Microbiocidal Pyrazole Derivatives

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

Certain compounds for use as fungicides are described in WO 2007/014290, WO 2008/013622, WO 2008/013925, WO 2008/091580, WO 2008/091594 and WO

2009/055514.

wherein,

G ¹ and G ² are independently O or S;

T is CR ¹⁷ or N;

Y ¹ and Y ² are independently CR ¹⁸ or N;

n is 1 or 2;

p is 1 or 2, providing that when n is 2, p is 1 ;

R ¹ and R ² each independently are CrC ₄ alkyl, or Ci-C ₄ haloalkyl or C ₃ -C ₅ cycloalkyl;

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, halogen, cyano, CrC ₄ alkyl, d- C ₄ alkoxy, Ci-C ₄ haloalkyl, C ₃ -C ₅ cycloalkyl or Ci-C ₄ alkylthio;

R ⁹ , R ¹⁴ and R ¹⁵ each independently are hydrogen, Ci-C ₄ alkyl, Ci-C ₄ haloalkyl or C ₃ - C ₅ cycloalkyl;

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen, halogen, cyano, CrC ₄ alkyl, d- C ₄ alkoxy, CrC ₄ haloalkyl, Ci-C ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy or C ₂ -C ₄ alkynyloxy;

R ¹⁶ is Ci-C ₄ alkyl, Ci-C ₄ haloalkyl or C ₃ -C ₅ cycloalkyl, formyl, CrC ₄ alkylcarbonyl, d- C ₄ alkoxycarbonyl, CrC ₄ haloalkylcarbonyl, C ₃ -C ₅ cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, CrC ₄ alkylsulfonyl, CrC ₄ haloalkylsulfonyl, C ₃ -C ₅ cycloalkylsulfonyl, arylsulfonyl or heteroarylsulfonyl; or

R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached, and, or R ¹⁵ and R ¹⁶ together with the nitrogen atom to which they are attached, independently form a saturated or partially unsaturated five- to seven-membered alicyclic ring, optionally comprising one or two ring members selected from O, N or S, said ring being optionally substituted by halogen, cyano, Ci-C ₄ alkyl, Ci-C ₄ alkoxy or Ci-C ₄ haloalkyl;

R ¹⁷ is hydrogen, halogen or hydroxyl;

R ¹⁸ is hydrogen, halogen or cyano;

or a salt or a N-oxide thereof.

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

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

Alkyl substituents may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso- propyl, iso-butyl, sec-butyl, tert-butyl, iso-amyl or pivaloyl.

Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl and allyl. The alkenyl groups are preferably C ₂ -C ₆ , more preferably C ₂ -C ₄ and most preferably C ₂ -C ₃ alkenyl groups.

Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl. The alkynyl groups are preferably C ₂ -C ₆ , more preferably C ₂ -C ₄ and most preferably C ₂ -C ₃ alkynyl groups.

Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH ₂ CI, CHCI ₂ , CCI ₃ , CH ₂ F, CHF ₂ , CF ₃ , CF ₃ CH ₂ , CH ₃ CF ₂ , CF ₃ CF ₂ or CCI ₃ CCI ₂ .

Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2- dichloro-2-fluoro-vinyl.

Haloalkynyl groups are alkynyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 1 -chloro-prop-2-ynyl. Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 - methylpropoxy and 2-methylpropoxy.

Cyano means a -CN group.

Amino means an NH ₂ group.

Hydroxyl or hydroxy stands for a -OH group.

Aryl means a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.

Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Monocyclic and bicyclic aromatic ring systems are preferred, monocyclic ring systems are more preferred. For example, monocyclic heteoraryl may be a 5- to 7-membered aromatic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and sulfur. Bicyclic heteroaryl may be a 9- to 1 1 -membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl,

benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, imiazothiazoyl, quinolinyl, quinoxalinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl, preferably pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furanyl, thienyl thiazolyl or thiadiazolyl. Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms. A link to a heteroaryl group can be via a carbon atom or via a nitrogen atom.

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

In each case, the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form. N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N- oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991 .

The following list provides definitions, including preferred definitions, for substituents and p with reference to compounds of formula I and other compounds of the invention carrying the same substituents. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

G ¹ and G ² are independently O or S.

G ¹ is preferably O.

G ² is preferably S.

T is CR ¹⁷ or N, preferably CH or N, more preferably CH.

Y ¹ and Y ² are independently CR ¹⁸ or N.

Y ¹ is preferably CH or N, more preferably N.

Y ² is preferably CH or N; more preferably CH.

n is 1 or 2, preferably 2.

p is 1 or 2, providing that when n is 2, p is 1 , preferably p is 1 .

Preferably, p is 1 and n is 2.

R ¹ and R ² each independently are CrC ₄ alkyl, d-C ₄ haloalkyl or C ₃ -C ₅ cycloalkyl.

Preferably R ¹ and R ² are each independently methyl or halomethyl, more preferably methyl, difluoromethyl or trifluoromethyl.

Preferably R ¹ is difluoromethyl or trifluoromethyl. Preferably R ² is methyl or

difluoromethyl. In one group of compounds R ¹ is trifluoromethyl and R ² is methyl. In another group of compounds R ¹ and R ² are both difluoromethyl.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, halogen, cyano, C C ₄ alkyl, CrC ₄ alkoxy, CrC ₄ haloalkyl, C ₃ -C ₅ cycloalkyl or CrC ₄ alkylthio; preferably hydrogen, halogen, methyl, halomethyl or methylthio, more preferably hydrogen or methyl, even more preferably hydrogen.

R ⁹ , R ¹⁴ and R ¹⁵ each independently are hydrogen, CrC ₄ alkyl, CrC ₄ haloalkyl or C ₃ -

C ₅ cycloalkyl; preferably hydrogen, CrC ₄ alkyl or C ₃ -C ₅ cycloalkyl; more preferably hydrogen or CrC ₄ alkyl, even more preferably hydrogen or methyl.

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen, halogen, cyano, CrC ₄ alkyl, d- C ₄ alkoxy, CrC ₄ haloalkyl, CrC ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy or C ₂ -C ₄ alkynyloxy; preferably hydrogen, halogen, CrC ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy or C ₂ -C ₄ alkynyloxy; more preferably hydrogen, halogen or C ₂ -C ₄ alkynyloxy; most preferably hydrogen or fluoro.

