N-cycloalkyl-N-(biheterocyclylethylene)-(thio)carboxamide derivatives

Abstract

The present invention relates to fungicidal N-cycloalkyl-N-(biheterocyclylethylene)carboxamide derivatives and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions. ##STR00001##

Claims

1. A compound of formula (I) ##STR00045## wherein: A is selected from the group consisting of: a heterocycle of formula (A) ##STR00046## wherein: R.sup.1, R.sup.2, and R.sup.3 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.2) ##STR00047## wherein: R.sup.4, R.sup.5, and R.sup.6 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.3) ##STR00048## wherein: R.sup.7 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; and R.sup.8 is a hydrogen atom or a substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.4) ##STR00049## wherein: R.sup.9, R.sup.10, and R.sup.11 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; amino; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.5) ##STR00050## wherein: R.sup.12 and R.sup.13 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; amino; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; and R.sup.14 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; amino; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.6) ##STR00051## wherein: R.sup.15 is a hydrogen atom; a halogen atom; cyano; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; R.sup.16 and R.sup.18 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkoxycarbonyl; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.17 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.7) ##STR00052## wherein: R.sup.19 is a hydrogen atom or a C.sub.1-C.sub.5-alkyl; and R.sup.20, R.sup.21, and R.sup.22 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.8) ##STR00053## wherein: R.sup.23 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.24 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.9) ##STR00054## wherein: R.sup.25 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.26 is a hydrogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.10) ##STR00055## wherein: R.sup.27 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.28 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; amino; substituted or non-substituted C.sub.1-C.sub.5-alkylamino; or substituted or non-substituted di(C.sub.1-C.sub.5-alkyl)amino; a heterocycle of formula (A.sup.11) ##STR00056## wherein: R.sup.29 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.30 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; amino; substituted or non-substituted C.sub.1-C.sub.5-alkylamino; or substituted or non-substituted di(C.sub.1-C.sub.5-alkyl)amino; a heterocycle of formula (A.sup.12) ##STR00057## wherein: R.sup.31 is a hydrogen atom or a substituted or non-substituted C.sub.1-C.sub.5-alkyl; R.sup.32 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.33 is a hydrogen atom; a halogen atom; nitro; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.13) ##STR00058## wherein: R.sup.34 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.3-C.sub.5-cycloalkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; substituted or non-substituted C.sub.2-C.sub.5-alkynyloxy or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; R.sup.35 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; cyano; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; amino; substituted or non-substituted C.sub.1-C.sub.5-alkylamino; or substituted or non-substituted di(C.sub.1-C.sub.5-alkyl)amino; and R.sup.36 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.14) ##STR00059## wherein: R.sup.37 and R.sup.38 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; or a substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; and R.sup.39 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.15) ##STR00060## wherein: R.sup.40 and R.sup.41 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.16) ##STR00061## wherein: R.sup.42 and R.sup.43 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; or amino; a heterocycle of formula (A.sup.17) ##STR00062## wherein: R.sup.44 and R.sup.45 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.18) ##STR00063## wherein: R.sup.47 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.46 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; or substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; a heterocycle of formula (A.sup.19) ##STR00064## wherein: R.sup.49 and R.sup.48 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.20) ##STR00065## wherein: R.sup.50 and R.sup.51 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.21) ##STR00066## wherein: R.sup.52 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.22) ##STR00067## wherein: R.sup.53 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; a heterocycle of formula (A.sup.23) ##STR00068## wherein: R.sup.54 and R.sup.56 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.55 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.24) ##STR00069## wherein: R.sup.57 and R.sup.59 are the same or different, and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.58 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; a heterocycle of formula (A.sup.25) ##STR00070## wherein: R.sup.60 and R.sup.61 are the same or different and are independently a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; and R.sup.62 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; and a heterocycle of formula (A.sup.26) ##STR00071## wherein: R.sup.65 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; substituted or non-substituted C.sub.3-C.sub.5-cycloalkyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; substituted or non-substituted C.sub.2-C.sub.5-alkynyloxy or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; R.sup.63 is a hydrogen atom; a halogen atom; substituted or non-substituted C.sub.1-C.sub.5-alkyl; cyano; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different; amino; substituted or non-substituted C.sub.1-C.sub.5-alkylamino or di(C.sub.1-C.sub.5-alkyl)amino; and R.sup.64 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl; T is O or S; n is 0, 1, 2, 3, or 4; L is a direct bond, CZ.sup.6Z.sup.7, O, S, SO, SO.sub.2, or NZ.sup.8; B.sup.1 is a substituted or non-substituted thienyl ring; a substituted or non-substituted benzothiophenyl ring; a substituted or non-substituted pyridinyl ring; a substituted or non-substituted furyl ring; a substituted or non-substituted imidazo[1,2-a]pyridin-2-yl ring; or a substituted or non-substituted benzofuranyl ring; B.sup.2 is a thienyl ring; a benzothiophenyl ring; a pyridinyl ring; a quinolinyl ring; a furyl ring; a benzofuranyl ring; or a pyrimidinyl ring; wherein B.sup.2 is optionally substituted by up to 6 Y groups which can be the same or different; with the proviso that B.sup.2 is not a pyridyl ring when L is a direct bond, CZ.sup.6Z.sup.7, an oxygen atom, a sulfur atom, or NZ.sup.8, and A is a 1-C.sub.1-C.sub.4-alkyl-3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl moiety; Z.sup.1 is a non-substituted C.sub.3-C.sub.7-cycloalkyl or a C.sub.3-C.sub.7-cycloalkyl substituted by up to 10 atoms or groups that are the same or different and that are selected from the group consisting of halogen atoms, cyano, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that are the same or different, C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different, C.sub.1-C.sub.8-alkoxycarbonyl, C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that are the same or different, C.sub.1-C.sub.8-alkylaminocarbonyl, and di-C.sub.1-C.sub.8-alkylaminocarbonyl; with the proviso that Z.sup.1 is not a non-substituted cyclopropyl when B.sup.1 is: a 5-substituted (by B.sup.2) pyridin-2-yl group, or a 6-substituted (by B.sup.2) pyridin-3-yl group, and B.sup.2 is a thienyl or furyl group; Z.sup.2, Z.sup.3, Z.sup.4 and Z.sup.5 are the same or different, and are independently a hydrogen atom; substituted or non-substituted C.sub.1-C.sub.8-alkyl; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; substituted or non-substituted C.sub.2-C.sub.8-alkynyl; cyano; isonitrile; nitro; a halogen atom; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; substituted or non-substituted C.sub.2-C.sub.8-alkenyloxy; substituted or non-substituted C.sub.2-C.sub.8-alkynyloxy; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl; amino; substituted or non-substituted C.sub.1-C.sub.8-alkylamino; substituted or non-substituted di-C.sub.1-C.sub.8-alkylamino; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbamoyl; substituted or non-substituted di-C.sub.1-C.sub.8-alkylcarbamoyl; or substituted or non-substituted NC.sub.1-C.sub.8-alkyl-C.sub.1-C.sub.8-alkoxy-carbamoyl; or Z.sup.i and Z.sup.i+1, wherein i is an integer from 2 to 4, are taken together with the carbon atom(s) to which they are attached to form a substituted or non-substituted C.sub.3-C.sub.7 cycloalkyl; or Z.sup.5 and the substituent X vicinal to the point of attachment of the B.sup.1 heterocyclic ring are taken together with the consecutive carbon atoms to which they are attached to form a substituted or non-substituted 5-, 6-, or 7-membered, partly saturated, carbo- or heterocycle comprising up to 3 heteroatoms and Z.sup.4 is as defined above; Z.sup.6 and Z.sup.7 are independently a hydrogen atom; a halogen atom; cyano; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising 1 to 5 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; or substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; or Z.sup.6 and Z.sup.7 are taken together with the carbon atom to which they are attached to form a C(O) carbonyl group; Z.sup.8 is a hydrogen atom; a substituted or non-substituted C.sub.1-C.sub.8-alkyl; a C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-halogenoalkenyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.3-C.sub.8-alkynyl; C.sub.3-C.sub.8-halogenoalkynyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogeno-cycloalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl-C.sub.1-C.sub.8-alkyl; formyl; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyl; C.sub.1-C.sub.8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted benzyl; or substituted or non-substituted phenylsulfonyl; each X, where present, is independently a halogen atom; nitro; cyano; isonitrile; hydroxy; amino; sulfanyl; pentafluoro-.sup.6-sulfanyl; formyl; formyloxy; formylamino; substituted