WO2011076510A1

WO2011076510A1 - Pyrazole derivatives

Info

Publication number: WO2011076510A1
Application number: PCT/EP2010/068184
Authority: WO
Inventors: Sarah Sulzer; Clemens Lamberth
Original assignee: Syngenta Participations Ag
Priority date: 2009-12-22
Filing date: 2010-11-25
Publication date: 2011-06-30
Also published as: ES2450424T3; EP2516424A1; BR112012016923A2; US20120258990A1; TW201139425A; US8629286B2; AR079550A1; EP2516424B1; CN102666532A

Abstract

The present invention relates to heterocyclic compounds of formula (I) which have microbiocidal activity, in particular fungicidal activity: formula (I) wherein G¹ and G² are independently O or S; T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O; Y¹ and Y² are independently CR¹⁴ or N; Q is -C(=O)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, -C(=O)-O-z, -N(R¹⁷)-C(=O)-z, -N(R¹⁸)-C(=S)-z, - N(R¹⁹)-C(=O)-O-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸; n is 1, 2, 3 or 4 when T is -C(R⁹R¹⁰)-, NR¹³ or O; n is 1, 2, 3 when T is -C(R¹¹)=C(R¹²)- or -C≡C-; R¹, R², R³, R⁴, R¹¹, R¹²and R¹⁴ each independently are hydrogen, halogen, cyano, C₁- C₄alkyl, or C₁-C₄haloalkyl; R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ each independently are hydrogen, C₁- C₄alkyl or C₁-C₄alkoxy; R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together from a carbonyl group (=O); R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together form a carbonyl group (=O); and R⁸ is phenyl, benzyl or group (a): formula (a) wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen, cyano, hydroxy and amino; or a salt or a N-oxide thereof.

Description

Pyrazole Derivatives

The present invention relates to heterocycles, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these heterocycles, to heterocyclic derivatives used as intermediates in the preparation of these heterocycles, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the heterocycles, to preparation of these compositions and to use of the heterocycles 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 heterocycles 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

G¹ and G² are independently O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ and Y² are independently CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁸)-C(=S)-z, - N(R¹⁹)-C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2, 3 or 4 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 , 2, 3 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R¹, R², R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, cyano, C₁- C₄alkyl, or C₁-C₄haloalkyl;

R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ each independently are hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy;

R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, Ci- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together from a carbonyl group (=0); R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together form a carbonyl group (=0); and

R⁸ is henyl, benzyl or group (a):

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen, cyano, hydroxy and amino;

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. Normally not more than three such optional substituents are present at the same time.

The term "halogen" stands for fluorine, chlorine, bromine or iodine.

The term "amino" stands for -NH₂. Alkyl, alkenyl or alkynyl 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. A haloalkyl group may contain one or more identical or different halogen atoms and, for example, may stand for CH₂CI, CHCl₂, CCI₃, CH₂F, CHF₂, CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCI₃CCI₂.

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. As a result of the presence of a possible aliphatic C=C double bond, geometric isomerism may occur, i.e. cis-trans or (E)-(Z) isomerism. 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.

Suitable salts of the compounds of formula I include those resulting after addition of acid such as those with an inorganic mineral acid e.g. hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid e.g. oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulfonic acid e.g. methane, benzene or toluene sulfonic acid.

Preferably the compound of formula I is a compound wherein:

G¹ and G² are independently O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or 0;

Y¹ and Y² are independently CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁹)-C(=0)-0-z or -

N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2 or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R¹, R², R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, C₁-C₄alkyl, or C₁-C₄haloalkyl;

R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁹, R²⁰ and R²¹ each independently are hydrogen or C₁-C₄alkyl; R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together form a carbonyl group (=0); and R⁸ is henyl, benzyl or group (a):

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyi, halogen, hydroxy and amino. Preferably the compound of formula I is a compound wherein:

G¹ and G² are independently O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2, or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷ each independently are hydrogen or C₁-C₄alkyl;

R⁶ and R⁷ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-

C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁- C haloalkyl, C₁-C₄haloalkoxy or together form a carbonyl group (=0); and

R⁸ is henyl, benzyl or group (a):

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyi, halogen, hydroxy and amino.

Preferably the compound of formula I is a compound wherein:

G¹ is O;

G² is O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, -C(=0)-0-z, or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸; n is 1 , 2 or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R⁵, R¹³, R¹⁵, R¹⁷ each independently are hydrogen or C₁-C₄alkyl;

R⁶ and R⁷ each independently are hydrogen, halogen, hydroxy, C₁-C₄alkyl, C₁-C^lkoxy, C₁- C₄haloalkyl, C₁-^haloalkoxy or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, hydroxy, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together form a carbonyl group (=0); and

R⁸ is benz l or group (a):

wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen and hydroxy.

Preferably the compound of formula I is a compound wherein:

G¹ is O;

G² is S;

T is -C(R⁹R¹⁰)-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴;

Q is -C(=0)-N(R¹⁵)-z or -C(=0)-0-z, in each case z indicates the bond that is connected to R⁸;

n is 2;

R¹ and R² are independently halogen, methyl or halomethyl;

R³, R⁴ and R¹⁴ each independently are hydrogen, halogen, methyl, or halomethyl;

R⁵, R¹³ and R¹⁵ each independently are hydrogen or methyl;

R⁶ and R⁷ each independently are hydrogen, halogen, methoxy or methyl;

R⁹ and R¹⁰ each independently are hydrogen, halogen, methoxy or methyl; and

R⁸ is benz l or group (a):

wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from methyl, halomethyl, and halogen.

Preferably the compound of formula I is a compound wherein:

G¹ is O;

G² is S;

T is -C(R⁹R¹⁰)-;

Y¹ is N;

Y² is CR¹⁴;

Q is -C(=0)-N(R¹⁵)-z, wherein z indicates the bond that is connected to R⁸;

n is 2;

R¹ and R² are independently methyl or trifluoromethyl;

R³, R⁴ and R¹⁴ each independently are hydrogen, fluoro or methyl;

R⁵ and R¹⁵ each independently are hydrogen or methyl;

R⁶ and R⁷ each independently are hydrogen, fluoro or methyl;

R⁹, and R¹⁰ each independently are hydrogen, fluoro or methyl; and

R⁸ is roup (a):

wherein group (a) is optionally substituted with 1 to 3 substituents independently selected from methyl, trifluoromethyl and fluoro.