R ¹⁶ is CrC ₄ alkyl, CrC ₄ haloalkyl, C ₃ -C ₅ cycloalkyl, formyl, CrC ₄ alkylcarbonyl, d- C ₄ alkoxycarbonyl, CrC ₄ haloalkylcarbonyl, C ₃ -C ₅ cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, CrC ₄ alkylsulfonyl, CrC ₄ haloalkylsulfonyl, C ₃ -C ₅ cycloalkylsulfonyl, arylsulfonyl or heteroarylsulfonyl.

Preferably R ¹⁶ is CrC ₄ alkylcarbonyl, CrC ₄ alkoxycarbonyl, Ci-C ₄ haloalkylcarbonyl, C ₃ - C ₅ cycloalkylcarbonyl, CrC ₄ alkylsulfonyl, CrC ₄ haloalkylsulfonyl or arylsulfonyl; more preferably CrC ₄ alkylcarbonyl, C ₃ -C ₅ cycloalkylcarbonyl, Ci-C ₄ alkylsulfonyl or d- C ₄ haloalkylsulfonyl; even more preferably CrC ₄ alkylcarbonyl or CrC ₄ alkylsulfonyl.

R ¹⁷ is hydrogen, halogen or hydroxyl; preferably hydrogen or hydroxyl, more preferably hydrogen.

R ¹⁸ is hydrogen, halogen or cyano; preferably hydrogen or cyano, more preferably hydrogen.

Preferably the compound of formula I is a compound wherein:

G ¹ is O

G ² is S;

T is CH or N;

Y ¹ and Y ² are independently CH or N;

n is 1 or 2;

p is 1 or 2, providing that when n is 2, p is 1 ;

R ¹ and R ² each independently are methyl or halomethyl;

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, halogen, cyano, CrC ₄ alkyl, d- C ₄ alkoxy, CrC ₄ haloalkyl, C ₃ -C ₅ cycloalkyl or CrC ₄ alkylthio;

R ⁹ , R ¹⁴ and R ¹⁵ each independently are hydrogen, CrC ₄ alkyl, CrC ₄ haloalkyl or C ₃ - C ₅ cycloalkyl;

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen, halogen, cyano, CrC ₄ alkyl, d- C ₄ alkoxy, CrC ₄ haloalkyl, CrC ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy or C ₂ -C ₄ alkynyloxy;

R ¹⁶ is CrC ₄ alkyl, CrC ₄ haloalkyl or C ₃ -C ₅ cycloalkyl, formyl, CrC ₄ alkylcarbonyl, d- dalkoxycarbonyl, d-dhaloalkylcarbonyl, d-dcycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, d-dcycloalkylsulfonyl, arylsulfonyl or heteroarylsulfonyl; or

R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached,

and, or R ¹⁵ and R ¹⁶ together with the nitrogen atom to which they are attached,

independently form a saturated or partially unsaturated five- to seven-membered alicyclic ring, optionally comprising one or two ring members selected from O, N, S or a carbonyl group, said ring being optionally substituted by halogen, cyano, d-dalkyl, d-dalkoxy or d-dhaloalkyl;

R ¹⁷ is hydrogen, halogen or hydroxyl;

R ¹⁸ is hydrogen, halogen or cyano;

or a salt or a N-oxide thereof.

Preferably the compound of formula I is a compound wherein: G ¹ is O

G ² is S;

T is CH or N;

Y ¹ and Y ² are independently CH or N;

n is 1 or 2;

p is 1 or 2, providing that when n is 2, p is 1 ;

R ¹ and R ² each independently are methyl or halomethyl;

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, halogen, methyl, halomethyl or methylthio;

R ⁹ , R ¹⁴ and R ¹⁵ each independently are hydrogen, d-C ₄ alkyl or C ₃ -C ₅ cycloalkyl;

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen, halogen, CrC ₄ haloalkoxy, C ₂ - C ₄ alkenyloxy or C ₂ -C ₄ alkynyloxy;

R ¹⁶ is CrC ₄ alkylcarbonyl, CrC ₄ alkoxycarbonyl, CrC ₄ haloalkylcarbonyl, C ₃ - C ₅ cycloalkylcarbonyl, Ci-C ₄ alkylsulfonyl, CrC ₄ haloalkylsulfonyl or arylsulfonyl;

R ¹⁷ is hydrogen, halogen or hydroxyl;

R ¹⁸ is hydrogen, halogen or cyano;

or a salt or a N-oxide thereof.

Preferably the compound of formula I is a compound wherein:

G ¹ is O

G ² is S;

T is CH or N;

Y ¹ and Y ² are independently CH or N;

n is 1 or 2;

p is 1 or 2, providing that when n is 2, p is 1 ;

R ¹ and R ² each independently are methyl or halomethyl;

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen or methyl;

R ⁹ , R ¹⁴ and R ¹⁵ each independently are hydrogen or CrC ₄ alkyl;

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen, halogen or C ₂ -C ₄ alkynyloxy;

R ¹⁷ is hydrogen, halogen or hydroxyl;

R ¹⁸ is hydrogen, halogen or cyano;

Preferably the compound of formula I is a compound wherein:

G ¹ is O

G ² is S;

T is CH or N;

Y ¹ and Y ² are independently CH or N;

n is 1 or 2;

p is 1 or 2, providing that when n is 2, p is 1 ;

R ¹ and R ² each independently are methyl, difluoromethyl or trifluoromethyl; R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen;

R , R and R each independently are hydrogen or methyl;

R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently are hydrogen or fluoro;

R ¹⁶ is CrC ₄ alkylcarbonyl or Ci-C ₄ alkylsulfonyl;

R ¹⁷ is hydrogen or hydroxyl;

R ¹⁸ is hydrogen or cyano;

or a salt or a N-oxide thereof.

Preferably the compound of formula I is a compound wherein G ¹ is O, G ² is S, T is CH, Y ¹ is N, and Y ² is CH.

Preferably the compound of formula I is a compound wherein R ¹ and R ² each independently are methyl, difluoromethyl or trifluoromethyl and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, or methyl, and preferably hydrogen.

For the avoidance of doubt, when n is 1 and p is 1 compounds of formula I have the formula according to formula l-a:

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ and Y ² have the definitions as described for formula I.

When n is 2 and p is 1 compounds of formula I have the formula according to formula-b:

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ and Y ² have the definitions as described for formula I.

When n is 1 and p is 2, compounds of formula I have the formula according to formula l-c:

in which R\ R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ and Y ² have the definitions as described for formula I.

