can also be prepared by the reaction of organometallic compounds of formula (Vla) with isocyanates of formula (Illa) in an inert organic solvent like diethyl ether or THF at temperatures between -78 °C and +40 °C as described in Angew. Chem. Int. Ed. 2012, 9173 —9175 and shown in scheme 4.

R10] R13\R2 R13\R2 R10]n R [Brl] R13 R2 0R9 R4 R4 R12 B —> | H R7 R11 N’ R3 R5 R6 (VI) R1 (VI)a R1 (Illa) (I) X: LI or Mg salt Scheme4 The preparation of organometallic compounds of formula (Vla) from compounds of formula (VI) by lithium-halogen exchange with an alkyl lithium reagent like s—butyl lithium or magnesium-halogen exchange with tri l magnesate in an ethereal solvent like THF at atures between -90 °C and +20 °C is generally known to a person skilled in the art, and is described in synthetic chemistry texts such as March’s Advanced Organic Chemistry.

As shown in scheme 5, carboxylic acids of formula (II) can be prepared by various methods and many are commercially available. Among the many reported s for their preparation, the following have been widely applied: 0 O AYL/ R13 OH 0 R13 R2 0 R13 R2 (VIIa) R11 N I")1 R1 ()Vll V(|)|b Scheme 5 W0 2017/153380 1)Transformation of anilines of formula (VII) to quinolones of a (Vllb) by reaction with a te derivative of formula (Vlla) in an inert solvent like diphenyl ether at temperatures between 100 °C and 260°C as described in US 20070015758, followed by well- known functional group onversion which is generally known to a person skilled in the art and also described in WO 2007133637. 2) Transformation of compounds of formula (VI) to organometallic intermediates of formula (Vla) by lithium-halogen exchange with an alkyl lithium reagent like s—butyl lithium or magnesium—halogen exchange with tri n-butyl magnesate in an ethereal solvent like THF at temperatures between -90 °C and +20 °C and subsequent reaction with C02. 3) Transformation of compounds of formula (VI) in the presence of a carbon de source, a base like triethylamine, water or an equivalent thereof and a suitably ligated transition metal catalyst containing for example palladium as described in J. Am. Chem. Soc. 2013, 2891—2894 (and nces therein) or Tetrahedron 2003, 640.

As shown in scheme 6, compounds of formula (IV) can be prepared from compounds of a (VI) by treatment with a cyanide source like zinc cyanide in the presence of a palladium, nickel or copper catalyst in an inert solvent like DMF at atures between 20 °C and 150 °C as described in J. Org. Chem. 2011, 665-668 or Bull. Chem. Soc. Jpn. 1993, 2776-8.

R13 R2 R13 I:32 R12 [CLBrJ] cyanide source R12 //N \ \ R11 N’ R3 Pd, NiorCu R11 N’ R3 R1 catalyst R1 W') (N) 6 As shown in scheme 7, compounds of formula (VI) can be prepared by treatment of compounds of formula (Vla) with a halogenating agent like N-iodosuccinimide, bromine or chlorine in an inert solvent as described in WO 2005113539 or JP 2001322979. Alternatively, compounds of formula (VI) can be prepared by treatment of propargylated anilines of formula (Vlb) with a halogenating agent like iodine in an inert solvent like itrile and a base like sodium hydrogen carbonate at temperatures between 0 °C and 80 °C as described in Org.

Lett. 2005, 763-766.

R13 R2 R13 R2 nating R12 halogenatingR \ agent [0' Br '1 agent R11 N/ R3—’ R1 Ramjla (Vla) R(Vlb) Scheme 7.

W0 53380 The preparation of propargylated anilines of formula (Vlb) from the corresponding commercially available anilines is trivial to a person skilled in the art and described in March’s Advanced Organic Chemistry, Smith and March, 6th edition, Wiley, 2007.

The synthesis of compounds of formula (Vla) is generally known to a person skilled in the art and a large ion of compounds is commercially available.

As shown in scheme 8, compounds of formula (V) can be prepared from carbonyl compounds of formula (Va) or (Vc) by treatment with an organometallic species of formula (Vb) or (Vd) respectively where X is lithium, an aluminum- or a magnesium—salt, in an inert solvent like diethyl ether at temperatures between -90 °C and 60 °C.

R9 R10] 0 n R4 R R10] R8 + /)\ R 9 ‘0] n R n + R8 R5 R7 6 HO R4 (— 9 R R5 R7 6 R6 Scheme 8 The general preparation, handling and reactivity of reagents with formula (Vb) and (Vd) is described in March’s Advanced c Chemistry, Smith and March, 6‘“ n, Wiley, 2007 and is lly known to a person skilled in the art. A large selection of compounds of formula (Va) and (V0), where R6,R7,R8,R9 and R10 as defined in the above, are also commercially available and their syntheses are well described in the scientific ture and tic chemistry text (such as March’s Advanced Organic Chemistry) and, further, are generally known to a person skilled in the art.

As shown in scheme 9, amines of formula (III) can be prepared from compounds of formula (Vc) by condensation with tertbutyl sulfinamide in the presence of a dehydrating agent like Ti(OEt)4 to form sulfimines of formula (Ve) which can then be treated with an organometallic reagent of formula (Vd), where X is lithium, an aluminum- or a magnesium-salt, in an inert solvent like THF at temperatures between -78 °C and + 70 °C, ed by an acidic hydrolysis of the sulfonamide; a sequence generally known to a person skilled in the art and also described in Chem. Rev. 2010, 3600—3740. atively, amines of formula (III) can be prepared from compounds of formula (Vcc) by condensation with tyl sulfinamide in the presence of a dehydrating agent like Ti(OEt)4 to form sulfimines of formula (Vee) which can then be treated with an organometallic reagent of a (Vdd), where X is lithium, an aluminum- or a magnesium-salt, in an inert solvent like THF at temperatures between -78 °C and + 70 °C, ed by an acidic hydrolysis of the sulfonamide.

W0 53380 9 o s R R O H N’ 7< ,5 9 10I 2 N R9 R10] R8 R + n R6R5% R4 —> 5 R4 R8 —> H2N R4 R7 R6 R7 X R5 R7 (VG) (Vd) 6 (Ve) (III) 0 o [Wowo s ,s H2N K' N [R10 7< R5 R4 + R R R4 R6+ 7 9 R8 R9 R8 X (V00) (Vee) de) Scheme9 Alternatively, amines of formula (III) can be also prepared from alcohols of a (V) by treatment with a strong acid like sulfuric acid in the presence of chloroacetonitrile in an organic solvent like acetic acid at temperatures between -10 °C and 50 °C to give amides of formula (lllb) which can be deprotected with thiourea in an organic solvent like ethanol or acetic acid at temperatures between 20 °C and 100 °C as described in Synthesis 2000, 1709 — 1712 and shown in scheme 10.

R9 R10] R10 n R9 R10] n / N RR98 n H R8 R Ho8 R CI\//, ‘(N R4 H2N R4 R R O 5 7 R5 R7 CI R6 R5 R7 R6 Re (V) (lllb) (Ill) Scheme 10 Alternatively, amines of formula (III) can be also prepared from carboxylic acids of formula (IX) through an intermediary isocyanate of a (Illa) or a ate of formula (lllc), where R14 is C1-C4 alkyl, is which can be hydrolyzed with s acid or base at temperatures between 0 °C and 100 °C as shown in scheme 11.

(IX) (Illa) (INC) ("D Among the various protocols reported for the transformation of acid (IX) to isocyanate (Illa), the following have found wide spread application: W0 2017/153380 1)Treatment of acid (IX) with diphenylphosphoryl azide and an amine base like tributylamine in an inert organic solvent like toluene at temperatures between 50 °C and 120 °C to give isocyanate (Illa) as described in Aust. J. Chem, 1973, 1591-3. 2) Treatment of acid (IX) with an activating agent like thionyl chloride or propylphosphonic anhydride in the ce of an azide source like sodium azide and an amine base like triethyl amine in an inert solvent like THF at atures between 20 °C and 100 °C as described in Synthesis 2011, 1477—1483. 3) Conversion of acid (IX) to the corresponding hydroxamic acids which can then be treated with a dehydrating agent like para-toluenesulfonyl chloride and a base like triethylamine in an inert c solvent like toluene at temperatures between 20 °C and 120 4) Conversion of acid (IX) to the corresponding primary carboxamide which can then be d with an oxidizing agent such as diacetoxyiodobenzene and an acid such as trifluoroacetic acid or para-toluenesulfonic acid in a solvent like acetonitrile at temperatures between 0 °C and 100 °C as described in J. Org. Chem. 1984, 4212-4216.

) Conversion of acid (IX) to the corresponding primary carboxamide which can then be treated with an oxidizing agent such as bromine and a base such as sodium hydroxide in a solvent like water or methanol at temperatures between 0 °C and 100 °C.

A person skilled in the art will iate that carboxylic acids of formula (IX) can be prepared from the corresponding esters. Similarly a person skilled in the art will iate that the alpha position of these esters can be functionalized by deprotonation with a strong base like lithium ropylamine in an inert solvent like THF at atures n -78 °C and °C followed by reaction with an electrophilic reagent like an alkyl iodide as described in March’s Advanced Organic Chemistry, Smith and March, 6th edition, Wiley, 2007. This reaction can be repeated to prepare acids of formula (IX) from commercially available esters.

Alternatively, amines of formula (III) can be also prepared by reduction of nitro compounds of formula (Xa) with a reducing agent like iron in an organic solvent like acetic acid at temperatures between 20 °C and 120 °C as shown in scheme 12. Nitro compounds of formula (Xa) in turn can be prepared from simpler nitro nds of a (X) by ent with a benzyl bromide and a base like sodium tert-butoxide in the presence of a copper catalyst in an inert solvent like hexanes at temperatures between 20 °C and 100 °C as described in J. Am. Chem. Soc. 2012, 9942—9945.

Mi}R9 R10] 9 H n R Re Rm]. R10 R89 .

N R4 O” Br R8 R4 red UCtl 0n H2 N R R OW :7 7 6 R6 0 R5 R5 R6R7 (X) (Xa) (III) W0 2017/153380 Scheme 12 The synthesis of compounds of formula (X) is generally known to a person skilled in the art and a large selection is commercially available.

Alternatively, amines of formula (III) can be also prepared by ent of compounds of formula (V) with trimethylsilyl azide and a lewis acid catalyst like B(Cst)3 in an inert solvent like toluene at temperatures between 0 °C and 100 °C as described in J. Am. Chem. Soc. 2015, 9555—9558, followed by reduction of the intermediary azides of formula (XI) with a reducing agent like hydrogen/palladium in an organic solvent like methanol at temperatures between 0 °C and 80°C as shown as shown in scheme 13.

R R10 R9 R10] 9 ] n R9 R10] n __N3 R n R8 /SI 8 R8 | N R4 HO R4 3 H2N R4 —) —> . . R5 R7 R5 R6R7 Iewns aCId R6 . R R reduction 5 7 (V) (XI) (III) Scheme 13 As shown in scheme 14, compounds of general formula (l-b) wherein X is S can be prepared from compounds of general formula (l-a) wherein X is O by treatment with a deoxothionating agent like P4810 or Lawesson reagent in an inert organic solvent like toluene at temperatures between 20 °C and 150 °C.

R1o]n R101“ R13 R2 R13 R2 N NR5 RE? WR5R57 “-8) (|-b) Scheme 14 Alternatively, the compounds of formula (l-a), wherein wherein R1, R2, R3, R4, R5, R5, R7, R8, R9, R10, R11, R12, R13 and n are as d for nds of a (I) and X is O, can be obtained by transformation of a compound of formula l-i, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R11, R12, R13 and n are as defined for formula (I) and X is O and Z represents chlorine, e or iodine in a solvent, in the presence of or absence of a base, and in the presence of a ng reagent and a metal catalyst. There are no particular limitations on the coupling agent, catalyst, solvent and bases, provided it is used in ordinary coupling reactions, such as those bed in “Cross-Coupling Reactions: A Practical Guide (Topics in t Chemistry)”, edited by Norio Miyaura und S.L. Buchwald (editions Springer), or “Metal- Catalyzed Cross—Coupling Reactions”, edited by Armin de Meijere and Francois ich (editions WILEY—VCH). This is shown in Scheme 15.

W0 2017/153380 Z ] R1o R9 R13 R2 0R9 R13 R2 0 R4 R8 R4 R12 R8 R12 l N R7 —> | H R7 / H R11 R5 R R11 R3 R5 R6 N R3 5 R1 R1 (I-i) (l-a) Scheme 15 Alternatively, the compounds of formula (I-a) wherein R1, R2, R3, R4, R5, R5, R7, R8, R9, R10, R11, R12, R13 and n are as defined for compounds of formula (I) and X is O, can be obtained by transformation of another, y related, nd of formula (I-a) using standard synthesis techniques known to the person skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or ophilic tution ons, nucleophilic substitution reactions, nucleophilic addition reactions, and halogenation reactions. n intermediates described in the above schemes are novel and as such form a further aspect of the ion.

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 l of ge microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of ation, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and may 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 athogenic microorganisms.

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

The term “fungicidally effective amount” means the ty 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 ion in or on a plant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the tion against fungal infections as well as against W0 2017/153380 phytopathogenic fungi occurring in the soil. The ation 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 compounds of formula (I) can also be applied to grains (coating), either by nating the seeds in a liquid ation or by coating them with a solid ation. 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 ng plant propagation material and to the plant propagation material so treated.

Furthermore the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood d 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.

Compounds of formula (I) and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant ens. They are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.

