WO2013000941A1

WO2013000941A1 - Microbiocidal heterocycles

Info

Publication number: WO2013000941A1
Application number: PCT/EP2012/062425
Authority: WO
Inventors: Sarah Sulzer-Mosse; Clemens Lamberth; Fredrik Emil Malcolm Cederbaum
Original assignee: Syngenta Participations Ag
Priority date: 2011-06-30
Filing date: 2012-06-27
Publication date: 2013-01-03
Also published as: TW201313704A; UY34169A; AR086784A1

Abstract

The present invention relates to heterocyclic compounds of formula (I) which have microbiocidal activity, in particular fungicidal activity, as well as methods of using the compounds of formula I to control microbes: formula (I) wherein A is x-C(=O)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-O-C(=O)-, x-O-C(=S)-, x-N(R¹⁴)-C(=O)-, x-N(R¹⁵)-C(=S)-, x-C(R¹⁶R¹⁷)-SO2- or x-N=C(R²⁶)-, in each case x indicates the bond that is connected to R¹; T is CR¹⁸ or N; G is O or S; Y¹and Y² are independently CR¹⁹ or N; Q is -C(=O)-z, -C(=S)-z, -C(=O)-O-z, -C(=S)-O-z, -C(=O)-N(R²⁰)-z, -C(=S)-N(R²¹)-z or -SO₂- z-, in each case z indicates the bond that is connected to R⁹; n is 1 or 2; p is 1 or 2, providing that when n is 2, p is 1; R¹ is formula (IA) R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R²⁶ each independently are hydrogen, halogen, cyano, C₁-C₄alkyl or C₁-C₄haloalkyl; R⁸, R¹⁴, R¹⁵, R²⁰ and R²¹ each independently are hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy; and R⁹ is phenyl, 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, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, halogen, cyano, hydroxyl, N(R²⁷)₂, SH, C₁-C₄ alkylthio, nitro, phenylsulfonyl and phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, halogen and cyano; each R²⁷ independently is hydrogen, C₁-C₄ alkyl, phenylsulfonyl or phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, halogen and cyano; or a salt or a N-oxide thereof.

Description

Microbiocidal Heterocycles

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 WO201 1/018401.

Because the ecological and economical requirements of modern crop protection agents are steadily changing, there is a continuing need for the discvovery and

development of novel fungicides with advanced properties compared to the known products. Surprisingly, it has now been found that the described bis(difluoromethyl)pyrazol derivatives have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

The present invention provides compounds of formula I:

wherein

A is x-C(=0)-, x-C(=S)-, x-C(R¹V¹)-C(=0)-, x-C(R¹ R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)-, x-N(R¹⁴)-C(=0)-, x-N(R¹⁵)-C(=S)-, x-C(R¹⁶R¹⁷)-S0₂- or x-N=C(R²⁶)-, in each case x indicates the bond that is connected to R¹ ;

T is CR¹⁸ or N;

G is O or S;

Y¹ and Y² are independently CR¹⁹ or N;

Q is -C(=0)-z, -C(=S)-z, -C(=0)-0-z, -C(=S)-0-z, -C(=O)-N(R²⁰)-z, -C(=S)-N(R²¹)-z or -S0₂-

Z-, in each case z indicates the bond that is connected to R⁹;

n is 1 or 2;

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

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰- R¹¹- R¹²' R¹³' R¹⁶' R¹⁷' R¹⁸' R¹⁹ and ^R26 eac^h independently are hydrogen, halogen, cyano, C₁-C₄al_kyl or C₁-C₄haioaikyl;

R⁸, R¹⁴, R¹⁵, R²⁰ and R²¹ each independently are hydrogen, C-|-C₄alkyl or C-|-C₄alkoxy; and R⁹ 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 C C alkyl, C C haloalkyi, C C alkoxy, C C haloalkoxy, halogen, cyano, hydroxyl, N(R²⁷)₂, SH, Ci-C alkylthio, nitro, phenylsulfonyl and phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from Ci-C alkyl, C C haloalkyi, Ci-C alkoxy, Ci- C haloalkoxy, halogen and cyano;

each R²⁷ independently is hydrogen, d-C alkyl, phenylsulfonyl or phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C C alkyl, C C haloalkyi, C C alkoxy, C C haloalkoxy, halogen and cyano; or a salt or a N-oxide thereof.

Where substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents. Normally not more than three such optional substituents are present at the same time.

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

The term "amino" refers to -NH₂.

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.

A haloalkyi group may contain one or more identical or different halogen atoms and, for example, may stand for CH₂CI, CHCI₂, 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:

A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)-, x-N(R¹⁴)-C(=0)-, x-N(R¹⁵)-C(=S)- or x-C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹;

T is CR¹⁸ or N;

G is O or S;

Y¹ and Y² are independently CR¹⁹ or N;

Q is -C(=0)-z, -C(=S)-z, -C(=0)-0-z, -C(=S)-0-z, -C(=O)-N(R²⁰)-z, -C(=S)-N(R²¹)-z or -S0₂- Z-, in each case z indicates the bond that is connected to R⁹;

n is 1 or 2;

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

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, cyano, CrC₄alkyl, or Ci-C₄haloalkyl;

R⁸, R¹⁴, R¹⁵, R²⁰ and R²¹ each independently are hydrogen or C C₄alkyl; and

R⁹ is phenyl, benzyl or group (a):

(a)

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

Preferably the compound of formula I is a compound wherein:

A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)- or x-C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹;

T is CR¹⁸ or N;

G is O or S;

Y¹ is N;

Y² is CR¹⁹ or N;

n is 1 or 2;

p is 1 ;

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, d-C₄alkyl, Ci-C₄haloalkyl;

R⁸, R²⁰ and R²¹ each independently are hydrogen or CrC₄alkyl; and

R⁹ 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 C-|-C₄ alkyl, C-|-C₄ haloalkyi, halogen, cyano, hydroxy, and amino.

