OA18061A

OA18061A - Fungicidal N'-[2-methyl-6-[2-alkoxy-ethoxy]3-pyridyl]-N-alkyl-formamidine derivatives for use in agriculture.

Info

Publication number: OA18061A
Application number: OA1201600371
Authority: OA
Inventors: Thomas James Hoffman; Sarah Sulzer-Mosse; Kurt Nebel; Fredrik Emil Malcolm Cederbaum
Original assignee: Syngenta Participations Ag
Priority date: 2014-04-11
Filing date: 2015-03-31
Publication date: 2018-04-06

Abstract

The invention relates to compounds of formula (I), wherein R1 , R2 , R3 , R4 , R5 and R6 are as defined in the claims. The invention further provides compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi. Formula I

Description

The présent invention relates to novel microbiocidal, in particular fungicidal, pyridylamidine compounds. It further relates to intermediates used in the préparation of these compounds, to compositions which comprise these compounds, and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Certain pyridylamidines dérivatives hâve been proposed in the literature as microbiocidal active ingrédients in pesticides. For example, WO 00/46184 and WO 03/093224 disclose pyridylamidines which are useful as fungicides. However, the biological properties of these known compounds are not entirely satisfactory for controlling or preventing infestation of plants by phytopathogenic microorganisms, which is why there is a need to provide other compounds which hâve microbicidal properties.

The présent invention relates to compounds of formula (I)

RO

wherein

R¹ représente hydrogen, halogen, cyano, OH, NH₂, C1-C4 alkyl, C₃-C₆ cycloalkyl, NH(CrC₄ alkyl), N(C_rC₄ alkyl)₂, CO(CrC₄ alkyl), 002(04-04 alkyl), CO₂H, 00ΝΗ(0!-0₄alkyl), CON(Ci-C₄ alkyl)₂, SO₂NH(Ci-C₄ alkyl), SO₂N(Ci-C4 alkyl)₂, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C-1-C4 alkyl-C-i-C₄ alkoxy or C₂-C₄ alkynyl;

R² represents C3-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, R⁷ or -Ci-C2alkyl-R⁷, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C-1-C4 alkyl, C1-C4 haloalkyl and C1-C4 haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, C_rC₄ alkyl or C₃-C₆cycloalkyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 3-6membered saturated cyclic group;

R⁵ represents H, C1-C4 alkyl or C1-C4 haloalkyl;

R⁶ represents C1-C4 alkyl, 0^04 alkoxy, C1-C4 haloalkyl or CrC4 haloalkoxy;

-2R⁷ représente a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated orfully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it being possible for the three- to ten-membered ring system itself to be optionally substituted by one or more groups independently selected from the group consisting halogen, CrC4haloalkyl, CrC4alkoxy and Ci-C₄haloalkoxy;

and tautomers/isomers/enantiomers/salts and N-oxides of these compounds

Substituents at a nitrogen atom are always different from halogen. A hydroxy, mercapto or amino substituent is not to be placed on an α-carbon relative to a heteroatom of a core fragment.

Halogen, either as a lone substituent or in combination with another substituent (e.g. haloalkyl) is generally fluorine, chlorine, bromine or iodine, and usually fluorine, chlorine or bromine.

Each alkyl moiety (including the alkyl moiety of alkoxy, alkylthio, etc.) is a straight or branched chain and, depending on the number of carbon atoms it contains, is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, /so-propyl, sec-butyl, /so-butyl, tert-butyl, neo-pentyl, n-heptyl or 1,3-dimethylbutyl, and usually methyl or ethyl.

The alkenyl and alkynyl groups can be mono- or di-unsaturated and examples thereof are derived from the above mentioned alkyl groups.

The alkenyl group is an unsaturated straight or branched chain having a carbon-carbon double bond and, depending on the number of carbon atoms it contains, is, for example ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-

1- propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-

2- pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-

1- butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, and usually 2-propenyl, 1-methyl-

2- propenyl, 2-butenyl, 2-methyl-2-propenyl.

-3The alkynyl group is an unsaturated straight or branched chain having a carbon-carbon triple bond and, depending on the number of carbon atoms it contains, is, for example ethynyl, 1-propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1 -butynyl, 1-methyl-2-butynyl, 1methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 3,3,-dimethyl-1-butynyl, 1 -ethyl-2butynyl, 1,1-dimethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1,1-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl.

Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2difluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, /so-propoxy, n-butoxy, /so-butoxy, sec-butoxy and tert-butoxy, and usually methoxy or ethoxy.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, n-butylthio, isobutylthio, sec-butylthio or terf-butylthio, and usually methylthio or ethylthio.

Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, isopropylsulphonyl, n-butylsulphonyl, /so-butylsulphonyl, sec-butylsulphonyl or tertbutylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.

Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, isopropylsulphinyl, n-butylsulphinyl, /so-butylsulphinyl, sec-butylsulphinyl or te/ï-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl.

Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, /so-propoxymethyl or /so-propoxyethyl.

Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl.

Carbocycle includes cycloalkyl groups and aryl groups.

-4Heterocycloalkyl is a non-aromatic ring that may be saturated or partially unsaturated, preferably fully saturated, containing carbon atoms as ring members and at least one heteroatom selected from O, S and N as ring members. Examples include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,4-dioxanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, oxazinanyl, morpholinyl, thiomorpholinyl, imidazolidinyl, pyrazolidinyl and piperazinyl, preferably morpholinyl, pyrrolidinyl, piperdinyl and piperazinyl, more preferably morpholinyl and pyrollidinyl.

Heteroaryl is, for example, a monovalent monocyclic or bicyclic aromatic hydrocarbon radical. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl. Examples of bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, benzimidazolyl, benzothiophenyl, and benzothiadiazolyl. Monocyclic heteroaryl groups are preferred, preferably pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, pyridyl and imidazolyl being most preferred.

The terms “heterocycle” and “heterocyclic ring” are used interchangeably and are defined to include heterocycloalkyl and heteroaryl groups. Any reference herein to a heterocycle or heterocyclic ring preferably refers to the spécifie examples given under the définition of heteroaryl and heterocycloalkyl above, and are preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl and imidazolyl. No heterocycle contains adjacent oxygen atoms, adjacent sulphur atoms, or adjacent oxygen and sulphur atoms.

Where a moiety is indicated as being (optionally) substituted, e.g. alkyl, this includes those moieties where they are part of a larger group, e.g. the alkyl in the alkylthio group. The same applies, e.g. to the phenyl moiety in phenylthio etc. Where a moiety is indicated as being optionally substituted by one or more other groups, preferably there are one to five optional substituents, more preferably one to three optional substituents. Where a moiety is substituted by a cyclic group, e.g. aryl, heteroaryl, cycloalkyl, preferably there are no more than two such substituents, more preferably no more than one such substituent.

The following list provides définitions, including preferred définitions, for substituents R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ with reference to compounds of formula I. For any one of these substituents, any of the définitions given below may be combined with any définition of any other substituent given below or elsewhere in this document.

R¹ represents hydrogen, halogen, cyano, OH, NH₂, C1-C4 alkyl, C₃-C₆ cycloalkyl, NH(Ci-C₄ alkyl), N(C_rC₄ alkyl)₂, CO(C_rC₄ alkyl), CO₂(Ci-C₄ alkyl), CO₂H, CONH(C_rC₄

-5alkyl), CON(C_rC₄ alkyl)₂, SO₂NH(Ci-C₄ alkyl), SO₂N(Ci-C₄ alkyl)₂, C_rC₄ haloalkyl, C_rC₄alkoxy, C_rC4 haloalkoxy, C1-C4 alkyl-CrC₄ alkoxy or C₂-C₄ alkynyl

Preferably, R¹ represents hydrogen, halogen, cyano, OH, NH₂, C1-C4 alkyl, C3-C₆cycloalkyl, NH(CrC₄ alkyl), N(CrC₄ alkyl)₂, CO(C_rC₄ alkyl), CO₂(C₁-C₄ alkyl), CO₂H, CONH(CrC₄ alkyl), CON(C_rC₄ alkyl)₂, SO₂NH(C₁-C₄ alkyl), SO₂N(C_rC₄ alkyl)₂, C_rC₄haloalkyl, C_rC₄ alkoxy, C1-C4 haloalkoxy, or C₂-C₄ alkynyl.

More preferably, R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NH(Ci-C₂ alkyl), N(C_rC₂ alkyl)₂, CO(C_rC₂ alkyl), CO₂(C_rC₂ alkyl), CO₂H, CONH(C_rC₂ alkyl), CON(C_rC₂ alkyl)₂, SO₂NH(C_rC₂ alkyl), SO₂N(C_rC₂ alkyl)₂, C_rC₄fluoroalkyl, C1-C4 alkoxy, C_rC₂ haloalkoxy or C₂-C₄ alkynyl.

Even more preferably, R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NHMe, NMe₂, COMe, CO₂Me, CO₂H, CONHMe, CONMe₂, SO₂NHMe, SO₂NMe₂, CHF₂, CF_3i OMe, OCHF₂ or acetylenyl.