These fungi and fungal vectors of disease, as well as athogenic ia and viruses, which may be controlled are for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. , A. tus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. ans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. , is spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. Iusitaniae, C. parapsilosis, C. alis, 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 Iata, 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 ri—virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium Iindbergi, Leveillula taurica, ermium seditiosum, Microdochium nivale, W0 53380 Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, ccidioides spp, llium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp.

Including P. , P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, sis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, xa betae, cercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. ing P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, laria spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, tonia spp, Rhizomucor pusillus, Rhizopus arrhizus, osporium spp, porium spp. including 8. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including 8. 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. num, T. pseudokoningii, T. viride, phyton spp, Typhula spp, Uncinula necator, Urocystis spp, go spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.

In particular, compounds of formula (I) and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the omycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.

These pathogens may include: Oomycetes, including Phytophthora diseases such as those caused by hthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citrico/a, Phytophthora citrophthora and hthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium lare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara /a, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosc/erospora sorghi and Sclerospora graminicola, Ascomycetes, including blotch, spot, blast or blight diseases andlor rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, W0 2017/153380 Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma ctiva, Phaeosphaeria richoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobo/us graminis, Leptosphaeria macm‘ans, Hendersonia creberrima, Helminthosporium irepentis, Setosphaeria turcica, Drechslera glycines, Didymez’ia bryom'ae, Cycloconium oleagineum, Corynespora cassiicofa, Coch/iobolus sativus, ris cactivora, Venturia inaequa/is, phora teres, Pyrenophora tritici—repentis, aria alternate, Alternaria brassicicola, Alternaria solani and aria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae—maydis, Cercosporefla capse/Iae and Cercospora/Ia herpotrichoides, Cladosporium carpophi/um, porium m, Passalora fulva, Cladosporium oxysporum, Dothistroma porum, psis clavispora, Mycosphaere/la fijiensis, Mycosphaere/Ia graminico/a, Mycovel/osiel/a koepkeii, Phaeoisariopsis batatico/a, Pseudocercospora vitis, PseudocercosporeIla herpotrichoides, Ramularia betico/a, ria col/o-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma a, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseo/orum, Discu/a destructiva, Gnomonia fructico/a, Greeneria uvicola, Melanconium jugiandinum, Phomopsis vitico/a, Sirococcus clavigignenti—jug/andacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, illus flavus, Aspergiffus fumigatus, Aspergi/lus nidulans, sporium caricae, Bfumerieiia jaapii, Candida spp., Capnodium ramosum, Cepha/oascus spp., Cephalosporium gramineum, cystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon ma/ae, Drepanopeziza campestris, Eisinoe ampe/ina, Epicoccum , Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibe/Iina cerealis, G/oeocercospora sorghi, G/oeodes pomigena, porium perennans; Gloeotinia temulenta, Griphospaeria cortico/a, Kabatie/Ia lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, nina graminico/a, Microdochium , Monilinia fructicola, Monographe/Ia albescens, Monosporascus cannonbaffus, yc/us spp., Ophiostoma novo-u/mi, Paracoccidioides brasi/iensis, Penicillium expansum, Pesta/otia rhododendri, Petriellidium spp., Pezicufa spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum ra, Physa/ospora abdita, Plectosporium tabacinum, Polyscyta/um pustu/ans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdoc/ine pseudotsugae, Rhynchosporium seca/is, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomt’, Sclerotinia sclerotiorum, Scierotinia minor, Sclerotium spp., Typhu/a ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphace/oma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yal/undae, Taphrina bu/Iata, Thielviopsis basicola, W0 2017/153380 2017/055273 Trichoseptoria gena, Zygophia/a jamaicensis; powdery mildew es for example those caused by Erysiphales such as B/umeria graminis, Erysiphe poiygoni, Uncinula necator, otheca fuligena, Podosphaera leucotricha, Podospaera macularis Go/ovinomyces cichoracearum, Levei/lula taurica, Microsphaera e, Oicliopsis gossypii, Phyl/actinia guttata and Oidium arachidis; molds for example those caused by Botryosphaeriales such as Dothiore/Ia aromatica, Dip/odia seriata, Guignardia bidwe/Iii, Botrytis cinerea, Botryotinia al/ii, tinia fabae, Fusicoccum amygdali, Lasiodip/odia theobromae, Macrophoma la, Macrophomina phaseo/ina, sticta cucurbitacearum; cnoses for example those caused by Glommerelales such as Colletotrichum g/oeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingu/ata, and Colletotrichum graminico/a; and wilts or blights for example those caused by Hypocreales such as Acremonium strictum, C/aviceps purpurea, Fusarium cu/morum, Fusarium graminearum, Fusarium virgu/iforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Ger/achia nivale, Gibbere/Ia fujikuroi, Gibberella zeae, G/iocladium spp., ecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Ven‘icillium theobromae.

Basidiomycetes, including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium flci, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, ia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia ormis f.sp. Secalis, Pucciniastrum cory/i, or Uredinales such as Cronan‘ium ribico/a, Gymnosporangium juniperi—viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopel/a ampe/osidis, Tranzsche/ia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium , ie/Ius inoderma, Mycena spp., Sphacelotheca reiliana, Typhu/a ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, tonia so/ani, Thanetephorus eris, Entyloma dahliae, Enty/ome/Ia microspora, Neovossia moliniae and Tilletia . cladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus, As well as diseases caused by other species and genera closely related to those listed above.

In addition to their fungicidal activity, the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwin/a caratovora, W0 2017/153380 Xanthomonas campestris, monas syringae, myces scabies and other related species as well as certain protozoa.

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, d, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, t, avocado, banana, , citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ss, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, o, 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, t, 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 .

The useful plants and / or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate— and glufosinate-resistant maize varieties commercially available under the trade names pReady® and LibertyLink®) and nematode tolerant varieties. By way of e, suitable genetically ed or engineered crop varieties include the Stoneville 55998R cotton and Stoneville 48928R cotton varieties.

The term "useful plants" and/or “target crops” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for e, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimatephosphate-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 a).

Examples of crops that have been rendered nt to herbicides or s of ides by genetic engineering methods include glyphosate- and glufosinate—resistant maize varieties commercially available under the trade names RoundupReady® l® and , Herculex LibertyLink®.

W0 2017/153380 The term "useful " and/or “target crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects. This includes plants ormed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin—producing bacteria. Examples of toxins which can be expressed include 8—endotoxins, vegetative icidal proteins (Vip), icidal proteins of bacteria colonising nematodes, and toxins produced by ons, arachnids, wasps and fungi. An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for icidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so- called stacked enic events when d by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex |® (Dow AgroSciences, Pioneer Hi-Bred International).

The term "useful plants" and/or “target crops” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising thogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A—0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for e, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Toxins that can be sed by transgenic plants include, for example, insecticidal ns from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus giensis, such as S-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1 F, Cry1Fa2, Cry2Ab, Cry3A, CryBBb1 or CryQC, 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 ed 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; inins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; d metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl—transferase, cholesterol es, ecdysone inhibitors, A—reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone W0 2017/153380 esterase, ic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to be tood by 8- endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, ted 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). ted toxins, for e a truncated Cry1Ab, are known.

In the case of modified toxins, one or more amino acids of the lly ing toxin are ed. 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 55, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WOO3/018810).

More examples of such toxins or enic plants e of synthesising such toxins are disclosed, for example, in EP-A—0 374 753, W093/07278, W095/34656, EP-A—0 427 529, EP—A—451 878 and WOO3/052073.

The processes for the preparation of such transgenic plants are generally known to the person d 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 s (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

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

W0 2017/153380 Further examples of such transgenic crops are: 1. Bt11 Maize from ta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.

Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been ed resistant to attack by the European corn borer (Ostrinia nubile/is and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from ta Seeds SAS, Chemin de l'Hobit 27, F—31 790 St.

Sauveur, France, registration number C/FR/96/05/10. cally modified Zea mays which has been ed resistant to attack by the European corn borer (Ostrinia nubi/a/is and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de t 27, F-31 790 St.

Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered -resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease ition sequence. The preparation of such transgenic maize plants is described in WC 810. 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 Cry38b1 toxin and has resistance to certain Coleoptera insects.

. IPC 531 Cotton from to Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, m, registration number C/ES/96/02. 6. 1507 Maize from Pioneer Overseas ation, Avenue o, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for ing resistance to certain ptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

W0 2017/153380 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 es soil, seeds, and seedlings, as well as ished vegetation.

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

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 may 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 may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds. idal agents ed to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection l 2009.

The compounds of formula (I) may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of ation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or ble solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations eg. 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, ams, viscosity regulators, binders or tackifiers as well as izers, micronutrient donors or other formulations for obtaining special effects.

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

W0 2017/153380 Wettable powders are in the form of finely d 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 ’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally n from 5% to 95% of the active ingredient plus a small amount of g, dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may t 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 ates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. l carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, te, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium te, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, te, 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 ic 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 e t in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the e 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 ng, or are naturally ing. Examples of such materials are vermiculite, sintered clay, , attapulgite clay, sawdust and granular carbon. Shell or membrane materials include l and synthetic rubbers, osic materials, styrene- W0 2017/153380 butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.

Pressurised rs, wherein the active ingredient is dispersed in finely—divided form as a result of vaporisation of a low boiling sant solvent carrier, may also be used. le agricultural adjuvants and carriers that are useful in formulating the itions 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, e, xylene, petroleum naphtha, crop oil, e, 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 , lene glycol abietate, lene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl ide, 1,4—dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2—ethyl l, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha , d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma—butyrolactone, glycerol, ol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, nyl 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 , 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, yl 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 r of choice for the dilution of concentrates.

Suitable solid carriers e, 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.

W0 53380 A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be d with r 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 ric in Character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical e active agents include salts of alkyl sulfates, such as diethanolammonium lauryl te; alkylarylsulfonate salts, such as m dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol—C.sub. 18 ethoxylate; alcohol-alkylene oxide addition ts, such as tridecyl alcohol-C.sub. 16 late; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium lnaphthalenesulfonate; 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; hylene glycol esters of fatty acids, such as polyethylene glycol te; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

Other nts commonly utilized in agricultural compositions include llisation 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, cides and/or plant growth regulators.

In addition, the compositions of the invention may also be applied with one or more ically acquired resistance rs (“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 compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These r 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, W0 2017/153380 nematicides, molluscicides or es 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 rganisms, comprising as active ingredient at least one compound of formula (I) or of at least one red individual compound as defined, 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 lturally acceptable carrier and optionally an adjuvant. An ltural 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 a (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. es of suitable additional active ingredients include the following: 1,2,4- azoles, 2,6—dinitroanilines, acylalanines, aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides, anilino-pyrimidines, quinones, otics, aryl- phenylketones, benzamides, benzene-sulfonamides, benzimidazoles, hiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids, nitriles, cinnamic acid amides, copper containing compounds, cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles, ethylene-thiazolidines, dicarbonitriles, dicarboxamides, dicarboximides, dimethylsulphamates, ophenol carbonates, dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiino nds, dithiocarbamates, dithioethers, dithiolanes, ethyl- amino-thiazole carboxamides, ethyl-phosphonates, furan carboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles, guanidines, herbicides/plant growth regulatosr, hexopyranosyl antibiotics, hydroxy(2-amino)pyrimidines, hydroxyanilides, hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growth regulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines, maleimides, mandelic acid amides, mectin derivatives, morpholines, norpholines, n-phenyl carbamates, tin compounds, oxathiin carboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines, phenyl- acetamides, phenylamides, phenylbenzamides, phenyl-oxo-ethyl—thiophenes amides, phenylpyrroles, phenylureas, phosphorothiolates, orus acids, phthalamic acids, W0 2017/153380 phthalimides, picolinamides, piperazines, piperidines, plant extracts, polyoxins, propionamides, pthalimides, pyrazolecarboxamides, pyrazolinones, pyridazinones, pyridines, pyridine carboxamides, pyridinyl-ethyl benzamides, pyrimdinamines, pyrimidines, dine-amines, pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones, quinolines, quinoline derivatives, quinolinecarboxylic acids, alines, spiroketalamines, strobilurins, sulfamoyl les, sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides, le carboxanides, anates, thiophene carboxamides, toluamides, triazines, triazobenthiazoles, triazoles, le—thiones, triazolo- pyrimidylamine, valinamide carbamates, ammonium methyl phosphonates, c- containing compounds, benyimidazolylcarbamates, carbonitriles, carboxanilides, carboximidamides, carboxylic phenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides, imidazoline acetates, isophthalates, isoxazolones, mercury salts, organomercury compounds, organophosphates, oxazolidinediones, pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates, phosphorothioates, l carboxamides, pyridyl furfuryl ethers, pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines..

A further aspect of invention is related to a method of lling or preventing an infestation of plants, e.g. useful plants such as crop plants, ation material thereof, e.g. seeds, hawested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage rganisms or organisms potentially harmful to man, especially fungal organisms, which ses 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 ation by insects or by phytopathogenic or spoilage microorganisms or sms ially 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 nd 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 . 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 nds 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.

W0 2017/153380 Aformulation, 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, ally, surface active compounds (surfactants).

The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as ng, atomizing, dusting, brushing on, dressing, scattering 0r pouring - which are to be selected to suit the intended aims of the prevailing circumstances — and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is preferably 19 to 2000 g of active ingredient per hectare, more ably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. When used as seed drenching agent, convenient dosages are from 10mg to 19 of active substance per kg of seeds.