The invention also relates to compounds of formula I wherein

G¹ is O;

G² is O, S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, , -C(=0)-0-z or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2, or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 , or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R¹ and R² each independently are methyl or halomethyl;

R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen or methyl.

R⁵, R¹³, R¹⁵ and R¹⁷ each independently are hydrogen or methyl; R⁶ and R⁷ each independently are hydrogen, halogen, methyl or methoxy or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, methyl or methoxy or together from a carbonyl group (=0); and

R⁸ is benz l or group (a):

(a)

wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from methyl, halomethyl and halogen.

The following list provides definitions, including preferred definitions, for substituents

G¹, G², T, Y¹, Y², Q, n, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ , R¹¹ , R¹² , R¹³ , R¹⁴ , R¹⁵ , R¹⁶ , R¹⁷ R¹⁸, R¹⁹, R²⁰ and R²¹ with reference to compounds of formula I. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below. The invention includes compounds of formula having all possible combinations of substituent definitions given below or elsewhere in this document.

Generally, in this document any substituent definition may be combined with any other substituent definition.

G¹ and G² are independently O or S.

Preferably, G¹ is O.

Preferably, G² is S.

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O.

Preferably, T is -C(R⁹R¹⁰)-, NR¹³ or O.

Preferably, T is -C(R⁹R¹⁰)-.

Y¹ and Y² are independently CR¹⁴ or N.

Preferably, Y¹ is N.

Preferably, Y² is CR¹⁴

Q is -C(=0)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁸)-C(=S)-z, - N(R¹⁹)-C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸.

Preferably, Q is -C(=0)-N(R¹⁵)-z_> -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁹)- C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸.

Preferably, Q is -C(=0)-N(R¹⁵)-z. -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸. Preferably, Q is -C(=0)-N(R¹⁵)-z, -C(=0)-0-z, or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸.

Preferably, Q is -C(=0)-N(R¹⁵)-z or -C(=0)-0-z, in each case z indicates the bond that is connected to R⁸.

Preferably, Q is -C(=0)-N(R¹⁵)-z, wherein z indicates the bond that is connected to R⁸. n is 1 , 2, 3 or 4 when T is -C(R⁹R¹⁰)-, NR¹³ or O; and n is 1 , 2, 3 when T is -C(R¹¹)=C(R¹²)- or -C≡C-.

Preferably, n is 1 , 2 or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O; and n is 1 or 2 when T is - C(R¹¹)=C(R¹²)- or -C≡C-.

Preferably, n is 2 when T is -C(R⁹R¹⁰)-, NR¹³ or O; and n is 1 when T is -C(R¹¹)=C(R¹²)- or - C≡C-.

R¹, R², R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, cyano, C₁- C₄alkyl, or C₁-C₄haloalkyl.

Preferably, R¹, R², R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, d- C₄alkyl, or C₁-C₄haloalkyl.

Preferably, R¹ and R² each independently are halogen, methyl, or halomethyl.

Preferably, R¹ and R² each independently are methyl or halomethyl.

Preferably, R¹ and R² each independently are methyl or trifluoromethyl;

Preferably, R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, methyl, or halomethyl.

Preferably, R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen or methyl. Preferably, R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, fluoro or methyl. R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ , R²⁰ and R²¹ each independently are hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy.

Preferably, R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ , R²⁰ and R²¹ each independently are hydrogen or C₁-C₄alkyl.

Preferably, R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ , R²⁰ and R²¹ each independently are hydrogen or methyl.

R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, CVdalkyl, C₁- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together from a carbonyl group (=0).

Preferably, R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, d- C₄alkyl, C₁-C₄alkoxy, d-dhaloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0).

Preferably, R⁶ and R⁷ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl, d-dhaloalkoxy or together from a carbonyl group (=0).

Preferably, R⁶ and R⁷ each independently are hydrogen, halogen, methyl or methoxy or together from a carbonyl group (=0). Preferably, R⁶ and R⁷ each independently are hydrogen, halogen, methoxy or methyl. Preferably, R⁶ and R⁷ each independently are hydrogen, fluoro or methyl.

R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄alkylthio, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄haloalkylthio or together from a carbonyl group (=0).

Preferably, R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁- C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0).

Preferably, R⁹ and R¹⁰ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0).

Preferably, R⁹ and R¹⁰ each independently are hydrogen, halogen, methyl or methoxy or together from a carbonyl group (=0).

Preferably, R⁹ and R¹⁰ each independently are hydrogen, halogen, methoxy or methyl. Preferably, R⁹ and R¹⁰ each independently are hydrogen, fluoro or methyl.

R⁸ is henyl, benzyl or group (a):

(a)

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyi, halogen, cyano, hydroxy and amino.

Preferabl R⁸ is phenyl, benzyl or group (a):

(a)

Preferabl R⁸ is benzyl or group (a):

(a) wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen and hydroxy.

Preferabl R⁸ is benzyl or group (a):

wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents inde endently selected from methyl, halomethyl, and halogen. Preferably, R⁸ is group (a):

In one group of compounds of the invention T is not -C(R⁹R¹⁰)-, e.g. T is - C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O, preferably NR¹³ or O.

In another group of compounds of the invention Q is not -C(=0)-N(R¹⁵)-z, -C(=S)-N(R¹⁶)-z, or -C(=0)-0-z, e.g. Q is -N(R¹⁷)-C(=0)-z, -N(R¹⁸)-C(=S)-z, -N(R¹⁹)-C(=0)-0-z or -N(R²⁰)- C(=0)-N(R²¹)-z, preferably is -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸,

For the avoidance of doubt, when n is 1 , compounds of formula I have the formula according to formula I':

in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and T are as defined for formula I. Likewise, when n is 2, compounds of formula I have the formula according to formula I":

in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and T are as defined for formula I. Likewise, when n is 3, compounds of formula I have the formula according to formula Γ":

in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and T are as defined for formula I, and so on.