Preferably the compound of formula I is a compound wherein:

A is x-C(=0)-, -x-CR¹⁰R¹¹-C(=O)-, x-0-C(=0)- or x-C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹ ;

T is CR¹⁸ or N;

G is S;

Y¹ is N;

Y² is CR¹⁹ or N; Q is -C(=0)-z, -C(=0)-0-z, -C(=O)-N(R²⁰)-z or -S0₂-z-, in each case z being the bond to R⁹; n is 1 or 2;

p is 1 ;

R⁸ and R²⁰ each independently are hydrogen or methyl; and

R⁹ 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, C C₄ haloalkyi, hydroxy and halogen.

Preferably the compound of formula I is a compound wherein:

A is x-C(=0)-, x-CH₂-C(=0)-, x-0-C(=0)- or x-CH₂-S0₂-, in each case x indicates the bond that is connected to R¹;

T is CH or N;

G is S;

Y¹ is N;

Y² is CH or N;

Q is -C(=0)-z, -C(=0)-0-z, -C(=0)-NH-z or -S0₂-z-, in each case z indicates the bond that is connected to R⁹;

n is 1 or 2;

p is 1 ;

R², R³, R⁴, R⁵, R⁶ and R⁷ are each hydrogen;

R⁸ is hydrogen; and

R⁹ 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 C C₄ alkyl, C C₄ haloalkyi, hydroxy and halogen.

Preferably the compound of formula I is a compound wherein:

A is x-CH₂-C(=0)- wherein x indicates the bond that is connected to R¹;

T is CH;

G is S;

Y¹ is N; Y² is CH;

Q is -C(=0)-z, -C(=0)-0-z or C(=O)-N(R²⁰)-z, in each case z indicates the bond that is connected to R⁹;

n is 2;

p is 1 ;

R₂, R3, R₄, R5, R6, and R₇ are each hydrogen;

R₈, is hydrogen;

R⁹ is henyl, benzyl or group (a):

(a)

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

The invention also provides a compound of formula I in which:

A is x-CH₂C(=0)-, x-CH₂C(=S)-, x-OC(=0)-, x-C(=0)- or x-CH₂-S0₂-, in each case x indicates the bond that is connected to R¹;

T is CH or N;

G is O or S;

Y¹ is N;

Y² is CH or N;

Q is -C(=0)-z, -C(=S)-z, -C(=0)0-z, -C(=0)NH-z or -S0₂-z, in each case z indicates the bond that is connected to R⁹;

n is 1 or 2;

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

R², R³, R⁴, R⁵, R⁶ and R⁷ are H;

R⁸ is H or methyl;

R⁹ is roup (i), Q), (k), (I) or (m):

(i) G) (k) (I) (m)

The following list provides definitions, including preferred definitions, for substituents A, T, G, Y¹, Y², Q, n, p, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ , R²⁶ and R²⁷ 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 or elsewhere in this document. The invention includes compounds of formula having all possible combinations of substituent definitions given below. Generally, in this document any substituent definition may be combined with any other substituent definition.

A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-O-

C(=S)-, x-N(R¹⁴)-C(=0)-, x-N(R¹⁵)-C(=S)-, x-C(R¹⁶R¹⁷)-S0₂- or x-N=C(R²⁶)-, in each case x indicates the bond that is connected to R¹. Preferably A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)- C(=0)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)-, x-N(R¹⁴)-C(=0)-, x-N(R¹⁵)-C(=S)-or x- C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹. More preferably, A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)- or x-C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹. Even more preferably, A is x-C(=0)-, -x-CR¹⁰R¹¹-C(=O)-, x-0-C(=0)- or x-C(R¹⁶R¹⁷)-S0₂-, in each case x indicates the bond that is connected to R¹. Yet more preferably, A is x-CH₂C(=0)-, x- CH₂C(=S)-, x-OC(=0)-, x-C(=0)- or x-CH₂-S0₂-, in each case x indicates the bond that is connected to R¹. Most preferably, A is x-CH₂-C(=0)- wherein x indicates the bond that is connected to R¹.

T is CR¹⁸ or N. Preferably, T is CH or N. More preferably, T is CH.

G is O or S. Preferably, G is S.

Y¹ is CR¹⁹ or N. Preferably, Y¹ is N.

Y² is CR¹⁹ or N. Preferably, Y² is CH or N. More preferably, Y² is CH.