When the combinations of the t 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 109 per kg of seed are generally sufficient. ly, 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 tional 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 on for seed treatment (LS), a water dispersible powder for seed ent (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an on concentrate (EC), a sion 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 trate (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 able adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, s and optionally other formulating ingredients such as surfactants, biocides, anti—freeze, rs, thickeners and nds that provide adjuvancy s). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be W0 2017/153380 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 sing agents and other compounds that provide adjuvancy effects, e.g. the ondensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl te, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous sion 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 e from 0.01 to 90% by weight of active agent, from 0 to 20% lturally acceptable surfactant and 10 to 99.99% solid or liquid ation inerts and adjuvant(s), the active agent consisting of at least the compound of a (I) together with component (B) and (C), and ally other active agents, ularly 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 , 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 trates, the end user will normally use dilute formulations.

EXAMPLES The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be ed by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for e 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the methods are: Method G: W0 2017/153380 Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), ary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650 I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector. Column: Waters UPLC HSS T3 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent , 1.8 pm, 30 Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH, nt: 10—100% B in 1.2 min; Flow (ml/min) 0.85 Method H: Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) ed with an electrospray source (Polarity: ve and negative ions), Capillary: 3.00 kV, Cone range: 30V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD or. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH, gradient: 10—100% B in 2.7 min; Flow (ml/min) 0.85 Method W: Spectra were ed on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, 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), DAD Wavelength range (nm): 210 to 400, and an y UPLC from Waters: Solvent degasser, binary pump, heated column compartment and array detector. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = Water/Methanol 9:1 ,0.1% formic acid, 8: Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75 Formulation es Wettable powders a) b) c) W0 2017/153380 active ingredient [compound of formula (l)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl e 3 % - 5 % sodium utylnaphthalenesulfonate - 6 % ‘IO % phenol hylene 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 dm seed treatment a) b) 0) active ingredient [compound of formula (l)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed c 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 (l)] 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 % exanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be ed from this concentrate by dilution with water.

W0 2017/153380 Dusts a) b) 0) Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 % - - Kaolin - 94 % - mineral filler — — 96 % Ready—for—use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder granules Active ingredient [compound of formula (I)] 15 % sodium ulfonate 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 ed and then dried in a stream of air.

Coated granules Active ingredient und of formula (I)] 8 % polyethylene glycol (mol. wt. 200) 3 % Kaolin 89 % The finely ground active ient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene . 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 Iignosulfonate 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 sions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material W0 2017/153380 can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable trate for seed treatment active ingredient [compound of formula (l)] 40 % propylene glycol 5 % mer butanol PO/EO 2 % tristyrenephenole with 10-20 moles E0 2 % 1,2-benzisothiazolinone (in the form of a 20% on in water) 0.5 % monoazo-pigment m salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene—polyphenylisocyanate- mixture (8:1). This mixture is fied 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 ted.

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 ation is applied to seeds as an s suspension in an apparatus suitable for that e.

Preparation es Example 1: Preparation of N-(1-benzyl-1,3-dimethyl-butyl)quinoline—3—carboxamide Step 1: preparation of 2,4-dimethylphenyl-pentanol W0 2017/153380 Jug 0H A solution of ylpentanone (3.0 g, 29.4 mmol) in diethyl ether (25 mL) was added drop wise to benzyl magnesium de in tetrahydrofuran (2 M in tetrahydrofuran, 22 mL, 44 mmol) at RT. The reaction mixture was then warmed to 35 °C and aged for 3 h at this temperature. After cooling to RT, aqueous HCI (2 M) was added to the reaction and the mixture was portioned between water and ethyl acetate. The organic layer was washed with brine, dried over Na2804, filtrated and concentrated in vacuo. The residue was ed by tography on silica gel to afford the title compound as colorless liquid. 1H NMR (400 MHz, CDCls) 6 .34 (m, 5H), 2.65-2.85 (m, 2H), 1.81-1.99 (m, 1H), 1.42 (dd, 2H), 1.15 (s, 3H), 0.98 (dd, 6H).

Step 2: preparation of N-(1-benzyl-1,3-dimethyl-butyl)chloro-acetamide OH N H To a solution of 2,4-dimethylphenyl-pentan-2—ol (3.6 g, 19 mmol) and chloroacetonitrile (2.4 mL, 37 mmol) in acetic acid (11 mL) cooled to 0—5 °C was added drop wise concentrated sulfuric acid (3.1 mL, 56 mmol). The resulting slurry was warmed to 20 °C and stirred for 3 h at this temperature. The reaction mixture was then diluted with water and extracted with ethyl e. The organic layer was washed with aqueous NaHCOs, brine, dried over MgSO4, filtrated and concentrated in vacuo. The residue was purified by chromatography on silica gel to afford the title compound as colorless solid. 1H NMR (400 MHz, CDCls) 6 7.20-7.34 (m, 3H), 7.08-7.16 (m, 2H), 6.13 (br. s., 1H), 3.94 (s, 2H), 3.21 (d, 1H), 2.90 (d, 1H), 1.86-1.95 (m, 1H), 1.73-1.86 (m, 1H), 1.54 (dd, 1H), 1.31 (s, 3H), 0.96 (dd, 6H).

Step 3: preparation of 2,4-dimethylphenyl-pentanamine NH NH2 A solution of N-(1-benzyl-1,3-dimethyl-butyl)chloro-acetamide (3.0 g, 11.2 mmol), acetic acid (3.9 mL, 67 mmol) and thiourea (1.02 g, 13.4 mmol) in ethanol (30 mL) was W0 2017/153380 warmed to 80 °C and stirred for 18 h at this temperature. The on mixture was then cooled to 20 °C, diluted with aqueous HCI (0.5 M) ted through a short pad of Celite. The filtrate was washed with ethyl acetate; the aqueous layer was then basified with 4 M NaOH and extracted with n-hexanes. The n-hexanes layer was washed with brine, dried over Na2804, filtrated and concentrated in vacuo to afford the title compound as light brown oil. 1H NMR (400 MHz, CDCI3) 6 .34 (m, 5H), 2.59—2.71 (m, 2H), .94 (m, 1H), 1.26—1.41 (m, 2H), 1.05 (s, 3H), 1.03 (br.s, 2H), 0.98 (dd, 6H).

Step 4: preparation of N-(1-benzyl-1,3-dimethyl-butyl)quinolinecarboxamide 0 o z —> H N N’ To a solution of quinolinecarboxylic acid (0.20 g, 1.15 mmol), 2,4-dimethylphenyl- pentan-2—amine (0.22 g, 1.15 mmol), triethylamine (0.14 g, 1.4 mmol) and 1-hydroxy azabenzotriazole (0.16 g, 1.15 mmol) in dry dimethylformamide (5 mL) was added N—(3- dimethylaminopropyl)-N'-ethylcarbodiimide HCI (0.22 g, 1.15 mmol) at RT and the resulting on was aged for 18 h at 20 °C. Water was added and the mixture was extracted with ethyl e. The organic phase was washed with brine, dried over Na2804, filtrated and concentrated in vacuo. The e was purified by chromatography on silica gel to afford the title compound as white solid, mp. 121 °C. 1H NMR (400 MHz, CDCls) 6 9.12 (d, 1H), 8.40 (d, 1H), 8.13 (d, 1H), 7.86 (d, 1H), 7.74- 7.82 (m, 1H), 7.56-7.64 (m, 1H), 7.16-7.30 (m, 5H), 5.73 (s, 1H), 3.46 (d, 1H), 2.98 (d, 1H), 2.17 (dd, 1H), 1.84-1.99 (m, 1H), 1.67 (dd, 1H), 1.43 (s, 3H), 1.02 (d, 6H).

Example 2: Preparation of N-(1-benzyl-1,3-dimethyl-butenyl)f|uoro-quino|ine carboxamide Step 1: preparation of 2-methyl-N-(1-methy|pheny|-ethy|idene)propane—2-suIfinamide 1—Phenylpropan—2—one (8.30 9,619 mmol) was dissolved in tetrahydrofuran (75 mL), titanium(lV)ethoxide (32.6 g, 92.8 mmol) and 2-methylpropane—2—sulfinamide (7.50 g, 61.9 mmol) was added sequentially at room temperature and the resulting mixture was warmed to 60 °C. After stirring for 2 h at 60 °C, the reaction was cooled to room temperature and W0 2017/153380 quenched with aqueous NaHCOs. The resulting mixture was filtrated and the filter cake was washed with ethyl acetate. The combined filtrates were extracted with ethyl acetate, the organic layer was washed with brine, dried over sodium sulfate, filtrated and concentrated in vacuo to afford the title compound as light yellow oil (purity >80%, ca. 4:1 ratio of cis-trans isomers) which was used as such for the next step. 1H NMR (400 MHz, CDCIs, major isomer) 6 7.17-7.43 (m, 5H), 3.72 (d, 1H), 3.70 (d, 1H), 2.32 (s, 3H), 1.23 (s, 9H) Step 2: preparation of N-(1-benzyl-1,3-dimethyl-butenyl)methyl-propane—2-sulfinamide A solution of crude 2-methyl-N-(1-methylphenyl-ethylidene)propane—2-sulfinamide (80% purity, 7.4 g, 24.9 mmol) in dichloromethane (100 mL) was added slowly to a commercially ble solution of 2—methylallylmagnesium chloride in THF (0.5 M, 75 mL, 37.4 mmol) maintained at -50°C. The reaction mixture was gradually warmed to 20 °C over 4 h and stirred ght at 20 °C. Saturated NH4C| solution was then added, the mixture was extracted with ethyl e and the organic layer was washed with brine, dried over sodium sulfate, filtrated and trated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as mixture diastereoisomers. 1H NMR (400 MHz, CDCls, major isomer) 6 6.94-7.18 (m, 5H), 4.82 (s, 1H), 4.71 (s, 1H), 3.39 (s, 1H), 2.76 (d, 1H), 2.55 (d, 1H), 2.21 (d, 2H), 1.63 (s, 3H), 1.06 (s, 3H), 0.94 (s, 9H).

Step 3: ation of N-(1-benzyl-1,3-dimethyl-butenyl)fluoro-quinolinecarboxamide O"NH 2 N \ N —» F_. H To an ice cold solution of N-(1-benzyl-1,3-dimethyl-butenyl)methyl-propane amide (5.2 g, 15.9 mmol) in methanol (16 mL) was added HCI in 1,4—dioxane (4 M, 6 mL, 24 mmol) and the resulting solution was stirred for 2 h at 0 — 5°C. All volatiles were then removed in vacuo to afford a brown, gummy residue which was triturated with a mixture of W0 2017/153380 diethyl ether/heptanes. The ing light brown solid was dried in vacuo and used as such for the next step.

A part of the solid hydrochloride salt obtained above (2 g, 8.0 mmol) was suspended in dichloromethane (40 mL) and 8-fluoroquinolinecarboxylic acid (1.68 g, 8.8 mmol), triethylamine (2.8 mL, 19.9 mmol), 1-hydroxyazabenzotriazol (1.2 g, 8.8 mmol) and N-(3- ylaminopropyl)—N'-ethylcarbodiimide-HC| (1.72 g, 8.8 mmol) was added tially at ambient temperature. The resulting mixture was aged for 2 h at 20 °C. Water was then added and the mixture was extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtrated and trated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as white solid, mp. 115-117°C 1H NMR (400 MHz, CDCls) 6 9.11-9.26 (m, 1H), 8.50 (s, 1H), 7.72 (d, 1H), 7.45-7.64 (m, 2H), .37 (m, 5H), 5.96 (s, 1H), 5.01 (s, 1H), 4.84 (s, 1H), 3.57 (d, 1H), 3.08 (dd, 2H), 2.46 (d, 1H), 1.89 (s, 3H), 1.47 (s, 3H). 19F NMR (377 MHz, CDCls) 6 -124.64 (3).

Example 3: N-(1-benzyl-3,3,3-trifluoromethyl-propyl)—7,8-difluoro-quinolinecarboxamide Step 1: preparation of ethyl 2-benzyl-4,4,4-trifluoromethyl-butanoate O O mJWE—’ 8&4F/\ /\O 'l'l'l'l n-Butyl lithium (2.5 M in s, 100 mL, 248.9 mmol) was added slowly to a solution of diisopropyl amine (35.2 mL, 248.9 mmol) in tetrahydrofuran (400 mL) at -70°C. The resulting solution was aged for 30 min at -70 °C and then ethyl trifluorobutyrate (36 g, 207.4 mmol) was added drop wise. The reaction was stirred for 2 h at -70 °C, benzyl bromide (43.2 g, 248.9 mmol) was added and the reaction mixture was gradually warmed to room temperature over ca. 2 h. Saturated NH4CI solution was added and the mixture was extracted with methyl tertbutyl ether. The organic layer was washed with water, brine, dried over MgSO4, filtrated and concentrated in vacuo. The al oil was passed through a short pad of silica gel, the pad was rinsed with cyclohexane:ethyl acetate (2:1) and the filtrate was concentrated in vacuo, affording ethyl 4,4,4-trifluoromethyl-butanoate as light orange oil. n—Butyl lithium (2.5 M in hexanes, 99 mL, 247.2 mmol) was added slowly to a solution of diisopropyl amine (35 mL, 247.2 mmol) in tetrahydrofuran (380 mL) at —70°C. The resulting solution was aged for 30 min at -70 °C and then the crude product obtained above (49.5 g, W0 2017/153380 190.2 mmol, diluted with tetrahydrofuran (30 mL)) was added slowly at — 70 °C. The resulting dark solution was stirred for 2 h at -70 °C before methyl iodide (13.1 mL, 209.3 mmol) was added. The on mixture was gradually warmed to 20 °C over ca. 3 h, then quenched with ted NH4C| solution and extracted with methyl tertbutylether. The organic layer was washed with water, brine, dried over M9804, filtrated and concentrated in vacuo. The residual oil was passed through a short pad of silica gel, the pad was rinsed with cyclohexanezethyl acetate (2:1) and the filtrate was concentrated in vacuo, affording the title compound as light brown oil (ca. 80% pure). 1H NMR (400 MHz, CDCls) 6 7.05-7.33 (m, 5H), 4.13 (q, 2H), 2.98 (d, 1H), 2.81-2.72 (m, 2H), .32 (m, 1H), 1.28 (s, 3H), 1.21 (t, 3H).