Preferred individual compounds are:

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-propyl)-thiazole-4- carboxylic acid methyl-(R)-1 ,2, 3, 4-tetrahydro-naphthalen-1-yl-amide (Compound No.

1.d.55);

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-propyl)-thiazole-4- carboxylic acid methyl-((R)-1-phenyl-ethyl)-amide (Compound No. 1.d.57);

2-(3-{[2-(3-difluoromethyl-5-methyl-pyrazol-1-yl)-acetyl]-methyl-amino}-propyl)-thiazole-4- carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No.

1.d.19);

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-propyl)-thiazole-4- carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1 -yl ester (Compound No. 1 .d.62);

2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethoxy)-thiazole-4- carboxylic acid methyl-(R)-1 ,2,3, 4-tetrahydro-naphthalen-1-yl-amide (Compound No.

1.g.55);

2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethoxy)-thiazole-4- carboxylic acid methyl-((R)-1-phenyl-ethyl)-amide (Compound No. 1.g.57);

2-(2-{[2-(3-difluoromethyl-5-methyl-pyrazol-1-yl)-acetyl]-methyl-amino}-ethoxy)-thiazole-4- carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No.

1.g.19);

2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethoxy)-thiazole-4- carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1 -yl ester (Compound No. 1 .g.62);

2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethyl)- amino]-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No. 1.q.55);

2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethyl)- amino]-thiazole-4-carboxylic acid methyl-((R)-1 phenyl-ethyl)-amide (Compound No. 1.q.57); 2-[(2-{[2-(3-difluoromethyl-5-methyl-pyrazol-1 -yl)-acetyl]-methyl-amino}-eth

amino]-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No. 1.q.19); and

2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-ethyl)- amino]-thiazole-4-carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1-yl ester (Compound No. 1.q.62).

Compounds of formula (I) can be made as shown in the following schemes. The compounds of formula I.A, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula I.B, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I. This is shown in Scheme 1.

Scheme 1

reduction, e.g.

H₂, catalyst (such as Pd/C, Raney-Ni, etc.

The compounds of formula I.B, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I , can be obtained by transformation of a compound of formula II, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 2.

Sonogashira coupling conditions, e.g.

Cul, Pd(PPh₃)₂CI₂

The compounds of formula II, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula V, wherein R⁵, R^s, R⁷ and n are as defined for formula I. This is shown in Scheme 3. Scheme 3

base with peptide coupl ing reagent

(such as BOP, PyBOP, EDC, HATU, etc.), c base alone

Alternatively, the compounds of formula I.B, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula VI, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I. This is shown in Scheme 4.

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), or base alone

The compounds of formula VI, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹ and Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula VII, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹ and Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 5.

The compounds of formula VII, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹ and Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, can be obtained by transformation of a compound of formula VIII, wherein R⁵, R⁶, R⁷ and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 6.

Sonogashira coupling conditions, ί

Cul, Pd(PPl3)₂CI₂

Alternatively, the compounds of formula I.A, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula IX, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I . This is shown in Scheme 7.

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), or base alone

The compounds of formula IX, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula X, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 8. Scheme 8

deprotection, e.g.

acid, base, hydrogenation or TB

The compounds of formula X, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, can be obtained by transformation of a compound of formula VII, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 9.

Scheme 9

reduction, e.g.

H₂, catalyst (such as Pd/C, Raney-Ni, etc

The compounds of formula I.C, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula I.B, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I. This is shown in Scheme 10. Scheme 10

selective reduction, e.g.

H₂, Lindlar catalyst or Li, NH₃

Alternatively, the compounds of formula I.C, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G¹, G², Q, Y¹, Y² and n are as defined for formula I can be obtained by transformation of a compound of formula XI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹¹, R¹², G¹ and n are as defined for formula I, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 1 1.

Scheme 11

Heck reaction conditions,

Pd(OAc)₂, KOAc

(I.C

The compounds of formula XI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹¹, R¹², G¹ and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹ , R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XII, wherein R⁵, R^s, R⁷, R¹¹, R¹² and n are as defined for formula I. This is shown in Scheme 12.

Scheme 12

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), c base alone

Alternatively, the compounds of formula I.C, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XIII, wherein R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G², Q, Y¹, Y² and n are as defined for formula I. This is shown in Scheme 13.

Scheme 13

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), or base alone

The compounds of formula XIII, wherein R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula XIV, wherein R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 14. Scheme 14

deprotection, e.g.

acid, base, hydrogenation or TB

The compounds of formula XIV, wherein R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC or Cbz, Teoc, can be obtained by transformation of a compound of formula VII , wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 15.

Scheme 15

selective reduction, e.g.

H₂, Li ndlar catalyst or Li, NIH

Alternatively, the compounds of formula XIV, wherein R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, can be obtained by transformation of a compound of formula XV, wherein R⁵, R⁶, R⁷, R¹¹, R¹² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 16.

Scheme 16

Heck reaction conditions,

Pd(OAc^, KOAc

(XIV) The compounds of formula I.D, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I , can be obtained by transformation of a compound of formula XVI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 17.

Scheme 17

Pd-catalysis, Cu-catalysis or

base

The compounds of formula XVI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I, can be obtained by transformation of a compound of formula XVII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I and R²⁴ is a protecting group, such as acetyl or 4-methoxybenzyl. This is shown in Scheme 18.

Scheme 18

deprotection, e.g .

acid, base, hydrogenation or TB

The compounds of formula XVII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, G¹ and n are as defined for formula I and R²⁴ is a protecting group, such as acetyl or 4-methoxybenzyl, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XVII I, wherein R⁵, R⁶, R⁷ and n are as defined for formula I and R²⁴ is a protecting group, such as acetyl or 4-methoxybenzyl. This is shown in Scheme 19.

