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.

The present invention provides compounds of formula I:

wherein,

G ¹ and G ² are independently O or S;

T is CR ¹² or N;

Y ¹ and Y ² are independently CR ¹³ 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 C C ₄ alkyl, C ₃ -C ₅ cycloalkyl or C ₁ -C ₄ haloalkyl;

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently are hydrogen, hydroxy, halogen, cyano, C-p C ₄ alkyl, C ^alkoxy, C ₃ -C ₅ cycloalkyl or C-rC ₄ haloalkyl;

R ⁹ and R ¹⁰ each independently are hydrogen, C-|-C ₄ alkyl, Cr^haloalkyl, C ₃ -C ₅ cycloalkyl, aryl, or heteroaryl, wherein aryl and heteroaryl are optionally substituted by one or more R or R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 5- to 10- membered isocyclic or heterocyclic ring optionally comprising one or two ring members selected from O, N, S or a carbonyl group, said isocyclic or heterocyclic ring being optionally substituted by one or more R ¹⁴ ;

X is O or N-R ¹⁵ R ¹¹ is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₅ cycloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₅ cycloalkylC.r C ₄ alkyl, aryl, CrC ₄ alkylsulfonyl, arylsulfonyl, heteroaryl, arylalkyl and heteroarylalkyl wherein alkyl, cycloalkyi, alkenyl are optionally substituted by halogen, and wherein aryl, heteroaryl, arylalkyl and heteroarylalkyl are optionally substituted by one or more R ¹⁴ ;

R ¹² is hydrogen, halogen or hydroxyl;

R ¹³ is hydrogen, halogen, cyano, CrC ₄ alkyl or CrC ₄ alkyoxy;

each R ¹⁴ independently is halogen, cyano, amino, nitro, hydroxyl, mercapto, Ci-C ₈ alkyl, C ₂ - C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkyl-Ci-C ₄ alkyl, C ₃ -C ₈ cycloalkyl-Cr C ₄ alkoxy, C ₃ -C ₈ cycloalkyl-Ci-C ₄ alkylthio, CrC ₈ alkoxy, C ₃ -C ₈ cycloalkoxy, CrC ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, Ci-C ₈ alkylthio, Ci-C ₈ alkylsulfonyl, CrC ₈ alkylsulfinyl, C ₃ -C ₈ cycloalkylthio, C ₃ - Cscycloalkylsulfonyl, C ₃ -C ₈ cycloalkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, aryl-Ci-C ₄ alkyl, aryl-C-rC ₄ alkoxy, aryl-C C ₄ alkylthio, heterocyclyl, heterocycyl-C C ₄ alkyl, heterocycyl-CrC ₄ alkoxy, heterocycyl-C C ₄ alkylthio, NH(C"rC ₈ alkyl), N(C ₁ -C ₈ alkyl) ₂ , C C ₄ alkylcarbonyl, C ₃ -C ₈ cycloalkylcarbonyl, C ₂ -C ₈ alkenylcarbonyl, C ₂ -C ₈ alkynylcarbonyl, wherein alkyl, alkenyl, alkynyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy and cycloalkoxy are optionally substituted by halogen, and wherein aryl and heterocyclyl are optionally substituted by one or more R ¹⁶ ; or R ¹⁴ is C=NOR ¹¹ ;

each R ¹⁵ independently is hydrogen, C -C ₄ alkyl _I C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C

C ₄ alkylsulfonyl, wherein alkyl, cycloalkyi and alkylsulfonyl are optionally substituted by halogen; and

each R ^1S independently is halogen, cyano, C-i-C ₄ alkyl, C C ₄ haloalkyl, CrC ₄ alkoxy or d-

C ₄ haloalkoxy; 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 C2-C3 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- d i ch I o ro-2-f I u oro-vi ny I .

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.

Isocyclic ring system includes aryl and in addition their saturated or partially unsaturated analogues.

Heterocyclyl and heterocyclic ring system are used interchangeably and is defined to include heteroaryl and in addition their saturated or partially unsaturated analogues. The different rings of bi- or tricyclic heterocyclic ring systems may be linked via one atom belonging to two different rings (spiro), via two adjacent ring atoms belonging to two different rings (annelated) or via two different, not adjacent ring atoms belonging to two different rings (bridged).

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

G ¹ , G ² , T, Y ¹ , Y ² , n, p, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^s , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ 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 ¹² or N, preferably CH or N, more preferably CH.

Y ¹ and Y ² are independently CR ¹³ 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 Ci-C ₄ alkyl, C ₃ -C ₅ cycloalkyl or Ci-C ₄ haloalkyl.

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, hydroxy, halogen, cyano, Ci-C ₄ alkyl, Ci-C ₄ alkoxy, C ₃ -C ₅ cycloalkyl or Ci-C ₄ haloalkyl, and preferably are hydrogen, halogen, Ci-C ₄ alkyl, Ci-C ₄ alkoxy, or CrC ₄ haloalkyl, more preferably hydrogen, halogen, or C-|-C ₄ alkyl; even more preferably hydrogen.

R ⁹ and R ¹⁰ each independently are hydrogen, Ci-C ₄ alkyl, C C ₄ haloalkyl, C ₃ - C ₅ cycloalkyl, aryl, or heteroaryl, wherein aryl and heteroaryl are optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 5- to 10-membered isocyclic or heterocyclic ring optionally comprising one or two ring members selected from O, N, S or a carbonyl group, said isocyclic or heterocyclic ring being optionally substituted by one or more R ¹⁴ ;

Preferably, R ⁹ and R ¹⁰ each independently are hydrogen, Ci-C ₄ alkyl, Ci-C ₄ haloalkyl, C ₃ -C ₅ cycloalkyl, aryl, or heteroaryl, wherein aryl and heteroaryl are optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 5- to 10-membered isocyclic or heterocyclic ring optionally comprising one or two ring members selected from O, N, S or a carbonyl group, said isocyclic or heterocyclic ring being optionally substituted by halogen, Ci-C ₄ alkyl, Ci-C ₄ haloalkyl, C ₃ -C ₅ cycloalkyl, d- C ₄ alkoxy, Ci-C ₈ alkylthio or C=NOR ¹¹ .

More preferably, R ⁹ and R ¹⁰ each independently are hydrogen, Ci-C ₄ alkyl, aryl, or heteroaryl wherein aryl and heteroaryl are optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 5- to 10-membered isocyclic or heterocyclic ring optionally comprising one or two ring members selected from O or a carbonyl group, said isocyclic or heterocyclic ring being optionally substituted by halogen, d-dalkyl, C ₃ -C ₅ cycloalkyl, d-C ₄ alkoxy, d-C ₈ alkylthio or C=NOR ¹¹ .

Even more preferably, R ⁹ and R ¹⁰ each independently are hydrogen, d-dalkyl or aryl, wherein aryl is optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ⁰ together with the carbon atoms to which they are attached form a 5 or 6-membered isocyclic ring, optionally comprising one or two ring members being C(=0) said isocyclic ring being optionally substituted by d-dalkyl, C ₃ -C ₅ cycloalkyl, d-dalkoxy, d-C ₈ alkylthio or C=NOR ¹¹ . Even more preferably, R ⁹ and R ¹⁰ each independently are hydrogen, C ₁ -C ₄ alkyl or aryl, wherein aryl is optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ⁰ together with the carbon atoms to which they are attached form a 6-membered isocyclic ring, optionally comprising one or two ring members being C(=0), said isocyclic ring being optionally substituted by d-C ₄ alkyl, C ₃ -C ₅ cycloalkyl, CrC ₄ alkoxy, CrC ₈ alkylthio, or C=NOR ¹¹ .