Step 2: preparation of 2-benzyl-4,4,4-trifluoromethyl-butanamide o o o /‘o HO F E H2N —’ E F —’ F F A solution of ethyl 2—benzyl—4,4,4-trifluoromethyl-butanoate (25.5 g, 93.0 mmol) in 1,4- e (45 mL)/ ethanol (45 mL) was d with NaOH (7.6 g, 186 mmol) at room temperature, the resulting solution was warmed to 90°C and aged for 1 h at 90 °C. After cooling to room temperature, the reaction mixture was concentrated to about 50% of the original volume. The residue was d with water and washed with cyclohexane. The water layer was then acidified with HCI (conc.) under ice cooling at temp < 25°C and the mixture was extracted with DCM. The c layer were washed with brine, dried with Na2804, filtrated and concentrated in vacuo to afford 2-benzyl-4,4,4-trif|uoromethyl—butanoic acid as dark yellow oil.

To a solution of crude 2-benzyl-4,4,4-trifluoromethyl-butanoic acid (6.7 g, 27.2 mmol) and dimethyl formamide (0.1 mL, 1.4 mmol) in dichloromethane (25 mL) was slowly added oxalyl chloride (2.5 mL, 28.6 mmol) at 20 °C. The resulting solution was stirred for 1 h at 20 °C and then all volatiles were removed in vacuo. The residue was dissolved in dichloromethane (25 mL) and the resulting solution was slowly added to ice cooled, y stirred aqueous a solution (25—wt%, 21 mL). The resulting mixture was gradually warmed to room temperature and stirred for 30 min. Water was then added and the mixture was extracted dichloromethane. The organic layer was washed with water, brine, dried with Na2804, filtrated and concentrated in vacuo to afford the title compound as light brown oil. 1H NMR (400 MHz, CDCls) 6 7.13-7.44 (m, 5H), 5.42 (br s, 2H), 3.13 (d, 1H), 2.97-3.09 (m, 1H), 2.67 (d, 1H), 2.18 (qd, 1H), 1.33 (s, 3H).

W0 2017/153380 Step 3: preparation of 4,4,4-trifluoromethylphenyl-butanamine H2N 'l'l'l'l 'I'I'I'I To a solution of 2—benzyl-4,4,4-trifluoromethyl-butanamide (6.6 g, 26.9 mmol) in acetonitrile (25 mL) / water (25 mL) was added oxyiodobenzene (9.73 g, 29.6 mmol) and trifluoroacetic acid (4.6 mL, 59.2 mmol) at room temperature and the resulting mixture was stirred for 18 h at room temperature. Acetonitrile was then removed in vacuo, the remaining aqueous emulsion was adjusted to pH1 with concentrated HCI and washed with methyl tertbutylether. The s layer was basified to pH12 with NaOH (8 M) and extracted with methyl tertbutylether. The organic layer was washed with brine, dried over Na2804, ted and concentrated in vacuo to afford the title nd as yellow oil. 1H NMR (400 MHz, CDCIs) 6 7.16-7.50 (m, 5H), 2.81 (s, 2H), 2.13-2.41 (m, 2H), 1.28 (s, 3H).

Step 4: preparation of N-(1-benzyl-3,3,3-trifluoromethy|—propyl)—7,8-difluoro-quinoline carboxamide F/E;:[;;TJL\OH o H2N F —, I F N F F To a solution of 7,8-difluoroquinolinecarboxylic acid (0.35 g, 1.67 mmol), 4,4,4-trifluoro methylphenyl-butanamine (0.40 g, 0.84 mmol), ylamine (0.6 mL, 4.2 mmol) and 1- hydroxyazabenzotriazol (0.27 g, 2.0 mmol) in dichloromethane (10 mL) was added N-(3- dimethylaminopropyl)—N’-ethylcarbodiimide-HCI (0.39 g, 2.0 mmol) at room temperature. The resulting mixture was stirred for 15 h at room temperature and then ed with water.

The mixture was extracted with dichloromethane, the organic layer was washed with water, brine, dried over Na2804, filtrated and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to afford the title compound as white solid, mp. 158- 160°C. 1H NMR (400 MHz, CDCIs) 6 9.07 (d, 1H), 8.38 (t, 1H), 7.62 (ddd, 1H), 7.47 (dt, 1H), 7.11- 7.38 (m, 5H), 6.14 (s, 1H), 3.62 (d, 1H), 3.46 (dd, 1H), 2.96 (d, 1H), 2.58 (qd, 1H), 1.50 (s, 3H). 19F NMR (377 MHz, CDCIs) 6 -59.75 (s, 1F), -132.03 (d, 1F), -150.23 (d, 1F).

W0 2017/153380 Example 4: Preparation of the single isomers: fl-[(1S)—1-benzyl-3,3,3-trifluoromethy|-propy|]—7,8—difluoro-quinoline—3-carboxamide and N-[(1R)benzy|—3,3,3-trifluoromethy|-propy|]—7,8-difluoro-quinolinecarboxamide The racemic enzyl-3,3,3-trifluoromethyl-propyl)—7,8—difluoro—quinoline carboxamide mixture was ted to chiral resolution by preparative HPLC chromathography using the conditions outlined hereafter.

Analytical HPLC method SFC:Waters Acquity Da PDA Detector Waters Acquity UPC2 Column: Daicel SFC CHIRALPAK® OZ, 3pm, 0.3cm x 10cm, 40°CMobiIe phase: A: C02 B: iPr gradient: 10% B in 2.8 min ABPR: 1800 psi Flow rate: 2.0 ml/min Detection: 233 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 uL Preparative HPLC method: rification System from Waters: 2767 sample Manager, 2489 UVNisible Detector, 2545 Quaternary Gradient Module.

Column: Daicel PAK® IF, 5pm, 1.0 cm x 25cm Mobile phase: TBME/EtOH 98/02 Flow rate: 10 ml/minDetection: UV 265 nm Sample concentration: 165mg/mL in EE/ACN Injection: 30-90ul, 5-15mg Results: ‘ First eluting enantiomer Second eluting enantiomer ‘ Retention time (min) ~ 1.05 Retention time (min) ~ 1.51 ‘ al purity (area% at 220 nm) 99 Chemical purity (area% at 220 nm) 99 Enantiomeric excess (%) > 99 Enantiomeric excess (%) > 99 The compound with the n time of 1.05 minute is N-[(1R)benzyl-3,3,3-trif|uoro methyl-propyl]-7,8-dif|uoro-quinolinecarboxamide, corresponding to compound F-38.

The compound with the elution time of 1.51 minutes is N-[(1S)—1—benzyl—3,3,3—trifluoro methyl—propyl]—7,8—difluoro-quinolinecarboxamide, corresponding to compound F-37.

W0 53380 Examgle 5: Pregaration of the single isomers: )—1-benzyl-3,3,3-trifluoromethy|-propy|]f|uoro-quinolinecarboxamide N-[(1R)—1-benzyI-3,3,3-trifluoromethy|—propyl]—8-f|uoro-quinolinecarboxamide The racemic N-(1-benzy|—3,3,3-trifluoromethyl-propy|)f|uoro-quino|ine carboxamide mixture was submitted to chiral resolution by preparative HPLC chromathography using the conditions outlined ter.

Analytical HPLC method SFC:Waters Acquity UPC2/QDa PDA Detector Waters Acquity UPC2 Column: Daicel SFC CHIRALPAK® ID, 3pm, 0.30m x 100m, 40°C Mobile phase: A: CO2 B: iPr gradient: 15% B in 2.8 min ABPR: 1800 psi Flow rate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 pL Preparative HPLC method: rification System from Waters: 2767 sample r, 2489 UVNisible Detector, 2545 Quaternary Gradient Module.

Column: Daicel CHIRALPAK® IF, 5pm, 1.0 cm x 25cm Mobile phase: Hept/EtOH 95/05 Flow rate: 10 ml/min Detection: UV 265 nm Sample concentration: 10 mg/mL in MeOH/DCM (1/1) Injection: 500u| First eluting enantiomer Second eluting enantiomer Retention time (min) ~ 1.49 Retention time (min) ~ 1.88 Chemical purity (area% at 235 nm) 99 Chemical purity (area% at 235 nm) 99 Enantiomeric excess (%) > 99 Enantiomeric excess (%) > 99 The compound with the n time of 1.49 minute is N-[(1S)benzyl-3,3,3-trif|uoro methyl-propyl]f|uoro-quinolinecarboxamide, corresponding to compound F-11.

The compound with the elution time of 1.88 minutes is N-[(1R)—1—benzy|—3,3,3—trifluoro methyl—propyl]—8—fluoro-quinolinecarboxamide, corresponding to compound F-12.

W0 2017/153380 Example 6: Preparation of the single isomers: N-[(1R)benzyI-1,3-dimethyI-buty|]f|uoro-quinolinecarboxamide and N-[(1S)—1-benzyl-1,3-dimethyl-butyl]—8-f|uoro-quinolinecarboxamide The racemic N-(1-benzyI-1,3-dimethyl-butyl)fluoro-quinolinecarboxamide mixture was submitted to chiral resolution by ative HPLC chromathography using the conditions outlined hereafter.

Analytical HPLC method: SFC:Waters Acquity UPC2/QDa PDA or Waters Acquity UPC2 Column: Daicel SFC CHIRALPAK® IA, 3pm, 0.3cm x 10cm, 40°C Mobile phase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 ml/min Detection: 240 nm Sample concentration: 1 mg/mL in Hept/EtOH 90/10 Injection: 3 ”L Preparative HPLC method: Autopurification System from Waters: 2767 sample Manager, 2489 UVNisible Detector, 2545 nary Gradient Module.

: Daicel CHIRALPAK® IE, 5pm, 1.0 cm x 25cm Mobile phase: Hept/EtOH 90/10 Flow rate: 10 ml/min ion: UV 265 nm Sample concentration: 100 mg/mL in MeOH/DCM (1/3) (filtered) Injection: 150u| - 250u| First eluting enantiomer Second eluting enantiomer Retention time (min) ~ 0.97 Retention time (min) ~ 1.32 al purity (area% at 240 nm) 99 Chemical purity (area% at 240 nm) 99 Enantiomeric excess (%) > 99 Enantiomeric excess (%) > 99 The nd with the elution time of 0.97 minute is N-[(1S)—1-benzyI-1,3-dimethyl-butyl]—8- fluoro-quinolinecarboxamide, corresponding to compound F-1.

The compound with the elution time of 1.88 minutes is N-[(1R)benzyl-1,3-dimethyI-buty|]- 8—fluoro—quinoline—3-carboxamide, corresponding to compound F—2.

Example 7: Preparation of the single isomers: W0 2017/153380 N-[(1R)—1-benzylfluoro-1,3-dimethyl-butyl]—8-fluoro-quinolinecarboxamide and N-[(1S)—1-benzylfluoro-1,3-dimethyl-butyl]—8-fluoro-quinolinecarb0xamide The racemic N-(1—benzylfluoro-1,3-dimethyl-butyl)fluoro—quinoline carboxamide mixture was submitted to chiral resolution by ative HPLC chromathography using the conditions outlined hereafter.

Analytical HPLC : SFC:Waters Acquity UPCZIQDa PDA Detector Waters Acquity UPC2 Column: Daicel SFC CHIRALPAK® IA, 3pm, 0.30m x 100m, 40°C Mobile phase: A: CO2 B: MeOH nt: 30% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 ml/min Detection: 230 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 ion: 1 pLPreparative HPLC method: Autopurification System from Waters: 2767 sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module.

Column: Daicel CHIRALPAK® IA, 5 m, 1.0 cm x 25cm Mobile phase: Hept/EtOH 90/10 Flow rate: 10 ml/min Detection: UV 265 nm Sample concentration: 127mg/mL in EE Injection: ul, 5-20mg First eluting enantiomer Second eluting enantiomer Retention time (min) ~ 0.88 Retention time (min) ~ 1.51 Chemical purity (area% at 235 nm) 99 Chemical purity (area% at 235 nm) 99 Enantiomeric excess (%) > 99 Enantiomeric excess (%) > 99 The nd with the elution time of 0.88 minute is N-[(1R)—1-benzyl—3-fluoro-1,3-dimethyl- butyl]—8-fluoro-quinolinecarboxamide, corresponding to compound F-23.

The compound with the elution time of 1.51 minutes is N-[(1S)—1-benzylfluoro-1 ,3- dimethyl-butyl]f|uoro-quinolinecarboxamide, corresponding to compound F-24.