Yet more preferably, Ri represents hydrogen, halogen, cyano, methyl, ethyl, cyclopropyl, CHF₂, CF₃, OMe, or OCHF₂.

Most preferably, R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano.

R² represents C3-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, R⁷ or-CrC₂alkyl-R⁷, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 alkyl, C-f-04 haloalkyl and C1-C4 haloalkoxy.

Preferably, R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃C₅cycloalkenyl, -Ci-C₂alkyl-C₃-C₆cycloalkyl, -Ci-C₂alkyl-C₃-C₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, Ci-C₂ alkyl, C_rC₂ haloalkyl and CrC₂ haloalkoxy.

More preferably, R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, -Ci-C₂alkyl-C₃-C₆cycloalkyl, -CrC₂alkyl-C₃-C₆cycloalkenyl which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, C_rC₂ alkyl, CrC₂fluoroalkyl and CrC₂fluoroalkoxy.

Yet more preferably, R² is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, npentyl, 2-methylbutyl, 2,2-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl -CH₂-cyclopropyl, -CH₂cyclobutyl, -CH₂-cyclopentyl, and -CH₂-cyclopentenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, methyl and difluoromethoxy.

-6Yet more preferably again, R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy.

Most preferably, R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or cyclopropyl.

In another group of compounds, R² represents C3-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, R⁷ or -Ci-C2alkyl-R⁷, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 alkyl and Ci-CMaloalkyl.

Preferably in this group of compounds, R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃C₆alkynyl, C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, -Ci-C₂alkyl-C₃-C6cycloalkyl, -CrC^alkyl-CsC₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C_rC₂ alkyl and CrC₂haloalkyl.

More preferably in this group of compounds, R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C6alkynyl, C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, -CrC₂alkyl-C₃-C₆cycloalkyl, -Ci-C₂alkyl-C₃C₆cycloalkenyl which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, Ci-C₂ alkyl and Ci-C₂fluoroalkyl.

Yet more preferably in this group of compounds, R² is n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, 2-methylpentyl, 3methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl -CH₂-cyclopropyl, -CH₂-cyclobutyl, -CH₂-cyclopentyl, and -CH₂-cyclopentenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and methyl.

Yet more preferably again in this group of compounds, R₂ is n-propyl, iso-propyl, nbutyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more fluoro.

R³ and R⁴ independently of each other represent hydrogen, C1-C4 alkyl or C₃-C₆cycloalkyl; or

Preferably, R³ and R⁴ independently of each other represent hydrogen, CrC₃ alkyl or C₃-C₅ cycloalkyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 4- or 5membered saturated cyclic group.

More preferably, R³ and R⁴ independently of each other represent hydrogen, methyl, ethyl, isopropyl or cyclopropyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 4membered saturated cyclic group.

-7In one group of compounds, R³is hydrogen or methyl;

R⁴ is methyl or ethyl.

Preferably in this group of compounds, R³ represents hydrogen or methyl;

R⁴ is ethyl.

R⁵ represents H, C1-C4 alkyl or C1-C4 haloalkyl.

Preferably, R⁵ represents H or CrC₄ alkyl.

More preferably, R⁵ represents H or methyl

Most preferably, R⁵ is hydrogen.

R⁶ represents C1-C4 alkyl, CrC4 alkoxy, CrC4 haloalkyl or C1-C4 haloalkoxy. Preferably, R⁶ represents C1-C4 alkyl or C1-C4 alkoxy.

More preferably, R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl, cyclopentyl, methoxy or ethoxy.

Even more preferably, R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl, or cyclopentyl.

Yet more preferably, R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl or cyclopentyl.

Even yet more preferably, R⁶ represents methyl, ethyl, n-propyl, iso-propyl, or cyclopropyl.

More preferably still, R⁶ represents methyl, ethyl, n-propyl or iso-propyl.

Most preferably, R⁶ is methyl.

When R⁵ and R⁶ are not the same, the compounds of formula (I) can occur in (at least) two enantiomeric forms: (la) and (Ib).

A racemic compound (I) is a 1:1 mixture ofthe compounds offormula (la) and (Ib). Other ratios of (la) and (Ib) are possible and part ofthe présent invention. Examples of such ratios of (la) to (Ib) are 1:99, 2:98, 5:95, 10:90, 20:80, 30:70; 40:60, 45:55; 55:45; 60;40, 70:30, 80:20, 90:10, 95:5, 98;2, and 99:1.

-8In one embodiment of the invention, the weight ratio of (Ib) to (la) is weighted towards compound of formula (la), for example, the the ratio of (Ib) to (la) being 1:99, 2:98, 5:95, 10:90, 20:80, 30:70; 40:60 or 45:55. More preferably in this embodiment of the invention, the compound of formula (I) consists essentially of the compound of formula (la); even more preferably, the compound of formula (I) is the compound of formula (la).

In another embodiment of the invention, the weight ratio of (la) to (Ib) is weighted towards compound of formula (Ib), for example, the the ratio of (la) to (Ib) being 1:99, 2:98, 5:95,10:90, 20:80, 30:70; 40:60 or 45:55. More preferably in this embodiment of the invention, the compound of formula (I) consists essentially of the compound of formula (Ib); even more preferably, the compound of formula (I) is the compound of formula (Ib).

R⁷ représente a three- to ten-membered monocyclic orfused bicyclic ring system which can be aromatic, partially saturated orfully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it being possible for the three- to ten-membered ring system itself to be optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 haloalkyl, CrC4alkoxy and C-1-C4 haloalkoxy.

Preferably, R⁷ représente C₃-C6cycloalkyl, C3-C₅cycloalkenyl, phenyl, naphthyl, anthracyl, fluorenyl, indanyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3dioxolanyl, 1,4-dioxanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, oxazinanyl, morpholinyl, thiomorpholinyl, imidazolidinyl, pyrazolidinyl, piperazinyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl, benzimidazolyl, benzothiophenyl, or benzothiadiazolyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C-1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.

More preferably, R⁷ represents C₃-C6cycloalkyl, C₃-C₅cycloalkenyl, phenyl, naphthyl, anthracyl, fluorenyl, indanyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl and triazolyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 haloalkyl, C1-C4 alkoxy and C-1-C4 haloalkoxy.

Yet more preferably, R⁷ represents C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, phenyl, naphthyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl and triazolyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4haloalkyl, Ci-C₄alkoxy and C1-C4 haloalkoxy.

-9Even more preferably, R⁷ represents C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, phenyl, morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl and triazolyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 haloalkyl, Ci-C₄alkoxy and C1-C4 haloalkoxy.

More preferably again, R⁷ represents C₃-C₆cycloalkyl, C₃-C₅cycloalkenyl, phenyl, morpholinyl, pyrollidinyl, pyridyl and imidazolyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 haloalkyl, Ci-C₄alkoxy and C1-C4 haloalkoxy.

Most preferably, R⁷ represents C₃-C₆cycloaikyl or C₃-C₅cycloalkenyl, each of which is optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4haloalkyl, Ci-C4alkoxy and CrC₄haloalkoxy

In one group of compounds of formula (I), R¹ represents hydrogen, halogen, cyano, OH, NH₂, C₁-C₄alkyl, C₃-C₆ cycloalkyl, NH(C_rC₄ alkyl), N(C_rC₄ alkyl)₂, CO(C_rC₄ alkyl), CO₂(Ci-C₄ alkyl), CO₂H, CONH(C_rC₄ alkyl), CON(C_rC₄ alkyl)₂, SO₂NH(C_rC₄ alkyl), SO₂N(CrC₄ alkyl)₂, C1-C4 haloalkyl, C_rC₄ alkoxy, C1-C4 haloalkoxy, or Ο₂-Ο₄ alkynyl;

R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃C₅cycloalkenyl, -CrCaalkyl-Cs-Cecycloalkyl, -CrC₂alkyl-C₃-C₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C1-C4 haloalkyl and C-1-C4 haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, C1-C4 alkyl or Ο₃-Οβ cycloalkyl; or

R⁵ represents H, C1-C4 alkyl or C1-C4 haloalkyl;

R⁶ represents C1-C4alkyl, C_rC4 alkoxy, C_rC4 haloalkyl or CrC4 haloalkoxy.

In another group of compounds of formula (I), R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NH(C-i-C₂ alkyl), N(Ci-C₂ alkyl)₂, CO(C-i-C₂ alkyl), CO₂(C_rC₂ alkyl), CO₂H, CONH(C_rC₂ alkyl), CON(C_rC₂ alkyl)₂, SO₂NH(C_rC₂ alkyl), SO₂N(C_rC₂ alkyl)₂, C1-C4 fluoroalkyl, C1-C4 alkoxy, C-|-C₂ haloalkoxy or C₂-C4 alkynyl;

R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃Cscycloalkenyl, -CrC₂alkyl-C₃-C₆cycloalkyl, -C₁-C₂alkyl-C₃-C₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C-|-C₂ haloalkyl and Ci-C₂ haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, C_rC₃ alkyl or C₃-C₅cycloalkyl; or

-10R³ and R⁴ together with the nitrogen atom to which they are attached form a 5membered saturated cyclic group;

R⁵ represents H or C_rC4 alkyl;

R⁶ represents C1-C4 alkyl, CrC4alkoxy, Ci-C4haloalkyl or C1-C4 haloalkoxy.