R ¹¹ is hydrogen, Ci-C ₄ alkyl, C ₃ -C ₅ cycloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ - C ₅ cycloalkylCi-C ₄ alkyl, aryl, Ci-C ₄ alkylsulfonyl, arylsulfonyl, heteroaryl, arylalkyl and heteroarylalkyl wherein alkyl, cycloalkyl, alkenyl are optionally substituted by halogen, and wherein aryl, heteroaryl, arylalkyl and heteroarylalkyl are optionally substituted by one or more R ¹⁴ ;

Preferably R ¹¹ is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₅ cycloalkyl, C ₃ -C ₅ cycloalkylCi-C alkyl, allyl, propargyl, C-rC ₄ alkylsulfonyl, or benzyl wherein alkyl, allyl, cycloalkyl and alkenyl are optionally substituted by halogen; more preferably R ¹¹ is hydrogen, C ₁ -C ₄ alkyl, allyl, propargyl, wherein alkyl is optionally substituted by chloro or fluoro.

X is O or N-R ¹⁵ , preferably X is O, NH, NMe, and more preferably O.

R ¹² is hydrogen, halogen or hydroxyl; preferably R ¹² is hydrogen or halogen, more preferably hydrogen,

R ¹³ is hydrogen, halogen, cyano, C C ₄ alkyl or C-|-C ₄ alkyoxy; preferably hydrogen or halogen, more preferably hydrogen,

Each R ¹⁴ independently is halogen, cyano, amino, nitro, hydroxyl, mercapto, Cr

C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkyl-Ci-C ₄ alkyl, C ₃ - C ₈ cycloalkyl-Ci-C alkoxy, C ₃ -C ₈ cycloalkyl-Ci-C ₄ alkylthio, CrC ₈ alkoxy, C ₃ -C ₈ cycloalkoxy, C C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, CrC ₈ alkylthio, Ci-C ₈ alkylsulfonyl, Ci-C ₈ alkylsulfinyl, C ₃ - C ₈ cycloalkylthio, C ₃ -C ₈ cycloalkylsulfonyl, C ₃ -C ₈ cycloalkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, aryl-CrC alkyl, aryl-CrC alkoxy, aryl-C-i-C alkylthio, heterocyclyl, heterocycyl-Ci-C ₄ alkyl, heterocycyl-Ci-C ₄ alkoxy, heterocycyl-CrC alkylthio, NH(Ci-C ₈ alkyl), N(Ci-C ₈ alkyl) ₂ , Ci-C alkylcarbonyl, C ₃ -C ₈ cycloalkylcarbonyl, C ₂ -C ₈ alkenylcarbonyl, C ₂ - C ₈ alkynylcarbonyl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy and cycloalkoxy are optionally substituted by halogen, and wherein aryl and heterocyclyl are optionally substituted by one or more R ⁶ ; or R ¹⁴ is C=NOR ¹¹ ;

Preferably R ¹⁴ independently is halogen, cyano, hydroxyl, mercapto, C.|-C ₄ alkyl, C ₂ - C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₅ cycloalkyl, Ci-C ₄ alkoxy, C-i-C alkenyloxy, C ₂ -C ₄ alkynyloxy, C C alkylsulfonyl, aryl, aryloxy, arylsulfonyl, aryl-Ci-C alkyl, aryl-Ci-C alkoxy, heterocyclyl, NH(C-|-C alkyl), N(Ci-C alkyl) ₂ , Ci-C alkylcarbonyl wherein alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy and cycloalkoxy are optionally substituted by halogen, and wherein aryl and heterocyclyl are optionally substituted by one or more R ¹⁶ ; or R ¹⁴ is

C=NOR ¹¹ More preferably R ¹⁴ independently is halogen, cyano, hydroxyl, C ₁ -C ₄ alkyl, ethynyl, C ₃ - C ₅ cycloalkyl, d-C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, NH(Ci-C alkyl), N(CrC alkyl) ₂ , CrC ₄ alkylcarbonyl wherein alkyl, cycloalkyl and alkoxy, are optionally substituted by halogen, or R ¹⁴ is C=NOR ¹¹

Even more preferably R ¹⁴ independently is halogen, cyano, Ci-C ₄ alkyl, methoxy, NH(CrC ₄ alkyl), N(Ci-C ₄ alkyl) ₂ , Ci-C ₄ alkylcarbonyl wherein alkyl is optionally substituted by halogen, or R ¹⁴ is C=NOH or CNOMe

Even more preferably R ¹⁴ independently is halogen, cyano, Ci-C ₄ alkyl, methoxy, NH(CrC ₄ alkyl), N(Ci-C ₄ alkyl) ₂ , Ci-C ₄ alkylcarbonyl wherein alkyl is optionally substituted by halogen.

Each R ¹⁵ independently is hydrogen, Ci-C ₄ alkyl, Ci-C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, d- C ₄ alkylsulfonyl, wherein alkyl, cycloalkyl and alkylsulfonyl are optionally substituted by halogen; preferably each R ¹⁵ independently is hydrogen, C ₁ -C ₄ alkyl, C C ₂ haloalkyl, C C ₂ alkylsulfonyl, wherein alkyl and alkylsulfonyl are optionally substituted by halogen; more preferably each R ¹⁵ independently is hydrogen, C C ₄ alkyl.

Each R ¹⁶ independently is halogen, cyano, C -C ₄ alkyl, Ci-C ₄ haloalkyl, C C ₄ alkoxy or Cr haloalkoxy; preferably each R ¹⁶ independently is halogen, C ₁ -C ₄ alkyl, Crdhaloalkyl, C alkoxy or CrCynaloalkoxy; more preferably each R ¹⁶ independently is halogen, C C ₄ alkyl, C C ₂ haloalkyl.