Table E: Physical data of nds of formula (I) No. IUPAC name STRUCTURE RT [M+H] Method MP °c (min) measure N-[2-(2- fluoropheny|)- 1,1 ,2-trimethyl- propyl]quinoline- 3-carboxamide N-[2—(2— pheny|)- 1,1-dimethylethyl ]quinoline- 3-carboxamide -dimethy|— G 145- 2-[2- 149 (trifluoromethox y)pheny|]ethy|]q uinoline—3- carboxamide yano(2- G 134- fluoropheny|) 139 methyl- ethyl]quinoline- 3-carboxamide N-(1-benzyl—1,2- dimethyl- propyl)—8—f|uoro— quinoline—3- carboxamide N—(1-benzyl-1,3- H 110- dimethyl-buty|)- 112 8-fluoro- quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-7 N-[2-(4- 1.51 368 W pheny|) cyano—1—methylethyl ]—8—fluoro— quinoline—3- carboxamide E-8 N-[1—cyano—2- 1.43 370 W (2,4— difluorophenyl)— 1-methyl-ethy|]- 8—fluoro- quinoline—3- carboxamide E-9 8-fluoro-N-[2-(2- 1.64 353 W ypheny|)- 1,1-dimethylethyllquinoline- 3-carboxamide E-10 yano—1 - 1.37 334 W methyl—2- phenyl-ethyl)—8— fluoro—quinoline- 3-carboxamide E-11 N-(1,1-dimethy|— 1.56 323 W 2-phenyl-ethy|)- 8-fluoro- quinoline carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-12 N-(1-benzyI-2,2- 163- dimethyl- 164 propyl)—8—fluoro- ine—3- carboxamide E-13 N-(1-benzyl—1,3- dimethyl- butyl)quinoline- oxamide E-14 N-(1-benzyl-1,3- 147- dimethyl-buty|)- 148 8—chloro- ine—3- carboxamide E-15 N-(1-benzyl-1,3- 92-94 dimethyl-butyl)— 8-fluoro methyl- quinoline—3- carboxamide E-16 N-(1-benzyl- 157- 4,4,4—trifluoro— 161 butyl)—8—f|uoro— quinoline—3- carboxamide E-17 N-(1-benzyl- 163- 4,4,4—trifluoro- 167 butyl)—8—chloro— quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) e E-18 N-[2-(2- 0 198 - chloropheny|) 203 cyano—1—methylethyl uoro— quinoline—3- carboxamide E-19 N-(1—benzyl- 158- 4,4,4—trifluoro— 161 butyl)—8—methy|— quinoline—3- carboxamide E-20 N-(1-benzyl-1,3- 132- dimethyl-buty|)- 133 8—methylquinoline carboxamide E-21 8—fluoro—N-[1 - 105- [(2- 106 fluorophenyl)me thyI]—1 ,3— dimethylbutyl ]quinoline- 3-carboxamide E-22 N-[1-[(2- 399-401 109- chloropheny|)me 110 thy|]-1 ,3- dimethyl-butyl]— 8-fluoro- quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-23 N-[1,3-dimethy|— G 125- 1-(0- 126 tolylmethyl)buty| ]-8—f|uoro— quinoline—3- amide E-24 8—fluoro—N—[1 - G 38-39 [(4- phenyl)me thy|]-1 ,3- dimethyl- butyl]quino|ine- 3—carboxamide E-25 N-[1-[(4- 399—401 G 57-59 chlorophenyl)me thyl]—1 ,3- dimethyl-butyl]— 8-fluoro- quinoline carboxamide E-26 8—fluoro—N—[1 - G 45-47 [(3- fluorophenyl)me thy|]—1 ,3- dimethylbutyl ]quino|ine- 3-carboxamide E-27 N-[1-[(3- 399—401 G 41-42 chlorophenyl)me thyl]-1 ,3- yl-butyl]— 8-fluoro- quinoline carboxamide No. IUPAC name URE RT [M+H] Method MP °C (min) measure E-28 N-(1-benzyI-3,3- 178- dimethyl-butyl)— 180 8—fluoro— quinoline—3- carboxamide E-29 N-(1—benzyl 136- methyl-butyl)—8— 139 fluoro—quinoline- 3-carboxamide E-30 N-(1-benzyl- 140- 3,3,3-trifluoro- 142 propyl)fluoro- quinoline—3- carboxamide E-31 N-[1,3-dimethy|— 1.21 379 116- 1-(p- 118 tolylmethyl)butyl ]-8—f|uoro- quinoline—3- carboxamide E-32 N-[1-[(4- 1.10 390 67-69 cyanophenyl)me thy|]-1 ,3- dimethyl-buty|]- 8-fluoro- ine—3- carboxamide E-33 N-[1,3-dimethy|— 1.20 379 94-96 1-(m- tolylmethyl)buty| ]f|uoro- ine—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure N-(1-benzyl- 1,3,3-trimethyl- butyl)—8—fluoro- quinoline—3- carboxamide N-(1-benzyl-1 ,3- dimethyl—but enyl)—8—f|uoro— ine—3- carboxamide N—(1-benzyl-1,3- dimethyl-but enyl)quinoline carboxamide N-(1-benzyI methyl-but—3- enyl)quinoline carboxamide E-38 N-(1-benzyI 1.08 349 methyl-but enyl)—8—f|uoro- quinoline—3- amide E-39 N-(1-benzyl- 1.06 391 158- 3,3,3-trifluoro—1 - 160 methyl-propy|)- 8-fluoro- quinoline carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure N-(1-benzyI-1,3- dimethyl-butyl)— 7—fluoro— quinoline—3- carboxamide N-(1-benzyl-1 ,3- dimethyl—butyl)— 1-oxido-quinolin- 1-ium carboxamide N-(1-benzyI methyl-butyl)—8— fluoro-quinoline- 3-carboxamide N-(1-benzyI methyl- butyl)quinoline- 3-carboxamide E-44 N-[1—[(2- 43-44 henyl)me thy|]-1 ,3- dimethyl-buty|]- 8-fluoro- quinoline—3- carboxamide E-45 (3- 1 .22 443-445 87-89 bromopheny|)m -1 ,3- dimethyl-butyl]— 8-fluoro— quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-46 N-[1-[(3- 1.10 45-46 cyanopheny|)me thyl]-1 ,3- dimethyl-butyl]— 8-fluoro— quinoline—3- carboxamide E-47 N-[1-benzyI 1.16 377 126- methyl—2-(1 - 129 methylcycloprop yl)ethy|]—8- -quinoline- 3—carboxamide E-48 N-(1-benzyl-1,3- 1.19 383 114- dimethyl-buty|)- 116 7,8—difluoro— quinoline carboxamide E-49 N-(1-benzyl-2— 1.11 363 ropyl—1 - methyl—ethyl)—8— fluoro—quinoline— oxamide E-50 N-(1-benzyl-3,3- 1.06 387 difluoro-1 - methyl-butyI) fluoro-quinoline- 3-carboxamide E-51 N-[1- 1.11 399 [difluoro(pheny|) methyl]-1,3- dimethyl-but enyl]-8—fluoro— quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-52 N-(1-benzyI-3,3- 1.05 369 131 - difluoro-1 - 133 methylbutyl )quinoline- 3-carboxamide E-53 N-(1-benzyl 2.01 389 cyclopropyl methyl—but enyl)—8—f|uoro— quinoline—3- carboxamide E-54 N-[1- 1.15 401 [difluoro(pheny|) methyl]-1,3- dimethyl-butyl]— 8-fluoro- quinoline carboxamide E-55 N-(1-benzyl-1,3- 1.16 381 94-96 dimethyl-but enyl)—7,8— difluoro— quinoline—3- carboxamide E-56 N-(1-benzyI 1.08 383 -1 ,3- dimethyl-buty|)- 8-fluoro- ine—3- carboxamide E-57 N-(1-benzyI 1.07 365 -1 ,3- dimethyl- butyl)quinoline- 3-carboxamide No. IUPAC name URE RT [M+H] Method MP °C (min) measure E-58 N-(1-benzyI hyd roxy-1 ,3- dimethyl-butyl)— 8-fluoro— quinoline—3- carboxamide E-59 N—[1 — [difluoro(pheny|) methyl]-1,3- dimethylbutyl ]quino|ine- 3—carboxamide E-60 N-(1-benzyl 3,3,3-trifluoro-1 - 144 methyl-propy|)- 8-chloro- ine carboxamide E-61 N-(1-benzyl- 120- 3,3,3-trifluoro—1 - 123 methyl-propy|)- 8—methyl- quinoline—3- carboxamide E-62 N-(1-benzyl- 175- 3,3,3-trifluoro—1 - 179 methyl-propy|)- 8-cyano- ine—3- carboxamide 2017/055273 No. IUPAC name STRUCTURE RT [M+H] Method MP °c (min) measure E-63 N-(1-benzyI-1,3- G 102 - dimethyl-butyl)— 105 6-meth0xy— quinoline—3- carboxamide E-64 N-(1-benzyl-1 ,3- 3 G 50 - 60 dimethyl—butyl)— -chloro— quinoline—3- carboxamide E-65 N—(1-benzyI-1,3- 381-383 G 172 - dimethyl-buty|)- 174 7-chloro- quinoline—3- carboxamide E-66 8-fluoro-N- 1.07 409 G 146 - [3,3,3-trifluoro 147 [(4- fluorophenyl)me thyl]methyl- propyl]quinoline- 3-carboxamide E-67 N-(1-benzyl-1 ,3- 1.14 372 G 170 - dimethyl—buty|)- 172 7-cyano- quinoline—3- amide E-68 N-(1-benzyl- 407—409 G 85 - 88 3,3,3-trifluoro-1 - methyl-propy|)- -chloro- quinoline carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-69 N-(1-benzyl- 407-409 174- 3,3,3-trifluoro 176 methyl-propy|)- 7-chloro- quinoline—3- amide E-70 N-(1—benzyl- 172- 3,3,3-trifluoro—1 - 174 methyl-propy|)- quinoline—3- carboxamide E-71 N—(1-benzyl-1,3- dimethyl-buty|)- 6-methylquinoline carboxamide E-72 N-(1-benzyl—1,3- dimethyl—butyl)— 7-methyl- quinoline—3- carboxamide E-73 N-(1-benzyl-1,3- dimethyl-buty|)- quinoline—3- carboxamide 2017/055273 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-74 N-(1-benzyI-1,3- dimethyl-butyl)— —fluoro— quinoline—3- carboxamide E-75 N-(1-benzyl-1 ,3- dimethyl—butyl)— -methoxy— quinoline—3- carboxamide E-76 N-(1-benzyl-1,3- yl-butyl)— 6-hyd roxy- quinoline carboxamide E-77 N-(1-benzyl- 3,3,3-trifluoro—1 - methyl-propy|)- 6—methyl- quinoline—3- carboxamide 2017/055273 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-78 N-(1-benzyl- 3,3,3-trifluoro-1 methyl-propy|)- 6-chloro- quinoline—3- carboxamide E-79 N-(1-benzyl- 3,3,3-trifluoro—1 methyl-propy|)- 7-methyl- quinoline—3- carboxamide E-80 N-(1-benzyl- 3,3,3-trifluoro-1 -propyl)— -fluoro— quinoline—3- carboxamide E-81 N-(1-benzyl- 3,3,3-trifluoro—1 methyl-propy|)- -methoxy— quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E-82 N-(1-benzyl- 3,3,3-trifluoro -propy|)- 6-hyd roxy— quinoline—3- carboxamide E-83 N-(1-benzyl-1,3- yl-buty|)- 6-chloro- quinoline—3- carboxamide E-84 N-(1-benzyl- 1.69 391 3,3,3-trifluoro—1 - methyl-propyl)— 6-fluoro— quinoline—3- carboxamide E-85 N—(1-benzyl-1,3- 1.17 361 79-81 dimethyl-butyl)— -methyl- quinoline—3- carboxamide E-86 N-(1-benzyl- 1.09 387 101 - 3,3,3-trifluoro 103 -propy|)- -methyl- quinoline—3- carboxamide WO 53380 No. IUPAC name STRUCTURE RT [M+H] Method MP °c (min) measure E-87 N-(1-benzyI-1,3- yl-butyl)— -hyd roxy— quinoline—3- carboxamide E-88 N-[(E)—1—benzy|— G 1-methyl—but—2- enyl]quino|ine amide E-89 N-(1-benzyl- G 3,3,3-trifluoro-1 - methyl-propy|)- 8-fluoro methyl- quinoline carboxamide N-(1-benzyl- 3,3,3-trifluoro—1 - 158 methyl-propy|)- 8—fluoro—4- methyl— quinoline—3- carboxamide E-91 N-[1-benzyI (trifluoromethyl) butyl]—8—f|uoro— quinoline—3- carboxamide E-92 N-[1-benzyI (trifluoromethyl) butenyl]-8— fluoro—quinoline— 3-carboxamide No. IUPAC name URE RT [M+H] Method MP °C (min) measure N-(1-benzyl- 3,3,3-trifluoro methyl-propy|)- 8—chloro—7— fluoro—quinoline— 3-carboxamide N-(1-benzyl-3,3- difluoro—1 - methyl-allyl)—8— —quinoline— 3—carboxamide N—(1-benzyl-3,3- difluoro—1 - methyl-propy|)- 8-fluoro- quinoline carboxamide N-(1-benzyl- 3,3,3-trifluoro—1 - methyl-propyl)— 4—chloro—8— fluoro—quinoline— 3-carboxamide E-97 N-(1-benzyI 1.10 9 chloro-3,3- difluoro—1- methyl-propy|)- 8-fluoro- quinoline—3- carboxamide E-98 8-fluoro-N- 1.07 409 131 - [3,3,3-trifluoro 133 [(2- fluoropheny|)me thyl]methyl- WO 53380 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure propyl]quino|ine- 3-carboxamide ro—N- G 149- [3,3,3-trifluoro—1 - 151 [(3- fluorophenyl)me 1—methy|— propyl]quino|ine- 3-carboxamide N-(1-benzyl- G 127- 3,3,3-trifluoro-1 - 129 methyl-propy|)- 7-fluoro-8— methyl- quinoline—3- carboxamide N-(1-benzyI G 127- ethyl-3,3,3- 129 trifluoro—propy|)- 8—fluoro— quinoline—3- carboxamide N-(1—benzyl- G 158- 3,3,3-trifluoro—1 - 160 methyl-propy|)- 7,8—difluoro- quinoline—3- carboxamide N-[1-benzyI G 147- (methoxymethyl) 149 methy|-but enyl]fluoro- quinoline carboxamide W0 2017!]53380 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure enzyl- 1.13 421 184- 3,3,3-trifluoro 186 methyl-propyl)— 8—chlor0—4- methyl— quinoline—3- carboxamide N-(1—benzyl- 1.07 412 194- 105 3,3,3-trifluoro—1 - 197 methyl-propy|)- 8—cyano methyl- quinoline—3- carboxamide N-(1-benzyl-1,3- 1.21 399 106- 106 dimethyl-buty|)- 108 2-chloro fluoro-quinoline- 3-carboxamide enzyl—1,3- 1.21 7 65-70 107 dimethyl—butyl)— 8—chloro—4- methyl- quinoline—3- carboxamide N—(1-benzyI-1,3- 1.14 372 160- 108 dimethyl-buty|)- 162 8-cyano- quinoline—3- carboxamide No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure N-(1-benzyI-1,3- dimethyl-butyl)— 8—cyano—4— methyl- quinoline—3- carboxamide N-(1-benzyl- 176- 3,3,3-trifluoro—1 - 179 methyl-propy|)- 8—chloro—2- quinoline—3- carboxamide N-(1-benzyI-2— 88-90 utyI methyl- ethyl)quino|ine- 3-carboxamide N-(1-benzyl-2— 125- cyclobutyl 127 methyl—ethyl)—8— fluoro—quinoline- 3-carboxamide N-(1-benzyl- 136— 3,3,3-trifluoro-1 - 140 methyl-propy|)- 8-cyano methyl- ine carboxamide W0 2017I153380 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure N-(1-benzyI-1,3- 1.28 382 150- dimethyl-butyl)— 153 8-fluoro- quinoline carbothioamide E-115 N-(1—benzyl- 1.19 408 173- 3,3,3—trifluor0-1 - 175 methyl—propyI) fluoro—quinoline- 3—carbothioamide N-(1-benzyI-2,2- 1.07 411 116 diethoxy methyl-ethyI) fluoro-quinoline- 3-carboxamide N-(1-benzyI 1.01 366 117 methoxyimino—1 - methyl-ethyl)—8— fluoro—quinoline- 3-carboxamide N-(1-benzyI 1.14 395 118- 118 methoxy—1 ,3- 120 dimethyl-butyl)— ine carboxamide N-(1-benzyI—3- 0.88 353 119 hydroxy methyl-propy|)- quinoline carboxamide W0 2017I153380 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure N-(1-benzyI 0.92 337 120 methyloxo- ethyl)—8—fluoro— ine—3- carboxamide N-(1-benzyI 1.02 367 121 methoxy—1 - methyl—propy|)- 8-fluoro— quinoline amide enzyI-1,3- 1.14 377 136- 122 dimethyl-buty|)- 138 7-methoxy- quinoline—3- carboxamide N-(1-benzyI-1,3- 1.11 377 155- 123 dimethyl-butyl)— 156 8-methoxy— quinoline—3- carboxamide N-(1-benzyI-1,3- 1.14 377 124 dimethyl-but IZ \N enyl)—8—f|uoro—2- methyl- quinoline carboxamide N-(1-benzyI-1,3- 1.23 383 125 dimethyl-buty|)- 2,8—difluoro— quinoline—3- carboxamide W0 153380 No. IUPAC name STRUCTURE RT [M+H] Method MP °C (min) measure E- N-(1-benzyI 1 .00 353 G 126 methoxy methyl-ethyl)—8— O fluoro—quinoline- \ n \ 3-carboxamide N E- N-(1-benzyI 1 .06 367 G 127 ethoxy—1- methyl—ethyl)—8— O fluoro—quinoline- \ N \/ 3—carboxamide N/ E- N-(1-benzyI 1.13 381 G 128 isopropoxy—1 - methyl-ethyI) O fluoro-quinoline- \ N H Y 3-carboxamide N/ Table F: Ph sical data of com ounds of formula I as individual omers No. IUPAC name STRUCTURE RT [M+H] [“1020 method (min) measu F-1 N-[(1R) 1.32 365 ° SFCI benzyl-1,3- Waters Acquity R UPC 2/QDa dimethyl- HN PDA Detector butyl]—8—fluor0- 0 Waters Acquity quinoline : N UPC 2Column: carboxamide F Daicel SFC CHIRALPAK® IA, W0 201?;‘153380 No. IUPAC name STRUCTURE RT [M+H] [@020 method (min) measu F'2 N'[(1S)'1' 0.97 365 +92.65° 3pm, 0ch X 10cm, benzyl-1,3- 40°C Mobile phase: dimethyl- A: 002 B: MeOH gradient. 25 /o B' - HN . o ‘ In butyl]—8—fluoro- 1.8 min ABPR: ne—3-. . \ O / 1800 psi Flow rate: carboxamide_ N F 2.0 ml/min Detection: 240 nm Sample concentration: 1 mg/mL in Hept/EtOH 90/10 Injection: 3 ”L F'3 N‘[(1R)'1' A 3.43 351 SFC:Waters Acq uity benzyI—3— AD UPC2/QDa methyl-butyl]- H N R PDA or \ Waters AchIty. \ 8-fluoro- 0 lumn: . . N/ qumoline F Daicel SFC car oxamlb ,de CHIRALPAK® ID F-4 N-[(1S) 2'61 351 3pm, 0.30m X 100m, benzyl 40°C Mobile phase: methyl-butyl]- ”N A: C02 B: iPr \ O 8-fluor0- l gradient: 15% B in quinoline—3- 4.8 min ABPR: carboxamide 1800 PSi Flow rate: 2.0 ml/min Detection: 235 nm Sample concentration: 1 mg/mL in r 50/50 Injection: 1 ”L F'5 N‘[(1R)‘1' 1.59 348 SFC:Waters Acq uity benzyl-1,3- UPCQIQDa PDA Detector dimethyl- R butyl]quinoline HN Waters AchIty UPC Column: _3_ \ 0 Daicel SFC carboxamide, N W0 2017!]53380 No. IUPAC name STRUCTURE RT [M+H] [@020 method (min) measu F-6 N-[(1S) 1.02 348 CHIRALPAK® IA -1,3- 3pm, 0.30m x 10cm, dimethyl— 40°C Mobile phase: ”N A: 002 BI EtOH quinoiine \ 0 gradient: 30% B in / 1.8 min ABPR: carboxamide. N 1800 pSI, Flow rate: 2.0 ml/min Detection: 232 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 ”L F'7 N‘[(1R)'1'[(2' 1.61 399 SFC:Waters Acquity chlorophenyl) UPCQIQDa methyl]—1,3- R PDA Detector HN Waters AchIty. dimethyl- \ O UPCgcolumn: butyl]-8—fluoro— , N Daicel SFC qumo "fie-3'r F CHIRALPAK® IA carboxamide 3pm, 0.3cm X 100m, F-8 N-[(1S)—1—[(2- 1.21 399 40°C chlorophenyl) CI Mobile phase: A: methyl]-1,3- i C02 B: MeOH dimethyl- \ ‘0; gradient: 20-40% B butyl]—8—fluoro- In 1.8 min ABPR: 1800 pSl ine—3- F Flow rate: 2.0 carboxamide- ml/min Detection: 235 nm Sample concentration: 1 mg/mL in r 50/50 Injection: 1 “L F-9 N-[(1S) 8.10 363 Waters UPLC — benzyl-1,3— Hclass DAD Detector Waters dimethyl-but- ? HN '- UPLC 3-enyl]-8— / 0 Column: Daicel fluoro- \N CHIRALPAK® IA, qumollne, , F 3pm, 0.46cm x carboxamide W0 2017!]53380 No. IUPAC name STRUCTURE RT [M+H] [@020 method (min) measu F-10 N-[(1R) 5.99 363 100m Mobile phase: benzy|-1’3- Hept/EtOH 80/20 yl-but- / Flow rate: 1.0 HN mllmin Detection.~ - ]—8— / o 235 nm Sample fluoro— l \ .

