Patent Publication Number: US-2010130560-A1

Title: Fungicide 2-pyridyl-methylene-thio carboxamide or 2-pyridyl-methylene-n-substituted carboximidamide derivatives

Description:
The present invention relates to 2-pyridyl-methylene-thiocarboxamide or 2-pyridyl-methylene-N-substituted-carboximidamide derivatives, their process of preparation, their use as fungicide active agents, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions. 
     In international patent application WO-01/11966 certain 2-pyridyl-methylene-carboxamide derivatives are generically embraced in a broad disclosure of numerous compounds. 
     
       
         
         
             
             
         
       
     
     However, this document does not specifically disclose nor suggest to select such compounds wherein the nitrogen atom of the carboxamide residue might be substituted by a cycloalkyl. 
     In international patent application WO-96/38419 certain 2-pyridyl-methylene-thiocarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula: 
     
       
         
         
             
             
         
       
     
     wherein X represents halogen, W can represent a sulphur atom, R 1  can represent C 1 -C 4 -alkyl, R 2  can represent C 3 -C 7 -cycloalkyl and R 3  can represent various substituents among that heterocycles. However, this document does not specifically disclose nor suggest to select such compounds wherein the nitrogen atom of the thiocarboxamide residue can be substituted by a cycloalkyl. 
     In international patent application WO-06/098128 certain 2-pyridyl-methylene-thiocarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula: 
     
       
         
         
             
             
         
       
     
     wherein W can represent a sulphur atom, Y can represent N-cycloalkyl and R 7  can represent various substituents among that heterocycles. However, this document does not specifically disclose nor suggest to select such compounds wherein the nitrogen atom of the thiocarboxamide residue can be substituted by a cycloalkyl. 
     It is always of high-interest in agriculture to use novel pesticide compounds in order to avoid or to control the development of resistant strains to the active ingredients. It is also of high-interest to use novel compounds being more active than those already known, with the aim of decreasing the amounts of active compound to be used, whilst at the same time maintaining effectiveness at least equivalent to the already known compounds. We have now found a new family of compounds that possess the above mentioned effects or advantages. 
     Accordingly, the present invention provides 2-pyridyl-methylene-thiocarboxamide or 2-pyridyl-methylene-N-substituted-carboximidamide derivatives of formula (I) 
     
       
         
         
             
             
         
       
     
     wherein
         A represents a carbo-linked, substituted or non substituted, unsaturated or partially saturated, 5-membered heterocyclyl group;   T represents S, N—R a , N—OR a , N—NR a R b  or N—CN;   Z 1  represents a substituted or non substituted C 3 -C 7  cycloalkyl;   Z 2  and Z 3 , that can be the same or different, represent a hydrogen atom; C 1 -C 5 -alkyl; C 2 -C 5 -alkenyl; C 2 -C 5 -alkynyl; cyano; nitro; a halogen atom; C 1 -C 5 -alkoxy; C 2 -C 5 -alkenyloxy; C 2 -C 5 -alkynyloxy; C 3 -C 7 -cycloalkyl; C 1 -C 5 -alkylsulphenyl; an amino; C 1 -C 5 -alkylamino; di-C 1 C 5 -alkylamino; C 1 -C 5 -alkoxycarbonyl; C 1 -C 5 -alkylcarbamoyl; di-C 1 -C 5 -alkylcarbamoyl; N—C 1 -C 5 -alkyl-C 1 -C 5 -alkoxycarbamoyl; or   Z 2  and Z 3  together with the carbon atom to that they are linked can form a 3-, 4-, 5- or 6-membered carbo-or heterocyclic ring, that can be substituted;   Y represents a C 1 -C 5 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;   X, that can be the same or different, represents a halogen atom; nitro; cyano; hydroxyl; a carboxyl group; C 1 -C 8 -alkyl; C 1 -C 6 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C 1 -C 8 -alkylamino; di-C 1 -C 8 -alkylamino; C 1 -C 8 -alkoxy; C 1 -C 6 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; C 1 -C 8 -alkylsulfanyl; C 1 -C 6 -halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different; C 2 -C 8 -alkenyloxy; C 2 -C 8 -halogenoalkenyloxy comprising up to 9 halogen atoms that can be the same or different; C 3 -C 8 -alkynyloxy; C 3 -C 8 -halogenoalkynyloxy comprising up to 9 halogen atoms that can be the same or different; C 3 -C 8 -cycloalkyl; C 1 -C 8 -alkoxycarbonyl; C 1 -C 8 -alkylsulphinyl; C 1 -C 8 -alkylsulphonyl; C 1 -C 8 -halogenoalkylsulphinyl comprising up to 9 halogen atoms that can be the same or different; C 1  C 8 -halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different or C 1 -C 6 -alkoximino-C 1 -C 6 -alkyl;   n represents 0, 1, 2 or 3;   R a  and R b , that can be the same or different, represent a hydrogen atom; C 1 -C 8 -alkyl; C 1 -C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl; C 2 -C 8 -alkenyl; C 2 -C 8 -halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different; C 2 -C 8 -alkynyl; C 2 -C 8 -halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different; C 3 -C 7 -cycloalkyl; C 3 -C 7 -cycloalkyl-C 1 -C 8 -alkyl; C 3 -C 7 -halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different; formyl; C 1 -C 8 -alkylcarbonyl; C 1 -C 8 -halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different; C 1 -C 8 -alkylsulphonyl; C 1 -C 8 -halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different; phenyl that can be substituted by up to 5 groups Q; naphthyl that can be substituted by up to 6 groups Q; phenylmethylene that can be substituted by up to 5 groups Q; phenylsulphonyl that can be substituted by up to 5 groups Q;   Q, that can be the same or different, represents a halogen atom; cyano; nitro; C 1 -C 8 -alkyl; C 1 -C 8 -alkoxy; C 1 -C 8 -alkylsulfanyl; C 1 -C 8 -halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; C 1 -C 8 -halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different;
 
