OA16803A

OA16803A - Microbiocidal heterocycles.

Info

Publication number: OA16803A
Application number: OA1201300546
Authority: OA
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: 2016-01-04

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)

Description

Microbiocidal Heterocvcles

The présent invention relates to heterocycles, e.g. as active ingrédients, which hâve microbiocidal activity, in particular fungicidal activity. The invention also relates to préparation of these heterocycles, to heterocyclic dérivatives used as intermediates in the préparation of these heterocycles, to préparation of these intermediates, to agrochemical compositions which comprise at least one of the heterocycles, to préparation 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.

Because the ecological and economical requirements of modem crop protection agents are steadily changing, there is a continuing need for the discvovery and development of novel fongicides with advanced properties compared to the known products. Surprisingly, it has now been found that the described bis(difluoromethyl)pyrazol dérivatives hâve, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fongi.

The présent invention provides compounds of formula I:

R

wherein

A is x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-O-C(=O)-, x-O-C(=S)-, x-N(R¹⁴)-C(=O)-, xN(R¹⁵)-C(=S)-, x-C(R¹⁶R¹⁷)-SO₂- orx-N=C(R³⁰)- in each case x indicates the bond that is connected to R¹;

TisCR¹⁸ or N;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁰ or N;

Q is O or S;

n is 1 or 2;

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

R¹ is

F

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³. R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R³⁰ each independently are hydrogen, halogen, cyano, Ci-C₄alkyl, or Ci-C₄haloalkyl;

R^a, R¹⁴ and R¹⁵ each independently are hydrogen or Ci-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_rC₄ alkyl, C_rC₄ haloalkyI, halogen, cyano, hydroxy and amino;

or a sait 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 présent 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-butyi, 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_T 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 froms, i.e. enantiomeric or diastereomeric forrns. As a resuit of the presence of a possible aliphatic C=C double bond, géométrie isomerism may occur, i.e. cis-trans or (E)-(Z) isomerism. Also atropisomers may occur as a resuit of restricted rotation about a single bond. Formula I is întended to include ail those possible isomeric forrns and mixtures thereof. The présent

invention includes ail those possible isomeric forms and mixtures thereof for a compound of formula I. Likewise, formula I is intended to include ail possible tautomers. The présent invention includes ail 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 sait form, e.g. an agronomically usable sait form.

N-oxides are oxidized forms of teriary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book Heterocyclic Noxides” 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 minerai 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(R¹⁰R¹¹)-C(=O)-> x-C(R¹²R¹³)-C(=S)-, x-O-C(=O}-, x-O-C(=S)-, x-N(R¹⁴)-C(=O)-, xN(R^1s)-C(=S)-or x-C(R¹⁶R¹⁷)-SO₂-, In each case x indicates the bond that is connected to R¹;

T is CR¹⁸ or N;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁹ or N;

Q is O or S;

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, Ci-C₄alkyl, or C_rC₄haloalkyl;

R®, R¹⁴ and R¹⁵ each independently are hydrogen or CrCjalkyl; 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 haloalkyl, halogen, cyano, hydroxy and amino;

or a sait or a N-oxide thereof.

Preferably the compound of formula I is a compound wherein:

A is x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)-, x-O-C(=O)-, x-O-C(=S)-, or x-C(R¹⁶R¹>SO₂-, in each case x indicates the bond that is connected to R¹;

T is CR¹⁸ or N;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁹ or N provîding that at least 2 of Y¹, Y², Y³, and Y⁴are CR¹⁹;

Q is O or S;

n is 1 or 2;

pis 1;

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹² R¹³, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently are hydrogen, halogen, C₁-C₄alkyl, CrC₄haloalkyl;

R⁸ is hydrogen or Ci-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 CrC₄ alkyl, Ci-C₄ haloalkyl, halogen, cyano, hydroxy and amino.

Preferably the compound of formula I is a compound wherein:

A is x-CR^l0R¹¹-C(=O)-, x-O-C(=O)-_t or x-CR’⁶R¹⁷-SOz-, ln each case x indicates the bond that is connected to R¹;

T is CR¹⁸;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁹ or N provîding that at least 2 of Y¹, Y², Y³, and Y⁴are CR¹⁹ and provîding that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴; Q is O or S;

n is 1 or 2;

pis 1;

R², R³, R⁴, R⁵, R⁸, R⁷, R¹⁰, R¹¹, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently are hydrogen, fluoro, or methyl;

R⁸ is 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 haloalkyl, hydroxy and halogen.

Preferably the compound of formula I is a compound wherein:

A is x-CH₂-C(=O)-₁ x-O-C(=O)- or X-CH2-SO2-, in each case x indicates the bond that is connected to R¹;

Tis CH;

Y¹, Y², Y³, and Y* are independently CH or N providing that at least 2 of Y¹, Y², Y³, and Y⁴are CH and providing that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴; Q is O;

n is 1 or 2;

pis 1;

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

R® Is 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 C_rC₄ alkyl, C1-C4 haloalkyl, hydroxy and halogen.