In another group of compounds of formula (I), R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NHMe, NMe₂, COMe, CO₂Me, CO₂H, CONHMe, CONMe₂, SO₂NHMe, SO₂NMe₂, CHF₂, CF₃, OMe, OCHF₂ or acetylenyl;

R² represents C₃-C₆alkyl, C3-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃C₅cycloalkenyl, -C-|-C₂alkyl-C₃-C₆cycloalkyl, -CrCLalkyl-Cs-Cscycloalkenyl which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, C-|-C₂alkyl, CrCzfluoroalkyl and C_rC₂fluoroalkoxy;

R³ and R⁴ independently of each other represent hydrogen, methyl, ethyl, isopropyl or cyclopropyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 5membered saturated cyclic group;

R⁵ represents H or methyl;

R⁶ represents C1-C4 alkyl or C-iAUalkoxy.

In another group of compounds of formula (I), Ri represents hydrogen, halogen, cyano, methyl, ethyl, cyclopropyl, CHF₂, CF₃, OMe, or OCHF₂;

R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl -CH₂-cyclopropyl, -CH₂-cyclobutyl, -CH₂cyclopentyl, and -CH₂-cyclopentenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, methyl and difluoromethoxy;

R³is hydrogen or methyl;

R⁴ is methyl or ethyl;

R⁵ represents H or methyl;

R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl, cyclopentyl, methoxy or ethoxy.

In another group of compounds of formula (I), R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy;

- 11 R³ représente hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl; .

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl or cyclopentyl.

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ represents methyl, ethyl, n-propyl or iso-propyl.

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ is methyl.

R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or cyclopropyl;

-12R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen;

R⁶ is methyl.

Tables 1 to 22: Compounds of formula (I)

The invention is further illustrated by making available the following individual compounds of formula (I) listed below in Tables 1 to 22.

Each of Tables 1 to 22, which follow Table A below, make available 47 compounds of the formula (I) in which R², R³, R⁴, R⁵ and R⁶ are the substituents defined in Table A and R¹is the substituent defined in the relevant Table 1 to 22. Thus Table 1 individualises 47 compounds of formula (I) wherein for each row of Table A, R¹ is as defined in Table 1. Similarly, Table 2 individualises 47 compounds of formula (I) wherein for each row of Table A, R¹ is as defined in Table 2; and so on for Tables 3 to 22.

Table A discloses 47 sets of meanings of the variables R², R³, R⁴, R⁵ and R⁶ in a compound of formula I.

Tables 23 to 44: Compounds of formula (la)

The invention is further illustrated by making available the following individual compounds of formula (la) listed below in Tables 23 to 44.

(la)

Each of Tables 23 to 44, which follow Table A below, make available 47 compounds of the formula (la) in which R², R³, R⁴, R⁵ and R⁶ are the substituents defined in Table A and R¹is the substituent defined in the relevant Table 23 to 44. Thus Table 23 individualises 47 compounds of formula (la) wherein for each row of Table A, R¹ is as defined in Table 23.

-13Similarly, Table 24 individualises 47 compounds of formula (la) wherein for each row of Table A, R¹ is as defined in Table 24; and so on for Tables 25 to 44.

Table A discloses 47 sets of meanings of the variables R², R³, R⁴, R⁵ and R⁶ in a compound of formula la.

Tables 45 to 66: Compounds of formula (Ib)

The invention is further illustrated by making available the following individual compounds of formula (Ib) listed below in Tables 45 to 66.

(Ib)

Each of Tables 45 to 66, which follow Table A below, make available 47 compounds of 10 the formula (Ib) in which R², R³, R⁴, R⁵ and R⁶ are the substituents defined in Table A and R¹is the substituent defined in the relevant Table 45 to 66. Thus Table 45 individualises 47 compounds of formula (Ib) wherein for each row of Table A, R¹ is as defined in Table 45. Similarly, Table 46 individualises 47 compounds of formula (Ib) wherein for each row of Table A, R¹ is as defined in Table 46; and so on for Tables 47 to 66.

Table A discloses 47 sets of meanings of the variables R², R³, R⁴, R⁵ and R⁶ in a compound of formula Ib.

- 14Table A

	R^z	R³	“R⁴	R^s	R^b
A.1.001	n-propyl	ethyl	ethyl	H	methyl
A.1.002	n-propyl	methyl	cyclopropyl	H	methyl
A.1.003	n-propyl	methyl	isopropyl	H	methyl
A.1.004	n-propyl	-CH₂-CH₂-CH2-CH₂-	H	methyl
A.1.005	n-propyl	methyl	methyl	H	methyl
A.1.006	n-propyl	ethyl	H	H	methyl
A.1.007	n-propyl	methyl	H	H	methyl
A.1.008	n-propyl	isopropyl	H	H	methyl
A.1.09	prop-2-enyl	ethyl	ethyl	H	methyl
A.1.010	prop-2-enyl	methyl	cyclopropyl	H	methyl
A.1.011	prop-2-enyl	methyl	isopropyl	H	methyl
A.1.012	prop-2-enyl	-CH₂-CH₂-CH2-CH₂-	H	methyl
A.1.013	prop-2-enyl	methyl	methyl	H	methyl
A.1.014	prop-2-enyl	ethyl	H	H	methyl
A.1.015	prop-2-enyl	isopropyl	H	H	methyl
A.1.016	prop-2-enyl	ethyl	methyl	H	methyl
A.1.017	isopropyl	ethyl	methyl	H	methyl
A.1.018	isopropyl	ethyl	methyl	methyl	methyl
A.1.019	propargyl	ethyl	methyl	H	methyl
A. 1.020	n-propyl	ethyl	methyl	H	methyl
A.1.021	prop-2-enyl	ethyl	methyl	methyl	methyl
A. 1.022	n-propyl	ethyl	methyl	methyl	methyl
A. 1.023	propargyl	ethyl	methyl	methyl	methyl
A. 1.024	3,3difluoropropyl	ethyl	methyl	H	methyl
A. 1.025	3,3,3trifluoropropyl	ethyl	methyl	methyl	methyl
A.1.026	3,3,3trifluoropropyl	ethyl	methyl	H	methyl
A. 1.027	3,3difluoroprop- 2-enyl	ethyl	methyl	H	methyl
A. 1.028	n-propyl	ethyl	methyl	H	ethyl
A. 1.029	prop-2-enyl	ethyl	methyl	H	ethyl
A.1.030	propargyl	ethyl	methyl	H	ethyl
A.1.031	n-propyl	ethyl	methyl	H	methoxymethyl
A. 1.032	prop-2-enyl	ethyl	methyl	H	methoxymethyl
A. 1.033	propargyl	ethyl	methyl	H	methoxymethyl
A.1.034	2,2-dimethylpropyl	ethyl	methyl	H	methyl
A.1.035	2-methylbutyl	ethyl	methyl	H	methyl
A.1.036	2,2-dimethylbutyl	ethyl	methyl	H	methyl
A.1.037	cyclopropyl	ethyl	methyl	H	methyl
A.1.038	cyclobutyl	ethyl	methyl	H	methyl
A.1.039	cyclopentyl	ethyl	methyl	H	methyl

	R^z	R³	R⁴	R^s	R^b
A. 1.040	cyclopent-3enyl	ethyl	methyl	H	methyl
A. 1.041	3-methyl-but- 2-enyl	ethyl	methyl	H	methyl
A. 1.042	but-2-enyl	ethyl	methyl	H	methyl
A. 1.043	cyclopropylmethyl	ethyl	methyl	H	methyl
A. 1.044	cyclobutylmethyl	ethyl	methyl	H	methyl
A. 1.045	cyclopentylmethyl	ethyl	methyl	H	methyl
A. 1.046	cyclopent-3enyl-methyl	ethyl	methyl	H	methyl
A. 1.047	n-propyl	-ch₂-c	4₂-CH₂-	H	methyl

Tables 1,23 and 45: Tables 1, 23 and 45 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is hydrogen and each ofthe variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in 5 the corresponding row of Table A. For example;

compound 1.1.016 has the following structure:

H '— compound 45.1.043 has the following structure:

Tables 2, 24 and 46: Tables 2, 24 and 46 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is chloro and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 3, 25 and 47: Tables 3, 25 and 47 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is bromo and each ofthe variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 4, 26 and 48: Tables 4, 26 and 48 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is iodo and each ofthe variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 5, 27 and 49: Tables 5, 27 and 49 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is methyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 6, 28 and 50: Tables 6, 28 and 50 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is ethyl and each ofthe variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 7, 29 and 51: Tables 7, 29 and 51 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is cyclopropyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 8, 30 and 52: Tables 8, 30 and 52 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is trifluoromethyl and each ofthe variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

-17Tables 9, 31 and 53: Tables 9, 31 and 53 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is difluoromethyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 10, 32 and 54: Tables 10, 32 and 54 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is ethynyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 11, 33 and 55: Tables 11, 33 and 55 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is methoxy and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 12, 34 and 56: Tables 12, 34 and 56 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is difluoromethoxy and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 13, 35 and 57: Tables 13, 35 and 57 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is methylamino and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 14, 36 and 58: Tables 14, 36 and 58 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is dimethylamino and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 15, 37 and 59: Tables 15, 37 and 59 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is Nmethylsulfonamide, wherein the broken line below indicates the point of attachment of the group R¹ to the remainder of the compound and each of the variables R², R³, R⁴, R⁵ and R⁶has the spécifie meaning given in the corresponding row of Table A.