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, Ci-C ₄ alkyl, C-p C ₄ alkoxy, or C-i-C ₄ haloalkyl;

R ⁹ and R ¹⁰ each independently are hydrogen, C.|-C ₄ alkyl, aryl, or heteroaryl wherein aryl and heteroaryl are optionally substituted by one or more R ¹⁴ , or

R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 5- to 10- membered isocyclic or heterocyclic ring optionally comprising one or two ring members selected from O or a carbonyl group, said isocyclic or heterocyclic ring being optionally substituted by halogen, Ci-C ₄ alkyl, C ₃ -C ₅ cycloalkyl, Ci-C ₄ alkoxy, Ci-C ₈ alkylthio or C=NOR ¹¹ ; X is O, NH or NMe; R ¹¹ hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₅ cycloalkyl, C ₃ -C ₅ cycloalkylC ₁ -C ₄ alkyl, allyl, propargyl, C C ₄ alkylsulfonyl, or benzyl wherein alkyl, allyl, cycloalkyi and alkenyl are optionally substituted by halogen;

each R ¹⁴ independently is halogen, cyano, hydroxyl, Ci-C ₄ alkyl, ethynyl, C ₃ -C ₅ cycloalkyl, d- C ₄ alkoxy, C ₃ -C alkenyloxy and C ₃ -C alkynyloxy, NH(Ci-C alkyl), N(CrC alkyl) ₂ , Cr

C ₄ alkylcarbonyl wherein alkyl, cycloalkyi and alkoxy, are optionally substituted by halogen, 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, difluoromethyl or trifluoromethyl;

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

R ⁹ and R ¹⁰ each independently are hydrogen, C dalkyl or aryl, wherein aryl is optionally substituted by one or more R ¹⁴ ; or R ⁹ and R ¹⁰ together with the carbon atoms to which they are attached form a 6-membered isocyclic ring, optionally comprising one or two ring members being C(=0), said isocyclic ring being optionally substituted by CrC ₄ alkyl, C ₃ - Cscycloalkyl, C C ₄ alkoxy, C C ₈ alkylthio, C=NOMe or C=NOH;

X is O;

R ¹¹ is hydrogen, Ci-C ₄ alkyl, allyl, propargyl, wherein alkyl is optionally substituted by chloro or fluoro.;

each R ¹⁴ independently is halogen, cyano, C-i-C ₄ alkyl, methoxy, NH(C C ₄ alkyl), N(d- C ₄ alkyl) ₂ , CrC ₄ alkylcarbonyl wherein alkyl is optionally substituted by halogen; and 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, Y ¹ is N, and Y ² is CH.

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 , G ¹ , G ² , T, X, 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 l-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 , G ¹ , G ² , T, X, 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 ¹ , R ² R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ¹ , G ² , T, X, 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.

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

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ , G ² , X, Y ¹ and Y ² have the definitions a: 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 , X, Y ¹ and Y ² are as defined for formula I.

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

in which R ¹ , R ² R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ and X have the definitions as described for formula I. Preferred definition, s of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ and X 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 , G ¹ , G ² , T, X, 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 , G ¹ , G ² , T, X, Y ¹ , Y ² ,n and p are as defined for formula I.

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

in which R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ¹ , G ² , T, X, 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 , G ¹ , G ² T, X, 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 , G ² , T, X, Y ¹ , Y ² ,n and p are as defined for a compound of formula I and E is hydrogen or a protecting group, such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. Ci-C ₄ alkylcarbonyl, benzyl or Ci-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 , G ² , T, X, Y ¹ , Y ² ,n and p are as defined for formula I.

The invention also includes compounds of formula III

wherein halogen is bromo, chloro, fluroro or iodo and R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² 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 ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² are as defined for formula I.

The invention also includes compounds of formula IV

wherein halogen is bromo, chloro, fluroro or iodo and R ⁹ , R ¹⁰ , R ¹¹ , G ² , X, Y ¹ , Y ² 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 ⁹ , R ¹⁰ , R ¹¹ , G ² , X, Y ¹ , Y ² are as defined for formula I.

The invention also includes compounds of formula V

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ² , X, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or

alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C1-C4 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 ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ¹ , G ² , X, Y ¹ , Y ² , n and p are as defined for formula I. The invention also includes compounds of formula VI

Wherein R ³ , R ⁴ , R ⁵ , R ^s , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² , n and p are as defined for a compound of formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or

alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C1-C4 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 , G ² , Y ¹ , Y ² , n and p are as defined for formula I.

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 , G ¹ , G ² , T, X, Y ¹ , Y ² , n and p are as defined for formula I, can be obtained by transformation of a compound of formula Ila, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ² , X, T, Y ¹ , Y ² , n and p are as defined for formula I, with a compound of formula VII, wherein R ¹ , R ² and G ¹ is as defined for formula I and Hal is halogen, preferably chloro, and a base, such as pyridine, trieth lamine, ethyl diisopropylamine. This is shown in Scheme 1.

Scheme 1

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 , G ¹ , G ² ,

T, X, Y ¹ , Y ² , n and p are as defined for formula I, can be obtained by transformation of a compound of formula Ila, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , X, G ² , T, Y ¹ , Y ² , n and p are as defined for formula I, with a compound of formula VIII , wherein R ¹ , R ² and G ¹ is as defined for formula I, an activating reagent such BOP, PyBOP, EDCI, CDI or HATU, and a base, such as pyridine, triethylamine, ethyl diisopropylamine. This is shown in Scheme 2.

Scheme 2

The compounds of formula I I, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , G ² , T, X, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C ₄ alkylcarbonyl, benzyl or C _r C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-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 , R ⁹ , R ¹⁰ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. Ci-C ₄ alkylcarbonyl, benzyl or C C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with a compound of formula X wherein R ¹¹ and X are as defined for formula I. This is shown in Scheme 3.

Scheme 3

The compounds of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as

alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. Ci-C alkylcarbonyl, benzyl or C C

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula XI, 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 hydrogen, a protecting group such as

alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C ₄ alkylcarbonyl, benzyl or C C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with a compound of formula XII, wherein R ⁹ and R ¹⁰ are as defined for formula I, and a base such as potassium bicarbonate. This is shown in Scheme 4.

Scheme 4 Alternatively, the compounds of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula XIII, 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 hydrogen, a protecting group such as

alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or CrC ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with a compound of formula XII, wherein R ⁹ and R ¹⁰ are as defined for formula I , and an oxidant such as

Scheme 5

Alternatively, the compounds of formula IX, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-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 , G ² , T, Y ¹ , Y ² and p are as defined for formula I and E is hydrogen, a protecting group such as

alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C C ₄

alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with a compound of formula XII, wherein R ⁹ and R ¹⁰ are as defined for formula I , and hydroxylamine and a chlorinatin agent such as sodium hypochlorite. This is shown in Scheme 6.

Scheme 6

The compounds of formula XI, 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 hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C-rC ₄ alkylcarbonyl, benzyl or C-rC ₄ alkoxycarbonyl, in particular acetyl, benzyl or tert-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 , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C1-C4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with hydroxalamine and chlorinating agent such as sodium hypochlorite. This is shown in Scheme 7.

The compounds of formula XIII , 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 hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C-|-C ₄ alkylcarbonyl, benzyl or C-|-C ₄ alkoxycarbonyl, in particular acetyl, benzyl or tert-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 , G ² , T, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. Ci-C ₄ alkylcarbonyl, benzyl or Ci-C ₄ alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with hydroxalamine. This is shown in Scheme 8.

The compounds of formula IXa, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. Ci-C alkylcarbonyl, benzyl or Ci-C alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula VI, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² , n and p are as defined for formula I, with h drogen and a catalyst. This is shown in Scheme 9.

Scheme 9

The compounds of formula VI , wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² , n and are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C ₁ -C4 alkylcarbonyl, benzyl or C -C ₄ alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula XV, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , n and p are as defined for formula I and R ¹⁷ is B(OH) ₂ or B(OR ¹⁸ ) ₂ with the two R ¹⁸ each independently being C ₁ -C4 alkyl or together form a four to six-membered ring with a compound of formula I I I, wherein R ⁹ , R ¹⁰ , G ² , Y ¹ and Y ² are as defined for formula I and halogen is chloro, bromo or iodo, and with a transition metal, such as tetrakis(triphenylphosphine)palladium, and a ligand. This is shown in Scheme 10.