The invention also relates to compounds of formula l-a, formula l-b and formula l-c as shown above.

in which R\ R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ and Y ² have the definitions as described for formula I. Preferred definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ and Y ² are as defined for formula I.

in which R , R , R , R ⁴ , R , R ^b , R ⁷ , R ⁸ , R ⁹ , R ^1U , R , R , R , R , R , R ^1b and T have the definitions as described for formula I. Preferred definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and T are as defined for formula I.

The invention also relates to compounds of formula l-f:

wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p have the definition as described for formula I. Preferred definitions of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I.

in which R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p have the definitions as described for formula I. Preferred definitions of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I.

in which R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p have the definitions as described for formula I. Preferred definitions of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I.

The invention includes compounds of formula II:

wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for a compound of formula I. These compounds, including salts and N-oxides thereof, are useful as intermediates in the synthesis of compounds of formula I. Preferred definitions of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I.

wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for a compound of formula I and E is a protecting group, such as Ci-C ₄ alkylcarbonyl, benzyl or d-C ₄ alkoxycarbonyl, in particular acetyl, benzyl or tert- butoxycarbonyl. These compounds, including salts and N-oxides thereof, are useful as intermediates in the synthesis of compounds of formula I. Preferred definitions of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I.

Compounds of the present invention can be made as shown in the following schemes.

The compounds of formula I, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ¹ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein R ¹ , R ² and G ¹ are as defined for formula I and R ¹⁹ is hydroxy, halogen, preferably fluoro, chloro or bromo, or alkoxy, such as methoxy or ethoxy, with a compound of formula II, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I, and a base or an activating agent. This is shown in Scheme 1. Scheme 1

The compounds of formula II, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I can be obtained by transformation of a compound of formula III, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie f-butoxycarbonyl, with a deprotecting agent such as a base, an acid or a hydrogenation system such as H ₂ /Pd. This is shown in Scheme 2.

Scheme 2

The compounds of formula III, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, can be obtained by transformation of a compound of formula V, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie/f- butoxycarbonyl, with a compound of formula VI, wherein R ¹⁵ and R ¹⁶ are as defined for formula I, and an acid or a Dean-Stark trap. This is shown in Scheme 3.

Scheme 3

The compounds of formula V, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, can be obtained by transformation of a compound of formula VII, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie f-butoxycarbonyl, with a compound of formula VIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, and hydroxylamine and sodium hypochlorite. This is shown in Scheme 4.

Scheme 4

(viii)

Alternatively, the compounds of formula V, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie/f-butoxycarbonyl, can be obtained by transformation of a compound of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, with a compound of formula VIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, and an oxidant such as sodium hypochlorite, /V-chlorosuccinimide or diacetoxyiodobenzene. This is shown in Scheme 5.

Scheme 5

(viii)

The compounds of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie/f- butoxycarbonyl, can be obtained by transformation of a compound of formula VII, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, with hydroxylamine. This is shown in Scheme 6. Scheme 6

(VII) (IX)

The compounds of formula VII, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or tert- butoxycarbonyl, can be obtained by transformation of a compound of formula X, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I, R ²⁰ is alkoxy, such as methoxy or ethoxy and E ¹ is a protecting group such as acetyl, benzyl or tert- butoxycarbonyl, and a reducing agent, such as diisobutyllithium aluminium hydride. This is shown in Scheme 7.

Scheme 7

The compounds of formula VIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, can be obtained by transformation of a compound of formula XI, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, and a phosphorous reagent and hydroquinone. This is shown in Scheme 8.

Scheme 8

The compounds of formula XI, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, can be obtained by transformation of a compound of formula XII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, and a organolithium reagent and a ketone. This is shown in Scheme 9. Scheme 9

Alternatively, The compounds of formula III, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie f-butoxycarbonyl, can be obtained by transformation of a compound of formula VII, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, with a compound of formula XIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are as defined for formula I, and hydroxylamine and sodium hypochlorite. This is shown in Scheme 10.

Scheme 10

(XIII) Alternatively, the compounds of formula III, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie/f-butoxycarbonyl, can be obtained by transformation of a compound of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or fe/f-butoxycarbonyl, with a compound of formula XIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are as defined for formula I, and an oxidant such as sodium hypochlorite, /V-chlorosuccinimide or

diacetoxyiodobenzene. This is shown in Scheme 1 1 . Scheme 1 1

defined for formula I, can be obtained by transformation of a compound of formula VIII, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined for formula I, with a compound of formula VI, wherein R ¹⁵ and R ¹⁶ are as defined for formula I, and an acid or a Dean-Stark trap. This is shown in Scheme 12.

Scheme 12

Alternatively, the compounds of formula III, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , T, Y ¹ , Y ² , n and p are as defined for formula I, G ² is S and E is a protecting group such as acetyl, benzyl or ie f-butoxycarbonyl, can be obtained by transformation of a compound of formula XIV, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , T, n and p are as defined for formula I and E is a protecting group such as acetyl, benzyl or ie f- butoxycarbonyl, with a compound of formula XV, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are as defined for formula I and Hal is halogen, preferably chloro or bromo, and a base. This is shown in Scheme 13.

Scheme 13

Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

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

It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula I before planting: seed, for example, can be dressed before being sown. The active ingredients 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.

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

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

The compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Alternaria spp.), Basidiomycetes (e.g. Corticium spp., Ceratobasidium spp., Waitea spp., Thanatephorus spp., Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp., Ustilago spp., Tilletia spp.), Ascomycetes (e.g. Venturia spp., Blumeria spp., Erysiphe spp., Podosphaera spp., Uncinula spp., Monilinia spp., Sclerotinia spp., Colletotrichum spp., Glomerella spp., Fusarium spp., Gibberella spp., Monographella spp., Phaeosphaeria spp., Mycosphaerella spp., Cercospora spp., Pyrenophora spp., Rhynchosporium spp., Magnaporthe spp., Gaeumannomyces spp., Oculimacula spp., Ramularia spp., Botryotinia spp.) and Oomycetes (e.g. Phytophthora spp., Pythium spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp. Bremia spp). Outstanding activity is observed against downy mildew (e.g. Plasmopara viticola) and late blight (e.g. Phytophthora infestans). Furthermore, the novel compounds of formula I are 5 effective against phytopathogenic gram negative and gram positive bacteria (e.g.

Xanthomonas spp, Pseudomonas spp, Erwinia amylovora, Ralstonia spp.) and viruses (e.g. tobacco mosaic virus).

Within the scope of present invention, target crops and/or useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize,

10 sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit

15 (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,

cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as turf and ornamentals.

The useful plants and / or target crops in accordance with the invention include

20 conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties. By way of example, suitable genetically enhanced or engineered crop varieties include the Stoneville

25 5599BR cotton and Stoneville 4892BR cotton varieties.