Q is -C(=0)-z, -C(=S)-z, -C(=0)-0-z, -C(=S)-0-z, -C(=O)-N(R²⁰)-z, -C(=S)-N(R²¹)-z or -S0₂-z-, in each case z indicates the bond that is connected to R⁹. Preferably, Q is -C(=0)- z, -C(=S)-z, -C(=0)0-z, -C(=0)NH-z or -S0₂-z, in each case z indicates the bond that is connected to R⁹. Preferably, Q is -C(=0)-z, -C(=0)-0-z, -C(=O)-N(R²⁰)-z or -S0₂-z-, in each case z indicates the bond that is connected to R⁹. More preferably, Q is -C(=0)-z, -C(=0)- O-z, -C(=0)-NH-z or -S0₂-z-, in each case z indicates the bond that is connected to R⁹. Even more preferably, Q is Q is -C(=0)-z, -C(=0)-0-z or C(=O)-N(R²⁰)-z, in each case z indicates the bond that is connected to R⁹. Most preferably Q is -C(=0)-z wherein z indicates the bond that is connected to R⁹.

n is 1 or 2. Preferably, n is 2.

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

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸, R¹⁹ each independently are hydrogen, halogen, cyano, C C₄alkyl, or Ci-C₄haloalkyl. Preferably, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ , R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, C C₄alkyl, or C C₄haloalkyl. More preferably, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ , R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, fluoro, or methyl. Even more preferably, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ , R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen.

R⁸, R¹⁴, R¹⁵, R²⁰, and R²¹ each independently are hydrogen or d-C₄alkyl. Preferably, R⁸, R¹⁴, R¹⁵, R²⁰, and R²¹ each independently are hydrogen or methyl.

More preferably, R⁸, R¹⁴, R¹⁵, R²⁰, and R²¹ each independently are hydrogen.

R⁹ 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, C1-C4 alkoxy, Ci-C₄ haloalkoxy, halogen, cyano, hydroxyl, N(R²⁷)₂, SH, C-|-C₄ alkylthio, nitro, phenylsulfonyl and phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, Ci- C₄ haloalkoxy, halogen and cyano. Preferably, R⁹ is phenyl, 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, h droxy and amino. Preferably, R⁹ is phenyl, benzyl or group (a):

(a)

wherein the phenyl, benzyl and group (a) are each optionally substituted with 1 to 3 substituents independently selected from C-|-C₄ alkyl, C-|-C₄ haloalkyi, hydroxy and halogen. More referably, R⁹ is phenyl, benzyl or group (a):

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

R²⁶ is hydrogen, halogen, cyano, CrC₄alkyl, or Ci-C₄haloalkyl. Preferably, R²⁶ is hydrogen, halogen, Ci-C₄alkyl, or Ci-C₄haloalkyl. Preferably, R²⁶ is hydrogen, fluoro, or methyl. More preferably, R²⁶ is hydrogen.

Each R²⁷ independently is hydrogen, d-C₄ alkyl, phenylsulfonyl or phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3

substituents independently selected from C C₄ alkyl, C C₄ haloalkyl, C C₄ alkoxy, C C₄ haloalkoxy, halogen and cyano. Preferably, R²⁷ is independently is hydrogen, Ci-C₄ alkyl, phenylsulfonyl or phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from halogen, methyl and halomethyl.

In one roup of compounds R⁹ is group (i), (j), (k), (I) or (m):

(i) G) (k) (I) (m)

In one group of compounds G is S, Y¹ is N and Y² is CH.

In one group of compounds p is 1 and n is 2.

In one group of compounds R², R³, R⁴, R⁵, R⁶ and R⁷ are H.

In one group of compounds Q is -C(=0)-z, wherein z indicates the bond that is connected to R⁹.

In one group of compounds A is x-CH₂-C(=0)-, wherein x indicates the bond that is connected to R¹.

In one group of compounds R⁹ is phenyl substituted by hydroxyl, and optionally substituted by one or two further substituents as defined above. Preferably the hydroxy is at the ortho position. Preferably one of the further substituents is halogen and is preferably at the meta position adjacent to the hydroxy.

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

in which A, T, G, Y¹ , Y², Q, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ 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

IB:

in which A, T, G, Y¹ , Y², Q, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ 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

I

The invention also relates to compounds of formula IA, formula IB and formula IC as shown above.

ula ID:

in which A, G, Y¹, Y², Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ have the definitions as described for formula I. Preferred definitions of A, G, Y¹ , Y², Q, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are as defined for formula I.

The invention also relates to compounds of formula IE:

in which A, Q, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ have the definitions as described for formula I. Preferred definitions of A, Q, R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are as defined for formula I.

The invention also relates to compounds of formula IF:

wherein T is CH or N

R⁸ is CH₃ or H; and

R¹ and R⁹ have the definitions as described for formula I. Preferred definitions of R¹ and R⁹ are as defined for formula I.

The invention also relates to compounds of formula IG:

wherein T is CH or N

R⁸ is CH₃ or H; and

R⁹ has the definition as described for formula I. Preferred definitions of R⁹ are as defined for formula I.

The invention also includes compounds of formula II:

wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, A, T, G, Y¹ , Y² , p and n are as defined for formula I. Preferred definitions of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, A, T, G, Y¹, Y² , p and n are as defined for formula I. Compounds of formula II are useful as intermediates in the synthesis of compounds of formula I.

The invention also includes compounds of formula VIII:

wherein R¹ , R², R³, R⁴, R⁶, R⁷, R⁸, A, T, G, Y¹ , Y² , p and n are as defined for formula I. Preferred definitions of R¹ , R², R³, R⁴, R⁶, R⁷, R⁸, A, T, G, Y¹ , Y² , p and n are as defined for formula I. Compounds of formula VII I are useful as intermediates in the synthesis of compounds of formula I .