Scheme 19

(XVIII) pl ing reagent

, EDC, HATU, etc.), c

Alternatively, the compounds of formula I.D, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XIX, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I . This is shown in Scheme 20.

Scheme 20

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), or base alone

The compounds of formula XIX, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I , can be obtained by transformation of a compound of formula XX, wherein R⁵, R⁶, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 21.

deprotection, e.g .

acid, base, hydrogenation or TB

The compounds of formula XX, wherein R⁵, R^s, R⁷, R⁸, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, can be obtained by transformation of a compound of formula XXI, wherein R⁵, R⁶, R⁷ and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 22.

Scheme 22

Pd-catalysis, Cu-catalysis or

base

The compounds of formula I.E, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹³, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula XXII wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹³, G¹ and n are as defined for formula I, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 23.

Scheme 23

The compounds of formula XXII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹³, G¹ and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XXII I, wherein R⁵, R⁶, R⁷, R¹³ and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 24. Scheme 24

base with peptide coupl ing reagent

(such as BOP, PyBOP, EDC, HATU, etc.), o

base alone

Alternatively, the compounds of formula I.E, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹³, G¹, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴ and G¹ are as defined for formula I and R²² is hydroxy or chloro, with a compound of formula XXIV, wherein R⁵, R⁶, R⁷, R⁸, R¹³, G², Q, Y¹, Y² and n are as defined for formula I. This is shown in Scheme 25.

base with peptide coupling reagent

(such as BOP, PyBOP, EDC, HATU, etc.), or base alone

The compounds of formula XXIV, wherein R⁵, R⁶, R⁷, R⁸, R¹³, G², Q, Y¹, Y² and n are as defined for formula I, can be obtained by transformation of a compound of formula XXV, wherein R⁵, R⁶, R⁷, R⁸, R¹³, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc. This is shown in Scheme 26.

deprotection, e.g.

acid , base, hydrogenation or TB/

The compounds of formula XXV, wherein R⁵, R⁶, R⁷, R⁸, R¹³, G², Q, Y¹, Y² and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, can be obtained by transformation of a compound of formula XXVI, wherein R⁵, R⁶, R⁷, R¹³ and n are as defined for formula I and R²³ is a protecting group, such as acetyl, benzyl, BOC, Cbz or Teoc, with a compound of formula III, wherein R⁸, G², Q, Y¹ and Y² are as defined for formula I and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 27.

Scheme 27

Pd-catalysis, Cu-catalysi

base

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., Pseud operonospora 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 may be 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 are normally 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 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.

Said fungicidal compositions may comprise 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 an insecticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities. Examples of suitable additional active ingredients include the following: Azoxystrobin (131860-33-8), Dimoxystrobin (149961 -52-4), Enestrobin (238410-11-2), Fluoxastrobin (193740-76-0), Kresoxim-methyl (143390-89-0), Metominostrobin (133408-50-1 ), Orysastrobin (248593-16- 0), Picoxystrobin (1 17428-22-5), Pyraclostrobin (175013-18-0), Azaconazole (60207-31 -0), Bromuconazole (1 16255-48-2), Cyproconazole (94361-06-5), Difenoconazole (119446-68- 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 (1251 16-23-6), Myclobutanil (88671 - 89-0), Oxpoconazole (174212-12-5), Pefurazoate (5801 1-68-0), Penconazole (66246-88-6), Prochloraz (67747-09-5), Propiconazole (60207-90-1 ), Prothioconazole (178928-70-6), Simeconazole (149508-90-7), Tebuconazole (107534-96-3), Tetraconazole (1 12281-77-3), Triadimefon (43121 -43-3), Triadimenol (55219-65-3), Triflumizole (99387-89-0),

Triticonazole (131983-72-7), Diclobutrazol (76738-62-0), Etaconazole (60207-93-4), Fluconazole (86386-73-4), Fluconazole-cis (1 12839-32-4), Thiabendazole (148-79-8), Quinconazole (103970-75-8), Fenpiclonil (74738-17-3), Fludioxonil (131341 -86-1 ),

Cyprodinil (121552-61 -2), Mepanipyrim (110235-47-7), Pyrimethanil (531 12-28-0),

Aldimorph (91315-15-0), Dodemorph (1593-77-7), Fenpropimorph (67564-91 -4),

Tridemorph (81412-43-3), Fenpropidin (67306-00-7), Spiroxamine (1 18134-30-8),

Isopyrazam (881685-58-1 ), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31 -3), Boscalid (188425-85-6), Penflufen (494793- 67-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (413615- 35-7), Dimethomorph (110488-70-5), Chlorothalonil (1897-45-6), Fluazinam (79622-59-6), Dithianon (3347-22-6), Metrafenone (220899-03-6), Tricyclazole (41814-78-2), Mefenoxam (70630-17-0), Metalaxyl (57837-19-1 ), Acibenzolar (126448-41 -7) (Acibenzolar-S-methyl (126448-41 -7)), Mancozeb (8018-01 -7), Ametoctradine (865318-97-4) Cyflufenamid (180409-60-3), Ipconazole (125225-28-7), Amisulbrom (348635-87-0), Ethaboxam (16650- 77-3), Fluopicolide (239110-15-7), 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 1120-44-1 ); 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 ,3-Dimethyl-1 H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1- methyl-indan-4-yl)-amide, 1 ,3-Dimethyl-1 H-pyrazole-4-carboxylic acid (4'-methylsulfanyl- biphenyl-2-yl)-amide, 1 ,3-Dimethyl-4H-pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2- methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4-dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6- methyl-phenyl)-methanone, (5-Bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy-6- methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1-methyl-prop-2-en-(E)- ylideneaminooxymethyl]-phenyl}-2-[(Z)-methox 3-[5-(4-Chloro- phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine.