Scheme 10

The compounds of formula I II, wherein R ⁹ , R ¹⁰ , G ² , Y and Y ² are as defined for formula I and halogen is chloro, bromo or iodo, can be obtained by transformation of a compound of formula XVI , wherein G ² , Y ¹ , Y ² are as defined for formula I, with a compound of formula XII , wherein R ⁹ and R ¹⁰ are as defined for formula I, and with hydroxylamine and a chlorinatin reagent such as sodium hypochlorite. This is shown in Scheme 1 1.

Scheme 1 1

Alternatively, the compounds of formula IXa, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , G ² , Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C4 alkylcarbonyl, benzyl or C-1-C4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula XVI I, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C ₁ -C4 alkylcarbonyl, benzyl or C ₁ -C4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, with a compounds of formula XVII I, wherein R ⁹ , R ¹⁰ are as defined for formula I and Hal is halogen, preferably chloro or bromo or iodo, and with a base. This is shown in Scheme 12.

Scheme 12

The compounds of formula V, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ , G ² , X, Y ¹ , Y ² , n and p are as defined for formula I and E is hydrogen, a protecting group such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C1-C4 alkylcarbonyl, benzyl or C1-C4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl, can be obtained by transformation of a compound of formula XV, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , n and p are as defined for formula I and R ¹⁷ is B(OH) ₂ or B(OR ¹⁸ ) ₂ with the two R ¹⁸ each independently being C1-C4 alkyl or together form a four to six-membered ring with a compound of formula IV, wherein R ⁹ , R ¹⁰ , R ¹¹ , G ² , X, Y ¹ and Y ² are as defined for formula I and halogen is chloro, bromo or iodo, and with a transition metal, such as tetrakis(triphenylphosphine)palladium, and a li and. This is shown in Scheme 13.

Scheme 13

The compounds of formula IV, wherein R ⁹ , R ¹⁰ , R ¹¹ , G ² , X, Y ¹ and Y ² are as defined for formula I and halogen is chloro, bromo or iodo,, can be obtained by transformation of a compound of formula III, wherein R ⁹ , R ¹⁰ , G ² , Y ¹ and Y ² are as defined for formula I and halogen is chloro, bromo or iodo, with a compound of formula X, wherein R ¹¹ and X are as defined for formula I. This is shown in Scheme 14.

Scheme 14

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 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, 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 (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 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 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) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and

LibertyLink®.

The term "useful plants" 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 5 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

10 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 (117428-22-5), Pyraclostrobin (175013-18-0), trifloxystrobin (141517-21-7),

15 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 (114369-43-6), 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

20 (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-

25 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),

30 Spiroxamine (118134-30-8), 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

35 (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- ylH2,3,4-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 5 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, 10 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 15 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. 20 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.

25 Preparation Examples:

Preparation of 2-[3,5-bis(difluoromethvnpyrazol-1 -yll-1-[4-r4-[10-methoxyimino-7.7-dimethyl- 4-oxa-3-azaspiror4.5ldec-2-en-2-yllthiazol-2-yll-1-piperidyl lethanone

30 2-chloro-1-[4-[4-[10-methoxyimino-7,7-dimethyl-4-oxa-3-azasp iro[4.5]dec-2-en-2-yl]thiazol-2- yl]-1-piperidyl]ethanone (156 mg) was added at 5°C to a mixture of 3,5-bis(difluoromethyl)- 1 H-pyrazole (61 mg) and potassium hydroxide solution (120mg; 20% in water) in dimethyl formamide (2 ml_). The reaction mixture was stirred for 16h at ambient temperature and for 3h at 65°C. Potassium hydroxide (60mg; 20% in water) was added and the reaction mixture

35 was stirred for further 45min at 65°C then diluted with water (1 OOmL) and filtrated. The residue was dried in a vacuum oven and purified over silica to give 2-[3,5- bis(difluoromethyl)pyrazol-1 -yl]-1-[4-[4-[10-methoxyimino-7,7-dimethyl-4-oxa-3- azaspiro[4.5]dec-2-en-2-yl]thiazol-2-yl]-1 -piperidyl]ethanone (106mg) as white foam LC-MS (Method A) UV Detection: 220 nm; Rt = 0.1 .08 MS: (M+1 ) = 585

Chloroacetylchloride (78.7mg) was added at 0-5°C to a solution of diisopropylethylamine (131 mg) and N-methoxy-7,7-dimethyl-2-[2-(4-piperidyl)thiazol-4-yl]-4-oxa -3-azaspiro[4.5]dec- 2-en-10-imine (250mg) in dichloromethane (3ml). After stirring for 90min at 0-5°C, the reaction mixture was quenched with water, diluted with dichloromethane (15ml) and washed 10 with hydrochloric acid (15ml, 1 M) and sodium bicarbonate (10% in water, 15ml). The organic phase was separated, dried over sodium sulfate, filtrated and concentrated. The residue was purified by chromatographie over silica to give 2-chloro-1-[4-[4-[10-methoxyimino-7,7- dimethyl-4-oxa-3-azaspiro[4.5]dec-2-en-2-yl]thiazol-2-yl]-1 -piperidyl]ethanone (280mg) as an oran e oil. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.1 .08 , MS: (M+1 ) = 453.

Sodium hydroxide (2.22ml_; 5M in water) was added to a solution of 1-[4-[4-[(10- methoxyimino-7,7-dimethyl-4-oxa-3-azaspiro[4.5]dec-2-en-2-yl ]thiazol-2-yl]-1 - piperidyl]ethanone (464mg) in ethanol (7.4ml). After stirring for 16h at 85°C the reaction mixture was concentrated and ethylacetate (50ml) was added, insoluble was filtered and the

20 filtrate washed with water. The organic phase was separated dried over magnesium sulfate and concentrated to give an orange solid. All solid material were suspended in ethanol and put for 1 min into an ultrasonic bath. Insoluble material was filtered and the filtrate was concentrated to give N-methoxy-7,7-dimethyl-2-[2-(4-piperidyl)thiazol-4-yl]-4-oxa -3- azaspiro[4.5]dec-2-en-10-imine (399mg) as orange solid. LC-MS (Method A) UV Detection:

25 2 = 0.82, MS: (M+1 ) = 377.

Sodium hypochlorite (11.8mL, 12% in water) was added dropwise over 40min to a solution of 2-(1 -acetyl-4-piperidyl)thiazole-4-carbaldehyde oxime (1 g) and N-methoxy-4,4-dimethyl-2- methylene-cyclohexanimine (2.75g; 24% solution in a dichloromethane/acetonitrile; 1/1 ) and triethylamine (40mg). After stirring for 90min at ambient temperature the reaction mixture was diluted with ethylacetate and water. The phases were separate ant the organic phase was washed with water, dried over sodium sulfate, filtrated and concentrated. The residue was purified over silica to give 1-[4-[4-[10-methoxyimino-7,7-dimethyl-4-oxa-3- 5 azaspiro[4.5]dec-2-en-2-yl]thiazol-2-yl]-1 -piperidyl]ethanone as a light yellow foam (616mg). LC-MS (Method A) UV Detection: 220 nm; Rt = 1.03, MS: (M+1 ) = 419.