as well as salts, N-oxides, metallic complexes, metalloidic complexes and optically active or geometric isomers thereof.
       

     Any of the compounds according to the invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term “scalemic” denotes a mixture of enantiomers in different proportions), and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods that are known per se by the man ordinary skilled in the art. 
     Any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods that are known per se by the man ordinary skilled in the art. 
     For the compounds according to the invention, the following generic terms are generally used with the following meanings:
         halogen means either one of fluorine, bromine, chlorine or iodine;   heteroatom can be nitrogen, oxygen or sulphur;   any alkyl group, alkenyl group or alkynyl group can be straight or branched;   in the case of an amino group or the amino moiety of any other amino-containing group, substituted by two substituents that can be the same or different, the two substituents together with the nitrogen to that they are attached can form a heterocyclyl group, preferably a 5 to 7-membered heterocyclyl group, that can be substituted and can contain other hetero atoms, for example morpholino or piperidinyl.       

     Preferred compounds of formula (I) according to the invention are those wherein A is selected in the list consisting of:
         a heterocycle of formula (A 1 )       

     
       
         
         
             
             
         
       
     
     wherein R 1  to R 3  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 2 )       

     
       
         
         
             
             
         
       
     
     wherein R 4  to R 6  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 3 )       

     
       
         
         
             
             
         
       
     
     wherein R 7  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
 
R 8  represents a hydrogen atom; C 1 -C 5 -alkyl or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 4 )       

     
       
         
         
             
             
         
       
     
     wherein R 9  to R 11  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; an amino; C 1 -C 5 -alkoxy; C 1 -C 5 -alkylsulfanyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 5 )       

     
       
         
         
             
             
         
       
     
     wherein 
     R 12  and R 13  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -alkoxy; an amino or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 14  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; an amino or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 6 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 15  represents a hydrogen atom; a halogen atom; a cyano; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 16  and R 18  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkoxycarbonyl; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 17  represent a hydrogen atom or C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 7 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 19  represents a hydrogen atom; C 1 -C 5 -alkyl or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl; 
     R 20  to R 22  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 8 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 23  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 24  represents a hydrogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 9 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 25  represents a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 26  represents a hydrogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 10 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 27  represents a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 28  represents a hydrogen atom; a halogen atom; an amino; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 11 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 29  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 30  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; an amino; C 1 -C 5 -alkylamino; di-C 1  C 5 -alkylamino;
         a heterocycle of formula (A 12 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 31  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl; 
     R 32  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 33  represents a hydrogen atom; a halogen atom; a nitro or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 13 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 34  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 3 -C 5 -cycloalkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 5 -alkoxy; C 2 -C 5 -alkynyloxy; C 1 -C 5 -halogenoalkoxy comprising up to 5 halogen atoms that can be the same or different or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl; 
     R 35  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; a cyano; C 1 -C 5 -alkoxy; C 1 -C 5 -alkylsulfanyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 5 -halogenoalkoxy comprising up to 5 halogen atoms that can be the same or different; an amino; C 1 -C 5 -alkylamino or di(C 1 -C 5 -alkyl)-amino; 
     R 36  represents a hydrogen atom; C 1 -C 5 -alkyl or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 14 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 37  and R 38  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 5 -alkoxy or a C 1 -C 5 -alkylsulfanyl; 
     R 39  represents a hydrogen atom; C 1 -C 5 -alkyl or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 15 )       