Tables 16, 38 and 60: Tables 16, 38 and 60 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is N,N18061

- 18dimethylsulfonamide, wherein the broken line below indicates the point of attachment of the group R¹ to the remainderof the compound and each of the variables R², R³, R⁴, R⁵ and R⁶has the spécifie meaning given in the corresponding row of Table A.

Tables 17, 39 and 61: Tables 17, 39 and 61 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is fluoro and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 18, 40 and 62: Tables 18, 40 and 62 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is acetyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 19, 41 and 63: Tables 19, 41 and 63 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is methoxyformyl wherein the broken line below indicates the point of attachment of the group R¹ to the remainder of the compound and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 20, 42 and 64: Tables 20, 42 and 64 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is hydroxy and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 21,43 and 65: Tables 21, 43 and 65 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is fluoromethyl and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

Tables 22, 44 and 66: Tables 22, 44 and 66 disclose 47 compounds of formula (I), 47 compounds of formula (la) and 47 compounds of formula (Ib) respectively wherein R¹ is

-19cyano and each of the variables R², R³, R⁴, R⁵ and R⁶ has the spécifie meaning given in the corresponding row of Table A.

It has now been found that the compounds of formula (I) according to the invention hâve, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisms, such as fungi, bacteria or viruses, in particular against diseases that are caused by fungi.

The invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingrédient to the plants, to parts thereof or the locus thereof.

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

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

The compounds of formula I can be used in the agricultural sector and related fields of use e.g. as active ingrédients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man.

The compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They hâve very useful curative, préventive and systemic properties and are used for protecting numerous useful plants. The compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later from phytopathogenic micro-organisms.

It is 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 quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include ail déviation from natural development, such as killing, retardation and the like, and prévention includes barrier or other défensive formation in or on a plant to prevent fungal infection.

A preferred method of applying a compound of formula (I) is foliar application. The frequency of application and the rate of application will dépend on the risk of infestation by the corresponding pathogen. However, the compounds of formula (I) may also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a

-20liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can be applied to the flooded rice field.

It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

The propagation material can be treated with a composition comprising a compound of formula I before planting: seed, for example, can be dressed before being sown. The active ingrédients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.

The term plant propagation material” dénotés ail generative parts of a plant, for example seeds or végétative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.

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

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

The compounds of formula I are for example, effective against Fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These Fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,

-21 Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Pénicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.

Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed râpe (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for

-22example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops are to be understood as also including those crops which hâve been rendered tolérant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been rendered tolérant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that hâve been rendered tolérant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

Crops are also to be understood as being those which naturally are or hâve been rendered résistant to harmful insects. This includes plants transformed 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 δ-endotoxins, végétative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, 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 insecticidal résistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be résistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can hâve the ability to express an insecticidal protein while at the same

-23time being herbicide tolérant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

The compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.

Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) as active ingrédient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.

To this end compounds of formula (I) and inert carriers are conveniently formulated in known manner to emulsifiable concentrâtes, coatable pastes, directly sprayable or dilutable solutions, dilute émulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining spécial effects.

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

A formulation, i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

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

-24Advantageous rates of application are normally from 5g to 2kg of active ingrédient (a.i.) per hectare (ha), preferably from 10g to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient rates of application are from 10mg to 1g of active substance per kg of seeds. The rate of application for the desired action can be determined by experiments. It dépends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.

Normally, in the management of a crop a grower would use one or more other agronomie chemicals in addition to the compound of the présent invention. Examples of agronomie chemicals include pesticides, such as acaricides, bactéricides, fungicides, herbicides, insecticides, nematicides, as well as plant nutrients and plant fertilizers.

Accordingly, the présent invention provides a composition comprising a compound of formula (I) according to the présent invention together with one or more pesticides, plant nutrients or plant fertilizers. The combination may also encompass spécifie plant traits incorporated into the plant using any means, for example conventional breeding or genetic modification. Such compositions may also contain one or more inert carriers as described above.

The invention also provides for the use of provides a composition comprising a compound of formula (I) according to the présent invention together with one or more pesticides, plant nutrients or plant fertilizers. The combination may also encompass spécifie plant traits incorporated into the plant using any means, for example conventional breeding or genetic modification.

Suitable examples of plant nutrients or plant fertilizers are calcium sulfate (CaSO₄), calcium nitrate (Ca(NO₃)2.4H₂O), calcium carbonate (CaCO₃), potassium nitrate (KNO₃), magnésium sulfate (MgSO₄), potassium hydrogen phosphate (KH₂PO₄), manganèse sulfate (MnSO₄), copper sulfate (CuSO₄), zinc sulfate (ZnSO₄), nickel chloride (NiCI₂), cobalt sulfate (CoSO₄), potassium hydroxide (KOH), sodium chloride (NaCI), boric acid (H₃BO₃) and métal salts thereof (Na₂MoO₄). The nutrients may be présent in an amount of 5% to 50% by weight, preferably of 10% to 25% by weight or of 15% to 20% by weight each. Preferred additional nutrients are urea ((NH₂)₂CO), melamine (C₃H₆N₆), potassium oxide (K₂O), and inorganic nitrates. The most preferred additional plant nutrient is potassium oxide. Where the preferred additional nutrient is urea, it is présent in an amount of generally 1% to 20% by weight, preferably 2% to 10% by weight or of 3% to 7% by weight.

Suitable examples of pesticides are acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides,

-25arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fongicides, benzimidazole fongicides, benzothiazole fongicides, botanical fongicides, bridged diphenyl fongicides, carbamate fongicides, carbanilate fongicides, conazole fongicides, copper fongicides, dicarboximide fongicides, , dinitrophenol fongicides, dithiocarbamate fongicides, dithiolane fongicides, furamide fongicides, furanilide fongicides, hydrazide fongicides, imidazole fongicides, mercury fongicides, morpholine fongicides, organophosphorous fongicides, organotin fongicides, oxathiin fongicides, oxazole fongicides, phenylsulfamide fongicides, polysulfide fongicides, pyrazole fongicides, pyridine fongicides, pyrimidine fongicides, pyrrole fongicides, quaternary ammonium fongicides, quinoline fongicides, quinone fongicides, quinoxaline fongicides, strobilurin fongicides, sulfonanilide fongicides, thiadiazole fongicides, thiazole fongicides, thiazolidine fongicides, thiocarbamate fongicides, thiophene fongicides, triazine fongicides, triazole fongicides, triazolopyrimidine fongicides, urea fongicides, valinamide fongicides, zinc fongicides, Benzoylureas, carbamates, chloronicotinyls, diacylhydrazines, diamides, fiproles, macrolides, nitroimines, nitromethylenes, organochlorines, organophosphates, organosilicons, organotins, phenylpyrazoles, phosphoric esters, pyrethroids, spinosyns, tetramic acid dérivatives, tetronic acid dérivatives, Antibiotic nematicides, avermectin nematicides, botanical nematicides, carbamate nematicides, oxime carbamate nematicides, organophosphorus nematicides, nematophagous fungi or bacteria, amide herbicides, anilide herbicides, arsenical herbicides, arylalanine herbicides, aryloxyphenoxypropionic herbicides, benzofuranyl herbicides, benzoic acid herbicides,benzothiazole herbicides, benzoylcyclohexanedione herbicides, carbamate herbicides, carbanilate herbicides, chloroacetanilide herbicides, chlorotriazine herbicides, cyclohexene oxmie herbicides, cyclopropylisoxazole herbicides, dicarboximide herbicides, dinitroaniline herbicides, dinitrophenol herbicides, diphenyl ether herbicides, dithiocarbamate herbicides, fluoroalkyltriazine herbicides, halogenated aliphatic herbicides, imidazolinone herbicides, inorganic herbicides, methoxytriazine herbicides, methylthiotriazine herbicides, nitrile herbicides, nitrophenyl ether herbicides, organophosphorous herbicides, oxadiazolone herbicides, oxazole herbicides, phenoxy herbicides, phenoxyacetic herbicides, phenoxybutyric herbicides, phenoxypropionic herbicides, phenylenediamine herbicides, phenylurea herbicides, phthalic acid herbicides, picolinic acid herbicides, pyrazole herbicides, pyridazine herbicides, pyridazinone herbicides, pyridine herbicides, pyrimidinediamine herbicides, pyrimidinyloxybenzylamine herbicides, pyrimidinylsulfonylurea herbicides, quaternary ammonium herbicides, quinolinecarboxylic acid herbicides, sulfonamide herbicides, sulfonanilide herbicides, sulfonylurea herbicides, thiadiazolylurea

-26herbicides, thioamide herbicides, thiocarbamate herbicides, thiocarbonate herbicides, thiourea herbicides, triazine herbicides,triazinone herbicides, triazinylsulfonylurea herbicides, triazole herbicides, triazolone herbicides, triazolopyrimidine herbicides, uracil herbicides, urea herbicides, microbiais, plant extracts, pheromones, macrobiais and other biologicals.