N concentration: 1 qUInOIIne_ _ F mglmL in ACN/Hept carboxam'de 50150 Injection: 2nL F-11 N-[(1S)—1- F 1.70 391 -109.9° SFC:Waters Acquity benzyl—3,3,3- F UPC z/QDa PDA DeteCtor trifluoro S Waters AchIty methyl-propy|]- \ 0 / UPC 2 Column: ro— N Darcel SFC. (immune—3'_ _ CHIRALPAK® ID, carboxamide 3pm, 0.3cm x 10cm, F42 N-[(1R)-1' 2'16 391 ”11-90 40°C Mobile phase: benzyl-3,3,3- A: 002 B: iPr trifluor0 nt: 15% B in methyl-propyl]- 2.8 min ABPR: 8-fluoro— N 1800 pSI Flow rate. 2.0. quinoline mllmin Detection: carboxamide. 235 nm Sample concentration: 1 mglmL in r 50/50 Injection: 1 ML F-13 N-[(1R)—1- 1.53 365 SFC:Waters Acquity benzyl-1,3- UPC 2/QDa PDA Detector dimethyl- Waters AchIty butyl]—7-fluoro- HN UPC 2Column: quinoline. . / Darcel SFC_ _ \ carboxamide F N CHIRALPAK® IA, F'14 N‘[(1S)‘1' 1-15 365 3pm, 0.3cm x10cm, benzyl-1,3- 40°C Mobile phase: dimethyl- A: 002 B: MeOH buty|]-7.f|uoro- gradient: 20-40 % B / i” 1'8 mi” quinoline—3- l \ ABPR' 1800 p3'-. carboxamide F N Flow rate: 2.0 ml/min Detection: No. IUPAC name URE RT [M+H] [@020 method (min) measu 230 nm Sample concentration: 1 mg/mL in ACN/iPr 50150 Injection: 1 ML F-15 N-[(1S)—1- 2.17 349 SFC:Waters Acq uity benzyl UPC2/QDa PDA Detector methyl—but—3_ Waters Acquity enyI]—8—fluor0- UP02Column: quinoline \ O Daicel SFC carboxamide N/ CHIRALPAK® IA, F 3pm, 0.30m X 10cm, F-16 )—1- 158 349 40°C Mobile phase: benzyl A: 002 B: MeOH \ gradient: 25% B in methyl-but R 4'8 min ABPR: enyl]—8—fluoro- HN 1800 psi qumollne. . \ 0 Flow rate: 2.0 carboxamide N/ ml/min Detection: F 235 nm Sample concentration: 1 mgz’mL in ACN/iPr 50150 Injection: 1 ML F-17 N—[(1R)—1- 1.45 379 SFC2Waters Acquity benzyl—1,3,3- UPC2/QDa hyl- HN PDA Detector \ 0 Waters y butyl]—8—fluoro- UPC2 - - N/ qumollne F : Daicel. carboxamide SFC CHIRALPAK® F-18 N-[(1S) 0.94 379 IA, 3pm, 0.30m x benzyl-1,3,3- 10cm, 40°C trimethyl- Mobile phase: A: butyl]—8—fluoro- 002 B: MeOH quinoline—3- gradient: 25% B in 1.8 min carboxamide ABPR: 1800 psi Flow rate: 2.0 mllmin Detection: 235 nm Sample concentration: 1 W0 2017!]53380 No. IUPAC name URE RT [M+H] [@020 method (min) measu mg/mL in ACN/iPr 50/50 Injection: 1 “L F—19 N-[(1S)—1- 4.96 381 : Daicel benzy|_1,3_ SFC CHIRALPAK® yl—but- 'A» 3mm, 0-3cm X 3—enyl]—7,8— we?" 40°C difluoro- : o l EASTEPESE A3 quinoline F N gradient: 15% B in carboxamide .8 min F-20 N-[(1R) 4.11 381 ABPR: 1800 psi benzyl-1,3- Flow rate: 2.0 dimethyl-but- R mI/min 3-enyl]—7,8— Detection: 233 nm / 0 difluoro- Sample quinoline F \N concentration: 1 F mg/mL in ACN/iPr carboxamide 50/50 Injection: 1 pL F—21 N—[(1R)—1- 1.50 383 SFC:Waters Acquity benzyl-1,3- UPC2/QDa PDA Detector dimethyl- R HN Waters Acquity -7, 8- \ \O UPCZ difluoro- Column: Daicel . _ N/ qu'm'me'3' F SFC CHIRALPAK® carboxamide IA, Bum, 03cm x F-22 N-[(1S) 1.09 383 10cm, 40°C benzyl-1,3- Mobile phase: A: dimethyl- s C02 B: MeOH —7,8— gradient: 25% B in \ O difluoro- 1-8 mi“ F N’ ABPR: 1800 psi quinonne_3_ Flow rate: 2.0 carboxamide ml/min Detection: 233 nm Sample concentration: 1 mgz’mL in ACN/iPr 50150 Injection: 1 ML W0 2017(153380 No. IUPAC name URE RT [M+H] [@020 method (min) measu F-23 N-[(1R) 0.88 383 SFC: benzyl IA, 3pm, 0.30m X fluoro—1,3- 100m, 40°C yl- Mobile phase: A: butyl]—8—fluoro- C02 B: MeOH quinoline—3- gradient: 30% B carboxamide in 1.8 min ABPR: F-24 N-[(1S) 1.51 383 1800 psi benzyl Flow rate: 2.0 fluoro-1,3- HN ml/min Detection: dimethyl- \ O 230 nm Sample butyl]—8—fluoro- N/ concentration: 1 quinoline—3- mgimL in ACN/iPr carboxamide 50150 Injection: 1 F-25 N-[(1S) 1.81 369 SFC: benzyl-3,3- Waters Acquity UPCZIQDa o HN PDA or methyl- W0 NI Waters Achity butyl]quinoline UPC2 Column: Daicel SFC carboxamide CHIRALPAK® IA, F-26 N-[(1R)—1- 1.30 369 3W“, 03cm x benzyl-3,3- 10cm, 40°C Mobile difluoro phase: A: CO2 B: methyl- W0 MeOH gradient: butyl]quinoline N/ 30% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 carboxamide ml/min Detection: 230 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 W0 2017!]53380 No. IUPAC name STRUCTURE RT [M+H] [@020 method (min) measu F-27 N-[(1S) 0.45 387 SFC:Waters Acquity benzyl-3,3,3- UPC 2/QD3 PDA Detector oro—1 - HN Waters AchIty methyl—propyl]- \ 0 / UPC 2 Column: 8—methyl- N Daicel SFC qu'"°""e'3'_ _ CHIRALPAK® AY, carboxamlde 3pm, 0.3cm X 10cm, F-28 N-[(1R)—1- 1.37 387 40°C Mobile phase: benzyl—3,3,3- A: C02 B: EtOH trifluoro nt: 30% B in methyl-propy|]- 1.8 min ABPR: yl- 1800 psi Flow rate: 2‘0 ml/min quinoline Detection: 2338 nm carboxamide.