     
       
         
         
             
             
         
       
     
     wherein R 40  and R 41  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 16 )       

     
       
         
         
             
             
         
       
     
     wherein R 42  and R 43  that can be the same or different represent a hydrogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; an amino or a phenyl substituted by a halogen atom or by a C 1 -C 5 -alkyl;
         a heterocycle of formula (A 17 )       

     
       
         
         
             
             
         
       
     
     wherein R 44  and R 45  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 18 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 46  represents a hydrogen atom; C 1 -C 5 -alkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different or C 1 -C 5 -alkylsulfanyl; 
     R 47  represents a hydrogen atom; a halogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 19 )       

     
       
         
         
             
             
         
       
     
     wherein R 48  and R 49  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 20 )       

     
       
         
         
             
             
         
       
     
     wherein R 50  and R 51  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 21 )       

     
       
         
         
             
             
         
       
     
     wherein R 52  represents a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 22 )       

     
       
         
         
             
             
         
       
     
     wherein R 53  represents a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different;
         a heterocycle of formula (A 23 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 54  and R 56  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 55  represents a hydrogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 24 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 57  and R 59  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 58  represents a hydrogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 25 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 60  and R 61  that can be the same or different represent a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl or C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; 
     R 62  represents a hydrogen atom or C 1 -C 5 -alkyl;
         a heterocycle of formula (A 26 )       

     
       
         
         
             
             
         
       
     
     wherein: 
     R 65  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; C 3 -C 5 -cycloalkyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 5 -alkoxy; C 2 -C 5 -alkynyloxy or C 1 -C 5 -halogenoalkoxy comprising up to 5 halogen atoms that can be the same or different; 
     R 63  represents a hydrogen atom; a halogen atom; C 1 -C 5 -alkyl; a cyano; C 1 -C 5 -alkoxy; C 1 -C 5 -alkylsulphanyl; C 1 -C 5 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 5 -halogenoalkoxy comprising up to 5 halogen atoms that can be the same or different; amino; C 1 -C 5 alkylamino or di(C 1 -C 5 -alkyl)amino; 
     R 64  represents a hydrogen atom or C 1 -C 5 -alkyl. 
     More preferred compounds of formula (I) according to the invention are those wherein A represents a 5-membered heterocycle that is substituted in position ortho. Such compounds can also be defined with A representing an α-substituted 5-membered heterocycle. 
     Still more preferred compounds of formula (I) according to the invention are those wherein A represents A 13 . 
     Still other preferred compounds of formula (I) according to the invention are those wherein T represents sulphur. 
     Other preferred compounds of formula (I) according to the invention are those wherein Z 1  represents a non-substituted C 3 -C 7  cycloalkyl, more preferably cyclopropyl. 
     Other preferred compounds of formula (I) according to the invention are those wherein Z 2  and Z 3 , that can be the same or different, represent a hydrogen atom or C 1 -C 5 -alkyl. 
     Still other preferred compounds of formula (I) according to the invention are those wherein Y represents trifluoromethyl. 
     Still other preferred compounds of formula (I) according to the invention are those wherein X, that can be the same or different, represents a halogen atom; C 1 -C 8 -alkyl; C 1 -C 6 -halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; C 1 -C 8 -alkoxy; C 1 -C 6 -halogenoalkoxy comprising up to 5 halogen atoms that can be the same or different. 
     Still other preferred compounds of formula (I) according to the invention are those wherein n represents 1. 
     The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention can be combined:
         preferred features of A with preferred features of T, Z 1 , Z 2 , Z 3 , Y, X and n;   preferred features of T with preferred features of A, Z 1 , Z 2 , Z 3 , Y, X and n;   preferred features of Z 1  with preferred features of A, T, Z 2 , Z 3 , Y, X and n;   preferred features of Z 2  with preferred features of A, T, Z 1 , Z 3 , Y, X and n;   preferred features of Z 3  with preferred features of A, T, Z 1 , Z 2 , Y, X and n;   preferred features of Y with preferred features of A, T, Y, Z 1 , Z 2 , Z 3 , Y, X and n;   preferred features of X with preferred features of A, T, Y, Z 1 , Z 2 , Z 3 , Y and n;   preferred features of n with preferred features of A, Y, Z 1 , Z 2 , Z 3 , Y and X.       