Preferably the compound of formula I is a compound wherein:

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

T Is CH;

Y¹, Y², Y³, and Y⁴ are independently CH;

Q is O;

n is 2;

P is 1;

R^z, R³, R⁴, R⁵, R^e, and R⁷ are each hydrogen;

R® is hydrogen or methyl; and

R⁹ is phenyl, benzyl or group (a)

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

The invention also relates to compounds of formula I wherein

A is x-CH2-C(=O)-, x-CH2C(=S)-, x-OC(=O)-, X-CH2SO2-, in each case x being the bond to

TisCH or N;

Y¹, Y², Y³, and Y⁴ are independently CH or N, provîding that at least 2 of Y¹, Y², Y³, and Y⁴are CH and provîding that there are no N-N bonds in the ring containing Y¹, Y², Y³;

Q is O or S;

n is 1 or 2;

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

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

R⁸ is hydrogen or methyl;

R⁹ is group (I), G), or (k):

(j)

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

R¹⁷, R¹⁸, R¹⁹, R²², R²³, R²⁴, R²⁵ and R³⁰ with reference to compounds of formula I. For any one of these substituents, any of the définitions given below may be combined with any définition of any other substituent given below. The invention includes compounds of formula having ail possible combinations of substituent définitions given below or elsewhere in this document. Generally, in this document any substituent définition may be combined with any other substituent définition.

A is 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)-or x-C(R¹⁶R¹⁷)-SO2-, in each case x indicates the bond that is connected to R¹. Preferably, A is x-C(R¹⁰R¹¹)-C(=O)-, x-C(R¹²R¹³)-C(=S)·, x-O-C(=O)-1 x-OC(=S)-, or x-C(R¹⁶R¹⁷)-SC>2-, in each case x indicates the bond that is connected to R¹. More preferably, A is x-CR¹⁰R¹¹-C(=O)-, x-O-C(=O)-, or x-CR¹⁶R¹⁷-SO2-, in each case x

indïcates the bond that is connected to R¹. Even more preferably, A is x-CH2-C(=O)-, xCH2C(=S)-, x-OC(=O)-, x-CH2SO2-, in each case x indicates the bond that is connected to R¹. Yet more preferably, A is x-CH2-C(=O)-₁ x-O-C(=O)- or x-CH₂-SO₂-, in each case x indicates the bond that is connected to R¹. Most preferably, A is x-CH₂-C(=O)·, wherein x indicates the bond that is connected to R¹.

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

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.

Y¹, Y², Y³, and Y⁴ are independently CR¹⁰ or N, e.g. Y¹, Y², Y³, and Y⁴ may be independently CH or N. More preferably, Y¹, Y², Y³, and Y⁴ are independently CR¹⁰ or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CR¹⁹. Even more preferably, Y¹, Y², Y³, and Y⁴ are independently CR¹⁰ or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CR¹⁰and providing that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴. Yet more preferably, Y¹, Y², Y³, and Y⁴ are independently CH or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CH and providing that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴.

Q is O or S. Preferably, Q is O.

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ each independently are hydrogen, halogen, cyano, Ci-C4alkyl, or Ci-C4haloalkyl. More preferably, R², R³, R⁴, R⁵, R⁸, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸, and R¹⁰ each independently are hydrogen, halogen, Ci-C4alkyl, CrC₄haloalkyl. Even more preferably, R², R³, R⁴, R⁵, R^s, R⁷, R¹⁰, R¹¹, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently are hydrogen, fluoro, or methyl. Yet more preferably, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹⁶, R¹⁷, R¹⁸, and R¹⁰ each are hydrogen.

R⁸, R¹⁴ and R¹⁵ each independently are hydrogen or CrC₄alkyl. Preferably, R⁸, R¹⁴and R¹⁵ each independently are hydrogen or methyl. Preferably, R⁸, R¹⁴ and R¹⁵ each are hydrogen.

R⁹ is phenyl, benzyl or group (a):

(a) wherein the phenyl, benzyl and group (a) are each optionaily substituted with 1 to 3 substituents independently selected from Ci-C₄ alkyl, Ci-C₄ haloalkyI, halogen, cyano, hydroxy and amino. Preferably, R⁹ is phenyl, benzyl or group (a):

More preferably, R⁰ 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 methyl, halomethyl, and halogen.

ln one group of compounds R⁹ is (i), (j), or (k):

(I) (j) (k)

R³⁰ is hydrogen, halogen, cyano, CrC4alkyl, or Ci-C4haloalkyl. Preferably, R³⁰ is hydrogen, halogen, Ci-C4alkyl, or Ci-C4haloalkyl. Preferably, R³⁰ is hydrogen, fluoro, or 15 methyl. More preferably, R³⁰ is hydrogen.

ln one group of compounds at least two of Y¹, Y², Y³ and Y⁴ are CH and the others of Y¹, Y², Y³ and Y⁴ are CH or N.

ln one group of compounds at least three of Y¹, Y², Y³ and Y⁴ are CH and the other of Y', Y², Y³ and Y⁴ is CH or N.

ln one group of compounds Y¹ and Y⁴ are CH, one of Y² and Y³ is CH and the other ofY²and Y³ is CH or N.

ln one group of compounds Y¹, Y² and Y⁴ are CH, and Y³ is N.

ln one group of compounds Y¹, Y³ and Y⁴ are CH, and Y² is N.

ln one group of compounds Y¹, Y², Y³ and Y⁴ are CH.

ln one group of compounds Y² is N.

ln one group of compounds Y³ is N.

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

ln one group of compounds R², R³, R⁴, R⁵, R^G and R⁷ are H.

In one group of compounds Q is O.

In one group of compounds A is x-CH2-C(=0)-_t in which x représente the bond that is connected to R¹.

In one group of compounds R® is hydrogen.

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

in which A, T, Y¹, Y², Y³, Y⁴, Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ hâve the définitions as described for formula I.

When n is 2 and p is 1, compounds of formula I hâve the formula according to formula

IB:

R³ R⁴

in which A, T, G, Y¹, Y², Y³, Y⁴, Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ hâve the définitions as described for formula I.