Alternative preparation of N-methoxy-7.7-dimethyl-2-r2-(4-piperidyl ^' )thiazol-4-yll-4-oxa-3- azaspiro[4.5ldec-2-en-10-imine

O-methylhydroxylamine hydrochloride (2.06 g) was added to a solution of 7,7-dimethyl-2-[2- (4-piperidyl)thiazol-4-yl]-4-oxa-3-azaspiro[4.5]dec-2-en-10- one (2.37g) in ethanol (31 ml_). The reaction mixture was stirred for 16h at 60°C, then cooled to 25°C, concentrated and diluted with ethylacetate and sodium hydrogen carbonate solution (10% in water). Insoluble 15 material was filtered and dried to give N-methoxy-7,7-dimethyl-2-[2-(4-piperidyl)thiazol-4-yl]- 4-oxa-3-azaspiro[4.5]dec-2-en-10-imine (2.22g) as beige powder. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.82, MS: (M+1 ) = 377.

20 A solution of HCI (10.6mL; 4M in dioxane) was added to a solution tert-butyl 4-[4-(7,7- dimethyl-10-oxo-4-oxa-3-azaspiro[4.5]dec-2-en-2-yl)thiazol-2 -yl]piperidine-1 -carboxylate (3.13g) in dioxane (28mL). After stirring for 4h at 25°C and 16h at 60°C the reaction mixture was cooled to 20°C and the precipitated solid was filtered. The solid was washed with ethylacetate to give 7,7-dimethyl-2-[2-(4-piperidyl)thiazol-4-yl]-4-oxa-3-azaspir o[4.5]dec-2-en-

25 10-one hydrochloride (2.47g) as white solid. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.71 , MS: (M+1 ) = 348.

Sodium hypochlorite (15.4g 12% in water) was added dropwise within 30min to a solution of 30 tert-butyl 4-[4-[hydroxyiminomethyl]thiazol-2-yl]piperidine-1-carboxyla te (3.8g), triethylamine (0.124g) and 4,4-dimethyl-2-methylene-cyclohexanone (1.86g in 50mL dichloromethane) in ethylacetate (60ml_). After stirring for 16h at 25°C the reaction mixture was diluted with ethylacetate and washed with water. The organic phase was separated, dried over sodium sulfate, concentrated and the residue was purified by chromatographie over silica to give tert- butyl 4-[4-(7,7-dimethyl-10-oxo-4-oxa-3-azaspiro[4.5]dec-2-en-2-yl )thiazol-2-yl]piperidine-1- carboxylate (3.13g) as white solid. LC-MS (Metod A) UV Detection: 220 nm; Rt = 1.17, MS: (M+1 ) = 348 (only Mass of deprotected compound was dedected).

Alternative preparation of 1-r4-i4-[10-methoxyimino-7.7-dimethyl-4-oxa-3-azaspiro[4.5ld ec-2- n-2-yllthiazol-2-yll-1-piperidyllethanone

To a solution of 1-acetylpiperidine-4-carbothioamide (0.1299 g) and 2-chloro-1-[(10- methoxyimino-7,7-dimethyl-4-oxa-3-azaspiro[4.5]dec-2-en-2-yl ]ethanone (0.200 g) in DMF (2 ml_) , was added sodium bromide (0.1076 g). The reaction mixture was stirred at 80°C for 2h, cooled to ambient temperature, dilutes with water and extracted with ethyl acetate. The combined organic phases were washed with water, dried over magnesium sulfate, filtered and concentrated. The residue was purified by chromatographie over silica to give 1-[4-[4- [10-methoxyimino-7,7-dimethyl-4-oxa-3-azaspiro[4.5]dec-2-en- 2-yl]thiazol-2-yl]-1- piperidyl]ethanone (0.216g) as a white foam. LC-MS (Method A) UV Detection: 220 nm; Rt = 1.03, MS: (M+) = 419.

A solution of 3-chloro-N-hydroxy-2-oxo-propanimidoyl chloride (2.1g) in ethylacetate (10ml) was added at 25°C within 30min to a well stirred mixture of N-methoxy-4,4-dimethyl-2- methylene-cyclohexanimine (5g; 30% in dichloromethane) and sodiumbicarbonate (4.52g) in ethylacetate (1 OmL). After stirring for 16h at 25°C the reaction mixture was diluted with etylacetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and concentrated and the residue was purified by chromatographie over silica to give 2-chloro-1-[10-methoxyimino-7,7-dimethyl-4-oxa-3-azaspiro[4. 5]dec-2-en-2-yl]ethanone (1.21g) as yellow oil. LC-MS (Method A) UV Detection: 220 nm; Rt = 1.13, MS: (M+) = 287.

Preparation of 2-(1 -acetyl-4-piperidvDthiazole-4-carbaldehvde oxime

Hydroxylamine hydrochloride was added to a solution of 2-(1-acetyl-4-piperidyl)thiazole-4- carbaldehyde (3.9g) in ethanol (65ml_). After stirring for 16h at 25°C the reaction mixture was concentrated and water was added and the insoluble material was filtrated and dried to give 2-(1 -acetyl-4-piperidyl)thiazole-4-carbaldehyde oxime (2.53g) as white solid. LC-MS (Method

= 0.54, MS: (M+) = 254.

Triethylamine (9.72g) was added at 0-5°C to a solution of 2-(4-piperidyl)thiazole-4- carbaldehyde dihydrochloride (8.0) in dichloromethane (100ml_). Acetylchloride (2.80g) was added at 0-5°C, the reaction mixture was warmed up and stirred for 16h at 25°C. The reaction mixture was poured onto sodium bicarbonate solution (300ml_; 20% in water) and extracted with dichloromethane. The combined organic phases were washed with brine dried over magnesiumsulfate, filtered and concentrated. The residue was purified by

chromatographie over silica to give 2-(1 -acetyl-4-piperidyl)thiazole-4-carbaldehyde (3.05g) as yellow oil. . LC-MS (Method A) UV Detection: 220 nm; Rt = 0.49, MS: (M+) = 239.

Pre aration of N-methoxy-4,4-dimethyl-2-methylene-cyclohexanimine

Acetonitrile (43mL) was added to a suspension of [2-methoxyimino-5,5-dimethyl- cyclohexyl]methyl-trimethyl-ammonium iodide (3.63g) in sodium hydroxide (16.6mL, 2M in water). After stirring for 15h at 80°C the reaction mixture was cooled and most of the acetonitrile was removed. The residue was diluted with dichloromethane. The organic phase was separated and the water phase was extracted with dichloromethane. The combined organic phases were dried over magnesium sulfate, filtered and carefully concentrated to give N-methoxy-4,4-dimethyl-2-methylene-cyclohexanimine (1.7g) which contains according to 1 HNMR 45% of dichloromethane. 1 H-NMR (CDCI3, 400 MHz): 5.38 (s, 1 H), 4.80 (s, 1 H), 3.90 (s,3H), 2.52 (t, 2H), 2.16 (s, 2H), 1.48 (t, 2H), 0.95 (s, 6H).