The following non-limiting Examples illustrate the above-described invention in greater detail without limiting it. Those skilled in the art will promptly recognise appropriate variations from the procedures both as to reactants and as to réaction conditions and techniques. Ail references mentioned herein are incorporated by reference in their entirety.

SYNTHETIC EXAMPLES

Using techniques analogous to those described in WO 12/146125 (pp.370-378) and further techniques known to the person skilled in the art, for example asfound in WO 08/101682 (pp.22-33), compounds of formula (I) may be prepared.

Préparation of (2R)-1-propoxypropan-2-ol

OH

To an ice-bath cooled solution of THF (400 mL) under inert atmosphère (Ar) and sodium hydride (12 g, 490 mmol, 5 equiv.) 1-propanol (40 mL, 490 mmol, 5 equiv) was added dropwise. The ice bath was removed and the reaction mixture was stirred at room température for 30 minutes then (2R)-2-methyloxirane (5.8 g, 99 mmol) was added dropwise and the reaction was stirred for 18h under heating at 50°C. After this time, GC-MS and NMR indicated that the starting material was consumed and the reaction mixture was allowed to reach room température before quenching with aqueous NH4CI solution and extracting with dichloromethane. The organic layer was dried over anhydrous Na₂SO₄ and filtered. The solvent was removed in vacuo (not dropping below 200 mbar) at 30°C and provided the title compound (4.4 g, 38% yield) as a yellow liquid.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 4.00 - 3.87 (1 H, m) 3.50 - 3.40 (m, 3H), 3.30 3.20 (m, 1H), 2.64 (d, 1H), 1.61 (m, 2H), 1.12 (d,3H), 0.95 (t, 3H)

Préparation of N'-r5-bromo-2-methyl-6-[(1 S)-1-methvl-2-propoxy-ethoxv1-3-pvridvll-Nethyl-N-methyl-formamidine

To a stirring suspension of N'-(5-bromo-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-Nmethyl-formamidine (0.75 g, 2.8 mmol) in THF (15 mL), (2R)-1-propoxypropan-2-ol (0.36 g, 3 mmol, 1.1 equiv) and triphenylphosphine (0.80 g, 3 mmol, 1.1 equiv) were added at room température under inert atmosphère (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.60 mL, 3 mmol, 1.1 equiv) was added dropwise over 10 minutes while keeping the température below 40°C. The reaction mixture was stirred for 24h at room température. After this time, LC-MS indicated that the starting material had been nearly consumed and the reaction mixture was quenched with water (40 mL). The water phase was extracted with ethyl acetate (3x50 mL). The organic layer was dried over anhydrous Na₂SO₄and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by préparative reverse phase chromatography to afford the desired (0.10 g, 10% yield).

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 - 7.30 (broad s, 1H), 7.24 (s, 1H), 5.40 - 5.30 (m, 1 H), 3.70 - 3.60 (m, 1 H), 3.55 - 3.45 (m, 3H), 3.45 - 3.30 (broad m, 2H), 3.00 (s, 3H),

2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Préparation of N'-f5-bromo-2-methvl-6-[(1 /?)-1-methvl-2-propoxv-ethoxv1-3-pyridvl1-Nethyl-N-methyl-formamidine

To an ice-bath cooled solution of (2R)-1-propoxypropan-2-ol (0.103 g, 0.88 mmol,1.2 equiv) in DMF (4 mL) under inert atmosphère (Ar), potassium tertbutoxide (0.25 g, 2.19 mmol, 3 equiv) and triphenylphosphine (0.14 g, 0.55 mmol, 1.5 equiv) was added. The reaction mixture was stirred for 20 minutes before N'-(5-bromo-6-fluoro-2-methyl-3-pyridyl)N-ethyl-N-methyl-formamidine (0.20 g, 0.73 mmol) was added. The reaction mixture was stirred for 4h at room température and was quenched with water upon completion. The water phase was extracted with ethyl acetate (2x50 mL). The organic layers were combined, washed with water (3x50 mL), dried over anhydrous Na₂SC>4, and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by préparative reverse phase chromatography to afford the desired compound (0.130 g, 13% yield).

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 - 7.30 (broad s, 1H), 7.24 (s, 1H), 5.40 - 5.30 (m, 1 H), 3.70 - 3.60 (m, 1 H), 3.55 - 3.45 (m, 3H), 3.50 - 3.30 (broad m, 2H), 3.00 (s, 3H),

2.35 (s, 3H), 1.65 - 1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Préparation of N'-r5-bromo-2-methyl-6-(1-methvl-2-propoxv-ethoxv)-3-pyridvl1-N-ethvlN-methyl-formamidine

OH

HOTo a stirring suspension of N'-(5-bromo-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-Nmethyl-formamidine (6.0 g, 22.05 mmol) in THF (30 mL), 1-propoxypropan-2-ol (3.53 mL, 26.46 mmol, 1.2 equiv) and triphenylphosphine (6.94 g, 26.46 mmol, 1.2 equiv) were added at room température under inert atmosphère (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (5.21 mL, 26.46 mmol, 1.2 equiv) was added dropwise over 10 minutes while keeping the température below 40°C. The reaction mixture was stirred for 1.5 h at room température. After this time, LC-MS indicated that the starting material had been consumed and the reaction mixture was concentrated in vacuo. Heptane was added to the residue and the mixture was cooled with an ice bath to recrystallize triphenylphosphine oxide. The brown residue was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate, v/v = 90/10 to 4/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (7.80 g, 95% yield) as a light yellow oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 - 7.30 (broad s, 1 H), 7.24 (s, 1 H), 5.40 - 5.30 (m, 1 H), 3.70 - 3.60 (m, 1 H), 3.55 - 3.45 (m, 3H), 3.45 - 3.30 (broad m, 2H), 3.00 (s, 3H),

2.35 (s, 3H), 1.65 - 1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Préparation of N'-r5-cvano-2-methvl-6-(1-methvl-2-propoxv-ethoxv)-3-pyridvll-N-ethvlN-methyl-formamidine

Br

-29To a stirred solution of N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]N-ethyl-N-methyl-formamidine (0.25 g, 0.67 mmol) in DMF (1 mL) under inert atmosphère (Ar), zinc cyanide (0.087 g, 0.74 mmol, 1.1 equiv) and tetrakis(triphenylphosphine)palladium (0.23 g, 0.20 mmol, 0.3 equiv) were added and the reaction mixture was stirred for 18h under heating at 120°C. After this time, TLC and LC-MS indicated that the starting material was consumed and the reaction mixture was allowed to reach room température before quenching with water. The water phase was extracted with ethyl acetate (2x30 mL). The organic layer was washed with brine (3x50 mL), dried over anhydrous Na₂SO₄ and fîltered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate, v/v = 90/10 to 70/30). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.207 g, 97% yield) as a colorless oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 - 7.30 (broad s, 1H), 7.20 (s, 1H), 5.50 - 5.40 (m, 1 H), 3.70 - 3.60 (m, 1 H), 3.55 - 3.40 (m, 3H), 3.45 - 3.30 (broad m, 2H), 3.00 (s, 3H), 2.40 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.90 (t, 3H).

Préparation of 3-chloro-6-methvl-5-nitro-pyridin-2-ol

To an ice-bath cooled suspension of 6-methyl-5-nitro-pyridin-2-ol (0.50 g, 3.24 mmol) in acetonitrile (5 mL) under inert atmosphère (Ar), was added N-chlorosuccinimide (0.43 g, 3.24 mmol, 1 equiv) portionwise. The reaction mixture was stirred for20h under heating at 67°C. At this time, LC-MS indicated that the starting material was consumed and the reaction mixture was cooled to 0°C and the precipitate was fîltered to give the title compound (0.36g, 48% yield) as a beige-white solid.

¹H NMR (400 MHz, CD₃OD): δ (ppm) 8.5 (s, 1H), 2.7 (s, 3H).

Préparation of 5-chloro-2-methvl-3-nitro-6-(o-tolvlmethoxv)pyridine

To a stirred solution of o-tolylmethanol (3.99 g, 32.1 mmol, 1.2 equiv) in THF (100 mL),

3-chloro-6-methyl-5-nitro-pyridin-2-ol (5.30g, 26.7 mmol) and triphenylphosphine (8.41 g,

-3032.1 mmol, 1.2 equiv) were added at room température under inert atmosphère (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (6.58 mL, 33.4 mmol, 1.25 equiv) was added dropwise over 10 minutes while keeping the température below 40°C. The reaction mixture was stirred for 16 h at room température. At this time, LC-MS indicated that the starting material was consumed and the reaction mixture was quenched with water (20 mL). A precipitate formed and was filtered and washed with a mixture of methanol/water (v/v = 5/1 ), suspended in toluene and concentrated in vacuo to give the title compound (5.28g, 47% yield) as a yellow solid.