     In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of A, T, Z 1 , Z 2 , Z 3 , Y, X and n so as to form most preferred subclasses of compounds according to the invention. 
     The present invention also relates to a process for the preparation of compounds of formula (I). Thus according to a further aspect of the present invention there is provided a process P1 for the preparation of compound of formula (I) wherein T represents S, as illustrated by the following reaction scheme: 
     
       
         
         
             
             
         
       
     
     wherein A, Z 1  to Z 3 , Y, X and n are as herein-defined. 
     Process P1 can be performed in the presence of a thionating agent. 
     Amide derivatives of formula (II) are known or can be prepared by known processes, for example as described in European patent application EP-06/356008. 
     Suitable thionating agents for carrying out process P1 according to the invention can be sulphur (S), sulfhydric acid (H 2 S), sodium sulfide (Na 2 S), sodium hydrosulfide (NaHS), boron trisulfide (B 2 S 3 ), bis(diethylaluminium) sulfide ((AlEt 2 ) 2 S), ammonium sulfide ((NH 4 ) 2 S), phosphorous pentasulfide (P 2 S 5 ), Lawesson&#39;s reagent (2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in  J. Chem. Soc. Perkin  1, (2001), 358, 
     In the presence or in the absence, of a catalytic or stoechiometric or more, quantity of a base such as an inorganic or an organic base. Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethyl-aminopyridine or N-methylpiperidine. 
     Suitable solvents for carrying out process P1 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; nitriles, such as acetonitrile, propionitrile, n-or i-butyronitrile or benzonitrile; sulphurous solvents, such as sulpholane or carbon disulfide. 
     When carrying out process P1 according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from 0° C. to 160° C., preferably from 10° C. to 120° C. A way to control the temperature for the processes according to the invention is to use micro-wave technology. 
     Process P1 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure. 
     When carrying out process P1 according to the invention, 1 mole or an excess of the sulphur equivalent of the thionating agent and from 1 to 3 moles of the base can be employed per mole of the amide derivative of formula (II). 
     It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods. 
     In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present. 
     According to a further aspect according to the invention, there is provided a process P2 for the preparation of a compound of formula (I), wherein T is selected in the list consisting of N—R a , N—OR a , N—NR a R b  or N—CN, as illustrated by the following reaction scheme: 
     
       
         
         
             
             
         
       
     
     wherein
         A, Z 1  to Z 3 , R a , R b , Y, X and n are as herein-defined;   W represents a chlorine atom or a methylsulfanyl group.       