This product was used in the next steps without further purification. Depending on workup this product can contain variable amounts of dichloromethane and acetonitrile.

lodomethane (16.6g) was added to a solution of 1-[2-methoxyimino-5,5-dimethyl-cyclohexyl]- Ν,Ν-dimethyl-methanamine (12.35g) in methanol (68ml_). The reaction mixture was stirred for 16h at ambient temperature then concentrated under reduced pressure to give [2- methoxyimino-5,5-dimethyl-cyclohexyl]methyl-trimethyl-ammoni um iodide (20.1g) as a yellow solid. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.60, MS: (M+) = 227.

Sodium acetate (6.44g) and O-methylhydroxyl amine hydrochloride (6.56g) were added to a solution of 2-(dimethylaminomethyl)-4,4-dimethyl-cyclohexanone (12g) in ethanol (80mL). After stirring for 3h at ambient temperature the reaction mixture was concentrated and to the residue sodium hydroxide (10% in water) was added. The mixture was extracted with diethyl ether and the combined organic phases were dried over magnesium sulfate, filtered and concentrated to give 1-[2-methoxyimino-5,5-dimethyl-cyclohexyl]-N,N-dimethyl-meth anamine (12.6g) as a colorless liquid. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.56+0.61 , MS: ( +1 ) = 213

Preparation of 4.4-dimethyl-2-methylene-cvclohexanone

Aluminiumoxide (12.2g; alox basic 50-200uM) was added to a solution of (5,5-dimethyl-2- oxo-cyclohexyl)methyl-trimethyl-ammonium iodide (14g) in dichloromethane (140mL). After stirring for 4h at 25°C the reaction mixture was filtered and the solid was washed with 20ml of dichloromethane. This solution contains 4,4-dimethyl-2-methylene-cyclohexanone (5.9 g) and was used in the next step without further purification.

The content of 4,4-dimethyl-2-methylene-cyclohexanone in the above solution was assumed to be same as in small scale test reaction with CD2CI2 as solvent. The conversion was followed by 1 H-NMR measurements. After 2h of stirring: 1 H-NMR(CD2CI2, 400 MHz): 5.68 (m,1 H); 5.00 (m,1 H); 2.33 (t, 2H); 2.29 (s, 2H); 1 .64 (t, 2H); 0.97 (s, 6H)

lodomethane (26.5g) was added to a solution of 2-(dimethylaminomethyl)-4,4-dimethyl- cyclohexanone (17g) in methanol (110mL). After stirring for 4h at 25°C the reaction mixture was concentrated to give (5,5-dimethyl-2-oxo-cyclohexyl)methyl-trimethyl-ammonium iodide (29.8g) as light yellow solid. LC-MS (Method A) UV Detection: 220 nm; Rt = 0.30, MS: (M+) = 198.

Dimethyl(methylene)ammonium chloride (16.1 g) was added to a solution of 4,4- dimethylcyclohexanone (20.5 g) in acetonitrile (82mL). After stirring at ambient temperature for 16h the reaction mixture was filtered and the white solid was washed with diethylether to give 2-(dimethylaminomethyl)-4,4-dimethyl-cyclohexanone hydrochloride (28.9g) as a white solid. 1 H-NMR (CDCI3, 400 MHz): 3.58 (m,1 H); 3.31 (m,1 H); 2.80 (d, 3H); 2.70 (d, 3H); 2.75- 2.51 (m, 2H); 2.27 (m, 1 H); 2.03 (m, 1 H); 1.72 (m, 1 H); 1.57 (m, 1 H); 1.37 (t, 1 H); 1.26 (s, 3H); 0.97 (s, 3H).

This solid was then suspended in diethylether (130ml) and triethylamine (65. Og) was added. After stirring for 3h at ambient temperature the reaction mixture was filtered and the filtrate was concentrated to give 2-(dimethylaminomethyl)-4,4-dimethyl-cyclohexanone (20.8g) as a colorless liquid which was used without further purification in next steps.

P rep a rati o n of l-^-^-rS-iN-methoxy-C-phenyl-carbonimidoyll^.S-dihvdroisoxaz ol-S- yllthiazol-2-yll-1-piperidyll-2-[5-methyl-3-(trifluoromethyl )pyrazol-1-yllethanone

To a cooled suspension (0°C) of N-methoxy-1-phenyl-1 -[3-[2-(4-piperidyl)thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]methanimine trifluoroacetic acid salt (0.1 11 g) in dichloromethane (1.15 mL) was added triethylamine (0.058 g) and the mixture was stirred for 5 min. Then a solution of 2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl chloride (0.053 g) in dichloromethane (3mL) was added slowly and the mixture was stirred at 0°C for 30 min, after which LCMS showed complete consumption of the starting material. The reaction mixture was diluted with water and the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with 1 M HCI, sat. aq. sodiumbicarbonate, brine, dried over

sodiumsulfate, filtered and concentrated under reduced pressure to give 1 10 mg of brown oil. The residue was purified by flash chromatography to give 1 -[4-[4-[5-[N-methoxy-C-phenyl- carbonimidoyl]-4,5-dihydroisoxazol-3-yl]thiazol-2-yl]-1 -piperidyl]-2-[5-methyl-3- (trifluoromethyl)pyrazol-1-yl]ethanone (51 mg) as a white foamy solid. LC-MS (Method B) UV Detection: 220 nm; Rt = 1.76, 1 .81 , MS: (M+1 ) = 561.

To a dry flask containing tert-butyl 4-[4-[5-[N-methoxy-C-phenyl-carbonimidoyl]-4,5- dihydroisoxazol-3-yl]thiazol-2-yl]piperidine-1-carboxylate (0.10 g) under an atmosphere of argon was added trifluoroacetic acid (1.0 ml_) and the mixture was stirred at rt for 1 h. LCMS indicated complete consumption of the starting material. Removal of trifluoroacetic acid under vacuo afforded N-methoxy-1-phenyl-1 -[3-[2-(4-piperidyl)thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]methanimine trifluoroacetic acid salt (0.12 g) as a colorless oil which was directly used in the next step without further purification. LC-MS (Method B) UV

Detection: 220 nm; Rt = 0.88, 0.91 , MS: (M+1 ) = 371.

To a solution of tert-butyl 4-[4-[hydroxyiminomethyl]thiazol-2-yl]piperidine-1 -carboxylate (0.440 g), bisacetoxy iodobenzene (0.660 g) and trifluoroacetic acid (0.0531 g) in methanol (29.0 mL) under an argon atmosphere was added N-methoxy-1-phenyl-prop-2-en-1-imine (0.58 g) was added and the white suspension was stirred at room temperature overnight. The colorless solution was concentrated and purified by flash chromatography to give tert- butyl 4-[4-[5-[N-methoxy-C-phenyl-carbonimidoyl]-4,5-dihydroisoxaz ol-3-yl]thiazol-2- yl]piperidine-1-carboxylate (680 mg) as a white foam. LC-MS (Method B) UV Detection: 220 nm; Rt = 1.96, 2.01 , MS: (M+Na) = 493. Preparation of N-methoxy-1 -phenyl-prop-2-en-1-imine

To a suspension of [3-methoxyimino-3-phenyl-propyl]-trimethyl-ammonium iodide (0.720 g) in acetonitrile (7.2 mL) was added an aqueous solution of sodium hydroxide (2.0 mol/L; 3.4 mL) and the mixture was stirred at room temperature for 3h. The reaction mixture was diluted with dichloromethane and water and the phases were separated. The aqueous phase was extracted with dichloromethane and the combined organic phases were washed with water, dried over sodiumsulfate, filtered and concentrated to give N-methoxy-1-phenyl-prop-2-en-1- imine (445 mg) as a pale yellow oil. LC-MS (Method B) UV Detection: 220 nm; Rt = 1 .48, 1.56, MS: (M+1 ) = 162.