When n is 1 and p is 2, compounds of formula I hâve the formula according to formula

in which A, T, G, Y¹, Y², Y³, Y⁴, Q, R¹, R², R³, R⁴, R⁵, R^s, R⁷, R⁸, and R^a hâve the définitions as described for formula I.

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

The invention also relates to compounds of formula ID;

(ID) wherein Y¹, Y², Y³, Y⁴, A, Q, R¹, R², R³, R⁴, R⁵, R^e, R⁷, R⁸, and R⁹ hâve the définitions as described for formula I as defined above. Preferred définitions of Y¹, Y², Y³, Y⁴, A, Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are as defined above.

The invention also relates to compounds of formula IE:

wherein Y¹, Y², Y³, Y⁴, A, Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ hâve the définitions as described for formula I as defined above. Preferred définitions of Y¹, Y², Y³, Y⁴, A, Q, R¹, R², R³, R⁴, R⁵, R⁸, R⁷, R⁸, and R⁹ are as defined above.

The invention also relates to a compound of formula IF:

O ^TY%An'^R' ^(IF)

Çi^{1 H} wherein T is N or CH;

Y² and Y³ are both CH, or one of Y³ and Y² is N and the other is CH; and

R¹ and R⁹ are as described for a compound of formula I as defined above. Preferred définitions of R¹ and R⁹ are as as defined above

The invention also relates to a compound of formula IG:

⁹ (IG)

wherein T is N or CH;

Y² and Y³ are both CH, or one of Y³ and Y² is N and the other is CH; and

R⁹ is as described for a compound of formula I as defined above. Preferred définitions of R⁹are as defined above.

The invention also relates to other intermediates useful in the préparation of compounds of formula I. Accordingly, the invention relates to a compound of formula II:

(H) wherein Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ hâve the définitions as described for formula I as defined above. Preferred définitions of Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R⁵, R^g and R⁷ are as defined above.

The invention relates to a compound of formula IV:

wherein Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R⁵ R⁶ and R⁷, hâve the définitions as described for formula I as defined above, and preferred définitions of Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R⁵ R⁶ and R⁷ are as defined above; and R²⁶ is CpCe alkyl or optionally substituted aryl. Preferably. R²⁶ is CrCs alkyl or phenyl optionally substituted with 1 to 3 substituents independently selected from C,-C₄ alkyl, C_rC₄ haloalkyl, hydroxyl, amino, cyano and halogen.

The invention relates to a compound of formula V:

(V) wherein Y¹, Y², Y³, Y⁴, A, Q, n, p, R¹, R^z, R³, R⁴, R⁶ and R⁷, hâve the définitions as described for formula I as defined above, and preferred définitions of Y¹, Y^z, Y³, Y⁴, A, Q, n, p, R¹, R², R³, R⁴, R⁶ and R⁷ are as defined above; and R²⁶ is CrC6 alkyi or optionally substituted aryl. Preferably, R²⁶ is Ci-C6 alkyi or phenyl optionally substituted with 1 to 3 substituents independently selected from C1-C4 alkyi, C1-C4 haloalkyI, hydroxyl, amino, cyano and halogen.

The invention relates to a compound of formula XI:

wherein Y¹, Y², Y³, Y⁴, A, Q, n, p, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷, hâve the définitions as described for formula I as defined above, and preferred définitions of Y¹, Y², Y³, Y⁴, A, Q, n, p, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined bove; Hal stands for halogen.

Compounds of formula (I) can be made in an analogous way to those described in WO2011/01Θ401 and as shown in the following schemes.

The compounds of formula I, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, A, T, Y¹, Y², Y³, and Y⁴, n, p and Q 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, A, T, Y¹, Y², Y³, and Y⁴, n, p and Q are as defined for formula I, with a compound of formula III, wherein R⁸ and R⁹ are as defined for formula I ,and a peptide coupling reagent, such as BOP, PyBOP, HATU. This is shown in Scheme 1.

Scheme 1

R³ R⁴

coupling reagent

R³ R⁴

The compounds of formula II, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, Y¹, Y², Y³, and

Y⁴, n, p and Q are as defined for formula I can be obtained by saponification of a compound 5 of formula IV, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, Y¹, Y², Y³, and Y⁴, n, p and Q are as defined for formula i and R²⁶ is Ci-C_ealkyl or optionally substituted aryl, with a base, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, etc.. This is shown in Scheme 2.

Scheme 2

The compounds of formula IV.1, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, Y¹, Y², Y³, and Y⁴, n, p and Q are as defined for formula I and R²⁶ is CrCealkyl or optionally substituted aryl, can be obtained by réduction of a compound of formula V, wherein R¹, R², R³, R⁴, R⁶, R⁷, A, Y¹, Y², Y³, and Y⁴ , n, p and Q are as defined for formula I and R²⁶ is CrCsalkyl or 15 optionally substituted aryl, and hydrogen with a catalyst, such as palladium on charcoal, raney-nickel, etc, or with lithium aluminum hydride. This is shown in Scheme 3.

Scheme 3

The compounds of formula V, wherein R¹, R², R³, R⁴, R⁶, R⁷, A, Y¹, Y², Y³, and Y⁴, n, p 5 and Q are as defined for formula I and R²⁶ is Ci-C6alkyl or optionally substituted aryl, can be obtained by transformation of a compound of formula VI, wherein R^z, R³, R⁵, R⁶, R⁷ n, p and A are as defined for formula I and R²⁷ and R²⁸ are each independently hydroxy or Cr Cgalkyl or together with the interjacent boron atom form a five- or six-membered saturated heterocyclic ring, with a compound of formula VII, wherein Y¹, Y², Y³, and Y⁴ and Q are as 10 defined for formula I, R²⁶ is Ci-C₆alkyl or optionally substituted aryl and Hal is halogen, preferably iodo, bromo or chloro, and a catalyst. This is shown in Scheme 4.