¹H NMR (400 MHz, DMSO): δ (ppm) = 8.60 (s, 1H), 7.45 (d, 1H), 7.30-7.20 (m, 3H), 5.50 (s, 2H), 2.70 (s, 3H), 2.35 (s, 3H).

Préparation of 6-benzvloxv-5-chloro-2-methyl-Dvridin-3-amine

A solution of 2-benzyloxy-3-chloro-6-methyl-5-nitro-pyridine (250 mg, 0.90 mmol), 10% platinum on carbon (12 mg, 0.062 mmol) in THF (5 mL) was placed under hydrogen (3 equiv., 2.70 mmol) pressure of 3 bar and the reaction was stirred for 18 h at 37°C. After this time, TLC indicated that the starting material has been consumed. The reaction mixture was filtered and the residue was washed with methanol. The organic layer was concentrated to give the title compound (0.216 g, 97% yield) which was used without further purification.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.50 - 7.45 (m, 1H), 7.25 - 7.15 (m, 3H), 7.0 (s, 1H), 5.35 (s, 2H), 3.40-3.10 (broad s, 2H), 2.42 (s, 3H), 2.30 (s, 3H).

Préparation of N'-(5-chloro-6-hvdroxv-2-methvl-3-pyridvl)-N-ethvl-N-methvlformamidine

To a solution of N-ethyl-N-methyl-formamide (1.29 g, 14.76 mmol, 1.1 equiv) in dichloromethane (70 mL) was added phosphorus oxychloride (1.38 mL, 14.76 mmol, 1.1 equiv). The solution was stirred for 1.5 h at room température and then a solution of 5-chloro2-methyl-6-(o-tolylmethoxy)pyridin-3-amine (3.52 g, 13.41 mmol) in dichloromethane (10 mL)

-31 was added dropwise. After being stirred for 20 h at room température the solid was filtered and washed with dichloromethane. The residue was purified by combiflash column chromatography (silica gel, dichloromethane / methanol + 5% triethylamine v/v = 10/0 to 9/1). Fractions containing the compound were collected and concentrated in vacuo to give the title compound (2.52 g, 82 % yield) as a yellow solid.

¹H NMR (400 MHz, CD₃OD): δ (ppm) 7.65 - 7.50 (broad s, 1 H), 3.50 - 3.30 (broad s, 1H), 3.0 (s, 2H), 2.25 (s, 3H), 1.35 (m, 3H), 1.25 (m, 3H).

Préparation of N'-f5-chloro-2-methvl-6-(1-methvl-2-propoxv-ethoxy)-3-pyridvll-N-ethvlN-methyl-formamidine

To a stirred solution of N'-(5-chloro-6-hydroxy-2-methyl-3-pyridyl)-N-ethyl-N-methylformamidine (0.25 g, 1.10 mmol) in THF (10 mL), 1-propoxypropan-2-ol (0.14 g, 1.21 mmol, 1.1 equiv) and triphenylphosphine (0.32 g, 1.21 mmol, 1.1 equiv) were added at room température under inert atmosphère (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.24 mL, 1.21 mmol, 1.1 equiv) was added dropwise over 10 minutes while keeping the température below 40°C. The reaction mixture was stirred for 16h under heating at 60°C. After this time, triphenylphosphine (0.15 g, 0.55 mmol, 0.5 equiv) and DIAD (diisopropyl diazodicarboxylate) (0.11 mL, 0.55 mmol, 0.5 equiv) were added again and the reaction mixture wasfurther stirred for 9 h. The reaction mixture was allowed to reach room température before quenching with water (10 mL) and 2M NaOH aqueous solution (2 mL). The water phase was extracted with ethyl acetate (1x25 mL). The organic layers were combined, dried over anhydrous Na₂SO₄ and filtered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate, v/v = 9/1 to 1/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.19 g, 53% yield) as an yellow oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 - 7.30 (broad s, 1H), 7.05 (s, 1H), 5.40-5.30 (m, 1 H), 3.70 - 3.60 (m, 1H), 3.55 - 3.40 (m, 3H), 3.45 - 3.30 (broad m, 2H), 3.00 (s, 3H),

2.35 (s, 3H), 1.65-1.50 (m, 2H), 1.35 (m, 3H), 1.20 (m, 3H), 0.85 (t, 3H).

Preparation of 5-bromo-2-methvl-6-(1-methyl-2-propoxy-ethoxv)-3-nitro-pyridine

To a stirred suspension of 3-bromo-6-methyl-5-nitro-pyridin-2-ol (0.23 g, 1 mmol) in THF (0.08 mL), 1-propoxypropan-2-ol (0.15 g, 1.2 mmol, 1.2 equiv) and triphenylphosphine (0.32 g, 1.2 mmol, 1.2 equiv) were added at room température under inert atmosphère (Ar). To this mixture, DIAD (diisopropyl diazodicarboxylate) (0.24 mL, 1.2 mmol, 1.2 equiv) was added dropwise over 10 minutes while keeping the température below 40°C. The reaction mixture was stirred for 12h under heating at 65°C. After this time, LC-MS still showed remaining starting material but the reaction mixture was allowed to reach room température and the solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ triethylamine, v/v = 95/5). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.20 g, 60% yield) as a beige oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 8.45 (s, 1 H), 5.50 - 5.40 (m, 1 H), 3.65 - 3.60 (m, 1 H), 3.65 - 3.50 (m, 1 H), 3.50 - 3.35 (m, 2H), 2.70 (s, 3H), 1.50 (m, 2H), 1.30 (m, 3H), 0.80 (t, 3H).

Préparation of 5-bromo-2-methvl-6-(1-methyl-2-propoxv-ethoxv)pyridin-3-amine

To a stirred suspension of 5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-nitropyridine (0.47 g, 1.41 mmol) in éthanol (10 mL) were added ammonium chloride (0.15 g, 2.82 mmol, 2 equiv), water (2.8 mL) and then iron (0.32 g, 5.64 mmol, 4 equiv). The reaction mixture was stirred for 4h under heating at 85°C. As reaction monitoring still showed a lot of remaining starting material, ammonium chloride (0.75 g, 1.41 mmol, 1 equiv) and iron (0.16 g, 2.82 mmol, 2 equiv) were added and reaction mixture was further stirred for 10h under heating at 85°C. After this time, LC-MS indicated that the starting material has been consumed and the reaction mixture was allowed to reach room température before filtering it over celite. The solvent was removed in vacuo and the residue was redissolved with ethyl acetate (15 mL). The organic phase was washed with a 2N aqueous NaOH solution (2x25 mL), dried over anhydrous Na₂SO₄ and fiitered. The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate + 10% triethylamine, v/v = 10/0 to 1/1). Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound (0.27 g, 63% yield) as an orange-brown oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm)7.10 (s, 1H), 5.25-5.15 (m, 1H), 3.65-3.60 (m,

H), 3.55 - 3.50 (m, 3H), 3.50 - 3.35 (broad m, 2H), 2.20 (s, 3H), 1.50 (m, 2H), 1.25 (m, 3H), 0.80 (t, 3H).

Préparation of N'-[5-bromo-2-methyl-6-(1 -methyl-2-propoxy-ethoxv)-3-pvridyl1-N-ethvlformamidine

Br'

NH

To a solution of N-ethylformamide (0.070 mL, 0.91 mmol, 1.1 equiv) in dichloromethane (6.6 mL) was added phosphorus oxychloride (0.085 mL, 0.91 mmol, 1.1 equiv). The solution was stirred for 1 h at room température. Then a solution of 5-bromo-2methyl-6-(1-methyl-2-propoxy-ethoxy)pyridin-3-amine (0.25 g, 0.83 mmol) in dichloromethane (3 mL) was added dropwise. The suspension was stirred for 2 h at room température then poured onto a mixture of 2N aqueous NaOH solution (25 mL) and ice. The aqueous layer was separated, extracted with dichloromethane (2x15 mL). The organic phase was washed with 2N aqueous NaOH solution (25 mL) and brine (25 mL), dried over anhydrous Na₂SO₄ and fiitered. The solvent was removed in vacuo to give a dark yellow residue, which was purified by reverse phase préparative HPLC to give the title compound (0.09 g, 29% yield) as an orange-brown oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm) 7.45 (s, 1 H), 7.25 (s, 1 H), 5.40 - 5.30 (m, 1 H), 4,70 - 4,50 (broad s, 1 H), 3.75 - 3.60 (m, 1 H), 3.55-3.45 (m, 3H), 3.50 - 3.35 (broad m, 2H), 2.30 (s, 3H), 1.60 -1.50 (m, 2H), 1,35 (m, 3H), 1.25 (m, 3H), 0.80 (t, 3H).