To a solution of 3-methoxyimino-N,N-dimethyl-3-phenyl-propan-1-amine (0.350 g) in methanol (3.0 mL) was added methyl iodide (0.484 g) and the mixture was stirred at room temperature for 3 h. Removal of the solvent under reduced pressure afforded [3- methoxyimino-3-phenyl-propyl]-trimethyl-ammonium iodide (0.570 g) as a pale yellow solid. LC-MS (Method B) UV Detection: 220 nm; Rt = 0.48, 0.57, MS: (M+) = 221.

To a solution of 3-(dimethylamino)-1-phenyl-propan-1-one (2.00 g) in ethanol (12 mL, 1.0 mol/L) were added sodium acetate (1.12 g) and O-methylhyroxylamine hydrochloride (1.15 g) and the reaction mixture was stirred at room temperature for 4 h. The solvent was removed under reduced pressure and the residue was basified with an aqueous solution of sodium hydroxide (10% w/w) until pH 13-14. The aqueous phase was extracted with diethylether and the combined organic phases were dried over sodiumsulfate, filtered and concentrated. The residue was purified by flash chromatography to give 3-methoxyimino- N,N-dimethyl-3-phenyl-propan-1 -amine (3.04 mmol, 660 mg) as a mixture of (E) and (Z) isomers. LC-MS (Method B) UV Detection: 220 nm; Rt = 0.43, 0.52, MS: (M - N(CH3)2) = 162. 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

In Table 1 below, Ί" refers to a carbon-oxygen single bond, "j" refers to a carbon-carbon single bond and "k" refers to a carbon-nitrogen double bond as shown below on the general formula (I):

Entry. R» R R

No.

001 H H H

002 Me H H

003 iPr H H

004 nPr H H

005 cyclopropyl H H

006 H H

JO

007 H H

¾? F

008 H H

F

009 H H

J?

CI

010 H H

V- Me

H ₃ C

N-OH

N-0

CH ₃

HO-N

O-N

H ₃ C

Op F

where a) 889 compounds of formula (la. a): wherein R , R , R are as defined in Table 1. b) 889 compounds of formula (la.b):

wherein R , R , R are as defined in Table 1. c) 889 compounds of formula (la.c):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. d) 889 compounds of formula (la.d):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. e) 889 compounds of formula (la.e):

wherein R , R , R are as defined in Table 1. f) 889 compounds of formula (la.f):

wherein R , R , R are as defined in Table 1. g) 889 compounds of formula (la.g):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. h) 889 compounds of formula (la.h):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. i) 889 compounds of formula (la.i):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. j) 889 compounds of formula (la.j):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. k) 889 compounds of formula (la.k):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. I) 889 compounds of formula (la. I):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. m) 889 compounds of formula (la.m):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined n) 889 compounds of formula (la.n)

wherein R ⁹ , R ⁰ , R are as defined in Table 1. o) 889 compounds of formula (la.o):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. p) 889 compounds of formula (la.p):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. q) 889 compounds of formula (la.q):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. r) 889 compounds of formula (la.r):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. s) 889 compounds of formula (lb. a):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. t) 889 compounds of formula (Ib.b): wherein R , R , R are as defined in Table 1. u) 889 compounds of formula (Ib.c):

wherein R ⁹ , R ⁰ , R ¹¹ are as defined in Table 1.. v) 889 compounds of formula (Ib.d):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. w) 889 compounds of formula (Ib.e):

wherein R , R , R are as defined in Table 1. x) 889 compounds of formula (Ib.f):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. y) 889 compounds of formula (Ib.g):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. z) 889 compounds of formula (Ib.h):

aa) 889 compounds of formula (Ib.i):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ab) 889 compounds of formula (Ib.j):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in ac) 889 compounds of formula (Ib.k): wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ad) 889 compounds of formula (lb. I):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1.. ae) 889 compounds of formula (Ib.m):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. af) 889 compounds of formula (Ib.n):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ag) 889 compounds of formula (Ib.o):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ah) 889 compounds of formula (Ib.p):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ai) 889 compounds of formula (Ib.q):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. aj) 889 compounds of formula (Ib.r):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ak) 889 compounds of formula (lea):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. al) 889 compounds of formula (Ic.b):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. am) 889 compounds of formula (Ice):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1.. an) 889 compounds of formula (led):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ao) 889 compounds of formula (Ice):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ap) 889 compounds of formula (Ic.f):

ar) 889 compounds of formula (Ic.h):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. as) 889 compounds of formula (Ic.i):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. at) 889 compounds of formula (lc.j):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. au) 889 compounds of formula (Ic.k): wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. av) 889 compounds of formula (Id):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1.. aw) 889 compounds of formula (Ic.m):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ax) 889 compounds of formula (Ic.n):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ay) 889 compounds of formula (Ic.o):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. az) 889 compounds of formula (Ic.p):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. ba) 889 compounds of formula (Icq):

wherein R , R , R are as defined in Table 1. bb) 889 compounds of formula (Ic.r):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. be) 889 compounds of formula (l.d.a):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in bd) 889 compounds of formula (Id.b):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. be) 889 compounds of formula (Id.c):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1.. bf) 889 compounds of formula (Id.d):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bg) 889 compounds of formula (Id.e):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bh) 889 compounds of formula (Id.f):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bi) 889 compounds of formula (Id.g):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bj) 889 compounds of formula (Id.h):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bk) 889 compounds of formula (Id.i):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bl) 889 compounds of formula (I.e. a):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bm) 889 compounds of formula (I.e.b): wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bn) 889 compounds of formula (le.c):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1.. bo) 889 compounds of formula (le.d):

Wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bp) 889 compounds of formula (le.e):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bq) 889 compounds of formula (le.f):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. br) 889 compounds of formula (le.g):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bs) 889 compounds of formula (le.h):

wherein R ⁹ , R ¹⁰ , R ¹¹ are as defined in Table 1. bt) 889 compounds of formula (le.i):

wherein R ⁹ , R ¹⁰ , R ¹¹ 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 methods are:

Method A

SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

Instrument Parameter:

Ionization method: Electrospray; Polarity: positive and negative ions; Capillary: 3.00 kV; Cone: 30V; 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

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 μΐη, 30 x 2.1 mm,

Temp: 60 °C

DAD Wavelength range (nm): 210 to 500

Solvent Gradient:

A = H20 + 5% MeOH + 0.05 % HCOOH; B= Acetonitril + 0.05 % HCOOH

Time A% B% Flow (ml/min)

0.00 90 10 0.85

1.20 0 100.0 0.85

1.50 0 100.0 0.85

Method B: ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Instrument Parameter:

Ionization method: Electrospray; Polarity: positive and negative ions; Capillary: 3.00 kV; Cone: 30 V; Extractor: 2.00 V; Source Temperature: 150°C; Desolvation Temperature: 350C; Cone Gas Flow: 50 L/Hr; Desolvation Gas Flow: 400 L/Hr; Mass range: 100 to 900 Da

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 μΐτι, 30 x 2.1 mm,

Temp: 60 °C

DAD Wavelength range (nm): 210 to 500

Solvent Gradient:

A = H20 + 5% MeOH + 0.05 % HCOOH; B= Acetonitril + 0.05 % HCOOH

Time A% B% Flow (ml/min)

0.00 90 10 0.85

2.70 0 100.0 0.85

3.00 0 100.0 0.85

Table 2: Melting point and LC/MS data for compounds compounds according to the invention ı52



160

ı63

ı64

ı65

ı66





ı73

ı77



180

The compounds according to the present invention can be prepared according to the 5 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

The compounds listed below are those from Table 2.