The term "useful plants" and/or "target crops" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase)

30 inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)

inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by

35 genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and

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

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

The term "locus" of a plant as used herein is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

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

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

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

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

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

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

The compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities. Examples of suitable additional active ingredients include the following: Azoxystrobin (131860-33-8), Dimoxystrobin (149961 -52-4), Enestrobin (238410-1 1 -2), Fluoxastrobin (193740-76-0), Kresoxim-methyl (143390-89-0), Metominostrobin (133408-50-1 ), Orysastrobin (248593-16- 0), Picoxystrobin (1 17428-22-5), Pyraclostrobin (175013-18-0), trifloxystrobin (141517-21 -7), Azaconazole (60207-31 -0), Bromuconazole (1 16255-48-2), Cyproconazole (94361 -06-5), Difenoconazole (1 19446-68-3), Diniconazole (83657-24-3), Diniconazole-M (83657-18-5), Epoxiconazole (13385-98-8), Fenbuconazole (1 14369-43-6), Fluquinconazole (136426-54- 5), Flusilazole (85509-19-9), Flutriafol (76674-21 -0), Hexaconazole (79983-71 -4), Imazalil (58594-72-2), Imibenconazole (86598-92-7), Ipconazole (125225-28-7), Metconazole (1251 16-23-6), Myclobutanil (88671 -89-0), Oxpoconazole (174212-12-5), Pefurazoate (5801 1 -68-0), Penconazole (66246-88-6), Prochloraz (67747-09-5), Propiconazole (60207- 90-1 ), Prothioconazole (178928-70-6), Simeconazole (149508-90-7), Tebuconazole

(107534-96-3), Tetraconazole (1 12281 -77-3), Triadimefon (43121 -43-3), Triadimenol (55219-65-3), Triflumizole (99387-89-0), Triticonazole (131983-72-7), Diclobutrazol (76738- 62-0), Etaconazole (60207-93-4), Fluconazole (86386-73-4), Fluconazole-cis (1 12839-32-4), Thiabendazole (148-79-8), Quinconazole (103970-75-8), Fenpiclonil (74738-17-3),

Fludioxonil (131341 -86-1 ), Cyprodinil (121552-61 -2), Mepanipyrim (1 10235-47-7),

Pyrimethanil (531 12-28-0), Aldimorph (91315-15-0), Dodemorph (1593-77-7),

Fenpropimorph (67564-91 -4), Tridemorph (81412-43-3), Fenpropidin (67306-00-7),

Spiroxamine (1 18134-30-8), Isopyrazam (881685-58-1 ), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31 -3), Boscalid (188425- 85-6), Penflufen (494793-67-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (413615-35-7), Dimethomorph (1 10488-70-5), Chlorothalonil (1897-45-6), Fluazinam (79622-59-6), Dithianon (3347-22-6), Metrafenone (220899-03-6), Tricyclazole (41814-78-2), Mefenoxam (70630-17-0), Metalaxyl (57837-19-1 ), Acibenzolar (126448-41 -7) (Acibenzolar-S-methyl (126448-41 -7)), Mancozeb (8018-01 -7), Ametoctradine (865318-97-4) Cyflufenamid (180409-60-3), and Kresoxim-methyl (143390-89-0), Ipconazole (125225-28- 7), Amisulbrom (348635-87-0), Cyflufenamid (180409-60-3), Ethaboxam (16650-77-3), Fluopicolide (2391 10-15-7), Fluthianil (304900-25-2), Isotianil (224049-04-1 ), Proquinazid (189278-12-4), Valiphenal (283159-90-0), 1 -methyl-cyclopropene (3100-04-7), Trifloxystrobin (141517-21 -7), Sulfur (7704-34-9), Copper ammoniumcarbonate (CAS 331 13-08-5); Copper oleate (CAS 1 120-44-1 ); Folpet (133-07-3), Quinoxyfen (124495-18-7), Captan (133-06-2), Fenhexamid (126833-17-8), Glufosinate and its salts (51276-47-2, 35597-44-5 (S-isomer)), Glyphosate (1071 -83-6 ) and its salts (69254-40-6 (Diammonium), 34494-04-7

(Dimethylammonium), 38641 -94-0 (Isopropylammonium), 40465-66-5 (Monoammonium), 70901 -20-1 (Potassium), 70393-85-0 (Sesquisodium), 81591 -81 -3 (Trimesium)), 1 -methyl-3- difluoromethyl-1 H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1 -methyl-indan-4- yl)-amide (1072957-71 -1 ), 1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (4'- methylsulfanyl-biphenyl-2-yl)-amide, 1 -methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1 -methyl-ethyl]-amide, (5-Chloro-2,4-dimethyl-pyridin-3- yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, (5-Bromo-4-chloro-2-methoxy-pyridin-3- yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1 - methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-m ethoxyimino]-N-methyl- acetamide, 3-[5-(4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyrid ine.

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

A further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by

phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.

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

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

A formulation, e.g. a composition containing the compound of formula I, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active

compounds (surfactants).

The agrochemical formulations and/or compositions 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.

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The following non-limiting examples illustrate the above-described invention in more detail.

Example 1 : This example illustrates the preparation of methanesulfonic acid [1 -{2-[3-(2-{1 -[2- (5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-thiazol-4-yl)-4,5-dihydro- isoxazol-5-yl]-phenyl}-ethylidene]-hydrazide (Compound No. I.bd.003) a) Preparation of methanesulfonic acid [1 -(2-vinyl-phenyl)-ethylidene]-hydrazide

A mixture of 0.30 g of 1 -(2-vinyl-phenyl)-ethanone and 0.33 g of methanesulfonyl hydrazone hydrochloride in 10 ml of ethanol was heated to reflux for 6 h. Subsequently the reaction mixture was cooled to room temperature and evaporated under reduced pressure. The residue was purified by chromatography on silica gel, using ethaly acxetate/ hexane 1 :1 as eluent system to give methanesulfonic acid [1 -(2-vinyl-phenyl)-ethylidene]-hydrazide as a pink wax. Ή-NMR (400 MHz, CDCI ₃ ): δ = 2.22 (s, 3H), 3.19 (s, 3H), 4.16 (q, 1 H), 5.31 (d, 1 H), 5.66 (d, 1 H), 6.85 (dd, 1 H), 7.05 (d, 1 H), 7.30 7.41 (m, 2H), 7.57 (d, 1 H). b) Preparation of methanesulfonic acid [1 -{2-[3-(2-chloro-acetyl)-4,5-dihydro-isoxazol-5- yl]-phenyl}-ethylidene]-hydrazide