Préparation of N'-r5-bromo-2-methyl-6-(1 -methvl-2-propoxv-ethoxv)-3-pvridvH-Nmethyl-formamidine

To a solution of N-methyl N-ethylformamide (0.30 g, 2.37 mmol, 1.1 equiv, 80% wt.) in dichloromethane (4.0 mL) was added phosphorus oxychloride (0.20 mL, 2.2 mmol, 1.1 equiv). The solution was stirred for 1h at room température. Then a solution of 5-bromo-2methyl-6-(1-methyl-2-propoxy-ethoxy)pyridin-3-amine (0.60 g, 2.0 mmol) in dichloromethane (0.5 mL) was added dropwise. The suspension was stirred for 2h at room température, then poured onto a mixture of 2N aqueous NaOH solution (25 mL) and ice. The aqueous layer was separated, extracted with dichloromethane (2x15 mL). The organic phase was washed with 2N aqueous NaOH solution (25 mL) and brine (25 mL), dried over anhydrous Na₂SO4 and filtered. The solvent was removed in vacuo to give a dark yellow residue, which was purified by reverse phase préparative HPLC to give the title compound (0.30 g, 40% yield) as an orange oil.

¹H NMR (400 MHz, CDCI₃): δ (ppm)7.47 (broad s, 1H), 7.25 (s, 1H), 5.40-5.30 (m, 2H), 3.70-3.64 (m, 3H), 3.60-3.40 (m, 3H), 2.94 (broad s, 2H) 2.35 (d, 3H), 1.65 - 1.50 (m, 2H), 1.35 (m, 3H), 1.25 (m, 6H), 0.90 (t, 3H).

Table 67

This table gives analytical data for compounds of formula (I) prepared using techniques analogous to those above, as well as those described in WO 12/146125 (pp.370-378) and further techniques known to the person skilled in the art, for example as found in WO 08/101682 (pp.22-33).

Compound No.	Structural formula	LC-Method: Rt (min); MS-ESI (m/z; (M+H)⁺);
67.001	5- [(E)-[ethyl(methyl)amino]methyleneamino]- 6- methyl-2-(1 -methyl-2-propoxyethoxy)pyridine-3-carboxamide	Method 1 0.9 min.; 337
67.002	N'-[5-bromo-2-methyl-6-[(1 S)-1 -methyl-2propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 0.76 min.; 372
67.003	N'-[5-bromo-2-methyl-6-[(1 R)-1 -methyl-2propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 0.76 min.; 372

Compound No.	Structural formula	LC-Method: R_t (min); MS-ESI (m/z; (M+H)⁺);
67.004	5-[(E)-[ethyl(methyl)amino]methyleneamino]N,N,6-trimethyl-2-(1-methyl-2-propoxyethoxy)pyridine-3-carboxamide	Method 1 0.8 min.; 361
67.005	5-[(E)-[ethyl(methyl)amino]methyleneamino]N,6-dimethyl-2-(1-methyl-2-propoxyeth oxy )pyri din e-3-carboxam ide	Method 1 0.8 min.; 351
67.006	5- [(E)-[ethyl(methyl)amino]methyleneamino]- 6- methyl-2-(1 -methyl-2-propoxyethoxy)pyridine-3-carboxylic acid	Method 1 0.7 min.; 338
67.007	N'-[5-cyano-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 0.78 min.; 319
67.008	N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine	oil
67.009	N'-[5-(difluoromethyl)-2-methyl-6-(1-methyl-2propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 2 13.04 min.; 342
67.010	N'-[5-(difluoromethoxy)-2-methyl-6-(1-methyl- 2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-Nmethyl-formamidine	Method 1 0.85 min.; 360
67.011	N '-[2,5-d i methyl-6-( 1 -methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 0.79 min.; 308
67.012	N-ethyl-N-methyl-N'-[2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]formamidine	Method 1 0.67 min.; 294
67.013	N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 0.76 min.; 372
67.014	N'-[6-(2-allyloxy-1-methyl-ethoxy)-5-chloro-2methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.08 min.; 326
67.015	N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 1 1.11 min.; 328
67.016	N'-[6-[1-(allyloxymethyl)-2-methoxy-ethoxy]-5bromo-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.02 min.; 400
67.017	N'-[6-(2-allyloxy-1-methyl-ethoxy)-5-cyano-2methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 0.96 min.; 317
67.018	N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine	oil

Compound No.	Structural formula	LC-Method: Rt (min); MS-ESI (m/z; (M+H)⁺);
67.019	Methyl 5-[(E)- [ethyl(methyl)amino]methyleneamino]-6methyl-2-(1 -methyl-2-propoxyethoxy)pyridine-3-carboxylate	Method 1 0.80 min.; 352
67.020	N'-[5-cyano-2-methyl-6-[1-methyl-2-[3(trifluoromethyl)phenoxy]ethoxy]-3-pyridyl]-Nethyl-N-methyl-formamidine	Method 3 1.33 min.; 422
67.021	N'-[6-[2-(4-chlorophenoxy)-1-methyl-ethoxy]- 5-cyano-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.29 min.; 387
67.022	N'-[5-cyano-2-methyl-6-(1-methyl-2-phenoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.21 min.; 353
67.023	N'-[5-chloro-2-methyl-6-[1 -methyl-2-[3(trifluoromethyl)phenoxy]ethoxy]-3-pyridyl]-Nethyl-N-methyl-formamidine	Method 3 1.38 min.; 430
67.024	N'-[5-chloro-6-[2-(4-chlorophenoxy)-1-methylethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.38 min.; 396
67.025	N'-[5-chloro-2-methyl-6-(1-methyl-2-phenoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.23 min.; 362
67.026	N'-[5-bromo-6-[2-(4-chlorophenoxy)-1-methylethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.37 min.; 440
67.027	N'-[5-bromo-2-methyl-6-[1-methyl-2-[3(trifluoromethyl)phenoxy]ethoxy]-3-pyridyl]-Nethyl-N-methyl-formamidine	Method 3 1.42 min.; 474
67.028	N'-[5-bromo-2-methyl-6-(1-methyl-2-phenoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine	Method 3 1.25 min.; 406
67.029	N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-cyclopropyl-N-methylformamidine	Method 1 0.77 min.; 371
67.030	1 -(azetidin-1 -yl)-N-[5-bromo-2-methyl-6-(1 methyl-2-propoxy-ethoxy)-3pyridyljmethanimine	Method 1 0.76 min.; 385

Analytical Methods Used

Method 1 : Mass spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity:

positive or négative ions, Capillary: 3.00 kV, Cône range: 30-60 V, Extractor: 2.00 V, Source Température: 150°C, Desolvation Température: 350°C, Cône Gas Flow: 0 L/Hr, Desolvation

-37Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3,1.8 m, 30 x2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH. Gradient: 0 min 0% B, 100%A; 1.2-1,5min 100% B: Flow (ml/min) 0.85.

Method 2: Mass spectra were recorded on a Mass Spectrometerfrom Shimadzu (SQD orZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or négative ions, Capillary: 1.5 kV, Cône range: unknown, Extractor: 5.00 V, Source Température: 200°C, Desolvation Température: 250°C, Cône Gas Flow: 90 L/Hr, Desolvation Gas Flow: 90 L/Hr, Mass range: 50 to 900 Da) and an SPD-20Afrom LC from Shimadzu: Solvent degasser, binary pump, heated column compartment and ultraviolet detector. Column: Diamonsil C18 (2) 5u 150*4.6 mm, Temp: 40 °C, SPD-20A Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 0.1 % F₃CCOOH, B= Acetonitrile + 0.1 % F3CCOOH; Gradient: 0 min 10% B, 90% A; 15min 100% B; Flow 1.00 (ml/min)

Method 3: Mass spectra were recorded on a ZQ2000 Mass Spectrometerfrom Waters (Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive ions, Capillary (kV) 3.5, Cône (V) 60.00, Extractor (V) 3.00, Source Température (°C) 150, Desolvation Température (°C) 350, Cône Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 800, Mass range: 140 to 800 Da) DAD Wavelength range (nm): 210 to 400, Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internai diameter of column: 2.1 mm; Particle Size: 1.8 micron; Température: 60°C. Solvent Gradient: A = water + 10% MeOH + 0.1 % HCOOH, B= Acetonitrile + 0.1 % HCOOH. Gradient: 0 min 0% B, 100% A; 2.5-2.8 min 100% B; 0% A; 3.0 min 100% A, 0% B: Flow (ml/min) 0.85.

Biological examples

Blumeria graminis f. sp. tritici (Erysiphe graminisf. sp. tritici) / wheat / leaf dise preventative (Powdery mildew on wheat)

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

-38The following compounds gave at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:

Q.002, Q.003, Q.007, Q.008, Q.009, Q.010, Q.011, Q.013, Q.014, Q.015, Q.016, Q.017, Q.018, Q.020, Q.021, Q.022, Q.023, Q.024, Q.025, Q.026, Q.027, Q.028, Q.029, Q.030.

Puccinia recondîta f. sp. fr/tfc/7 wheat / leaf dise preventative (brown rust)

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

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

Q.002, Q.003, Q.007, Q.008, Q.009, Q.010, Q.011, Q.013, Q.014, Q.015, Q.016, Q.017, Q.018, Q.020, Q.021, Q.022, Q.023, Q.024, Q.025, Q.026, Q.028, Q.029, Q.030..