Another aspect of invention is related to the use of a compound of formula I, e.g. of a preferred individual compound as above-defined, of a composition comprising at least one compound of formula I , e.g. at least one preferred individual compound as above-defined, or of a fungicidal mixture comprising at least one compound of formula I , e.g. 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 or spoilage microorganisms or microorganisms potentially harmful to man. Preferably said microorganisms are fungal miocroorganisms. In particular, the invention relates to the use of a compound of formula I, e.g. a preferred individual compound as above-defined, of a composition comprising at least one compound of formula I, e.g. at least one preferred individual compound as above- defined, or of a fungicidal mixture comprising at least one compound of formula I , e.g. 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, by phytopathogenic microorganisms. Preferably said microorganisms are 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 mircroorganisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I , e.g. 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, to the harvested crop, or to any part of the non-living materials. In particular, the invention relates 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, by phytopathogenic microorganisms, which comprises the application of a compound of formula I, e.g. a preferred individual compound as above-defined, as active ingredient to the plants, to parts of the plants or to the locus thereof, or to the propagation material thereof. Preferably said microorganisms are fungal microorganisms.

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

A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.

However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation, e.g. a composition containing the compound of formula I, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants). The agrochemical formulations and/or compositions will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant. Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. The following non-limiting example illustrates the above-described invention in more detail.

Example 1 : This example illustrates the preparation of 2-(3-{methyl-[2-(5-methyl-3- trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-propyl)-thiazole-4-carboxylic acid methyl-(R)- 1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No. 1.d.55) a) Preparation of 2-[3-(tert-butoxycarbonyl-methyl-amino)-prop-1-ynyl]-thiazole-4-carboxylic acid ethyl ester¹

To a solution of ethyl 2-bromothiazole-4-carboxylate (3.54 g, 15 mmol) in dry degassed THF (10 mL) was added diisopropylamine (2.27 g, 22.5 mmol), followed by Cul (0.14 g, 0.75 mmol) and Pd(PPh₃)₂CI₂ (0.52 g, 0.75 mmol). After stirring 5 min at RT, methyl-prop-2-ynyl-carbamic acid tert-butyl ester² (2.54 g, 15 mmol) was added dropwise to the reaction mixture over 5 min. After stirring overnight at RT, reaction mixture was diluted with THF (20 mL) and filtered through celite. Solvent was then evaporated and the resulting crude mixture was purified by column chromatography on silica gel

(ethylacetate/cyclohexane 3:7) to give 2-[3-(tert-butoxycarbonyl-methyl-amino)-prop-1-ynyl]- thiazole-4-carboxylic acid ethyl ester (2.32 g, 47 %). ¹H-NMR (400 MHz, CDCI₃): δ = 8.15 (s, 1 H), 4.49-4.42 (q, 2H), 4.38-4.26 (m, 2H), 2.95 (s, 3H), 1.49 (s, 9H), 1.43-1.393 (t, 3H) . MS: m/z = 347 (M+23). b) Preparation of 2-[3-(tert-butoxycarbonyl-methyl-amino)-prop-1-ynyl]-thiazole-4-carboxylic acid

To a solution of 2-[3-(tert-butoxycarbonyl-methyl-amino)-prop-1-ynyl]-thiazole-4- carboxylic acid ethyl ester (1.22 g, 3.76 mmol) in THF (10 mL) was added aqueous solution of sodium hydroxide (2 M, 2.82 mL, 5.64 mmol) at RT. After stirring 3 h at RT, the reaction mixture was acidified with 2M aqueous solution of HCl until pH 2, and the solution was extracted with ethylacetate (20 mL). The aqueous layer was re-extracted with ethylacetate (20 mL) and the combined organic layers were washed with brine (10 mL), dried over sodium sulfate, filtered, and evaporated under reduced pressure to 2-[3-(tert- butoxycarbonyl-methyl-amino)-prop-1-ynyl]-thiazole-4-carboxylic acid (1 .1 1 g, quant.), which can be used in the next step without further purification. ¹H-NMR (400 MHz, d6- DMSO): δ = 13.2 (br, 1 H), 8.55 (s, 1 H), 4.37 (s, 2H), 2.89 (s, 3H), 1.45 (s, 9H). MS: m/z = 297 (M+1 ). For similar Sonogashira reaction, see Wipf, P., Wang, Z. WO 2008/106080.

² For the synthesis of methyl-prop-2-ynyl-carbamic acid tert-butyl ester, see Bradbury, B. J.;

Baumgold, J.; Jacobson, K. A J. Med. Chem. 1990, 33, 741 -8. c) Preparation of methyl-{3-[4-((R)-methyl-1 ,2,3,4-tetrahydro-naphthalen-1-yl-carbamoyl)- thiazol-2-yl]-prop-2-ynyl}-carbamic acid tert-butyl ester

To a solution of 2-[3-(tert-butoxycarbonyl-methyl-amino)-prop-1-ynyl]-thiazole-4- carboxylic acid (1.1 1 g, 3.75 mmol) in DMF (20 ml_) was added diisopropylethylamine (1.93 ml_, 1 1.3 mmol), followed by 2-(1 H-7-azabenzotriazol-1 -yl)-1 ,1 ,3,3-tetramethyl uronium hexafluorophosphate methanaminium (1.57 g, 4.13 mmol). After stirring 15 min at RT, (1 R)- 1 ,2,3,4-tetrahydro-N-methyl-1-naphthalenamine (0.60 g, 3.75 mmol) was added to the reaction mixture. After stirring overnight at RT, solvent was evaporated and the resulting brown oil was dissolved in ethylacetate (30 ml_), washed with saturated aqueous sodium bicarbonate solution (50 ml_), 1 M HCl solution (50 ml_), and brine (50 ml_). The organic layer was dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel

(ethylacetate/cyclohexane 2:8 to 3:7) to give methyl-{3-[4-((R)-methyl-1 ,2,3,4-tetrahydro- naphthalen-1-yl-carbamoyl)-thiazol-2-yl]-prop-2-ynyl}-carbamic acid tert-butyl ester (1.01 g, 61 %). ¹H-NMR (400 MHz, CDCI₃): δ = 7.75 (s, 1 H (conformers)), 7.03-6.92 (m, 4H), 5.58- 5.46 (m, 1 H (conformers)), 4.18-4.09 (br, 2H), 2.75 (s, 3H (conformers)), 2.61 (s, 3H), 2.11 - 1.63 (m, 6H), 1.33 (s, 9H (conformers)). MS: m/z = 462 (M+23). d) Preparation of methyl-{3-[4-((R)-methyl-1 ,2,3,4-tetrahydro-naphthalen-1-yl-carbamoyl)- thiazol-2-yl]-propyl}-carbamic acid tert-butyl ester