To a solution of 0.22 g of N-hydroxy-2-oxo-3-chloropropanimidoyl chloride and 0.36 g of methanesulfonic acid [1 -(2-vinyl-phenyl)-ethylidene]-hydrazide in 10 ml of acetonitrile was added 0.37 g of sodium bicarbonate. The reaction mixture was stirred for 24 h at room temperature, subsequently filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica gel, using ethyl acetate/hexane 1 :1 as eluent system to give methanesulfonic acid [1 -{2-[3-(2-chloro-acetyl)-4,5-dihydro-isoxazol-5-yl]- phenyl}-ethylidene]-hydrazide as white foam. Ή-NMR (400 MHz, CDCI ₃ ): δ = 2.27 (s, 3H), 2.33 (d, 1 H), 3.02 (dd, 1 H), 3.15 (s, 3H), 3.88 (dd, 1 H), 4.74 (dd, 2H), 6.21 (dd, 1 H), 7.38 7.47 (m, 2H), 7.53 (dd, 1 H), 7.70 (s, 1 H). c) Preparation of methanesulfonic acid [1 -{2~[3-(2-{1 -[2~(5-methyl-3-trifluoromethyl- pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-thiazol-4-yl)-4^-dihydro-isoxaz ol-5-yl]-phenyl}- ethylidene]-hydrazide (Compound No. I.bd.003)

To a solution of 0.26 g of methanesulfonic acid [1 -{2-[3-(2-chloro-acetyl)-4,5-dihydro- isoxazol-5-yl]-phenyl}-ethylidene]-hydrazide and 0.24 g of 1 -[2-(5-methyl-3-trifluoromethyl-py razol-1 -yl)-acetyl]-piperidine-4-carbothioic acid amide in 15 ml of ethanol was added 0.12 g of sodium bicarbonate. The reaction mixture was heated to reflux for 8 h, then cooled to room temperature and evaporated under reduced pressure. The residue was taken up in ethyl acetate, the organic phase washed with water, dried over sodium sulphate and concentrated under reduced pressure. The remainder was purified by chromatography on silica gel, using ethyl acetate/ methanol 10:1 as eluent system to give methanesulfonic acid [1 -{2-[3-(2-{1 -[2~(5-methyl-3-trifIuoromethyl- pyrazoH -yl>-acetyl]-piperidin-4-yl}-thiazol-4-yl)- 4,5-dihydro-isoxazol-5-yl]-phenyl}-ethylidene]-hydrazide (Compound No. I.bd.003) as a pale yellow solid. M.p. 85 - 86 °C. ^"' H-N R (400 MHz, CDCI ₃ ): δ = 1 .73 - 1.93 (m, 2H), 1.94 - 2.07 (m, 2H), 2.30 (s, 3H), 2.46 - 2.61 (m, 2H), 2.67 - 2.96 (m, 3H), 3.19 (s, 3H), 3.23 - 3.37 (m, 3H), 3.83 - 3.95 (m, 2H), 4.56 (d, 1 H), 5.08 - 5.21 (m, 2H), 5.93 (dd, 1 H), 6.66 (t, 1 H), 6.75 (s, 1 H), 6.87 (t, 1 H), 7.26 (t, 1 H). 7.47 - 7.56 (m. 2H). 7.66 (s, 1 H), 8.12 (dd, 1 H).

Example 2: This example illustrates the preparation of N-[(Z}-1 -[2-[3-[2-[1 -[2-[3,5- bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5- yI]phenyl]ethyIideneamino]methanesuIfonamide (Compound No. I.bd.075) a) Preparation of 2-(4-piperidyl)thiazole-4-carbaldehyde dihydrochloride

In a 2.5 L reactor with a mechanic stirrer, tert-butyl 4-(4-formyl-1 ,3-thiazol-2-yl)tetrahydro- 1 (2H)-pyridinecarboxyIate (90.0 g, 295 mmol) was dissolved in 1 ,4-dioxane (736 mL, 295 mmol) and then HCI in dioxane (295 mL, 1 180 mmol) was added dropwise under a flow of argon. The reaction mixture was stirred for 3 days at rt. The precipitate was filtered, washed with ether and dried under vacuum to give 2-(4-piperidyl)thiazole-4-carbaldehyde dihydrochloride as a light yellow powder. The product was used in the next step without further purification. ¹ H NMR (400 MHz, DMSO) δ ppm 1 .92 - 2.04 (m, 2H), 2.22 (d, J=1 1.7 Hz, 2H), 2.97 - 3.09 (m, 2H), 3.34 (d, J=12.8 Hz, 2H), 3.44 (tt, J=1 1 .4, 3.8 Hz, 1 H), 7.28 (br s, 1 H), 8.69 (s, 1 H), 9.01 (br s, 1 H), 9.18 (br s, 1 H), 9.91 (s, 1 H) b) Preparation of 2-[1 -[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazole- 4-carbaldehyde

To a solution of 2-(4-piperidyl)thiazole-4-carbaldehyde dihydrochloride (81 .7 g, 304 mmol) in dichloromethane (759 mL, 304 mmol) in a 2.5L reactor, was added DIPEA (157 g, 210 mL, 1210 mmol) followed by HOAt (49.6 g, 364 mmol), EDCI (69.8 g, 364 mmol) and 2-[3.5- bis(difluoromethyl)pyrazol-1 -yl]acetic acid (68.6 g, 304 mmol). The reaction mixture was stirred overnight at rt. The reaction mixture was washed with HCI 1 M (x2) and the aqueous phase extracted with DCM. The combined organic layers were washed with a sat. solution of NaHCOS (x2), dried over Na ₂ S0 ₄ , concentrated and purified by Isco combiflash Torrent using a cyclohexane/AcOEt gradient as eluent to give 2-[1 -[2-[3,5-bis(difluoromethyl)pyrazol- 1 -yl]acetyl]-4-piperidyl]thiazole-4-carbaldehyde as a yellow oil. Ή NMR (400 MHz, CDCI ₃ ) δ ppm 1 .78 - 1 .98 (m, 2H), 2.18 - 2.35 (m, 2H), 2.94 (t, J= 1 1 .2 Hz, 1 H), 3.36 (dtt, J=1 1 .2, 7.4, 7,4, 3.5, 3.5 Hz, 2H), 3.94 (d, J=13.6 Hz, 1H), 4.60 (d, J=13.9 Hz, 1H), 5.10 - 5.22 (m, 2H), 6.67 (t, J=56 Hz, 1H), 6.77 (s, 1H), 6.88 (t, J=56 Hz, 1H), 8.12 (s, 1H), 10.01 (s, 1H) c) Preparation of (4E)-2-[1-[2-[3,5-bis(dif1uoromethyl)pyrazol-1-yl]acetyl]-4- piperidyl]