Compounds of formula (I) can be made in an analogous way to those described in WO201 1 /018401 and as shown in the following schemes.

The compounds of formula I, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ , R⁸, R⁹, A, T, G, Y¹ , Y², n, p and Q are as defined for formula I can be obtained by transformation of a compound of formula I I , wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, A, T, G, Y¹ , Y², n, p and Y are as defined for formula I with a compound of formula I I I, wherein R⁹ and Q are as defined for formula I and X is a hydroxy, halogen, preferably fluoro, chloro or bromo or alkoxy, such as methoxy, ethoxy. This is shown in Scheme 1 .

Scheme 1

The compounds of formula 11.1 , wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I , can be obtained by transformation of a compound of formula IV, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I with an azide, such as diphenyl phosphoryl azide and subsequent Curtius rearrangement of the resulting acyl azide with an alcohol R²⁸-OH, wherein R²⁸ is Ci-C₆alkyl or optionally substituted aryl and following carbamate cleavage with a mineral acid, such as hydrochloric acid, sulfuric acid or an organic acid, such as trifluoroacetic acid. This is shown in Scheme 2.

Scheme 2

1. DPPA, R²⁸-OH

2. deprotection

or

1. i) CDI

The compounds of formula IV, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I can be obtained by saponification of a compound of formula V, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is CrC₆alkyl or optionally substituted aryl with a base, such as sodium hydroxide, potassium hydroxide or lithium hydroxide. This is shown in Scheme 3.

Scheme 3

The compounds of formula V, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is C-|-C₆alkyl or optionally substituted aryl can be obtained by transformation of a compound of formula VI, wherein R², R³, R⁴, R⁵, R⁶, R⁷, T, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is C Cealkyl or optionally substituted aryl with a compound of formula VII, wherein R¹ and A are as defined for formula I and X is a hydroxy, halogen, preferably fluoro, chloro or bromo or alkoxy, such as methoxy, ethoxy. This is shown in Scheme 4. Scheme 4

Alternatively, the compounds of formula 1.1 , wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, Y¹ and Y² are as defined for formula I and R²⁹ is Ci-C₆alkyl can be obtained by transformation of a compound of formula 1.2, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, Y¹ and Y² are as defined for formula I with an alkyl halide R²⁹-Hal, wherein R²⁹ is C C₆alkyl and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 5.

Scheme 5

The compounds of formula I.2, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, p, Y¹ and Y² are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I with an azide, such as diphenyl phosphoryl azide and subsequent Curtius rearrangement of the resulting acyl azide with a Grignard reagent R⁹-Mg-Hal, wherein R⁹ is as defined for formula I and Hal is halogen, preferably chloro, bromo or iodo, or a boronic acid R⁹-B(OH)₂, wherein R⁹ is as defined for formula I and a catalyst, such as bis(1 ,5- cyclooctadiene)rhodium(l) hydroxide. This is shown in Scheme 6. Scheme 6

Alternatively, the compounds of formula 1.3, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, p, Y¹ and Y² are as defined for formula I and R²⁹ is CrC₆alkyl can be obtained by transformation of a compound of formula 1.4, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, p, Y¹ and Y² are as defined for formula I with an alkyl halide R²⁹-Hal, wherein R²⁹ is C C₆alkyl and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 7.

Scheme 7

The compounds of formula I.4, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, p, Y¹ and Y² are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I with an azide, such as diphenyl phosphoryl azide and subsequent Curtius rearrangement of the resulting acyl azide with an alcohol R⁹-OH, wherein R⁹ is as defined for formula I as defined for formula I. This is shown in Scheme 8.

Scheme 8

Alternatively, the compounds of formula 1.5, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, Y¹ and Y² are as defined for formula I and R²⁹ is CrC₆alkyl can be obtained by transformation of a compound of formula 1.6, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, Y¹ and Y² are as defined for formula I with an alkyl halide R²⁹-Hal, wherein R²⁹ is C C₆alkyl and Hal is halogen, preferably chloro or bromo. This is shown in Scheme 9. Scheme 9

The compounds of formula 1.6, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁹, A, T, G, n, p, Y¹ and Y² are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, G, n, p, Y¹ and Y² are as defined for formula I with an azide, such as diphenyl phosphoryl azide and subsequent Curtius rearrangement of the resulting acyl azide with an amine R⁹-NH₂, wherein R⁹ is as defined for formula I. This is shown in Scheme 10.

Scheme 10

Alternatively, the compounds of formula 1.7, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, G, n, p, Y¹, Y² and Q are as defined for formula I, can be obtained by reduction of a compound of formula VIII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, G, n, p, Y¹, Y² and Q are as defined for formula I with hydrogen and a catalyst, such as palladium on charcoal, platinum or raney-nickel. This is shown in Scheme 1 1.