(VI)

The compounds of formula VI, wherein R¹, R², R³, R⁴, R⁶, R⁷ n, p and A are as defined for formula I and R²⁷ and R²⁸ are each Independently hydroxy or CrCealkyl or together with the interjacent boron atom form a five- or six-membered saturated heterocyclic ring, can be obtained by transformation of a compound of formula VIII, wherein R¹, R^z, R³, R⁴, R⁶, R⁷, n and p are as defined for formula I and R²⁷ and R²⁸ are each independently hydroxy or CrC_salkyi or together with the interjacent boron atom form a five20 or six-membered saturated heterocyclic ring, with a compound of formula IX, wherein R¹

and A are as defined for formula I and R²⁹ is hydroxy or halogen, preferably, fluoro, chloro or bromo, and a peptide coupling reagent or a base, such as pyridine, triethylamîne, ethyl diîsopropylamine etc.. This is shown in Scheme 5.

Scheme 5

_r28 (VIII) ⁺ R1/^A\R29 (IX)

(VI)

Alternative^, the compounds of formula V, wherein R¹, R², R³, R⁴, R⁶, R⁷, A, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I and R²⁶ is CrC6alkyl or optionally substituted aryl, can be obtained by transformation of a compound of formula X, wherein R², R³, R⁴, R^G, 10 R⁷ A, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I and R²⁶ is Ci-C6alkyl or optionally substituted aryl, with a compound of formula IX, wherein R¹ and A are as defined for formula I and R²⁹ is hydroxy or halogen, preferably, fluoro, chloro or bromo, and a peptide coupling reagent or a base, such as pyridine, triethylamîne, ethyl diisopropylamine etc.. This is shown in Scheme 6.

Scheme 6

base

Alternative^, the compounds of formula I, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁰, A, T, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I can be obtained by transformation 5 of a compound of formula Xi, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I and Hal is halogen, preferably fluoro, chloro or bromo, with a compound of formula III, wherein R® and R⁰ are as defined for formula I, with a base, such as pyridine, triethylamine, ethyl diisopropylamine etc.. This is shown in Scheme 7.

Scheme 7

R³ R⁴

base

The compounds of formula XI, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, T, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I and Hal is halogen, preferably fluoro, chloro or bromo, can be obtained by transformation of a compound of formula II, wherein R¹, R², R³,

R⁴, R⁵, R⁶, R⁷, A, T, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I, with a phosphoryl halide, such as phosphoryl chloride or phosphoryl bromide, or a thionyl halide, such as thionyl chloride or thionyl bromide. This is shown in Scheme 8.

Scheme 8

The compounds of formula IV.2, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, A, Y¹, Y², Y³, Y⁴, n, p and Q are as defined for formula I and R²⁶ is Ci-C6alkyl or optionally substituted aryl, can be obtained by transformation of a compound of formula XII, wherein R¹, R², R³, R⁴, R⁶, R⁷n, p and A are as defined for formula I, with a compound of formula VII, wherein Y¹, Y², Y³, Y⁴ and Q are as defined for formula I, R²⁶ is Ci-C6alkyl or optionally substituted aryl and Hal is halogen, preferably iodo, bromo or chloro. This is shown in Scheme 9.

Scheme 9

(XII)

Surprisingly, it has now been found that the novel compounds of formula I hâve, 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 ingrédients 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 hâve very useful curative, préventive 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 10 of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rlce), 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 ingrédients according to the invention can also be 15 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 présent 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.), Ascomycètes 30 (e.g. Venturia spp., Blumeria spp., Erysiphe spp., Podosphaera spp., Uncinula spp., Monilinîa 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 négative 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 présent 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 (râpe, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpklns, 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 naturel 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 résistant (e.g. Bt. and VIP varieties) as well as disease résistant, herbicide tolérant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolérant 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 hâve been rendered tolérant 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-3phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a resuit of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolérant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer râpe (Canola). Examples of crops that hâve been rendered tolérant 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 hâve 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 hâve been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a sélective action, such as, for example, the sœcalled 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 produclng 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 15 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 fleld, on which crop plants are growing.

The term “plant propagation material” is understood to dénoté generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and végétative 20 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 25 “plant propagation material is understood to dénoté 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 mannerto emulsifiable concentrâtes, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute émulsions, wettable powders, 30 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 35 well as fertilizers, micronutrient donors or other formulations for obtaining spécial 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 minerai 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 préparations, which influence the growth of plants. They can also be sélective herbicides or non-selective herbicides as well as insecticides, fongicides, bactéricides, nematicides, molluscicides or mixtures of several of these préparations, if desired together with further carriers, surfactants or application promotlng 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 15 ingrédient at least one compound of formula I or of at least one preferred Individual compound as above-deflned, in free form or in agrochemîcally usable sait form, and at least one of the above-mentioned adjuvants

The Invention provides a fungicidal composition comprising at least one compound formula I, an agrlcuiturally acceptable carrier and optionally an adjuvant. An agricultural 20 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 ingrédient in addition to the compound of formula I.