thiazolo-4-carbaldehyde oxime

To a solution of 2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piper idyl]thiazole-4- carbaldehyde (75 g, 185.5 mmol) in ethanol (618 ml_, 185.5 mmol) was added hydroxylamine hydrochloride (19.33 g, 278.2 mmol) followed by AcO a (24.34 g, 296.7 mmol). The reaction mixture was stirred for 2h30 at rt. AH the volatiles were removed under vacuum and the residue was dissolved in AcOEt and water. The combined organic layers were washed with water (x2), dried over Na ₂ S0 ₄ , filtered, concentrated and purified by Isco combiflash Rf using a DCM/AcOEt gradient as eluent to give (4E)-2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1- yl]acetyl]-4-piperidyl]thiazole-4-carbaldehyde oxime as a yellow foam consisting of a 55/45 mixture of isomers. Major isomer: ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 1.72 - 1.96 (m, 2H), 2.13 - 2.33 (m, 2H), 2.82 - 3.01 (m, 1H), 3.25 - 3.42 (m, 2H), 3.86 - 3.99 (m, 1H), 4.51 - 4.67 (m, 1H), 5.08 - 5.27 (m, 2H), 6.67 (t, J=55.0 Hz, 1H), 6.76 (s, 1H), 6.89 (t, J=55.0 Hz, 1H), 7.74 (s, 1H), 8.14 (s, 1H), 10.43 (br s, 1H). Minor isomer: ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 1.72 - 1.96 (m, 2H), 2.13 - 2.33 (m, 2H), 2.82 - 3.01 (m, 1H), 3.25 - 3.42 (m, 2H), 3.86 - 3.99 (m, 1H), 4.51 - 4.67 (m, 1H), 5.08 - 5.27 (m, 2H), 6.67 (t, J=55.0 Hz, 1H), 6.76 (s, 1H), 6,88 (t, J=55.0 Hz, 1H), 7,43 (s, 1H), 8,21 (s, 1H), 8.44 (br s, 1H) d) Preparation of 1-[4-[4-[5-(2-acetylphenyl)-4,5-dihydroisoxazol-3-yl]thiazol -2-yl]-1- piperidyl]-2-[3,5-bis(difluoromethyl)pyrazol-1-yl]ethanone

To a solution of 1 -(2-vinylphenyl)ethanone (6.52 g, 44.6 mmol) in methanol (405 mL, 40.5 mmol) was added TFA (0.0462 g, 0.405 mmol) followed by iodobenzenediacetate (14.4 g, 44.6 mmol) and (4E)-2-[1 -[2-[3,5-bis(drfluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazole-4- carbaldehyde oxime (17.0 g, 40.5 mmol). The reaction mixture was stirred 1h30 at rt. The volatiles were removed under vacuum and the resulting oil was purified by isco combiflash Rf using a DCM/AcOEt gradient as eluent to give 1-[4-[4-[5-(2-acetylphenyl)-4,5- dihydroisoxazol-3-yl]thiazol-2-yl]-1-piperidyl]-2-[3,5-bis(d ifluoromethyl)pyrazol-1-yl]ethanone as a light yellow foam. ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 1.72 - 1.92 (m, 2H), 2.13-2.30 (m, 2H), 2.66 (s, 3H), 2.92 (t, J=1 .2 Hz, 1H), 3.16 (dd, J=17.6, 7.0 Hz, 1H), 3.27 - 3.37 (m, 2H), 3.90 (d, J=14.7 Hz, 1H), 4.08-4.19 (m, 1H), 4.54 (d, J=13.2 Hz, 1H), 5.14 (s, 2H), 6.28 (dd, J=11.0, 7.0 Hz, 1H), 6.66 (t, J=56 Hz, 1H), 6.75 (s, 1H), 6.88 (t, J =56, 1H), 7.42 (td, J=7.6, 1.3 Hz, 1H), 7.55 (s, 1H), 7,57 (td, J=7.6, 1.3 Hz, 1H), 7.78 (dd, J=7.1, 1.1 Hz, 1H), 7.88 (dd, J=7.7, 1,1 Hz, 1H) e) Preparation of N-[(Z)-1 -[2-[3-[2-[1 -[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4- piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5- yl]phenyl]ethylideneamino]methanesulfonamide (Compound I.bd.075)

To a solution of 1 -[4-[4-[5-(2-acetylphenyl>-4 _^ 5-dihydroisoxazol-3-yl]thiazol-2-yl]-1 -piperidyl]- 2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]ethanone (18.0 g, 31 ,9 mmol) in ethanol (106 mL, 31 .9 mmol) was added methanesulfonohydrazide (3.87 g, 35.1 mmol). The reaction mixture was stirred for 72h at 80°C. Water was then added followed by AcOEt and a saturated solution of NaHCCs. The solution was extracted with AcOEt. The combined organic layers were washed with brine, dried over Na ₂ S0 ₄ , filtered, concentrated and purified by Isco combiflash Rf using a DCM/MeOH gradient as eluent to give N-[(Z)-1 -[2-[3-[2-[1 -[2-[3,5- bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5- yl]phenyl]ethylideneamino]methanesulfonamide (Compound l.bd.075) as a white solid consisting of a 85/15 mixture of isomers. Major isomer: ¹ H NMR (400 MHz, CDCI ₃ ) δ ppm 1 .74 - 1 .93 (m, 2H), 2.13 - 2.28 (m, 2H), 2.28 (s, 3H), 2.94 (br s, 1 H), 3,1 1 (s, 3H), 3,25 - 3.39 (m, 3H), 3.90 (d, J=13.9 Hz, 1 H), 4.1 1 (dd, J=17.4, 1 1 .2 Hz, 1 H), 4.54 (d, J=1 1 .0 Hz, 1 H), 5.14 (s, 2H), 6.09 (dd, J=1 1 .0, 8.4 Hz, 1 H), 6.66 (t, J=57.0 Hz, 1 H), 6.76 (s, 1 H), 6.88 (t, J=55,0 Hz, 1 H), 7.34 - 7.38 (m, 2H), 7.39 - 7.46 (m, 1 H), 7.53 - 7.58 (m, 2H), 7.66 (d, J=7.7 Hz, 1 H)

Table 1 below illustrates examples of individual compounds of formula I according to the invention.