Scheme 1 1

The compounds of formula VIII, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, G, n, p, Y¹, Y² and Q are as defined for formula I can be obtained by cross coupling of a compound of formula IX, wherein R⁸, R⁹, G, Y¹, Y² and Q are as defined for formula I and Hal is halogen, preferably chloro, bromo or iodo with a compound of formula X, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and A are as defined for formula I and R³⁰ is B(OH)₂ and a transition metal, such as tetrakis(triphenylphosphine)palladium, and a ligand, such as. This is shown in Scheme 12. Scheme 12

catalyst,

ligand

Alternatively, the compounds of formula V.1 , wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, A, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is C-|-C₆alkyl or optionally substituted aryl can be obtained by reduction of a compound of formula XI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is CrC₆alkyl or optionally substituted aryl with hydrogen and a catalyst, such as palladium on charcoal, platinum or raney-nickel. This is shown in Scheme 13.

Scheme 13

The compounds of formula XI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, G, n, p, Y¹ and Y² are as defined for formula I and R²⁸ is CrC₆alkyl or optionally substituted aryl can be obtained by cross coupling of a compound of formula XII, wherein G, Y¹ and Y² are as defined for formula I, R²⁸ is Ci-C₆alkyl or optionally substituted aryl and Hal is halogen, preferably chloro, bromo or iodo with a compound of formula XIII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and A are as defined for formula I and R³⁰ is B(OH)₂ and a transition metal, such as bis-(triphenylphosphine)palladium(ll) chloride. This is shown in Scheme 14. Scheme 14

catalyst,

ligand

Alternatively, the compounds of formula VIII, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, G, n, p, Y¹, Y² and Q are as defined for formula I, can be obtained by cross coupling of a compound of formula XIV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, G, n, p, Y¹, and Y² are as defined for formula I with a compound of formula XV, wherein R⁸, R⁹ and Q are as defined for formula I and a ligand such as Xantphos or dimethylethylenediamine and a catalyst, such as Pd(OAc)₂ or copperiodide. This is shown in Scheme 15.

Scheme 15

(^χν)

The compounds of formula XIV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, G, n, p, Y¹ and Y² are as defined for formula I can be obtained by cross coupling of a compound of formula XVI, wherein G, Y¹ and Y² are as defined for formula I, with a compound of formula XIII, wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷ and A are as defined for formula I and R³⁰ is B(OH)₂ and a transition metal, such as bis-(triphenylphosphine)palladium(ll) chloride. This is shown in Scheme 16. Scheme 16

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 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 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 (238410-1 1 -2), Fluoxastrobin (193740-76-0), Kresoxim-methyl (143390-89-0), Metominostrobin (133408-50-1 ), Orysastrobin (248593-16- 0), Picoxystrobin (1 17428-22-5), Pyraclostrobin (175013-18-0), Azaconazole (60207-31-0), Bromuconazole (1 16255-48-2), Cyproconazole (94361 -06-5), Difenoconazole (1 19446-68- 3), Diniconazole (83657-24-3), Diniconazole-M (83657-18-5), Epoxiconazole (13385-98-8), Fenbuconazole (1 14369-43-6), Fluquinconazole (136426-54-5), Flusilazole (85509-19-9), Flutriafol (76674-21-0), Hexaconazole (79983-71-4), Imazalil (58594-72-2), Imibenconazole (86598-92-7), Ipconazole (125225-28-7), Metconazole (1251 16-23-6), Myclobutanil (88671 - 89-0), Oxpoconazole (174212-12-5), Pefurazoate (5801 1-68-0), Penconazole (66246-88-6), Prochloraz (67747-09-5), Propiconazole (60207-90-1 ), Prothioconazole (178928-70-6), Simeconazole (149508-90-7), Tebuconazole (107534-96-3), Tetraconazole (1 12281-77-3), Triadimefon (43121-43-3), Triadimenol (55219-65-3), Triflumizole (99387-89-0),

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

Cyprodinil (121552-61 -2), Mepanipyrim (1 10235-47-7), Pyrimethanil (531 12-28-0),

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

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

Isopyrazam (881685-58-1 ), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31 -3), Boscalid (188425-85-6), Penflufen (494793- 67-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (413615- 35-7), Dimethomorph (1 10488-70-5), Chlorothalonil (1897-45-6), Fluazinam (79622-59-6), Dithianon (3347-22-6), Metrafenone (220899-03-6), Tricyclazole (41814-78-2), Mefenoxam (70630-17-0), Metalaxyl (57837-19-1 ), Acibenzolar (126448-41-7) (Acibenzolar-S-methyl (126448-41-7)), Mancozeb (8018-01-7), Ametoctradine (865318-97-4) 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, 1 -methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1 -methyl-3- difluoromethyl-4H-pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1 -methyl- ethyl]-amide, (5-Chloro-2,4-dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)- methanone, (5-Bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)- methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1 -methyl-prop-2-en-(E)- ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl-acetamide, 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 or of a preferred individual compound as above-defined, of a composition comprising at least one compound of formula I or at least one preferred individual compound as above-defined, or of a fungicidal mixture comprising at least one compound of formula I or at least one preferred individual compound as above-defined, in admixture with other fungicides, as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by phytopathogenic microorganisms, preferably fungal organisms.

A further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.

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

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

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

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

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

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds.

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

The following non-limiting example illustrates the above-described invention in more detail.