A solution of methyl-{3-[4-((R)-methyl-1 ,2,3,4-tetrahydro-naphthalen-1-yl-carbamoyl)- thiazol-2-yl]-prop-2-ynyl}-carbamic acid tert-butyl ester (0.176 g, 0.4 mmol) in methanol (3 ml_) was pumping through Pd/C cartridge using H-Cube apparatus (50 °C, 80 bar, 1 mL/min.). The solvent was then evaporated under reduce pressure to give methyl-{3-[4- ((R)-methyl-l ,2,3,4-tetrahydro-naphthalen-1-yl-carbamoyl)-thiazol-2-yl]-propyl}-carbamic acid tert-butyl ester (0.133 g, 75 %), which can be used in the next step without further purification. ¹H-NMR (400 MHz, CDCI₃): δ = 7.54 (s, 1 H (conformers)), 7.03-6.87 (m, 4H), 5.54-5.46 (m, 1 H (conformers)), 3.12-2.98 (m, 2H), 2.83-2.71 (m, 2H (conformers)), 2.63 (s, 3H (conformers)), 2.61-2.51 (m, 5H), 2.04-1.56 (m, 6H), 1.20 (s, 9H (conformers)). MS: m/z = 444 (M+1 ). e) Preparation of 2-(3-methylamino-propyl)-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4- tetrahydro-naphthalen-1-yl-amide hydrochloride salt

To a solution of methyl-{3-[4-((R)-methyl-1 ,2,3,4-tetrahydro-naphthalen-1-yl- carbamoyl)-thiazol-2-yl]-propyl}-carbamic acid tert-butyl ester (0.133 g, 0.3 mmol) was added a solution of 1 M HCl in dioxane (0.65 ml_) at RT. After stirring overnight at RT, the solvent was evaporated under reduce pressure. The resulting solid was triturated with diethylether, and filtered to give 2-(3-methylamino-propyl)-thiazole-4-carboxylic acid methyl- (R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide hydrochloride salt (0.097 g, 94 %). ¹H-NMR (400 MHz, CDCI₃): δ = 9.82-9.58 (br, 2H), 7.79 (s, 1 H (conformers)), 7.12-7.03 (m, 4H), 5.43-5.54 (m, 1 H (conformers)), 3.45-3.22 (m, 2H), 3.21-3.02 (m, 2H), 2.98-2.64 (m, 5H), 2.61-2.24 (m, 5H), 2.22-1 .66 (m, 4H). MS: m/z = 330 (M+1 ). MS: m/z = 344 (M+1 ). f) Preparation of 2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}- propyl)-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.d.55)

To a solution of (5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetic acid (0.053 g, 0.25 mmol) in acetonitrile (3 mL) was added diisopropylethylamine (0.17 ml_, 1.01 mmol), followed by 2-(1 H-7-azabenzotriazol-1-yl)-1 ,1 ,3,3-tetramethyl uronium

hexafluorophosphate methanaminium (0.11 g, 0.3 mmol). After stirring 15 min at RT, 2-(3- methylamino-propyl)-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 - yl-amide hydrochloride salt (0.096 g, 0.25 mmol) was added to the reaction mixture. After stirring overnight at RT, solvent was evaporated and the resulting yellow oil was dissolved in ethylacetate (20 mL), washed with saturated aqueous sodium bicarbonate solution (30 mL), 1 M HCl solution (10 mL), and brine (10 mL). The organic layer was dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (ethylacetate/cyclohexane 7:3) to give 2-(3-{methyl-[2- (5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-amino}-propyl)-thiazole-4-carboxylic acid methyl-(R)-1 ,2, 3,4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.d.55, 83 mg, 61%). ¹H-NMR (400 MHz, CDCI₃): δ = 7.75-7.80 (s, 1 H (conformers)), 7.31 -7.29 (m, 1 H), 7.20- 7.06 (m, 3H), 6.35-6.25 (s, 1 H (conformers)), 6.05-5.55 (m, 1 H (conformers)), 5.05-4.75 (s, 2H (conformers)), 3.55-3.46 (m, 2H), 3.10-2.90 (s, 3H (conformers)), 3.08-3.05 (m, 1 H), 2.90-2.75 (s, 3H (conformers) + m, 3H), 2.30-2.20 (s, 3H (conformers)), 2.15-1.61 (m, 6H). MS: m/z = 534 (M+1 ).

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

Compound

R¹ R⁵ Q R⁸ No.

01 CF₂H H -C(=0)N(CH₃)-

where

a) 77 compounds of formula (I. a):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. b) 77 compounds of formula (l.b):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. c) 77 compounds of formula (I. c):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. d) 77 compounds of formula (l.d):

wherein R , R , Q and R are as defined in Table 1. e) 77 compounds of formula (l.e):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. f) 77 compounds of formula (I .f):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. g) 77 compounds of formula (l.g):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. h) 77 compounds of formula (l.h):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. i) 77 compounds of formula (l.i):

wherein R , R⁵, Q and R are as defined in Table 1. j) 77 compounds of formula (l.j):

wherein R , R , Q and R are as defined in Table 1. k) 77 compounds of formula (I. k):

wherein R , R , Q and R are as defined in Table 1. m) 77 compounds of formula (l.m):

wherein R , R⁵, Q and R are as defined in Table 1. n) 77 compounds of formula (l.n):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. o) 77 compounds of formula (l.o):

wherein R , R⁵, Q and R are as defined in Table 1. p) 77 compounds of formula (l.p):

wherein R , R , Q and R are as defined in Table 1. q) 77 compounds of formula (I . q):

wherein R , R , Q and R are as defined in Table 1. r) 77 compounds of formula (l.r):