Table 1 : individual compounds of formula I according to the invention

Comp. R R T Y G Y R R

No.

001 F ₃ C H ₃ C CH N S CH H H

002 F ₃ C H ₃ C CH N S CH F H

003 F ₃ C H ₃ C CH N s CH H CH ₃

004 F ₃ C H ₃ C CH N s CH F CH ₃

005 F ₃ C H ₃ C CH N s N H H

006 F ₃ C H ₃ C CH N s N F H

007 F ₃ C H ₃ C CH N s N H CH ₃

008 F ₃ C H ₃ C CH N s N F CH ₃

009 F ₃ C H ₃ C CH N 0 CH H H

010 F ₃ C H ₃ C CH N 0 CH F H

011 F ₃ C H ₃ C CH N 0 CH H CH ₃

012 F ₃ C H ₃ C CH N 0 CH F CH ₃

013 F ₃ C H ₃ C N N s CH H H F ₃ C H ₃ C N N S CH F H

F ₃ C H ₃ C N N S CH H CH ₃

F ₃ C H ₃ C N N S CH F CH ₃

F ₃ C H ₃ C N N S N H H

F ₃ C H ₃ C N N S N F H

F ₃ C H ₃ C N N S N H CH ₃

F ₃ C H ₃ C N N S N F CH ₃

F ₃ C H ₃ C N N 0 CH H H

F ₃ C H ₃ C N N 0 CH F H

F ₃ C H ₃ C N N 0 CH H CH ₃

F ₃ C H ₃ C N N 0 CH F CH ₃

H ₃ C H ₃ C CH N S CH H H

H ₃ C H ₃ C CH N S CH F H

H ₃ C H ₃ C CH N S CH H CH ₃

H ₃ C H ₃ C CH N S CH F CH ₃

H ₃ C H ₃ C CH N S N H H

H ₃ C H ₃ C CH N S N F H

H ₃ C H ₃ C CH N S N H CH ₃

H ₃ C H ₃ C CH N S N F CH ₃

H ₃ C H ₃ C CH N 0 CH H H

H ₃ C H ₃ C CH N 0 CH F H

H ₃ C H ₃ C CH N 0 CH H CH ₃

H ₃ C H ₃ C CH N 0 CH F CH ₃

H ₃ C H ₃ C N N S CH H H

H ₃ C H ₃ C N N S CH F H

H ₃ C H ₃ C N N S CH H CH ₃

H ₃ C H ₃ C N N S CH F CH ₃

H ₃ C H ₃ C N N s N H H

H ₃ C H ₃ C N N s N F H

H ₃ C H ₃ C N N s N H CH ₃

H ₃ C H ₃ C N N s N F CH ₃

H ₃ C H ₃ C N N 0 CH H H

H ₃ C H ₃ C N N 0 CH F H

H ₃ C H ₃ C N N 0 CH H CH ₃

H ₃ C H ₃ C N N 0 CH F CH ₃

F ₂ HC H ₃ C CH N s CH H H

F ₂ HC H ₃ C CH N s CH F H F ₂ HC H ₃ C CH N S CH H CH ₃

F ₂ HC H ₃ C CH N S CH F CH ₃

F ₂ HC H ₃ C CH N S N H H

F ₂ HC H ₃ C CH N S N F H

F ₂ HC H ₃ C CH N S N H CH ₃

F ₂ HC H ₃ C CH N S N F CH ₃

F ₂ HC H ₃ C CH N 0 CH H H

F ₂ HC H ₃ C CH N 0 CH F H

F ₂ HC H ₃ C CH N 0 CH H CH ₃

F ₂ HC H ₃ C CH N 0 CH F CH ₃

F ₂ HC H ₃ C N N S CH H H

F ₂ HC H ₃ C N N S CH F H

F ₂ HC H ₃ C N N S CH H CH ₃

F ₂ HC H ₃ C N N S CH F CH ₃

F ₂ HC H ₃ C N N S N H H

F ₂ HC H ₃ C N N S N F H

F ₂ HC H ₃ C N N S N H CH ₃

F ₂ HC H ₃ C N N S N F CH ₃

F ₂ HC H ₃ C N N 0 CH H H

F ₂ HC H ₃ C N N 0 CH F H

F ₂ HC H ₃ C N N 0 CH H CH ₃

F ₂ HC H ₃ C N N 0 CH F CH ₃

F ₂ HC F ₂ HC CH N S CH H H

F ₂ HC F ₂ HC CH N S CH F H

F ₂ HC F ₂ HC CH N S CH H CH ₃

F ₂ HC F ₂ HC CH N S CH F CH ₃

F ₂ HC F ₂ HC CH N S N H H

F ₂ HC F ₂ HC CH N s N F H

F ₂ HC F ₂ HC CH N s N H CH ₃

F ₂ HC F ₂ HC CH N s N F CH ₃

F ₂ HC F ₂ HC CH N 0 CH H H

F ₂ HC F ₂ HC CH N 0 CH F H

F ₂ HC F ₂ HC CH N 0 CH H CH ₃

F ₂ HC F ₂ HC CH N 0 CH F CH ₃

F ₂ HC F ₂ HC N N s CH H H

F ₂ HC F ₂ HC N N s CH F H

F ₂ HC F ₂ HC N N s CH H CH ₃ 088 F ₂ HC F ₂ HC N N S CH F CH ₃

089 F ₂ HC F ₂ HC N N S N H H

090 F ₂ HC F ₂ HC N N S N F H

091 F ₂ HC F ₂ HC N N S N H CH ₃

092 F ₂ HC F ₂ HC N N S N F CH ₃

093 F ₂ HC F ₂ HC N N 0 CH H H

094 F ₂ HC F ₂ HC N N 0 CH F H

095 F ₂ HC F ₂ HC N N 0 CH H CH ₃

096 F ₂ HC F ₂ HC N N 0 CH F CH ₃

097 F ₃ C F ₃ C CH N S CH H H

098 F ₃ C F ₃ C CH N S CH F H

099 F ₃ C F ₃ C CH N S CH H CH ₃

100 F ₃ C F ₃ C CH N S CH F CH ₃

101 F ₃ C F ₃ C CH N S N H H

102 F ₃ C F ₃ C CH N S N F H

103 F ₃ C F ₃ C CH N S N H CH ₃

104 F ₃ C F ₃ C CH N S N F CH ₃

105 F ₃ C F ₃ C CH N 0 CH H H

106 F ₃ C F ₃ C CH N 0 CH F H

107 F ₃ C F ₃ C CH N 0 CH H CH ₃

108 F ₃ C F ₃ C CH N 0 CH F CH ₃

109 F ₃ C F ₃ C N N S CH H H

110 F ₃ C F ₃ C N N S CH F H

11 1 F ₃ C F ₃ C N N S CH H CH ₃

112 F ₃ C F ₃ C N N S CH F CH ₃

113 F ₃ C F ₃ C N N S N H H

114 F ₃ C F ₃ C N N S N F H

115 F ₃ C F ₃ C N N s CH H CH ₃

116 F ₃ C F ₃ C N N s CH F CH ₃

117 F ₃ C F ₃ C N N 0 CH H H

118 F ₃ C F ₃ C N N 0 CH F H

119 F ₃ C F ₃ C N N 0 CH H CH ₃

120 F ₃ C F ₃ C N N 0 CH F CH ₃

where

a) 120 compounds of formula (I. a):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. b) 120 compounds of formula (I. b):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. c) 120 compounds of formula (I. c): d) 120 compounds of formula (I. d):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ) 120 compounds of formula (l.e):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. f) 120 compounds of formula (l.f):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. g) 120 compounds of formula (l.g):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. h) 120 compounds of formula (l.h):

i) 120 compounds of formula (l.i):

wherein R ¹ , R ² , R ¹³ , G ² T, Y ¹ and Y ² are as defined in Table 1.

k) 120 compounds of formula (I. k):

) 120 compounds of formula (I.I):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. m) 120 compounds of formula (I. m):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. n) 120 compounds of formula (I. n):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. p) 120 compounds of formula (l.p):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. q) 120 compounds of formula (l.q):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. r) 120 compounds of formula (l.r):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. s) 120 compounds of formula (I. s):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. t) 120 compounds of formula (I. t):

u) 120 compounds of formula (I. u):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

v) 120 compounds of formula (l.v):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. w) 120 compounds of formula (l.w):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. x) 120 compounds of formula (l.x):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. y) 120 compounds of formula (l.y):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. z) 120 compounds of formula (l.z):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1 ad) 30 compounds of formula (I. ad):

ae) 30 compounds of formula (I. ae):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

ag) 30 compounds of formula (Lag):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

ai) 30 compounds of formula (l.ai):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. aj) 30 compounds of formula (l.aj): wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ak) 30 compounds of formula (l.ak):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. al) 30 compounds of formula (l.al):