Example 1 : This example illustrates the preparation of N-(2-{1 -[2-(3,5-bis-difluoromethyl- pyrazol-1-yl)-acetyl]-piperidin-4-yl}-thiazol-4-yl)-3-chloro-2-hydroxy-benzamide (Compound No. I.g.006) a) Preparation of 4-(4-hydroxycarbamoyl-thiazol-2-yl)-piperidine-1-carboxylic acid tert- butyl ester

To a solution of 4-(4-carboxy-thiazol-2-yl)-piperidine-1 -carboxylic acid tert-butyl ester (3.45 g, 0.01 mol) in acetonitrile (90 mL) is added slowly carbonyldiimidazol (1.93 g, 0.012 mol). After stirring 2h at RT, hydroxylamine hydrochloride (1.38 g, 0.02 mol) is added slowly to the reaction mixture. After stirring 1 h at RT, the reaction mixture is evaporated to half of the volume, and then the resulting oil is washed with aqueous saturated sodium bicarbonate solution, the aqueous phase is re-extracted with ethylacetate. The combined organic layers are washed with 1 M HCI solution and brine. Diethylether is added and then solid filtered, dry under high vacuum to give 4-(4-hydroxycarbamoyl-thiazol-2-yl)-piperidine-1-carboxylic acid tert-butyl ester which can be used in the next step without further purification. ¹H-NMR (400 MHz, CDCI₃): δ = 1 .45 (s, 9H), 1 .68-1.72 (m, 2H), 2.08-2.1 1 (m, 2H), 2.88-2.93 (m, 2H), 3.12-3.16 (m, 1 H), 4.15-4.22 (m, 2H), 8.00 (s, 1 H), 9.00 (br, 1 H). MS: m/z = 328 (M+1 ) b) Preparation of 4-(4-amino-thiazol-2-yl)-piperidine-1 -carboxylic acid tert-butyl ester To a solution of 4-(4-hydroxycarbamoyl-thiazol-2-yl)-piperidine-1 -carboxylic acid tert- butyl ester (0.2 g, 0.61 1 mmol) in dry DMF (3 mL) is added anhydrous dipotassium carbonate (0.085 g, 0.61 1 mmol) at RT. After stirring 2h at 85°C, the reaction mixture is cooled down to RT and water is added. The aqueous layer is washed with ethylacetate and the combined organic layers are washed with brine, dried over sodium sulafte, filtered, and evaporated under reduced pressure to give 4-(4-amino-thiazol-2-yl)-piperidine-1-carboxylic acid tert-butyl ester which can be used in the next step without further purification. ¹H-NMR (400 MHz, CDCI₃): δ = 1 .45 (s, 9H), 1 .55-1.65 (m, 2H), 1.90-2.01 (m, 2H), 2.72-2.81 (m, 2H), 2.90-2.97 (m, 1 H), 3.92-4.00 (m, 2H), 4.07-4.13 (br, 2H), 5.72 (s, 1 H). MS: m/z = 284 (M+1 ); 184 (M-100 +1 ). c) Preparation of 4-[4-(3-chloro-2-hydroxy-benzoylamino)-thiazol-2-yl]-piperidine-1 - carboxylic acid tert-butyl ester

To a solution 3-chlorosalicyclic acid (2.89 g, 16.7 mmol) in dry acetonitrile (20 mL) is added carbonyldiimidazol (2.71 g, 16.7 mmol). After stirring 3h at 60°C, a solution of DBU (3.18 g, 20.9 mmol) and 4-(4-amino-thiazol-2-yl)-piperidine-1-carboxylic acid tert-butyl ester (3.95 g, 13.9 mmol) in acetonitrile (10 mL) is added to the reaction mixture. After stirring overnight at RT, solvent is evaporated, the residue is dissolved in ethylacetate, washed with 0.5M HCI, the combined organic layers are washed with sodium bicarbonate, then with brine, dried over sodium sulafte, filtered, and evaporated under reduced pressure, diethyl ether is added to the residue oil and solid precipitated, filtered to give 4-[4-(3-chloro-2-hydroxy- benzoylamino)-thiazol-2-yl]-piperidine-1 -carboxylic acid tert-butyl ester. ¹H-NMR (400 MHz, CDCI₃): δ = 1 .45 (s, 9H), 1 .62-1.71 (m, 2H), 1.92-2.01 (m, 2H), 2.72-2.81 (m, 2H), 2.95-3.02 (m, 1 H), 4.08-4.17 (m, 2H), 6.80 (t, 1 H), 7.47-7.52 (m, 2H), 7.58 (s, 1 H). MS: m/z = 438 (M+1 ). d) Preparation of 3-chloro-2-hydroxy-N-(2-piperidin-4-yl-thiazol-4-yl)-benzamide

hydrochloride salt

To a solution of 4-[4-(3-chloro-2-hydroxy-benzoylamino)-thiazol-2-yl]-piperidine-1 -carboxylic acid tert-butyl ester (2.0 g, 4.57 mmol) in methanol (9mL) is added a solution of 4M HCI in dioxane (5.71 mL, 22.8 mmol)) at RT. After stirring overnight at RT, the solvent is evaporated under reduced pressure to give 3-chloro-2-hydroxy-N-(2-piperidin-4-yl-thiazol-4- yl)-benzamide hydrochloride salt. ¹H-NMR (400 MHz, MeOD): δ = 1 .99 (q, 2H), 2.30 (d, 2H), 3.12 (t, 2H), 3.31 3.37 (m, 1 H), 3.43 (d, 2H), 6.89 (t, 1 H), 7.51 (d, 1 H), 7.67 (s, 1 H), 7.86 (d, 1 H). MS: m/z = 338 (M+1 ). e) Preparation of N-(2-{1 -[2-(3,5-bis-difluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-y l}-thiazol-4-yl)-3-chloro-2-hydroxy-benzamide (Compound No. I.g.006)