     Process P2 can be performed in the presence of an acid binder or in the presence of a solvent. 
     Amine derivatives of formula (III) are known or can be prepared by known processes or can be prepared by known processes, for example as described in WO-2001/11966 pages 20, 21 and 23. 
     N-substituted carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Houben-Weyl, “Methoden der organischen Chemie” (1985), E5/1, 628-633 and Patai, “The chemistry of amidines and imidates” (1975), 296-301. 
     N-substituted or N,N-disubstituted hydrazonoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron, 1991, 47, p 447 and Journal of Heterocyclic Chemistry, 1983, 20, p 225. 
     N-cyano carboximidoyl chloride of formula (IV) are known or can be prepared by known processes, for example as described in Tetrahedron Letters, 1968, p 5523 and Bioorganic and Medicinal Chemistry, 2006, p 4723. 
     Suitable acid binders for carrying out process P2 according to the invention can be inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives; alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate; alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate; alkaline earth metal or alkali metal hydrides, such as sodium hydride or potassium hydride; alkaline earth metal or alkali metal alcoolates, such as sodium methylate, sodium ethylate, sodium propylate or potassium t-butylate; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethyl-aminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diaza-bicycloundecene (DBU); or a polymer-supported acid scavenger (for example as detailed in http://www.iris-biotech.de/downloads/scavengers.pdf). 
     It is also possible to work in the absence of any additional acid binder. 
     Suitable solvents for carrying out process P2 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n-or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane. 
     When carrying out process P2 according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from 0° C. to 160° C., preferably from 10° C. to 120° C. A way to control the temperature for the processes according to the invention is to use micro-wave technology. 
     Process P2 according to the invention is generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure. 
     When carrying out process P2 according to the invention, the amine derivative of formula (III) can be employed as its salt, such as chlorhydate or any other convenient salt. 
     When carrying out process P2 according to the invention, 1 mole or an excess of the amine derivative of formula (III) and from 1 to 3 moles of the acid binder can be employed per mole of the N-substituted carboximidoyl chloride of formula (IV). 
     It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods. 
     In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or recrystallization, from any impurities that can still be present. 
     Compounds of formula (I) according to the invention can be prepared according to the herein described processes. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt these processes according to the specifics of each of the compounds that it is desired to be synthesised. 
     In a further aspect, the present invention also relates to a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I). 
     The expression “effective and non-phytotoxic amount” means an amount of composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the crops, and that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials, that are within the capabilities of a person skilled in the art. 
     Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler. 
     According to the invention, the term “support” denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used. 
     The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition. 
     Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques. 
     In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight. 
     Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions that are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions that must be diluted before application to the crop. 
     The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have normally a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous. 
     Examples of suitable fungicide mixing partners can be selected in the following lists:
         (1) Inhibitors of the nucleic acid synthesis, for example benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolinic acid.   (2) Inhibitors of the mitosis and cell division, for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate-methyl and zoxamide.   (3) Inhibitors of the respiration, for example diflumetorim as CI-respiration inhibitor; bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (9R-component), isopyrazam (9S-component), mepronil, oxycarboxin, penthiopyrad, thifluzamide as CII-respiration inhibitor; amisulbrom, azoxystrobin, cyazofamid, dimoxystrobin, enestroburin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin as CIII-respiration inhibitor.   (4) Compounds capable to act as an uncoupler, like for example binapacryl, dinocap, fluazinam and meptyldinocap.   (5) Inhibitors of the ATP production, for example fentin acetate, fentin chloride, fentin hydroxide, and silthiofam.   (6) Inhibitors of the amino acid and/or protein biosynthesis, for example andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil.   (7) Inhibitors of the signal transduction, for example fenpiclonil, fludioxonil and quinoxyfen.   (8) Inhibitors of the lipid and membrane synthesis, for example biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclofos-methyl and vinclozolin.   (9) Inhibitors of the ergosterol biosynthesis, for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, triforine, triticonazole, uniconazole, viniconazole and voriconazole.   (10) Inhibitors of the cell wall synthesis, for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, prothiocarb, validamycin A, and valiphenal.   (11) Inhibitors of the melanine biosynthesis, for example carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon and tricyclazole.   (12) Compounds capable to induce a host defence, like for example acibenzolar-S-methyl, probenazole, and tiadinil.   (13) Compounds capable to have a multisite action, like for example bordeaux mixture, captafol, captan, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations such as copper hydroxide, copper sulphate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, oxine-copper, propamidine, propineb, sulphur and sulphur preparations including calcium polysulphide, thiram, tolylfluanid, zineb and ziram.   (14) Further compounds like for example 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one, ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, N-{2-[1,1′-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide, (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide, 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide, N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide, 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide, (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide, (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide, 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate, N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide, N′-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, O-{1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl} 1H-imidazole-1-carbothioate, N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamide, 5-chloro-7-(4-methylpiperid in-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine, 5-amino-1,3,4-thiadiazole-2-thiol, propamocarb-fosetyl, 1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl 1H-imidazole-1-carboxylate, 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and salts, 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine, 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, quinolin-8-ol, quinolin-8-ol sulfate (2:1) (salt), benthiazole, bethoxazin, capsimycin, carvone, chinomethionat, chloroneb, cufraneb, cyflufenamid, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomezine, dicloran, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomate, ferimzone, flu metover, fluopicolide, fluoroimide, flusulfamide, fosetyl-aluminium, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, isotianil, methasulfocarb, methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3-methoxyacrylate, methyl isothiocyanate, metrafenone, (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone, mildiomycin, tolnifanide, N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide, N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts, phenazine-1-carboxylic acid, phenothrin, phosphorous acid and its salts, propamocarb fosetylate, propanosine-sodium, proquinazid, pyrroInitrine, quintozene, S-prop-2-en-1-yl 5-amino-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-2,3-dihydro-1H-pyrazole-1-carbothioate, tecloftalam, tecnazene, triazoxide, trichlamide, 5-chloro-N′-phenyl-N′-prop-2-yn-1-ylthiophene-2-sulfonohydrazide and zarilamid.       