The compound of formula (I) may be the sole active ingrédient of a composition or it may be admixed with one or more additional active ingrédients such as an insecticide, 25 fongicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingrédient may, in some cases, resuit in unexpected synergistic activities. Examples of suitable additional active ingrédients 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 (248593-1630 0), Picoxystrobin (117428-22-5), Pyraclostrobin (175013-18-0), Azaconazole (60207-31-0), Bromuconazole (116255-48-2), Cyproconazole (94361-06-5), Difenoconazole (119446-683), 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 35 (86598-92-7), Ipconazole (125225-28-7), Metconazole (125116-23-6), Myclobutanil (8867189-0), Oxpoconazole (174212-12-5), Peforazoate (58011-68-0), 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 (112281-77-3), Triadimefon (43121-43-3), Triadimenol (55219-65-3), Triflumlzole (99387-89-0), Triticonazole (131983-72-7), Diclobutrazol (76738-62-0), Etaconazole (60207-93-4), Fluconazole (86386-73-4), Fluconazole-cîs (112839-32-4), Thiabendazoie (148-79-8), Quinconazole (103970-75-8), Fenpiclonil (74738-17-3), Fludioxonil (131341-86-1), Cyprodinil (121552-61-2), Mepanipyrim (110235-47-7), Pyrimethanil (53112-28-0), Aldîmorph (91315-15-0), Dodemorph (1593-77-7), Fenpropimorph (67564-91-4), Tridemorph (81412-43-3), Fenpropidin (67306-00-7), Spiroxamlne (118134-30-8), Isopyrazam (881685-58-1), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31-3), Boscalid (188425-85-6), Penflufen (49479367-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (41361535-7), Dimethomorph (110488-70-5), Chlorothalonil (1897-45-6), Fluazlnam (79622-59-6), Dithlanon (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), Ametoctradïne (865318-97-4) Cyflufenamid (180409-60-3), Ipconazole (125225-28-7), Amlsulbrom (348635-87-0), Ethaboxam (1665077-3), Fluopicolide (239110-15-7), Fluthianil (304900-25-2), Isotlanil (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 33113-08-5): Copper oleate (CAS 1120-44-1); Folpet (133-07-3), Quinoxyfen (124495-187), 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 (Dimethylammonlum), 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 (2dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide, 1-methyl-3-dlfluoromethyl-1Hpyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-aiTiide, 1-methyl-3difluoromethyl-4H-pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1 -methylethyl]-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-Chlorophenyl)-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-defîned, 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 5 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 spoîlage 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 ingrédient 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 spoîlage 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 dépend 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 25 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 rîce 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 grindîng 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 ingrédient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.l./ha, most preferably from 20g to

600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.

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

The following non-lïmiting example illustrâtes the above-described Invention in more 10 detail.

Example 1: This example Illustrâtes the préparation of 3-{4-[2-(3,5-bis-difluoromethyl-pyr azol-1 -yl)-acetyl]-piperazln-1 -y l}-N-(R )- 1,2,3,4-tetrahydro-naphthalen-1 -yl-benzamide (Compound No. I.z.001)

a) Préparation of 4-{3-[(R)-(1,2,3,4-tetrahydro-naphthalen-1-yl)carbamoyl]-phenyl}-piper azine-1-carboxylic acid tert-butyl ester

HATU (6.6 g, 14.4 mmol) and ethyldiisopropylamine (4.1 g, 26 mmol) were added consecutively to a suspension of 4-(3-carboxy-phenyl)-piperazine-1-carboxylic acid tert20 butyl ester (4.0 g, 13 mmol) in 30 ml of N,N-dimethylformamide. This mixture was stirred for 10 min at room température, then a solution of R-(-)-1,2,3,4-tetrahydro-1-naphthylamine (1.9 g, 13 mmol) in 20 ml of Ν,Ν-dimethylformamide was added. The reaction mixture was stirred for 4 h at room température. Subsequently the solvent was removed in vacuo, the remaining oil dissolved in ethyl acetate and washed with a saturated aqueous sodium bicarbonate solution, 0.5 N hydrochloric acid and brine. The organic layer was dried over sodium sulfate and evaporated, the residue was purified by column chromatography on silica gel (ethylacetate/cyclohexane 3:7) to give 4-{3-[(R)-(1,2,3,4-tetrahydro-naphthalen-1yl)carbamoyl]-phenyl)-piperazine-1-carboxylic acid tert-butyl ester. ¹H-NMR (400 MHz, CDCI₃):5= 1.51 (s, 9H), 1.86-1.95 (m, 2H), 2.02-2.16 (m, 2H), 2.82-2.91 (m, 2H), 3.20 (t, 4H), 3.61 (t, 4H), 5.37 (t, 1 H). 7.12 - 7.19 (m, 4H), 7.26 (q, 1 H), 7.37 (t, 2H), 7.48 (d, 1H), 8.69 (bs, 1H). MS: m/z = 436 (M+1 ).

b) Préparation of 3-piperazin-1-yl-N-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-benzamide

To a solution of 4-{3-[(R)-(1,2₁3₁4-tetrahydro-naphthalen-1-yl)carbamoyl]-phenyl}35 piperazine-1-carboxylic acid tert-butyl ester (5.7 g, 13 mmol) in 150 ml of dioxane was added 33 ml of 4 N hydrochloric acid. The reaction mixture was stirred for 16 h at room

température. Subsequently the solvent was removed in vacuo, the residue dissolved in ethyl acetate and washed with a saturated aqueous sodium bicarbonate solution. The organic layer was dried over potassium carbonate and evaporated, delivering 3-piperazin-1yl-N-(R)-1,2,3,4-tetrahydro-naphthalen-l-yl-benzamide, which was pure enough to be transformed in the next step without further purification. ¹H-NMR {400 MHz, MeOD): δ =

1.83 - 1.92 (m, 2H), 2.02 (q, 1 H), 2.13 (q, 1 H), 2.83 - 2.89 (m, 2H), 3.00 (t, 4H), 3.21 (t, 4H), 5.34 (t, 1 H), 7.11 - 7.19 (m, 4H), 7.27 (q, 1 H), 7.34 (d, 2H), 7.48 (d, 1 H). MS: m/z = 336 (M+1).