Sample tration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 pL F-29 N-[(1S) 1.97 405 SFC:Waters Acquity benzyl-3,3,3- UPC 2/QDa PDA Detector trifluoro—1- HN Waters AchIty methyl-propyl]- / 0 UPC n: 8—fluoro—4- \ Daicel SFC methyl- CHIRALPAK® OZ, qUInollne 3pm, 0.30m X 10cm, carboxamlde 40°C Mobile phase: F-30 N-[(1R)—1- 1.03 405 A: C02 B: iPr benzyl-3,3,3- gradient: 15% B in trifluoro 1.8min methyl-propy|]- ABPR: 1800 psi \N Flow rate: 2.0 8—flu0ro F ml/min Detection: methyl- 220 nm Sample quinoline_ _ concentration:_ 1 carboxam'de_ mg/mL in ACN/iPr 50/50 Injection: 1 pL No. IUPAC name URE RT [M+H] [@020 method (min) measu F-31 N-[(1R) 1.84 373 SFC: benzyl-3,3- Waters Acquity UPC 2/QDa difluoro—1 - PDA Detector -propyl]— Waters Acq uit \ y 8—fluoro— / UPC 2 qumollne 3. . _ _ N Column: Daicel carboxam'de SFC CHIRALPAK® F-32 N-[(1S) 1.03 373 IF, Bum, 0.3cm x —3,3- F 10cm, 40°C difluoro Mobile phase: A: -propyl]— C02 B: MeOH 8—fluoro- \ nt: 30% B in quinoline—3- N/ 4‘8 min ABPR: 1800 ' F W carboxamide Flow rate: 2.0 ml/min Detection: 220 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 ML F—33 N-[(1S)—1- 3.05 405 SFC:Waters Acquity benzyl-3,3,3- UPC z/QDa PDA Detector trifluoro—1- HN Waters AchIty methyl—propy|]- / 0 \ UPC 3Column: 8—fluoro N F Daicel SFC met y 'h | CHIRALPAK® IC, qUInollne 3pm, 0.30m X 100m, carboxamlde 40°C Mobile phase: F-34 N-[(1R) 3.67 405 A: 002 B: iPR benzyl-3,3,3- gradient: 10% B in trifluoro 4-8 min methyl-propyl]— / ABPR: 1800 psi 8—flu0ro ‘N Flow rate: 2.0 F ml/min Detection: methyl 220 nm Sample qurnollne. . concentration:_ 1 carboxam'de_ mgz’mL in ACN/iPr 50150 Injection: 1 ML No. IUPAC name STRUCTURE RT [M+H] [@020 method (min) measu F-35 N-[(1S) F 4.99 407 SFC:Waters Acquity benzyl-3,3,3- F UPC 2/QDa trifluoro—1 - S PDA DeteCtor Waters Acquity methyl-propyl]- \ 0 UPC 2 : 8 chloro N/ CI Daicel SFC “mum—3', , CHIRALPAK® oz, carboxamide 3pm, 0.3cm X 10cm, F-36 N-[(1R)—1- 1.16 407 40°CMobiIe phase: benzyl—3,3,3- A: 002 B: iPr trifluoro gradient: 15% B in methyl-propyl]— 2.8min ABPR: 1800 8-chloro- N/ psi Flow rate: 2.0 CI ml/minDetection: quinoline 237nm Samp 6| carboxamide concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 ”L F-37 N-[(1S) F 1.05 409 SFC:Waters Acquity benzyl-3,3,3- F UPC 2/QDa trifluoro—1 _ HN PDA Detector \ 0 Waters Acquity methyl-propyl]- UPC 2 Column: . F N/ 7,8—dlfluoro- F Daicel SFC qumo "19l' CHIRALPAK® oz, carboxamide 3pm, 0.3cm X 10cm, P38 N_[(1R)_1_ 1'51 409 40°C Mobile phase: benZyl-3,3,3- A: 002 B: iPr oro gradient: 10% B in methyl-propyl]— Wm) 2.8 minABPR: 1800 F N/ fluoro- pSl Flow rate: 2.0 ml/min Detection: ine 233 nm Samp 6| carboxamide concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 “L F-39 N-[(1S) I 3.30 387 SFC:Waters Acquity benzyl-3,3- O UPCZIQDa E FF o_1- \ N PDA Detector I H Waters Acquity methyl—butyl]- N F UPC2 Column: 8-fluoro— No. IUPAC name URE RT [M+H] [@020 method (min) measu quinoline Daicel SFC carboxamide PAK® OZ, Sum, 0.3cm X 100m, F-40 N-[(1R)—1- 2.10 387 40°CMobile phase: benzyl-3,3- A: 002 B: iPr difluoro—1 - gradient: 12% B in methyl-butyl]- 4.8 min ABPR: 8—fluoro- 1800 psi Flow rate: quinoline 2.0 ml/min carboxamide Detection: 234 nm Sample tration: 1 mglmL in ACN/iPr 50l50 Injection: 1 uL Biological examples Botryotlnia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels . 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 of Tables E and F gave at least 80% control of Botryotinia fucke/iana at 200 ppm when compared to untreated control under the same conditions, which showed extensive e development: E-1, E-2, E—3, E-5, E-6, E-7, E-8, E-10, E-11, E-12, E-13, E-14, E-15, E-16,E-17, E-18, E-19, E-20, E-21, E—22, E-23, E-24, E-25, E-26, E-27, E-28, E-29, E-30, E-31, E—32, E-33, E-34, E- 35, E-36, E—37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E—47, E-48, E-49, E- 50, E-51, E—52, E—53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61, E—62, E-63, E-64, E- 65, E-66, E—67, E-69, E-70, E-71, E-72, E-73, E-74, E-75, E-76, E-77, E—79, E-80, E-81, E- 82, E-84, E—85, E—86, E—87, E-88, E-89, E-90, E-91, E-92, E-93, E-94, E—95, E-96, E—97, E- 98, E-99, E-100, E-101, E-102, E-103, E-104, E-106, E-107, E-109, E-110, E-111, E-112, E- 113, E-114, E-115, E-116, E-117, E-118, E-119, E-121, E-123, E-124, E-125, F-1, F-2, F-3, F—4, F—5, F—6, F—7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-16, F—17, F—18, F—19, F-20, F-21, W0 2017/153380 F-22, F-23, F—24, F—25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33, F—34, F-35, F-36, F- 37, F-38, F—39, F-40 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 nd 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 of Tables E and F gave at least 80% control of Fusarium culmorum at 200 ppm when compared to ted control under the same conditions, which showed extensive disease development: E-1, E-2, E—4, E-5, E-6, E-7, E-8, E-10, E-11, E-12, E-13, E-14, E-15, E—16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25, E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33, E-34, E- 35, E-36, E—37, E—38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E- 50, E-51, E—52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61, E-62, E-64, E-65, E- 66, E-67, E-68, E-69, E—70, E-71, E-72, E-73, E-74, E-75, E-76, E-77, E-78, E-79, E—80, E- 81, E-82, E-84, E-85, E—86, E—87, E-88, E-89, E-90, E-91, E-92, E-93, E—94, E-95, E—96, E— 97, E-98, E-99, E-100, E-101, E-102, E-103, E-104, E-105, E-106, E-107, E-109, E-110, E- 111,E—112,E—113,E-114,E-115,E-116,E-117,E-118,E—119,E—120,E—121,E-123,E-124, E—125, F—1, F—2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F—12, F—13, F—14, F-16, F-17, F- 18, F—19, F—20, F—21, F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F—30, F—31, F-32, F-33, F-34, F—35, F—36, F-37, F-38, F-39, F-40 Fusarium culmorum / wheat/ spike/et preventative (Head blight) Wheat ets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound d in water. The ets are inoculated with a spore suspension of the fungus 1 day after ation. The inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi ss followed by 12 h light/ 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease l compared to untreated when an appropriate level of disease damage appears on untreated check ets (6 - 8 days after application).

The following compounds of Tables E and F gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E—1, E—5, E—6, E—10, E-11, E-12, E-13, E-15, E-16, E-17, E-19, E—20, E—21,E—22, E-23, E-24, E-25, E—26, E—28, E-29, E-30, E-35, E-36, E-38, E-39, E-42, E-43, E—44, E—48, E-49, E-50, E- W0 2017/153380 51, E-52, E—55, E-56, E-57, E-58, E-59, E-60, E-61, E-62, E-66, E-67, E—69, E-70, E-71, E- 72, E-74, E—75, E-76, E—77, E-79, E-80, E-81, E-82, E-84, E-85, E-86, E—88, E-89, E—90, E- 91, E-92, E—93, E-94, E—95, E—96, E-97, E-98, E-99, E-100, E-101, E-102, E-103, E-104, E— 105, E-106, E-107, E-109, E-113, E-114, E-125, F-1, F-2, F-3, F-4, F-5, F-9, F-10, F-11, F- 12, F—13, F—14, F—16, F-17, F-18, F-19, F-20, F-21, F-23, F—24, F—25, F—26, F—27, F-28, F-29, F—31, F—32, F—33, F-35, F-36, F-37, F-39, F-40 ella lagenarium (Colletotrichum lagenarium) / liquid e acnose) 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 of Tables E and F gave at least 80% control of G/omerel/a rium at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1, E-2, E—5, E-6, E—12, E-13, E-14, E-15, E-20, E-21, E-22, E-23, E-24, E-25, E—26, E—27, E-28, E-29, E-30, E—31, E—32, E—33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E—42, E—43, E— 44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58, E- 60, E—61, E—62, E—66, E-69, E-79, E-86, E-87, E-89, E-90, E—91, E—92, E—93, E—94, E-95, E- 96, E—97, E—98, E—99, E-100,E-101,E-102,E-103,E-104,E-106,E—111,E—112,E-113,E- 114, E—115, E—118, E-125, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F—9, F—10, F—11, F-12, F-13, F-14, F-16, F—17, F-18, F-19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F—27, F-28, F-29, F- , F-31, F—32, F-33, F-34, F-35, F-36, F-37, F-38, F-39, F-40 Gaeumannomyces graminis / liquid culture (Take-all of cereals) Mycelial nts of the fungus from cryogenic storage were 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 iss W0 2017/153380 added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after ation.

The following compounds of Tables E and F gave at least 80% control of Gaeumannomyces graminis at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E—1, E—2, E—6, E—7, E-8, E-10, E-13, E-14, E-17, E-19, E-20, E—21, E—22, E—23, E-24, E-25, E- 26, E—27, E—28, E—35, E-37, E-38, E-39, E-40, E-42, E-43, E-45, E—46, E—47, E—48, E-53, F-1, F-2, F-3, F—4, F—5, F-6, F-7, F-8, F-10, F-16, F-17, F-18 Monographella niva/is (Microdochium niva/e) / liquid culture (foot rot cereals) Conidia of the fungus from cryogenic storage are directly mixed into nt broth (PDB potato dextrose . 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 tion of growth is determined photometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control of Monographe/Ia nivalis at 200 ppm when ed to untreated control under the same conditions, which showed extensive disease pment: E-1, E-2, E-5, E-6, E-12, E-13, E-14, E-20, E-21, E-22, E-23, E-24, E-26, E-27, E-28, E-30, E-31, E-33, E-34, E-35, E-36, E-37, E-38, E-42, E-43, E-45, E-48, E-49, E-53, E-54, E-55, E- 56, E—57, E—58, E—59, E-60, E-61, E-88, E-92, E-97, E-99, E-103, E-112, E-114, E-116, E- 117, E-118, E-121, E-122, E-123, F-1, F-2, F-4, F-5, F-8, F-9, F-10, F-18, F-20, F-23, F-24, F-25, F-26, F-27, F-29, F-30, F-32, F-39 Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato se 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 W0 2017/153380 test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control of Mycosphaerella dis at 200 ppm when compared to ted control under the same conditions, which showed ive disease development: E—2, E—35, E—55, F-26 Magnaporthe grisea (Pyricularia oryzae) / liquid culture (Rice Blast) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato se 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 nds of Tables E and F gave at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated control under the same conditions, which showed ive disease development: E-5, E-6, E-12, E-14, E—15, E-16, E-17, E-19, E-20, E-21, E-22, E-23, E-24, E-25, E—26, E- 27, E-28, E-29, E-30, E—31, E—32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E—42, E— 43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E- 58, E—59, E—60, E—61, E-62, E-65, E-66, E-69, E-114, F-1, F—37, F—38, F—39, F—40.