or non-substituted (hydroxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted (C.sub.1-C.sub.8-alkoxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted (C.sub.2-C.sub.8-alkenyloxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted (C.sub.2-C.sub.8-alkynyloxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted (benzyloxyimino)-C.sub.1-C.sub.8-alkyl; carboxy; carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-halogenoalkenyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkynyl; C.sub.2-C.sub.8-halogenoalkynyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; C.sub.1-C.sub.8-halogenoalkoxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; C.sub.1-C.sub.8-halogenoalkylsulfanyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl; C.sub.1-C.sub.8-halogenoalkylsulfinyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylamino; substituted or non-substituted di-C.sub.1-C.sub.8-alkylamino; substituted or non-substituted C.sub.2-C.sub.8-alkenyloxy; C.sub.2-C.sub.8-halogenoalkenyloxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.3-C.sub.8-alkynyloxy; C.sub.2-C.sub.8-halogenoalkynyloxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogenocycloalkyl comprising 1 to 9 halogen atoms; substituted or non-substituted (C.sub.3-C.sub.7-cycloalkyl)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted C.sub.4-C.sub.7-cycloalkenyl; C.sub.4-C.sub.7-halogenocycloalkenyl comprising 1 to 9 halogen atoms; substituted or non-substituted (C.sub.3-C.sub.7-cycloalkyl)-C.sub.2-C.sub.8-alkenyl; substituted or non-substituted (C.sub.3-C.sub.7-cycloalkyl)-C.sub.2-C.sub.8-alkynyl; substituted or non-substituted tri(C.sub.1-C.sub.8)alkylsilyl; substituted or non-substituted tri(C.sub.1-C.sub.8)alkylsilyl-C.sub.1-C.sub.8-alkyl; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyl; C.sub.1-C.sub.8-halogenoalkylcarbonyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyloxy; C.sub.1-C.sub.8-halogenoalkylcarbonyloxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonylamino; C.sub.1-C.sub.8-halogenoalkylcarbonylamino comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkyloxycarbonyloxy; C.sub.1-C.sub.8-halogenoalkoxycarbonyloxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbamoyl; substituted or non-substituted di-C.sub.1-C.sub.8-alkylcarbamoyl; substituted or non-substituted C.sub.1-C.sub.8-alkylaminocarbonyloxy; substituted or non-substituted di-C.sub.1-C.sub.8-alkylaminocarbonyloxy; substituted or non-substituted N(C.sub.1-C.sub.8-alkyl)hydroxy carbamoyl; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbamoyl; substituted or non-substituted N(C.sub.1-C.sub.8-alkyl)-C.sub.1-C.sub.8-alkoxycarbamoyl; aryl optionally substituted by up to 6 Q groups which are the same or different; aryl-C.sub.1-C.sub.8-alkyl optionally substituted by up to 6 Q groups which are the same or different; aryl-C.sub.2-C.sub.8-alkenyl optionally substituted by up to 6 Q groups which are the same or different; aryl-C.sub.2-C.sub.8-alkynyl optionally substituted by up to 6 Q groups which are the same or different; aryloxy optionally substituted by up to 6 Q groups which are the same or different; arylsulfanyl optionally substituted by up to 6 Q groups which are the same or different; arylamino optionally substituted by up to 6 Q groups which are the same or different; aryl-C.sub.1-C.sub.8-alkyloxy optionally substituted by up to 6 Q groups which are the same or different; aryl-C.sub.1-C.sub.8-alkylsulfanyl optionally substituted by up to 6 Q groups which are the same or different; or aryl-C.sub.1-C.sub.8-alkylamino optionally substituted by up to 6 Q groups which are the same or different; each Y, where present, is independently a halogen atom; cyano; hydroxy; amino; sulfanyl; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; C.sub.1-C.sub.8-halogenoalkoxy comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; C.sub.1-C.sub.8-halogenoalkylsulfanyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl; C.sub.1-C.sub.8-halogenoalkylsulfinyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylamino; substituted or non-substituted di-C.sub.1-C.sub.8-alkylamino; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyl; C.sub.1-C.sub.8-halogenoalkylcarbonyl comprising 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising 1 to 9 halogen atoms; or aryl optionally substituted by up to 6 Q groups which are the same or different; each Q, where present, is independently a halogen atom, cyano, nitro, substituted or non-substituted C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that are the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that are the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl, C.sub.1-C.sub.8-halogenoalkylsulfanyl comprising up to 9 halogen atoms that are the same or different, substituted or non-substituted tri(C.sub.1-C.sub.8)alkylsilyl, substituted or non-substituted tri(C.sub.1-C.sub.8)alkylsilyl-C.sub.1-C.sub.8-alkyl, substituted or non-substituted (C.sub.1-C.sub.8-alkoxyimino)-C.sub.1-C.sub.8-alkyl, or substituted or non-substituted (benzyloxyimino)-C.sub.1-C.sub.8-alkyl; or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