c) Préparation of 3-{4-[2-(3,5-bis-difluoromethyl-pyrazol-1-yl)-acetyl]-piperazin-1-yl}N-(R)-1 ^.SAtetrafiydro-naphthalen-l-yl-benzamide (Compound No. I.z.001)

To solution of 2-[3,5-bis(difluoromethyl)pyrazO'1-yl]acetic acid (0.1 g, 0.5 mmol) in 5 ml of dichloromethane was added at room température one drop of Ν,Ν-dimethylformamide, then oxalyl chloride (0.07 g, 0.6 mmol). This mixture was stirred for 15 min at room température 15 and then evaporated. The residue was redissolved in 5 ml of dichloromethane and slowly added at 0 oC to a solution of S-piperazin-l-yl-N-tRJ-I^.S^-tetrahydro-naphthalen-l-ylbenzamide (0.2 g, 0.5 mmol) and triethylamine (0.3 g, 2.7 mmol) in 5 ml of dichloromethane. The reaction mixture was stirred for 2 h at room température, then diluted with water and dichloromethane. The organic layer was washed with water 1 N hydrochloric 20 acid and brine, dried over sodium sulfate and evaporated. The remainder was purified by column chromatography on silica gel (ethylacetate/cyclohexane 3:7) to give 3-{4-[2-(3,5-bisdifluoromethyl-pyrazol-1-yl)-acetyl]-piperazin-1-yl}-N-(R)-1,2,3,4-tetrahydro-naphthalen-1-ylbenzamide (Compound No. I.z.001 ). ¹H-NMR (400 MHz, CDCI₃): δ = 1.62 (t, 1H), 1.79 1.90 (m, 2H), 2.07 (q, 1H), 2.75 (q, 2H), 3.19 (s, 2H), 3.24 (s, 2H), 3.60 (s, 2H), 3.72 (s,

2H), 5.08 (s, 2H), 5.31 (q, 1H), 6.26 (d, 1H), 6.69 (d, 1H), 6.97 (q, 1H), 7.04-7.13 (m, 3H), 7.22 (t, 2H), 7.40 (s, 1H). MS: m/z = 544 (M+1).

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

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

Compound	R1	A	Q	R⁸
No.

1	f₂hc. _N V chf₂	-CH₂C(=0)-	0	'Ÿ)
2	^F2^HC\^N V chf₂	-CH₂C(=0)-	s	Ό)
3	^hc^n X chf₂	-CH_zC(=O)-	0	ÇH₃ 'U
4	f₂hc^_n V chf₂	-CH₂C(=0)-	s	Ç^H3 nO
5	F₂HC N V chf₂	-CH₂C(=0)-	0	-V)
6	V chf₂	-CH_zC(=0)-	s
7	^P2HC. _N V chf₂	-CH₂C(=O)-	0

8	^F2^HCX^N P¹· chf₂	-CH₂C(=OF	s
9	f₂hc_x	Q- chf₂	-CH₂C(=O)-	0
10	f₂hc_x	ç- chf₂	-CH₂C(=O)-	s
11	f₂hc_s	ç- chf₂	-CH₂C(=O)-	0	X)
12	f₂hc_x	Q- chf₂	-CH₂C(=O)-	s	X)
13	f₂hc_v	ç- chf₂	-CH₂C(=S)-	0	-¾
14	F_zHC<	chf₂	-CH₂C(=S)-	s

15	F₂HC _N V CHF_Z	-CH_zC(=S)-	0	ÇH₃ U
16	^hc^n V chf₂	-CH₂C(=S)-	s	ÇH₃ '‘U
17	F₂HC _N V chf₂	-CH₂C(=S)-	0	-¾
18	^F2^HCx^N V chf₂	-CH₂C(=S)-	s	-¾
19	^f ₂hc^_n V chf₂	-CH₂C(=S)-	0
20	^F ₂HC.m V chf₂	-CH₂C(=S)-	s
21	chf₂	-CH₂C(=S)-	0

22	f₂hc_x	Q- chf₂	-CH₂C(=S)-	s	no
23	f₂hc_x	n chf₂	-CH₂C(=S)-	0
24	f₂hc_x	Q- chf₂	-CH₂C(=S)-	s	Ό
25	f₂hc\	ç- chf₂	-0C(=0)-	0	O)
26	f₂hc_x	Q- chf₂	-0C(=0)-	s
27	f₂hc_x	Q- chf₂	-0C(=0)-	0	ÇH₃ Où
28	f₂hc_x	yA Q- chf₂	-0C(=0)-	s	Çh₃ V

29	f₂hc_v	ç- chf₂	-OC(=O)-	0
30	f₂hc_v	ç- chf₂	-00(=0)-	s
31	f₂hc_x	ç- chf₂	-00(=0)-	0
32	f₂hc_x	Q- chf₂	-00(=0)-	s
33	f₂hc_x	•pA Q- chf₂	-00(=0)-	0
34	F₂HC_x	Q- chf₂	-00(=0)-	s
35	f₂hc_x	-pA V' chf₂	-00(=0)-	0	Ό

36	f₂hc_x	Q- chf₂	-00(=0)-	s
37	f₂hc\	ç- chf₂	- CH₂SO₂-	0
38	f₂hc_x	Q- chf₂	- CH₂SO₂-	s	'2)
39	f₂hc_v	Q- chf₂	- CH₂SO₂-	0	ÇH₃
40	f₂hc_x	γ=Α ç- chf₂	-ch₂ so₂-	s	ÇH₃
41	f₂hc_x	ç- chf₂	- CH₂SO₂-	0
42	f₂hc_x	Q- chf₂	-ch₂ so₂-	s	25