Puccinia recondîta f. sp. fr/T/c/Z wheat / leaf dise curative (Brown rust)

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

The following compounds gave at200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development:

Q.002, Q.003, Q.007, Q.008, Q.009, Q.010, Q.011, Q.012, Q.013, Q.014, Q.015, Q.016, Q.017, Q.018, Q.019, Q.020, Q.021, Q.022, Q.023, Q.024, Q.025, Q.026, Q.027, Q.028, Q.029, Q.030..

Phakopsora pachyrhizi on sovbean, préventive treatment

-39The compound activity was tested under 1 day préventive conditions. Soybean plants with a fully enfolded first trifoliate leaf were sprayed with a track sprayer and 50 l/ha spray volume with the test compounds, either solo or in tankmix as shown in the table below. 1 day after application leaf dises were eut from the first trifoliate leaf and placed in multiwell 5 plates on water-agar. 5 leaf dises per treatment where infested with spores of a triazole tolérant soybean rust strain. The multiwell plates where sealed and placed in an incubator 48 h in darkness and 12 h light/dark cycle afterwards. Rust infestation on leaf dises was evaluated visually 11 days after application and average activity calculated in relation to disease severity on untreated check leaf dises.

Q.002, Q.003, Q.007, Q.008, Q.009, Q.010, Q.011, Q.012, Q.013, Q.014, Q.015, Q.016, Q.017, Q.018, Q.019 Q.020, Q.023, Q.024, Q.025, Q.026, Q.027, Q.028, Q.029, 15 Q.030..

Claims

WHAT IS CLAIMED IS wherein

R¹ représente hydrogen, halogen, cyano, OH, NH₂, CrC₄ alkyl, C₃-C₆ cycloalkyl, NH(CrC₄ alkyl), N(C_rC₄ alkyl)₂, CO(C_rC₄ alkyl), CO₂(C_rC₄ alkyl), CO₂H, CONH(C_rC₄alkyl), CON(C₁-C₄ alkyl)₂, SO₂NH(C_rC₄ alkyl), SO₂N(Ci-C₄ alkyl)₂, C_rC₄ haloalkyl, C_rC₄alkoxy, Ci-C₄ haloalkoxy, Ci-C₄ alkyl-CrC₄ alkoxy or C₂-C₄ alkynyl;

R² représente C3-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, R⁷ or-Ci-C2alkyl-R⁷, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C-|-C₄ alkyl, C-|-C₄ haloalkyl and C_rC₄ haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, CrC₄ alkyl or C₃-C₆cycloalkyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 3-6membered saturated cyclic group;

R⁵ représente H, CrC₄ alkyl or C_rC₄ haloalkyl;

R⁶ represents Ci-C₄alkyl, C_rC₄ alkoxy, Ci-C₄ haloalkyl or C_rC₄ haloalkoxy;

R⁷ represents a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated orfully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it being possible for the three- to ten-membered ring system itself to be optionally substituted by one or more groups independently selected from the group consisting halogen, Ci-C₄ haloalkyl, C_rC₄ alkoxy and Ci-C₄ haloalkoxy;

and tautomers/isomers/enantiomers/salts and N-oxides of these compounds.
2. A compound of formula (I) according to claim 1 wherein

R¹ represents hydrogen, halogen, cyano, OH, NH₂, C_rC₄ alkyl, C₃-C₆ cycloalkyl,

NH(Ci-C₄ alkyl), N(C_rC₄ alkyl)₂, CO(C_rC₄ alkyl), CO₂(C_rC₄ alkyl), CO₂H, CONH(CrC₄

-41 alkyl), CON(C₁-C₄ alkyl)₂, SO₂NH(Ci-C₄ alkyl), SO₂N(C!-C₄ alkyl)₂, C_rC₄ haloalkyl, C_rC₄alkoxy, C_rC₄ haloalkoxy, or C₂-C₄.alkynyl;

R² représente C₃-C_Balkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃C₅cycloalkenyl, -CrC₂alkyl-C₃-C₆cycloalkyl, -CrC2alkyl-C₃-C₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, C_rC₂alkyl, CrC₂ haloalkyl, C_rC₂ alkoxy and C-|-C₂ haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, C_rC₄ alkyl or C₃-C₅cycloalkyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 3-6membered saturated cyclic group;

R⁵ represents H, Ci-C₄ alkyl or C_rC₄ haloalkyl;

R⁶ represents CrC₄ alkyl, CrC₄ alkoxy, Ci-C₄ haloalkyl or C_rC₄ haloalkoxy.
3. A compound of formula (I) according to either claim 1 or claim 2 wherein

R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NH(Cr C₂ alkyl), N(C_rC₂ alkyl)₂, CO(C_rC₂ alkyl), CO₂(C_rC₂ alkyl), CO₂H, CONH(C_rC₂ alkyl), CON(CrC₂ alkyl)₂, SO₂NH(C₁-C₂ alkyl), SO₂N(Ci-C₂ alkyl)₂, CrC₄fluoroalkyl, CrC₄ alkoxy, Ci-C₂ haloalkoxy or C₂-C₄ alkynyl;

R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₃C₅cycloalkenyl, -CrC^alkyl-Cs-Cecycloalkyl, -Ci-C₂alkyl-C₃-C₆cycloalkenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting halogen, CrC₂alkyl, C-i-C₂ haloalkyl and C-|-C₂ haloalkoxy;

R³ and R⁴ independently of each other represent hydrogen, C-t-C₃ alkyl or C₃-C₅cycloalkyl; or

R³ and R⁴ together with the nitrogen atom to which they are attached form a 5membered saturated cyclic group;

R⁵ represents H or C-i-C₄ alkyl;

R⁶ represents Ci-C₄ alkyl, CrC₄ alkoxy, C_rC₄ haloalkyl or C_rC₄ haloalkoxy.
4. A compound of formula (I) according to any preceding claim wherein

R¹ represents hydrogen, halogen, cyano, OH, NH₂, methyl, ethyl, cyclopropyl, NHMe, NMe₂, COMe, CO₂Me, CO₂H, CONHMe, CONMe₂, SO₂NHMe, SO₂NMe₂, CHF₂, CF₃, OMe, OCHF₂ or acetylenyl;

R² represents C₃-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyi, C₃C₅cycloalkenyl, -Ci-C₂alkyl-C₃-C₆cycloalkyl, -Ci-C₂alkyl-C₃-C₆cycloalkenyl which may be

-42optionally substituted by one or more groups independently selected from the group consisting fluoro, C1-C2alkyl, C_rC₂ fluoroalkyl and Ci-C₂fluoroalkoxy;

R³ and R⁴ independently of each other represent hydrogen, methyl, ethyl, isopropyl or cyclopropyl; or
5 R³ and R⁴ together with the nitrogen atom to which they are attached form a 5membered saturated cyclic group;

R⁵ represents H or methyl;

R⁶ represents CrC₄ alkyl or CrC₄ alkoxy.

10 5. A compound of formula (I) according to any preceding claim wherein

Ri represents hydrogen, halogen, cyano, methyl, ethyl, cyclopropyl, CHF₂, CF₃, OMe, orOCHF₂;

R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl,

15 cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl -CH₂-cyclopropyl, -CH₂-cyclobutyl, -CH₂cyclopentyl, and -CH₂-cyclopentenyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro, methyl and difluoromethoxy;

R³ is hydrogen or methyl;

20 R⁴ is methyl or ethyl;

R⁵ represents H or methyl;

R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl, cyclopentyl, methoxy or ethoxy.

25
6. A compound of formula (I) according any preceding claim wherein

R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy;

30 R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ represents methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, cyclobutyl, cyclopentyl, methoxy or ethoxy.
7. A compound of formula (I) according any preceding claim wherein

R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyi, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy;

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ represents methyl, ethyl, n-propyl, iso-propyi, cyclopropyl, cyclobutyl or cyclopentyl.
8. A compound of formula (I) according any preceding claim wherein

R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyi, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy;

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ represents methyl, ethyl, n-propyl or iso-propyi.
9. A compound of formula (I) according any preceding claim wherein

R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyi, n-butyl, iso-butyl, sec-butyl, each of which may be optionally substituted by one or more groups independently selected from the group consisting fluoro and difluoromethoxy;

R³ represents hydrogen or methyl;

R⁴ is ethyl;

R⁵ is hydrogen or methyl;

R⁶ is methyl.
10. A compound of formula (I) according any preceding claim wherein

R¹ represents hydrogen, Cl, Br, methyl, CHF₂ or cyano;

R₂ is n-propyl, iso-propyi, n-butyl, iso-butyl, sec-butyl or cyclopropyl;

R³ represents hydrogen or methyl;

R⁴ is ethyl;

-44R⁵ is hydrogen;

R⁶ is methyl.
11. A composition comprising a fungicidally effective amount of a compound of formula

5 (I) as defined in any one of claims 1 to 10, optionally comprising at least one additional active ingrédient.
12. A method of controlling or preventing phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus

10 thereof or propagation material thereof a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 10.