wherein R , R ² , R ¹³ , G ² , T, Y and Y ² are as defined in Table 1. am) 30 compounds of formula (I. am):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1 an) 30 compounds of formula (I. an):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ao) 30 compounds of formula (l.ao):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ap) 30 compounds of formula (Lap):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. aq) 30 compounds of formula (l.aq):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ar) 30 compounds of formula (l.ar):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. as) 30 compounds of formula (I. as):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. t) 30 compounds of formula (I. at):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. au) 30 compounds of formula (l.au):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. av) 30 compounds of formula (l.av):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ax) 30 compounds of formula (I. ax):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ay) 30 compounds of formula (Lay):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. az) 30 compounds of formula (l.az):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. ba) 30 compounds of formula (l.ba):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bb) 30 compounds of formula (l.bb):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. be) 30 compounds of formula (I. be):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bd) 30 compounds of formula (l.bd):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. be) 30 compounds of formula (I. be):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bf) 30 compounds of formula (l.bf):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. g) 30 compounds of formula (l.bg):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bh) 30 compounds of formula (l.bh):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bi) 30 compounds of formula (l.bi):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bj) 30 compounds of formula (l.bj): wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1. bk) 30 compounds of formula (l.bk):

wherein R ¹ , R ² , R ¹³ , G ² , T, Y ¹ and Y ² are as defined in Table 1.

Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is:

Spectra were recorded on a Mass Spectrometer from Waters equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30- 60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas 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 μπι, 30 x 2.1 mm, Temp: 60 °C, DAD

Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: gradient: 0 min 0% B, 100%A; 1.2- 1 .5min 100% B; Flow (ml/min) 0.85

Table 2: Melting point and LC/MS data for compounds of Table 1

Compound No. Melting point (°C) LC/MS

I.j.003 77 - 78

l.t.001 79 - 80

l.t.003 74 - 75

l.x.003 92 - 93

l.af.003 76 - 77

l.as.075 61 - 62

l.ax.001 70 - 71

l.bd.075 82 - 83

l.bd.001 81 - 82 l.bd.003 85 - 86

l.bj.001 88 - 89

l.r.001 85 - 86

l.k.003 72 - 73

l.v.001 98 - 99

The compounds according to the present invention can be prepared according to the above-mentioned reaction schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

Biological examples

Phytophthora infestans I tomato / leaf disc preventative (tomato late blight)

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

Compound l.bd.075, l.bd.001 , l.bd.003, l.bj.001 and l.r.001 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Phytophthora infestans I potato / preventative (potato late blight)

2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a sporangia suspension 2 days after application. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (5 - 7 days after application).

Compound l.bd.075. I.bd.001 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Phytophthora infestans I potato / curative (potato late blight) 2-week old potato plants cv. Bintje are inoculated by spraying them with a sporangia suspension one day before application. The inoculated plants are sprayed in a spray chamber with the formulated test compound diluted in water. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (3 - 4 days after application).

Compound l.bd.075 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Phytophthora infestans I potato / long lasting (potato late blight)

2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a sporangia suspension 6 days after application. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (9 - 1 1 days after application). Compound l.bd.075, l.bd.001 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola I grape / leaf disc preventative (grape downy mildew)

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

Compound l.bd.075, l.bd.001 , l.bd.003, l.bj.001 and l.k.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola I grape / preventative (grape downy mildew) 5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants plants are inoculated by spraying a sporangia suspension on their lower leaf surface one day after application. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (6 - 8 days after application).

Compound l.bd.075, l.bd.001 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola I grape / curative (grape downy mildew)

5-week-old grape seedlings cv. Gutedel are inoculated by spraying a sporangia suspension on their lower leaf surface one day before application. The inoculated grape plants are sprayed in a spray chamber with the formulated test compound diluted in water. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (4 - 6 days after application). Compound l.bd.075 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola I grape / long lasting (grape downy mildew)

5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying a sporangia suspension on their lower leaf surface 6 days after application. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (1 1 - 13 days after application).

Compound l.bd.075, l.bd.001 and l.bd.003 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.