wherein R , R , Q and R are as defined in Table 1. s) 77 compounds of formula (l.s):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. t) 77 compounds of formula (l.t):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. u) 77 compounds of formula (l.u):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. v) 77 compounds of formula (I. ):

wherein R , R⁵, Q and R are as defined in Table 1. w) 77 compounds of formula (l.w):

wherein R , R⁵, Q and R are as defined in Table 1. x) 77 compounds of formula (l.x):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. y) 77 compounds of formula (l.y):

wherein R , R⁵, Q and R are as defined in Table 1. z) 77 compounds of formula (l.z):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. aa) 77 compounds of formula (l.aa):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. ab) 77 compounds of formula (l.ab):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. ac) 77 compounds of formula (l.ac):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1 ad) 77 compounds of formula (I. ad):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. ae) 77 compounds of formula (l.ae):

wherein R , R , Q and R are as defined in Table 1. af) 77 compounds of formula (l.af):

wherein R , R⁵, Q and R are as defined in Table 1. ag) 77 compounds of formula (l.ag):

wherein R , R , Q and R are as defined in Table 1. ah) 77 compounds of formula (I. ah):

wherein R¹, R⁵, Q and R⁸ are as defined in Table 1. Throughout this description, temperatures are given in degrees Celsius and

"m.p." means melting point. LC/MS means Liquid Chromatography Mass

Spectroscopy and the description of the apparatus and the method is: (HP 1100 HPLC from Agilent, Phenomenex Gemini C18, 3 μιτι particle size, 1 10 Angstrom, 30 x 3 mm column, 1 .7mL/min., 60 °C, H₂0 + 0.05% HCOOH (95%) / CH₃CN/MeOH 4:1 + 0.04% HCOOH (5%) - 2 min. - CH₃CN/MeOH 4:1 + 0.04% HCOOH (5%) - 0.8 min., ZQ Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source

Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400)).

Table 2 shows selected m.p. data and selected LC/MS data for compounds of Table 1.

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

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

Biological examples

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

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

Compound l.d.55, l.d.37 and l.t.55 at 200 ppm gives 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 / preventative (potato late blight)

2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a sporangia suspension 2 days after application. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (5 - 7 days after application). Compound l.d.55 and l.t.55 at 200 ppm gives 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).

Compound l.d.55 and l.t.55 at 200 ppm gives at least 60% 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)

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

Compound l.d.55 and l.t.55 at 200 ppm gives 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)

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

Compound l.d.55, l.d.37 and l.t.55 at 200 ppm gives at least 70% 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 / preventative (grape downy mildew)

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

Compound l.d.55 and l.t.55 at 200 ppm gives 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 / long lasting (grape downy mildew)

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

Compound l.d.55 and l.t.55 at 200 ppm gives 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 / curative (grape downy mildew)

5-week-old grape seedlings cv. Gutedel are inoculated by spraying a sporangia suspension on their lower leaf surface one day before application. The inoculated grape plants are sprayed in a spray chamber with the formulated test compound diluted in water. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (4 - 6 days after application).

Compound l.d.55 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Claims

What is claimed is:

1. A compound of formula I:

wherein

G¹ and G² are independently 0 or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C- NR¹³ or O;

Y¹ and Y² are independently CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z. -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁸)-C(=S)-z, - N(R¹⁹)-C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2, 3 or 4 when T is -C(R⁹R¹⁰)-, NR¹³ or 0;

n is 1 , 2 or 3 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ , R²⁰ and R²¹ each independently are hydrogen, C₁- C₄alkyl or C₁-C₄alkoxy;

R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, d-dalkylthio, d-dhaloalkyl, d-dhaloalkoxy, d-dhaloalkylthio or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C alkoxy, d-dalkylthio, C₁-C₄haloalkyl, d-dhaloalkoxy, C₁-C₄haloalkylthio or together form a carbonyl group (=0); and

R⁸ is henyl, benzyl or group (a):

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyi, halogen, cyano, hydroxy and amino;

or a salt or a N-oxide thereof.

2. The compound according to claim 1 , wherein

G¹ and G² are independently O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C- NR¹³ or O;

Y¹ and Y² are independently CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z. -C(=S)-N(R¹⁶)-z, -C(=0)-0-z, -N(R¹⁷)-C(=0)-z, -N(R¹⁹)-C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸; n is 1 , 2 or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or 0;

n is 1 or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁹, R²⁰ and R²¹ each independently are hydrogen or C₁-C₄alkyl; R⁶ and R⁷ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0); R⁹ and R¹⁰ each independently are hydrogen, halogen, cyano, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together form a carbonyl group (=0); and R⁸ is henyl, benzyl or group (a):

(a)

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C4 haloalkyi, halogen, hydroxy and amino.

3. The compound according to claim 1 , wherein

G¹ and G² are independently 0 or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴ or N;

n is 1 , 2, or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R¹, R², R³, R⁴, R¹¹, R¹² and R¹⁴ each independently are hydrogen, halogen, C₁-C₄alkyl, or C₁-C₄haloalkyl; R⁵, R¹³, R¹⁵, R¹⁶, R¹⁷ each independently are hydrogen or C₁-C₄alkyl;

R⁶ and R⁷ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁- C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0);

R⁹ and R¹⁰ each independently are hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁- C₄haloalkyl, C₁-C₄haloalkoxy or together form a carbonyl group (=0); and R⁸ is henyl, benzyl or group (a):

(a)

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C1-C4 haloalkyi, halogen, hydroxy and amino.