To solution of 2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetic acid (0.024 g, 0.107 mmol) in dichloromethane (2 mL) is added one drop of DMF, followed by oxalyl chloride (0.015 g, 0.1 17 mmol) at RT. After gas evolution stopped, solvent and excess of oxalyl chloride are evaporated and the residue oil is dissolved in dichloromethane (2 mL) and is added to a solution of 3-chloro-2-hydroxy-N-(2-piperidin-4-yl-thiazol-4-yl)-benzamide hydrochloride salt and diisopropyllethylamine (0.069 g, 0.535 mmol) in dichloromethane (8 mL) at 0°C. After stirring 2h at RT, water is added to the reaction mixture, the combined organic layers are washed with 1 M HCI, then with brine, dried over sodium sulafte, filtered, and evaporated under reduced pressure. The residue is purified by column chromatography on silica gel (ethyl acetate/cyclohexane 7:3) to give N-(2-{1-[2-(3,5-bis-difluoromethyl-pyrazol-1-yl)- acetyl]-piperidin-4-yl}-thiazol-4-yl)-3-chloro-2-hydroxy-benzamide (Compound No. I.g.006). ¹ H-NMR (400 MHz, CDCI₃): δ = 1 .70-1.82 (m, 2H), 2.05-2.21 (m, 2H), 2.81-2.97 (m, 1 H), 3.1 1-3.20 (m, 1 H), 3.20-3.31 (m, 1 H), 3.80-3.90 (m, 1 H), 4.48-4.56 (m, 1 H), 5.09 (d, 2H), 6.6-6.82 (m, 2H), 6.82 (t, 1 H), 7.45 (d, 2H), 7.6 (s, 1 H), 9.02 (br, 1 H), 12.1 1 (br, 1 H). MS: m/z = 546 (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

034

035

036

037

038

039

where

a) 139 compounds of formula (I. a):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. b) 139 compounds of formula (l.b):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. c) 139 compounds of formula (l.c):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. d) 139 compounds of formula (l.d):

wherein A, Q, R¹ and R⁹ are as defined in Table 1 e 139 compounds of formula (l.e):

wherein A, Q, R¹ and R⁹ are as defined in Table 1 f 139 compounds of formula (l.f):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. g) 139 compounds of formula (l.g):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. h) 139 compounds of formula (l.h):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. i) 139 compounds of formula (I. i):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. j) 139 compounds of formula (l.j):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. k) 139 compounds of formula (l.k):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. m) 139 compounds of formula (l.m):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. n) 139 compounds of formula (l.n):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. o) 139 compounds of formula (l.o):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. p) 139 compounds of formula (l.p):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. q) 139 compounds of formula (l.q):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. r) 139 compounds of formula (l.r):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. s) 139 compounds of formula (l.s):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. t 139 compounds of formula (l.t):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. u 139 compounds of formula (l.u):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. v 139 compounds of formula (I. v):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. w 139 compounds of formula (l.w):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. x 139 compounds of formula (I. x):

wherein A, Q, R¹ and R⁹ are as defined in Table 1. 139 compounds of formula (l.y):

wherein A, Q, R¹ and R⁹ 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: (ACQUITY UPLC from Waters,

Phenomenex Gemini C18, 3 μηη 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., ACQUITY SQD Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700)).

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

Compound No. Melting point (°C) LC/MS

I.g.006 Rt=1 .93 min;MS: m/z=546 (M+1 ) Biological examples

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

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

Compound l.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf discs 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.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Phytophthora infestans I potato / long lasting 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 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).

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.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development. Plasmopara viticola I grape / leaf disc preventative (grape downy mildew)

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

Compound l.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf discs 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).

Plasmopara viticola I grape / long lasting 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 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.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development. Plasmopara viticola I grape / curative (grape downy mildew)

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

Compound l.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development. 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 2-3 days after application.

Compound l.g.006 at 200 ppm gives at least 80% disease control in this test when compared to untreated control culture under the same conditions, which show extensive disease development.

Pythium ultimum / cotton / soil drench (seedling damping off)

The test is carried out in plastic containers (650 ml volume) using a mixture of (50%

Vermiculit + sterile 50% Cugy soil) + 10% v/v water. 10 seeds (cotton, cv. Sure Grow 747) are sown in 2 rows of 5 seeds per container (3 replicates for evaluation of the activity, 3 replicates for evaluation of phytotox). Application is carried out directly after sowing by pouring 10 ml compound diluted in water per row over the seeds. Just afterwards the seeds are covered with a thin layer of the same soil and the inoculation is happening. Pythium ultimum is cultivated for 14 days on carrot slices in Roux bottles. For inoculation, the content of the Roux bottles is mixed and homogenously dispensed over the plastic containers without further filtering (70ml suspension per container). Incubation conditions: 20°C, 12h/12h day/night period in the greenhouse. The activity of a compound is assessed as percent disease control relative to untreated check plants when an appropriate level of disease damage appears in untreated check plants (13 - 16 days after application).