     The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous. Examples of suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations. 
     The compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops. Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow. 
     The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant. 
     Among the plants that may becan be protected by the method according to the invention, mention may becan be made of cotton; flax; vine; fruit or vegetable crops such as  Rosaceae  sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches),  Ribesioidae  sp.,  Juglandaceae  sp.,  Betulaceae  sp.,  Anacardiaceae  sp.,  Fagaceae  sp.,  Moraceae  sp.,  Oleaceae  sp.,  Actimidaceae  sp.,  Lauraceae  sp.,  Musaceae  sp. (for instance banana trees and plantins),  Rubiaceae  sp.,  Theaceae  sp.,  Sterculiceae  sp.,  Rutaceae  sp. (for instance lemons oranges and grapefruit);  Solanaceae  sp. (for instance tomatoes),  Liliaceae  sp.,  Asteraceae  sp. (for instance lettuces),  Umbelliferae  sp.,  Cruciferae  sp.,  Chenopodiaceae  sp.,  Cucurbitaceae  sp.,  Papilionaceae  sp. (for instance peas),  Rosaceae  sp. (for instance strawberries); major crops such as  Graminae  sp. (for instance maize, lawn or cereals such as wheat, rye, rice, barley and triticale),  Asteraceae  sp. (for instance sunflower),  Cruciferae  sp. (for instance colza),  Fabacae  sp. (for instance peanuts),  Papilionaceae  sp. (for instance soybean),  Solanaceae  sp. (for instance potatoes),  Chenopodiaceae  sp. (for instance beetroots),  Elaeis  sp. (for instance oil palm); horticultural and forest crops; as well as genetically modified homologues of these crops. 
     Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of: 
     Powdery Mildew Diseases such as
       Blumeria  diseases caused for example by  Blumeria graminis;        Podosphaera  diseases caused for example by  Podosphaera leucotricha;        Sphaerotheca  diseases caused for example by  Sphaerotheca fuliginea;        Uncinula  diseases caused for example by  Uncinula necator ;      

     Rust Diseases such as
       Gymnosporangium  diseases caused for example by  Gymnosporangium sabinae;        Hemileia  diseases caused for example by  Hemileia vastatrix ;        Phakopsora  diseases caused for example by  Phakopsora pachyrhizi  and  Phakopsora meibomiae;        Puccinia  diseases caused for example by  Puccinia recondita, Puccinia graminis  or  Puccinia striiformis ;        Uromyces  diseases caused for example by  Uromyces appendiculatus ;      

     Oomycete Diseases such as
       Albugo  diseases caused for example by  Albugo candida;        Bremia  diseases caused for example by  Bremia lactucae;        Peronospora  diseases caused for example by  Peronospora pisi  and  Peronospora brassicae;        Phytophthora  diseases caused for example by  Phytophthora infestans;        Plasmopara  diseases caused for example by  Plasmopara viticola;        Pseudoperonospora  diseases caused for example by  Pseudoperonospora humuli  and  Pseudoperonospora cubensis;        Pythium  diseases caused for example by  Pythium ultimum ;      

     Leaf spot, Leaf blotch and Leaf Blight Diseases such as
       Alternaria  diseases caused for example by  Alternaria solani;        Cercospora  diseases caused for example by  Cercospora beticola;        Cladiosporium  diseases caused for example by  Cladiosporium cucumerinum;        Cochliobolus  diseases caused for example by  Cochliobolus sativus  ( Conidiaform: Drechslera,  Syn:  Helminthosporium ) or  Cochliobolus miyabeanus;        Colletotrichum  diseases caused for example by  Colletotrichum lindemuthianum;        Cycloconium  diseases caused for example by  Cycloconium oleaginum;        Diaporthe  diseases caused for example by  Diaporthe citri;        Elsinoe  diseases caused for example by  Elsinoe fawcettii;        Gloeosporium  diseases caused for example by  Gloeosporium laeticolor;        Glomerella  diseases caused for example by  Glomerella cingulata;        Guignardia  diseases caused for example by  Guignardia bidwelfii;        Leptosphaeria  diseases caused for example by  Leptosphaeria maculans  and  Leptosphaeria nodorum;        Magnaporthe  diseases caused for example by  Magnaporthe grisea;        Mycosphaerella  diseases caused for example by  Mycosphaerella graminicola,        Mycosphaerella arachidicola  and  Mycosphaerella fijiensis;        Phaeosphaeria  diseases caused for example by  Phaeosphaeria nodorum;        Pyrenophora  diseases caused for example by  Pyrenophora teres  or  Pyrenophora tritici repentis;        Ramularia —diseases caused for example by  Ramularia collo - cygni  or  Ramularia areola;        Rhynchosporium  diseases caused for example by  Rhynchosporium secalis;        Septoria  diseases caused for example by  Septoria apii  and  Septoria lycopersici;        Typhula  diseases caused for example by  Thyphula incamata;        Venturia  diseases caused for example by  Venturia inaequalis ;      