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

The following compounds of Tables E and F gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive e pment: E-14, E-26, E-55, E-114 Mycosphaerella gram/nico/a (Septoria tritici) / liquid culture (Septoria blotch) Conidia of the fungus from cryogenic storage are ly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a W0 2017/153380 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 ined photometrically 4-5 days after application.

The ing compounds of Tables E and F gave at least 80% control of Mycosphaerella graminicola at 200 ppm when compared to untreated l under the same conditions, which showed extensive disease development: E-2, E—6, E-55, E-58, E-61, F-2, F-3, F-6, F-24, F-26 Sclerotinia sclerotiorum / liquid culture (cottony rot) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth s broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth ning the fungal material is added.

The test plates are incubated at 24 °C and the inhibition of growth is determined etrically 3-4 days after application.

The following compounds of Tables E and F 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: E-6, E-14, E-15, E-20, E-24, E-25, E-26, E-28, E-29, E-34, E-35, E-36, E-39, E-47, E-114, F- 1, F—2, F—3, F—10 W0 2017/153380

Claims (18)

1. A compound of formula (I): R10] R13 R2 X \ N | H R7 R11 N R3 R5 R5 5 (I) wherein X is O or 8; R1 is hydrogen, halogen, methyl, methoxy or cyano; R2 and R3 are each independently hydrogen, halogen or methyl; 10 R4 is hydrogen, cyano, C1-C4 alkyl, or C3-C4 cycloalkyl, wherein the alkyl and cycloalkyl, may be optionally tuted with 1 to 3 substituents independently selected from halogen, cyano, C1-Cs alkyl, C1-C3 alkoxy and C1-C3 alkylthio; R5 and Rs are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1- C4 alkoxy and C1-C4 alkylthio; or 15 R5 and R5 together with the carbon atom to which they are ed ent C=O, C=NORC , Cs-Cs cycloalkyl or C2-C5 alkenyl, n the cycloalkyl and alkenyl may be optionally substituted with 1 to 3 substituents independently ed from halogen, cyano, C1-Cs alkyl, C1-Cs alkoxy and 01-03 alkylthio; R7 is hydrogen, C1'C5 alkyl, C3-C5 cycloalkyl, C2-C5 alkenyl, C3-Cs cycloalkenyl, or C2- 20 05 alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 4 substituents ndently selected from halogen, cyano, C1-Cs alkyl, C1-C3 alkoxy, hydroxyl and 01-03 alkylthio; R8 and R9 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C1—C4 ; or 25 R3 and R9 er with the carbon atom to which they are attached represent C3-C5 cycloalkyl, wherein the cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from halogen, cyano, C1-03 alkyl, C1-Cs alkoxy and 01-03 alkylthio; each R10 independently represents halogen, nitro, cyano, formyl, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 , C3-C5 alkenyloxy, C3-C5 alkynyloxy, C1-C5 alkylthio, -C(=NORc)C 1-C5 alkyl, or C1-C5 alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy and alkylthio may be 5 ally substituted with 1 to 5 substituents independently selected from halogen, C1-C3 alkyl, C1-C3 alkoxy, cyano and C1-C3 alkylthio; n is 0, 1, 2, 3, 4 or 5; each Rc is independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C3-C4 alkynyl, C3-C4 cycloalkyl(C1-C2)alkyl and C3-C4 cycloalkyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 10 substituents independently ed from halogen and cyano; R11 is hydrogen, halogen, , methoxy or cyano; R12 and R13 are each independently selected from hydrogen, halogen, methyl, methoxy or hydroxyl; and salts and/or N-oxides thereof; 15 provided that the compound is not one of the following nds: , or 20 a nd wherein R1 is hydrogen, R2 is hydrogen, R3 is methyl, R4 is hydrogen, R5 is hydrogen, R6 is en, R7 is hydrogen, R8 is hydrogen, R9 is hydrogen, n is 1, R10 is 2-methyl, R11 is fluoro, R12 is hydrogen, R13 is hydrogen, and X is O.

2. A compound according to claim 1 wherein R1 is hydrogen, fluoro, chloro, methyl, or cyano. 5

3. A compound according to claim 1 or 2 wherein R2 and R3 are each independently hydrogen or methyl.

4. A compound according to any one of claims 1 - 3 wherein R4 is hydrogen, cyano, C1- C3 alkyl, or cyclopropyl, wherein the alkyl and cycloalkyl, may be optionally 10 substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy and thio.

5. A compound according to any one of claims 1 – 4 wherein R5 and R6 are each independently selected from hydrogen, fluoro, C1-C2 alkyl, C1-C2 alkoxy and C1-C2 15 alkylthio; or R5 and R6 together with the carbon atom to which they are attached represent C=O or cyclopropyl, wherein the cyclopropyl may be ally tuted with 1 to 2 substituents ndently selected from fluoro, methyl and cyano.

6. A compound according to any one of claims 1 – 5 n R7 is C1-C4 alkyl, C3-C4 20 cycloalkyl, C2-C4 alkenyl, or C2-C3 alkynyl, wherein the alkyl, cycloalkyl, l, alkynyl, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, hydroxyl and methylthio.

7. A nd according to any one of claims 1 – 6 wherein R8 and R9 are each 25 independently selected from hydrogen, fluoro, C1-C2 alkyl and C1-C2 alkoxy; or R8 and R9 together with the carbon atom to which they are attached represent cyclopropyl, wherein the cyclopropyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, cyano, and methyl. 30

8. A compound according to any one of claims 1 – 7 wherein each R10 independently represents halogen, cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C1-C2 alkylthio, n the alkyl, cyclopropyl, alkenyl, alkynyl, methoxy, allyloxy, gyloxy and alkylthio may be optionally tuted with 1 to 3 substituents independently selected from , , methyl, 35 and cyano; n is 0, 1, 2 or 3.

9. A compound according to any one of claims 1 – 8 wherein R11 is hydrogen, fluoro, chloro, methyl or cyano; and R12 and R13 are each independently selected from en, fluoro, methyl and hydroxyl. 5 10. A compound according to claim 1 wherein X is O or S; R1 is hydrogen, fluoro, chloro, methyl, or cyano; R2 and R3 are each independently hydrogen or methyl; R4 is hydrogen, cyano, C1-C3 alkyl, or cyclopropyl, wherein the alkyl and cycloalkyl, may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, and methylthio; R5 and R6 are each ndently

10 selected from en, fluoro, C1-C2 alkyl, C1-C2 alkoxy and C1-C2 hio; or R5 and R6 together with the carbon atom to which they are attached represent C=O or cyclopropyl, n the cyclopropyl may be optionally substituted with 1 to 2 substituents ndently selected from fluoro, methyl and cyano; R7 is C1-C4 alkyl, C3-C4 cycloalkyl, C2-C4 alkenyl, or C2-C3 alkynyl, wherein the alkyl, cycloalkyl, alkenyl, 15 alkynyl, may be optionally substituted with 1 to 3 substituents ndently selected from fluoro, chloro, cyano, methyl, hydroxyl and methylthio; R8 and R9 are each independently selected from hydrogen, fluoro, C1-C2 alkyl and C1-C2 alkoxy; or R8 and R9 together with the carbon atom to which they are attached represent cyclopropyl, wherein the cyclopropyl may be optionally substituted with 1 to 2 substituents 20 independently selected from fluoro, cyano, and ; each R10 independently represents halogen, cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, cyclopropyl, methoxy, allyloxy, propargyloxy, or C1-C2 alkylthio, wherein the alkyl, ropyl, alkenyl, alkynyl, methoxy, allyloxy, propargyloxy and alkylthio may be optionally substituted with 1 to 3 substituents independently selected from , chloro, methyl, 25 and cyano; n is 0, 1, 2 or 3; R11 is en, fluoro, chloro, methyl or cyano; and R12 and R13 are each independently selected from hydrogen, fluoro, methyl and hydroxyl; or a salt or e thereof.

11. A compound ing to claim 1 wherein X is O or S; R1 is hydrogen, fluoro, methyl, 30 or cyano; R2 is hydrogen and R3 is hydrogen or methyl; or R2 is hydrogen or methyl and R3 is hydrogen; R4 is hydrogen, cyano, methyl or ethyl, wherein the methyl and ethyl may be optionally substituted with 1 to 3 substituents ndently selected from fluoro and y; R5 and R6 are each independently selected from hydrogen, fluoro, methyl, methoxy and methylthio; or R5 and R6 together with the carbon atom to 35 which they are attached represent cyclopropyl; R7 is C1-C4 alkyl, C3-C4 cycloalkyl, or C2-C4 alkenyl, wherein the alkyl, cycloalkyl and alkenyl may be optionally substituted with 1 to 3 substituents ndently selected from fluoro, chloro, hydroxyl, cyano and methyl; R8 and R9 are each independently ed from hydrogen, fluoro and methyl; or R8 and R9 together with the carbon atom to which they are ed represent cyclopropyl; each R10 ndently represents fluoro, chloro, cyano, methyl, cyclopropyl, methoxy or methylthio, wherein the methyl, cyclopropyl, methoxy and methylthio may be optionally substituted with 1 to 3 substituents independently 5 selected from fluoro and chloro; n is 0, 1 or 2; R11 is en, fluoro, methyl or chloro; and R12 and R13 are each independently selected from hydrogen, fluoro and methyl; or a salt or N-oxide thereof.

12. A compound according to claim 1 wherein X is O or S; R1 is hydrogen or fluoro; R2 10 and R3 are both hydrogen; R4 is methyl or ethyl (wherein the methyl and ethyl may be ally substituted with 1 to 3 fluoro substituents); R5 and R6 are each independently selected from hydrogen and fluoro; R7 is methyl, ethyl, n-propyl, isopropyl , sec-butyl, tert-butyl, C3-C4 lkyl, or C2-C4 alkenyl, wherein the methyl, ethyl, n-propyl, iso-propyl, sec-butyl, tert-butyl, cycloalkyl and alkenyl may be 15 optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro and methyl; R8 and R9 are each independently ed from hydrogen or ; each R10 independently represents fluoro, chloro, cyano or methyl, wherein the methyl may be optionally tuted with 1 to 3 fluoro substituents; n is 0, 1 or 2; and R11 is hydrogen or fluoro; R12 and R13 are both hydrogen; or a salt or N-oxide f.

13. A compound according to to any one of claims 1 – 12 wherein X is O.

14. A ition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 – 13.

15. A composition according to claim 14, wherein the composition further comprises at least one additional active ingredient and/or a diluent.

16. A method of combating, preventing or controlling phytopathogenic diseases which 30 ses applying to a phytopathogen, to the locus of a phytopathogen, or to a plant susceptible to attack by a phytopathogen, or to propagation material thereof, a fungicidally effective amount of a compound of formula (I) as d in any of claims 1 – 13 or a composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 – 13.

17. A compound ing to claim 1 selected from: N-[1-benzyl2-(1-methylcyclopropyl)ethyl]fluoro-quinolinecarboxamide (compound E-47), Nbenzyl-3,3,3-trifluoromethyl-propyl)methyl-quinolinecarboxamide (compound E-61), Nbenzyl-3,3,3-trifluoromethyl-propyl)chloro-quinolinecarboxamide (compound E-60), 5 nzyl-3,3,3-trifluoromethyl-propyl)fluoro-quinolinecarboxamide (compound E-39), Nbenzyl-3,3,3-trifluoromethyl-propyl)-7,8-difluoro-quinolinecarboxamide (compound E-102), N-(1-benzyl-1,3-dimethyl-butyl)-7,8-difluoro-quinolinecarboxamide (compound E- 10 48), enzyl-1,3-dimethyl-butyl)difluoro-quinolinecarboxamide (compound E-35), N-(1-benzyl-1,3-dimethyl-butyl)-7,8-difluoro-quinolinecarboxamide (compound E- 55), 8-fluoro-NN-[1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinolinecarboxamide 15 und E-26), 8-fluoro-N-[3,3,3,-trifluoro[(3-fluorophenyl)methyl]methyl-propyl]quinoline carboxamide (compound E-99), N-(1-benzyl-3,3-difluoromethyl-butyl)fluoro-quinolinecarboxamide (compound E-50), 20 N-(1-benzylfluoro-1,3-methyl-butyl)fluoro-quinolinecarboxamide (compound E-56), N-(1-benzyl-1,3,3-trimethyl-butyl)fluoro-quinolinecarboxamide (compound E-34), N-(1-benzyl-1,3-dimethyl-butyl)fluoro-quinolinecarboxamide (compound E-6), N-(1-benzyl-1,3-dimethyl-butyl)methyl-quinolinecarboxamide (compound E-20), 25 N-(1-benzyl-1,3-dimethyl-butyl)chloro-quinolinecarboxamide und E-14), and N-(1-benzyl-1,3-dimethyl-butyl)quinolinecarboxamide (compound E-13).

18. A compound according to claim 1, substantially as herein described with reference to any one of the Examples thereof.