Claims

What is claimed is:

wherein

A is x-C(=0)-, x-C(=S)-, x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-0-C(=0)-, x-0-C(=S)-, x-N(R¹⁴)-C(=0)-, x-N(R¹⁵)-C(=S)-, x-C(R¹⁶R¹⁷)-S0₂- or x-N=C(R²⁶)-, in each case x indicates the bond that is connected to R¹ ;

T is CR¹⁸ or N;

G is O or S;

Y¹ and Y² are independently CR¹⁹ or N;

n is 1 or 2;

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

R¹ is

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R²⁶ each independently are hydrogen, halogen, cyano, C₁-C₄alkyl or C₁-C₄haloalkyl;

R⁸, R¹⁴, R¹⁵, R²⁰ and R²¹ each independently are hydrogen, CrC₄alkyl or d-C₄alkoxy; and R⁹ 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, C1-C4 alkoxy, C1-C4 haloalkoxy, halogen, cyano, hydroxyl, N(R )₂, SH, C1-C4 alkylthio, nitro, phenylsulfonyl and phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, Ci- C₄ haloalkoxy, halogen and cyano;

each R²⁷ independently is hydrogen, C1-C4 alkyl, phenylsulfonyl or phenylsulfinyl, wherein the phenylsulfonyl and phenylsulfinyl are optionally substituted by 1 to 3 substituents independently selected from C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, C1-C4 haloalkoxy, halogen and cyano;

or a salt or a N-oxide thereof.

2. The compound according to claim 1 , wherein

T is CR¹⁸ or N;

G is O or S;

Y¹ and Y² are independently CR¹⁹ or N;

n is 1 or 2;

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

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, cyano, CrC₄alkyl or d-C₄haloalkyl;

R⁸, R¹⁴, R¹⁵, R²⁰, and R²¹ each independently are hydrogen or C C₄alkyl; and

R⁹ 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.

3. The compound according to claim 1 , wherein

T is CR¹⁸ or N; G is O or S;

Y¹ is N;

Y² is CR¹⁹ or N;

n is 1 or 2;

p is 1 ;

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, d-C₄alkyl or CrC₄haloalkyl;

R⁸, R²⁰ and R²¹ each independently are hydrogen or Ci-C₄alkyl; and

R⁹ 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 C C₄ alkyl, C C₄ haloalkyi, halogen, cyano, hydroxy and amino.

4. The compound according to claim 1 , wherein

T is CR¹⁸ or N;

G is S;

Y¹ is N;

Y² is CR¹⁹ or N;

Q is -C(=0)-z, -C(=0)-0-z, -C(=O)-N(R²⁰)-z or -S0₂-z-, in each case z being the bond to R⁹; n is 1 or 2;

p is 1 ;

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ , R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently are hydrogen, fluoro or methyl;

R⁸ and R²⁰ each independently are hydrogen or methyl; and

R⁹ is phenyl, 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, hydroxy and halogen. 5. The compound according to claim 1 , wherein

T is CH or N;

G is S;

Y¹ is N;

Y² is CH or N;

n is 1 or 2;

p is 1 ;

R², R³, R⁴, R⁵, R⁶ and R⁷ are each hydrogen;

R⁸ is hydrogen; and

R⁹ 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, hydroxy and halogen.

6. The compound according to claim 1 , wherein

A is x-CH₂-C(=0)- wherein x indicates the bond that is connected to R¹;

T is CH;

G is S;

Y¹ is N;

Y² is CH;

n is 2;

p is 1 ;

R2_> R3_> R_4> Rs, R6_> and R₇ are each hydrogen;

R₈, is hydrogen; R⁹ is henyl, benzyl or group (a)

(a)

wherein the phenyl, benzyl and group (a) are optionally substituted with 1 to 3 substituents

5 independently selected from halogen, hydroxy, methyl and halomethyl.

7. The compound according to any one of claims 1 to 6, wherein G is S, Y¹ is N and Y² is CH.

10 8. The compound according to any one of claims 1 to 7, wherein p is 1 and n is 2.

9. The compound according to any one of the claims 1 to 8, wherein R², R³, R⁴, R⁵, R⁶ and R⁷ are H.

15 10. The compound according to any one of claims 1 to 9, wherein Q is -C(=0)-z, wherein z indicates the bond that is connected to R⁹.

1 1. The compound according to any one of claims 1 to 10, wherein R⁹ is phenyl substituted by hydroxy and optionally substituted by one or two further substituents.

20

12. The compound according to claim 1 1 , wherein the hydroxy is at the ortho position.

25 wherein R¹ , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, A, T, G, Y¹ , Y², n and p are as defined for formula I in any one of claims 1 to 12; or a compound of formula VIII:

wherein R¹ , R², R³, R⁴, R⁶, R⁷, R⁸, A, T, G, Y¹, Y² , p and n are as defined for formula I in any one of claims 1 to 12. 14. A fungicidal composition comprising at least one compound as defined in any one of claims 1 to 12 and an agriculturally acceptable carrier, optionally comprising an adjuvant, and optionally comprising at least one additional fungicidally active compound.

15. 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 organisms potentially harmful to man, which comprises the application of a compound as defined in any one of claims 1 to 12, to the plant, to parts of the plants or to the locus thereof, to propagation material thereof or to any part of the non-living materials; wherein the phytopathogenic microorganisms are preferably fungal organisms.