     Root-, Sheath and Stem Diseases such as
       Corticium  diseases caused for example by  Corticium graminearum;        Fusarium  diseases caused for example by  Fusarium oxysporum;        Gaeumannomyces  diseases caused for example by  Gaeumannomyces graminis;        Rhizoctonia  diseases caused for example by  Rhizoctonia solani;        Sarocladium  diseases caused for example by  Sarocladium oryzae;        Sclerotium  diseases caused for example by  Sclerotium oryzae;        Tapesia  diseases caused for example by  Tapesia acuformis;        Thielaviopsis  diseases caused for example by  Thielaviopsis basicola;      

     Ear and Panicle Diseases including Maize cob such as
       Alternaria  diseases caused for example by  Alternaria  spp.;     Aspergillus  diseases caused for example by  Aspergillus flavus;        Cladosporium  diseases caused for example by  Cladiosporium cladosporioides;        Claviceps  diseases caused for example by  Claviceps purpurea;        Fusarium  diseases caused for example by  Fusarium culmorum;        Gibberella  diseases caused for example by  Gibberella zeae;        Monographella  diseases caused for example by  Monographella nivalis ;      

     Smut- and Bunt Diseases such as
       Sphacelotheca  diseases caused for example by  Sphacelotheca reiliana;        Tilletia  diseases caused for example by  Tilletia caries;        Urocystis  diseases caused for example by  Urocystis occulta;        Ustilago  diseases caused for example by  Ustilago nuda ;      

     Fruit Rot and Mould Diseases such as
       Aspergillus  diseases caused for example by  Aspergillus flavus;        Botrytis  diseases caused for example by  Botrytis cinerea;        Penicillium  diseases caused for example by  Penicillium expansum  and  Penicillium purpurogenum;        Rhizopus  diseases caused by example by  Rhizopus  stolonifer     Sclerotinia  diseases caused for example by  Sclerotinia sclerotiorum;        Verticillium  diseases caused for example by  Verticillium alboatrum;      

     Seed- and Soilborne Decay, Mould, Wilt, Rot and Damping-off diseases
       Alternaria  diseases caused for example by  Alternaria brassicicola;        Aphanomyces  diseases caused for example by  Aphanomyces uteiches;        Ascochyta  diseases caused for example by  Ascochyta lentis;        Aspergillus  diseases caused for example by  Aspergillus flavus;        Cladosporium  diseases caused for example by  Cladosporium herbarum;        Cochliobolus  diseases caused for example by  Cochliobolus sativus ; ( Conidiaform: Drechslera, Bipolaris  Syn:  Helminthosporium );     Colletotrichum  diseases caused for example by  Colletotrichum coccodes;        Fusarium  diseases caused for example by  Fusarium culmorum;        Gibberella  diseases caused for example by  Gibberella zeae ;        Macrophomina  diseases caused for example by  Macrophomina phaseolina;        Microdochium  diseases caused for example by  Microdochium nivale;        Monographella  diseases caused for example by  Monographella nivalis;        Penicillium  diseases caused for example by  Penicillium expansum;        Phoma  diseases caused for example by  Phoma lingam;        Phomopsis  diseases caused for example by  Phomopsis sojae;        Phytophthora  diseases caused for example by  Phytophthora cactorum;        Pyrenophora  diseases caused for example by  Pyrenophora graminea;        Pyricularia  diseases caused for example by  Pyricularia oryzae;        Pythium  diseases caused for example by  Pythium ultimum;        Rhizoctonia  diseases caused for example by  Rhizoctonia solani;        Rhizopus  diseases caused for example by  Rhizopus oryzae;        Sclerotium  diseases caused for example by  Sclerotium rolfsii;        Septoria  diseases caused for example by  Septoria nodorum;        Typhula  diseases caused for example by  Typhula incamata;        Verticillium  diseases caused for example by  Verticillium dahliae;      

     Canker, Broom and Dieback Diseases such as
       Nectria  diseases caused for example by  Nectria galligena;      

     Blight Diseases such as
       Monilinia  diseases caused for example by  Monilinia laxa;      

     Leaf Blister or Leaf Curl Diseases including deformation of blooms and fruit such as
       Exobasidium  diseases caused for example by  Exobasidium vexans.        Taphrina  diseases caused for example by  Taphrina deformans;      

     Decline Diseases of Wooden Plants such as
       Esca  disease caused for example by  Phaeomoniella clamydospora, Phaeoacremonium aleophilum  and  Fomitiporia mediterranea;        Ganoderma  diseases caused by example by  Ganoderma boninense;      

     Diseases of Flowers and Seeds such as
       Botrytis  diseases caused for example by  Botrytis cinerea ;      

     Diseases of Tubers such as
       Rhizoctonia  diseases caused for example by  Rhizoctonia solani;        Helminthosporium  diseases caused for example by  Helminthosporium solani;      

     Club root diseases such as
       Plasmodiophora  diseases, caused for example by  Plamodiophora brassicae;      

     Diseases caused by Bacterial Organisms such as
       Xanthomanas  species for example  Xanthomonas campestris  pv.  oryzae;        Pseudomonas  species for example  Pseudomonas syringae  pv.  lachrymans;        Erwinia  species for example  Erwinia amylovora.      