43	f₂hc_x	ç- chf₂	- CH₂SO₂-	0	^0
44	F₂HC_x	Q- chf₂	- CH₂SO₂-	s
45	f₂hc_x	Q- chf₂	- CH₂SO₂-	0
46	f₂hc_x	ç- chf₂	- CH₂SO₂-	s	•Ό
47	f₂hc_x	1^' ç- chf₂	- CH₂SO₂-	0
48	f₂hc_x	Q- chf₂	- CH₂SO₂-	s

where

a) 48 compounds of formula (La):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

b) 48 compounds of formula (l.b):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

c) 48 compounds of formula (l.c):

wherein A, Q, R¹ and R^g are as defined in Table 1.

d) 48 compounds of formula (l.d):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

e) 48 compounds of formula (I.e):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

f) 48 compounds of formula (l.f):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

g) 48 compounds of formula (l.g):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

h) 48 compounds of formula (l.h):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

i) 48 compounds of formula (l.i):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

j) 48 compounds of formula (l.j):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

k)48 compounds of formula (l.k):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

m) 48 compounds of formula (l.m):

wherein A. Q, R¹ and R⁹ are as defined in Table 1.

η) 48 compounds of formula (l.n):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

o) 48 compounds of formula (l.o):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

p) 48 compounds of formula (l.p):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

q) 48 compounds of formula (l.q):

wherein A, Q, R¹ and R⁰ are as defined in Table 1.

r) 48 compounds of formula (l.r):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

s) 48 compounds of formula (l.s):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

t) 48 compounds of formula (l.t):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

u) 48 compounds of formula (l.u):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

v)48 compounds of formula (l.v):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

w) 48 compounds of formula (l.w):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

x) 48 compounds of formula (l.x):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

y) 48 compounds of formula (l.y):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

aa) 48 compounds of formula (laa):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ab)48 compounds of formula (l.ab):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ac) 48 compounds of formula (Lac):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ad) 48 compounds of formula (Lad):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ae) 48 compounds of formula (l.ae):

) wherein A, Q, R¹ and R⁹ are as defined in Table 1.

af) 48 compounds of formula (l.af):

.af) wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ag) 48 compounds of formula (Lag):

•ag) wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ah) 48 compounds of formula (l.ah):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ai) 48 compounds of formula (Lai):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

aj) 48 compounds of formula (l.aj):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ak) 48 compounds of formula (lak):

_riA_n^ q (l.ak)

CH₃ wherein A, Q, R¹ and R⁹ are as defined in Table 1.

am) 48 compounds of formula (l.am):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

an) 48 compounds of formula (Lan):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ao) 48 compounds of formula (l.ao):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ap) 48 compounds of formula (l.ap):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

aq) 48 compounds of formula (l.aq):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ar) 48 compounds of formula (l.ar):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

as) 48 compounds of formula (l.as):
R<_a.nQL	^(las)

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

at) 48 compounds of formula (l.at):
r<_a-O	(lat)

wherein A, Q, R¹ and R⁹ are as defined in Table 1,

au) 48 compounds of formula (l.au):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

av) 48 compounds of formula (l.av):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

aw) 48 compounds of formula (l.aw):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ax) 48 compounds of formula (l.ax):

wherein A, Q, R¹ and R⁹ are as defined in Table 1.

ay) 48 compounds of formula (l.ay):

•ay) wherein A, Q, R¹ and R⁹ are as defined in Table 1.

Throughout this description, températures are glven in degrees Celsius and

m.p. means melting point. LC/MS means Liqutd Chromatography Mass

Spectroscopy and the description of the apparatus and the method is: (ACQUITY

UPLC from Waters, Phenomenex Gemini C18, 3 pm particle size, 110 Angstrôm, 30 x 3 mm column, 1.7mL/min., 60 °C, H₂O + 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, Cône (V) 20.00, Extractor (V) 3.00, Source Température (°C) 150, Desolvation Température (°C) 400, Cône 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.v.001		Rt=1.10 min; MS: m/z=544 (M+1 )
l.z.001		Rt=1.88 min; MS: m/z=544 (M+1)
l.ah.001		Rt=1.25 min; MS: m/z=545 (M+1)

Bioloqlcal examples

Phytophthora infestans / tomato / leaf dise preventative (tomato late bliqht)

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 régime 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.v.001, l.z.001 and l.ah.001 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf dises under the same conditions, which show extensive disease development.

Phytophthora infestans ! potato I preventative (potato late bliqht)

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.v.001,1.2.001 and I.ah.001 at 200 ppm give 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 ! ootato / long lasting preventative (potato late bliaht)

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 sporangîa 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 15 untreated check plants (9-11 days after application).

Compound l.v.001, l.z.001 and l.ah.001 at 200 ppm give 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 / ootato i curative (potato late blight)

2-week old potato plants cv. Bintje are Inoculated by spraying them with a sporangîa 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 25 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.v.001, l.z.001 and l.ah.001 at 200 ppm give at least 80% disease control 30 in this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola t grâce / leaf dise preventative (grape downv mildew)

Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and 35 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 régime 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).

Plasmopara viticole / grâce / preventative (qrape 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 15 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 ! qrape / long lastinq preventative (qrape downy mlldew)

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 25 sporangia suspension on their lower leaf surface 6 days after application. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (11-13 days after application).

Compound l.v.001, l.z.001 and l.ah.001 at 200 ppm give at least 80% disease control în this test when compared to untreated control plants under the same conditions, which show extensive disease development.