10

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

15 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).

Compounds 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 20 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 , 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 104 , 105 , 106 , 107 , 108 , 109 , 110 , 1 1 1 , 1 12 , 113 , 114 , 1 15 , 1 16 , 117 , 1 18 , 119 , 120 , 121 , 122 , 123 , 124 , 125 , 127 , 129 , 131 , 132 , 133 , 25 135 , 136 , 137 , 139 , 140 , 141 , 142 , 143 , 144 , 145 , 146 , 147 , 148 , 149 , 150 , 151 , 152 , 153 , 155 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 164 , 165 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.

30 Phytophthora infestans I tomato / leaf disc curative (tomato late blight) Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and the leaf disks are inoculated with a spore suspension of the fungus. The inoculated leaf disks are incubated at 16°C and 75% rh in darkness in a climate cabinet. 20 hours after inoculation the leaf disks are sprayed with the formulated test compound diluted in water and the leaf disks are incubated at 16°C and 75% rh under 5 a light regime of 12 h light / 12 h darkness in a climate cabinet. 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 (4 - 6 days after inoculation).

Compounds 1 , 2 , 5 , 7 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 35 , 36 , 37 , 38 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 ,

10 53 , 54 , 55 , 56 , 57 , 59 , 60 , 61 , 62 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 78 , 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 96 , 97 , 98 , 99 , 100 , 101 , 103 , 104 , 105 , 106 , 107 , 108 , 109 , 110 , 1 1 1 , 1 12 , 114 , 115 , 1 16 , 1 17 , 118 , 120 , 121 , 122 , 123 , 124 , 125 , 127 , 132 , 133 , 139 , 140 , 141 , 142 , 143 , 144 , 145 , 146 , 147 , 148 , 149 , 150 , 151 , 152 , 153 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 165 at 200 ppm give at least 80% disease

15 control in this test when compared to untreated control leaf disks 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 20 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).

Compounds 1 , 2 , 7 , 9 , 10 , 13 , 15 , 16 , 19 , 20 , 22 , 23 , 24 , 26 , 31 , 32 , 42 , 45 , 52 , 56 , 59 , 25 69 , 71 , 74 , 78 , 80 , 84 , 91 , 92 , 94 , 96 , 105 , 106 , 107 , 110 , 114 , 1 15 , 1 16 , 117 , 120 , 125 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.

Phytophthora infestans I potato / curative (potato late blight)

30 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).

35 Compounds 1 , 2 , 7 , 9 , 10 , 13 , 15 , 16 , 19 , 20 , 22 , 23 , 24 , 26 , 31 , 42 , 45 , 52 , 56 , 59 , 69 , 71 , 74 , 78 , 80 , 84 , 91 , 92 , 94 , 96 , 105 , 106 , 107 , 110 , 114 , 115 , 1 16 , 1 17 , 120 , 125at 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.

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).

Compounds 1 , 2 , 7 , 9 , 10 , 13 , 15 , 16 , 19 , 20 , 22 , 23 , 24 , 26 , 31 , 32 , 42 , 45 , 52 , 56 , 59 , 5 69 , 71 , 74 , 78 , 80 , 84 , 91 , 92 , 94 , 96 , 105 , 106 , 107 , 110 , 114 , 1 15 , 1 16 , 117 , 120 , 125 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.

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

10 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 15 damage appears in untreated check leaf disks (6 - 8 days after application).

Compounds 1 , 2 , 4 , 5 , 6 , 7 , 9 , 10 , 11 , 12 , 13 , 15 , 16 , 17 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 35 , 36 , 37 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 65 , 66 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 78 , 79 , 80 , 81 , 82 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 100 , 101 , 103 , 20 104 , 105 , 106 , 107 , 109 , 110 , 111 , 112 , 1 13 , 1 14 , 115 , 116 , 1 17 , 1 18 , 120 , 121 , 122 , 123 , 124 , 125 , 127 , 129 , 132 , 133 , 134 , 135 , 139 , 140 , 141 , 142 , 143 , 144 , 145 , 146 , 147 , 148 , 149 , 150 , 151 , 152 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 164 , 165 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.

25

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

30 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).

Compounds 1 , 2 , 7 , 9 , 10 , 13 , 15 , 16 , 19 , 20 , 22 , 23 , 24 , 26 , 31 , 32 , 33 , 34 , 37 , 40 , 42 , 44 , 45 , 47 , 50 , 51 , 52 , 56 , 59 , 69 , 71 , 74 , 78 , 80 , 84 , 91 , 92 , 94 , 96 , 105 , 106 , 107 , 1 10 , 114 , 115 , 116 , 1 17 , 120 , 125 , 133 , 151 , 152 at 200 ppm give at least 80% disease control in this

35 test when compared to untreated control leaf disks 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 40 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). Compounds 1 , 7 , 13 , 15 , 16 , 19 , 20 , 23 , 26 , 31 , 42 , 45 , 52 , 56 , 59 , 74 , 78 , 80 , 91 , 92 , 94 , 96 , 105 , 106 , 107 , 1 10 , 1 14 , 1 15 , 116 , 1 17 at 200 ppm give at least 80% disease control in this 5 test when compared to untreated control leaf disks 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 10 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 (11 - 13 days after application).

Compounds 1 , 7 , 9 , 10 , 13 , 15 , 16 , 19 , 20 , 22 , 23 , 24 , 26 , 31 , 42 , 45 , 52 , 56 , 59 , 69 , 71 , 15 74 , 78 , 80 , 84 , 91 , 92 , 94 , 96 , 106 , 107 , 1 10 , 114 , 115 , 1 16 , 1 17 , 120 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.

20 Pythium ultimum I liquid culture (seedling damping off)

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

25 2-3 days after application.

Compounds 1 , 7 , 13 , 15 , 16 , 17 , 19 , 20 , 22 , 23 , 24 , 31 , 33 , 35 , 36 , 37 , 41 , 42 , 43 , 44 , 50 , 51 , 52 , 53 , 54 , 56 , 60 , 61 , 62 , 68 , 69 , 71 , 79 , 80 , 84 , 88 , 91 , 92 , 93 , 94 , 96 , 105 , 107 , 110 , 133 , 162 , 163 , 165 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.