     The fungicide composition according to the invention can also be used against fungal diseases liable to grow on or inside timber. The term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention, or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means. 
     The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment. 
     It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated. 
     The fungicide composition according to the invention can also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into genome of that a heterologous gene encoding a protein of interest has been stably integrated. The expression “heterologous gene encoding a protein of interest” essentially means genes that give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the modified plant. 
     The compounds or mixtures according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses,  trichophyton  diseases and candidiases or diseases caused by  Aspergillus  spp., for example  Aspergillus fumigatus.    
     The various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation example. 
     The table 1 illustrates in a non-limiting manner examples of compounds according to the invention. In table 1, M+H (or M−H) means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Example 
                 A 
                 X 
                 Y 
                 Z 2   
                 Z 3   
                 T 
                 logP 
                 M + 1 
               
               
                   
               
               
                 1 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 3-Cl 
                 5-CF 3   
                 H 
                 H 
                 S 
                 3.65 
                 407 
               
               
                   
               
               
                 2 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 3-Cl 
                 5-CF 3   
                 H 
                 H 
                 S 
                 3.69 
                 425 
               
               
                   
               
               
                 3 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 3-Cl 
                 5-CF 3   
                 H 
                 H 
                 S 
                 4.41 
                 461 
               
               
                   
               
            
           
         
       
     
     The following example illustrate in a non-limiting manner the preparation of the compounds of formula (I) according to the invention. 
     General Preparation Example: Thionation of Amide of Formula (I) on Chemspeed Apparatus 
     In a 13 ml Chemspeed vial is weighted 0.27 mmole of phosphorous pentasulfide (P 2 S 5 ). 3 ml of a 0.18 molar solution of the amide (I) (0.54 mmole) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 80° C. and 2.5 ml of water are added. The mixture is heated at 80° C. for one more hour. 2 ml of water are then added and the reaction mixture is extracted twice by 4 ml of dichloromethane. The organic phase is deposited on a basic alumina cardridge (2 g) and eluted twice by 8 ml of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS. 
    
    
     EXAMPLE A 
     In Vivo Test on  Pyrenophora teres  (Barley Net Blotch) 
     The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material concentration. 
     Barley plants (Express variety), sown on a 50/50 peat soil-pozzolana substrate in starter cups and grown at 12° C., are treated at the 1-leaf stage (10 cm tall) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material. 
     After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of  Pyrenophora teres  spores (12,000 spores per ml). The spores are collected from a 12-day-old culture. The contaminated barley plants are incubated for 24 hours at about 20° C. and at 100% relative humidity, and then for 12 days at 80% relative humidity. 
     Grading is carried out 12 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds: 1, 2 and 3. 
     EXAMPLE B 
     In Vivo Test on  Sphaerotheca Fuliginea  (Powdery Mildew) 
     The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/water. This suspension is then diluted with water to obtain the desired active material concentration. 
     Gherkin plants (Vert petit de Paris variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 20° C./23° C., are treated at the cotyledon Z10 stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. 
     After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of  Sphaerotheca fuliginea  spores (100 000 spores per ml). The spores are collected from a contaminated plants. The contaminated gherkin plants are incubated at about 20° C./25° C. and at 60/70% relative humidity. 
     Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants. 
     Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds: 1, 2 and 3. 
     EXAMPLE C 
     In Vivo Test on  Puccinia recondita  (Brown Rust) 
     The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, then diluted with water to obtain the desired active material. Wheat plants (Scipion variety) sown on 50/50 peat soil-pozzolana substrate in starter cups and grown at 12° C., are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. 
     Plants, used as controls, are treated with an aqueous solution not containing the active material. 
     After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of  Puccinia recondita  spores (100,000 spores per ml). The spores are collected from a 10-day-old contaminated wheat and are suspended in water containing 2.5 ml/l of tween 80 10%. The contaminated wheat plants are incubated for 24 hours at 20° C. and at 100% relative humidity, and then for 10 days at 20° C. and at 70% relative humidity. Grading is carried out 10 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 70%) or total protection is observed at a dose of 500 ppm with the following compounds: 3.