Plasmopara viticola i qrape / curative (qrape 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).

Claims

1. A compound of formula I:

wherein

A is 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)-or x-C(R¹⁶R¹⁷)-SO2-, x-N=C(R³⁰}-1 in each case x indicates the bond that is connected to R¹:

T is CR¹⁸ or N;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁹ or N;

Q is O or S;

n is 1 or 2;

p is 1 or 2, provîding that when n is 2, p is 1.

R¹ is

F

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹, R¹², R¹³, R¹⁸, R¹⁷, R¹⁸,R¹⁹ and R³⁰ each independently are hydrogen, halogen, cyano, Ci-C₄alkyl, or C₁-C₄haloalkyl;

R⁸, R¹⁴ and R¹⁵ each independently are hydrogen or CrC₄alkyl; 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 Cî-C^ alkyl, C1-C4 haloalkyl, halogen, cyano, hydroxy and amino;

or a sait or a N-oxide thereof.

2. The compound according to claim 1, wherein

A is x-C(R¹⁰R¹¹ )-0(=0)-, x-C(R¹²R¹³)-C(=S)-, x-O-C(=O)-, x-O-C(=S)-, or x-C(R¹⁶R¹⁷)SO₂-, in each case x indicates the bond that is connected to R¹;

T is CR¹⁸ or N;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁰ or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CR¹⁰;

Q is O or S;

n is 1 or 2;

pis 1;

R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹’, R¹², R¹³, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ each independently are hydrogen, halogen, C-i-C^alkyl, CrCihaloalkyl;

R⁸ is hydrogen or Ci-C^alkyl; 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 haloalkyl, halogen, cyano, hydroxy and amino.

3. The compound according to claim 1, wherein

A is x-CR¹⁰R¹¹-C(=O)-, x-O-C(=O)-, or x-CR¹⁶R¹⁷-SO₂-, in each case x indicates the bond that is connected to R¹;

T is CR¹⁸;

Y¹, Y², Y³, and Y⁴ are independently CR¹⁹ or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CR¹⁰ and providing that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴;

Q is O or S;

n is 1 or 2;

pis 1;

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

R⁸ is hydrogen or methyl; and

R⁹ is phenyl, benzyl or group (a):

(a) wherein the phenyl, benzyl and group (a) are each optionaily substituted with 1 to 3 substituents independently selected from C_rC₄ alkyl, CrC₄ haloalkyl, hydroxy and halogen.

4. The compound according to claim 1, wherein

A is x-CH₂-C(=O)-, x-O-C(=O)- or x-CH₂-SO₂-, in each case x indicates the bond that is connected to R¹;

Tis CH;

Y¹, Y², Y³, and Y⁴ are independently CH or N providing that at least 2 of Y¹, Y², Y³, and Y⁴ are CH and providing that there are no N-N bonds in the ring containing Y¹, Y², Y³, and Y⁴;

Q is O;

n is 1 or 2;

P is 1;

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

R⁸ is hydrogen or methyl; and

R⁹ is phenyl, benzyl or group (a):

(a) wherein the phenyl, benzyl and group (a) are each optionaily substituted with 1 to 3 substituents independently selected from Ci-C₄ alkyl, C_rC₄ haloalkyl, hydroxy and halogen.

5. The compound according to claim 1, wherein

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

T is CH;

Y¹, Y², Y³, and Y⁴ are independently CH;

Q is O;

n is 2;

pis 1;

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

R® is hydrogen or methyl; and

R⁹ is phenyl, benzyl or group (a):

6. The compound accordîng to any one of daims 1 to 5, wherein at least three of Y¹,

Y², Y³ and Y⁴ are CH and the other of Y¹, Y², Y³ and Y⁴ is CH or N.

7. The compound accordîng to any one daims 1 to 6, wherein Y²is N.

8. The compound accordîng to any one of daims 1 to 7, wherein p is 1 and n is2.

9. The compound accordîng to any one of daims 1 to 8, wherein R², R³, R⁴, R⁵,R® and R⁷ are H.

10. The compound accordîng to any one of daims 1 to 9, wherein Q Is O.

wherein Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ hâve the définitions as described for formula I as defined in any one of daims 1 to 10;

(IV) wherein Y¹, Y², Y³, Y⁴, A, Q, T, n, p, R¹, R², R³, R⁴, R^s, R⁶ and R⁷ hâve the définitions as described for formula I as defined in any one of daims 1 to 10; and R²⁶ is C_rC₆ alkyl or optionally substituted aryl;

wherein Y¹, Y², Y³, Y⁴, A, Q, n, p, R¹, R², R³, R⁴, R⁶ and R⁷, hâve the définitions as described for formula I as defined in any one of daims 1 to 10; and

R²⁶ is CrCe alkyl or optionally substituted aryl;

wherein Y¹, Y², Y³, Y⁴, A, Q, n, p, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷, hâve the définitions as described for formula I as defined in any one of daims 1 to 10; and Hal stands for halogen.

12. A compound according to claim 11, wherein R²⁶ is Ci-C_G alkyl or phenyl optionally substituted with 1 to 3 substituents independently selected from C1-C4 alkyl, C1-C4 haloalkyl, hydroxyl, amino, cyano and halogen.

13. A fungicidal composition comprising at least one compound as defined in any one of daims 1 to 10 and an agriculturally acceptable carrer, optionally comprising an adjuvant, and optionally 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 organisms potentially harmful to man, which comprises the application of a compound as defined in any one of daims 1 to 10 to the plant, to parts of the plant or to the locus thereof, or to the propagation material thereof, or to any part of the non-living materials.

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