4. The compound according to claim 1 , wherein

G is O;

G² is O or S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N ;

Y² is CR¹⁴ or N;

Q is -C(=0)-N(R¹⁵)-z, -C(=0)-0-z, or -N(R¹⁷)-C(=0)-z, in each case z indicates the bond that is connected to R⁸;

n is 1 , 2 or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 or 2 when T is -C(R¹¹ )=C(R¹²)- or -C≡C-;

R¹ , R², R³, R⁴, R¹¹ , R¹² and R¹⁴ each independently are hydrogen, halogen, C₁-C₄alkyl, or C₁-C₄haloalkyl;

R⁵, R¹³, R¹⁵, R¹⁷ each independently are hydrogen or C₁-C₄alkyl;

R⁶ and R⁷ each independently are hydrogen, halogen, hydroxy, C₁-C₄alkyl, Ci- C₄alkoxy, C₁-C₄haloalkyl, C₁-C₄haloalkoxy or together from a carbonyl group (=0); R⁹ and R¹⁰ each independently are hydrogen, halogen, hydroxy, C₁-C₄alkyl, C₁- C₄alkoxy, C₁-C₄haloalkyl, C-i-C₄haloalkoxy or together form a carbonyl group (=0); and R⁸ is benzyl or group (a):

(a)

wherein the benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C₁-C₄ alkyl, C_!-C₄ haloalkyi, halogen and hydroxy.

5. The compound according to claim 1 , wherein

G¹ is O;

G² is S;

T is -C(R⁹R¹⁰)-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴;

n is 2;

R¹ and R² are independently halogen, methyl or halomethyl;

R³, R⁴ and R¹⁴ each independently are hydrogen, halogen, methyl, or halomethyl; R⁵, R¹³ and R¹⁵ each independently are hydrogen or methyl;

R⁶ and R⁷ each independently are hydrogen, halogen, methoxy or methyl;

R⁹ and R¹⁰ each independently are hydrogen, halogen, methoxy or methyl; and R⁸ is benz l or group (a):

(a)

6. The compound according to claim 1 , wherein

G¹ is O;

G² is S;

T is -C(R⁹R¹⁰)- Y¹ is N;

Y² is CR¹⁴; Q is -C(=0)-N(R¹⁵)-z, wherein z indicates the bond that is connected to R⁸;

n is 2;

R¹ and R² are independently methyl or trifluoromethyl;

R³, R⁴ and R¹⁴ each independently are hydrogen, fluoro or methyl;

R⁵ and R¹⁵ each independently are hydrogen or methyl;

R⁶ and R⁷ each independently are hydrogen, fluoro or methyl;

R⁹, and R¹⁰ each independently are hydrogen, fluoro or methyl; and

R⁸ is roup (a):

(a)

7. The compound according to claim 1 , wherein

G¹ is O;

G² is O, S;

T is -C(R⁹R¹⁰)-, -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or O;

Y¹ is N;

Y² is CR¹⁴ or N;

n is 1 , 2, or 3 when T is -C(R⁹R¹⁰)-, NR¹³ or O;

n is 1 , or 2 when T is -C(R¹¹)=C(R¹²)- or -C≡C-;

R¹ and R² each independently are methyl or halomethyl;

R⁵, R¹³, R¹⁵ and R¹⁷ each independently are hydrogen or methyl;

R⁶ and R⁷ each independently are hydrogen, halogen, methyl or methoxy or together from a carbonyl group (=0);

R⁸ is benzyl or group (a):

(a)

8. The compound according to claim 1 , wherein the compound is:

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-propyl)-thiazole- 4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No. 1.d.55);

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-propyl)-thiazole- 4-carboxylic acid methyl-((R)-1-phenyl-ethyl)-amide (Compound No. 1.d.57);

2-(3-{[2-(3-difluoromethyl-5-methyl-pyrazol-1 -yl)-acetyl]-methyl-amino}-propyl)-thiazole- 4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide (Compound No. 1.d.19);

2-(3-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-propyl)-thiazole- 4-carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1-yl ester (Compound No. 1.d.62); 2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-ethoxy)- thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.g.55);

2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-ethoxy)- thiazole-4-carboxylic acid methyl-((R)-1 -phenyl-ethyl)-amide (Compound No. 1.g.57); 2-(2-{[2-(3-difluoromethyl-5-methyl-pyrazol-1 -yl)-acetyl]-methyl-amino}-ethoxy)- thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.g.19);

2-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-ethoxy)- thiazole-4-carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1-yl ester (Compound No. 1.g.62);

2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-ethyl)- amino]-thiazole-4-carboxylic acid methyl-(R)-1 ,2, 3, 4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.q.55);

2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-amino}-ethyl)- amino]-thiazole-4-carboxylic acid methyl-((R)-1 phenyl-ethyl)-amide (Compound No. 1.q.57);

2-[(2-{[2-(3-difluoromethyl-5-methyl-pyrazol-1-yl)-acetyl]-methyl-amino}-ethyl)-methyl- amino]-thiazole-4-carboxylic acid methyl-(R)-1 ,2, 3, 4-tetrahydro-naphthalen-1 -yl-amide (Compound No. 1.q.19); or 2-[methyl-(2-{methyl-[2-(5-methyl-3-trifluoromethyl-^^

amino]-thiazole-4-carboxylic acid 1 ,2,3,4-tetrahydro-naphthalen-1-yl ester (Compound No. 1.q.62).

9. The compound according to claim 1 , wherein T is -C(R¹¹)=C(R¹²)-, -C≡C-, NR¹³ or 0;

10. The compound according to claim 1 , wherein Q is -N(R¹⁷)-C(=0)-z, -N(R¹⁸)- C(=S)-z, -N(R¹⁹)-C(=0)-0-z or -N(R²⁰)-C(=O)-N(R²¹)-z, in each case z indicates the bond that is connected to R⁸.

11. A fungicidal composition comprising at least one compound as defined in any one of claims 1 to 10 and an agriculturally acceptable carrier.

12. The fungicidal composition according to claim 1 1 , comprising an adjuvant.

13. The fungicidal composition according to claim 1 1 or claim 12, comprising at least one additional fungicidally active compound.

14. A method of controlling or preventing an infestation of plants, propagation material thereof, harvested crops or non-living materials by phytopathogenic or spoilage microorganisms or microorganisms potentially harmful to man, which comprises the application of a compound as defined in any one of claims 1 to 10 to the plant, to parts of the plant, to the locus thereof, or to the propagation material thereof, to the harvested crop, or to any part of the non-living materials.

15. The method according to claim 14, wherein the microorganisms are fungal microorganisms.