2. The compound according to claim 1, wherein: A is selected from the group consisting of A.sup.2; A.sup.3; A.sup.5; A.sup.6; A.sup.10; and A.sup.13, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

3. The compound according to claim 2, wherein: A is A.sup.13; R.sup.34 is a substituted or non-substituted C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that are the same or different; substituted or non-substituted C.sub.1-C.sub.5-alkoxy; R.sup.35 is a hydrogen atom or a halogen atom; and R.sup.36 is a substituted or non-substituted C.sub.1-C.sub.5-alkyl, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

4. The compound according to claim 1, wherein: T is O, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

5. The compound according to claim 1, wherein: Z.sup.1 is a non-substituted cyclopropyl or a 2-C.sub.1-C.sub.5-alkylcyclopropyl, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

6. The compound according to claim 1, wherein: Z.sup.2, Z.sup.3, Z.sup.4 and Z.sup.5 are independently a hydrogen atom or C.sub.1-C.sub.8-alkyl, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

7. The compound according to claim 1, wherein: L is a direct bond, an oxygen atom, a methylene group or a carbonyl group, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

8. The compound according to claim 1, wherein: each X, where present, is independently a halogen atom; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms which are the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; tri(C.sub.1-C.sub.8-alkyl)silyl; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; or substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

9. The compound according to claim 1, wherein: each Y, where present, is independently a halogen atom; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms which are the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; or C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms which are the same or different, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

10. A compound of formula (IIa) ##STR00072## wherein: n is 0, 1, 2 or 3; L is a direct bond or CZ.sup.6Z.sup.7; and Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5, Z.sup.6, Z.sup.7, B.sup.2, and X are as defined in claim 1; or a compound of formula (IIb), (IIc), or (IId) ##STR00073## wherein: n is 0, 1 or 2; L is a direct bond or CZ.sup.6Z.sup.7; and Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5, Z.sup.6, Z.sup.7, B.sup.2, and X are as defined in claim 1, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof.

11. A fungicide composition comprising, as an active ingredient, an effective amount of the compound of formula (I) according to claim 1, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, and an agriculturally acceptable support, carrier, or filler.

12. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of the compound of formula (I) according to claim 1, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.

13. A process for producing a composition for controlling phytopathogenic harmful fungi, comprising mixing the compound of formula (I) according to claim 1, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, with extenders and/or surfactants.

14. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of the composition according to claim 11 to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.

15. The compound of formula (I) according to claim 1 or a salt thereof.

16. The fungicide composition of claim 11, comprising the compound of formula (I) or a salt thereof.

17. The method of claim 12, comprising applying the compound of formula (I) or a salt thereof.

Description

Preparation Example 1: Preparation of n-Cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-n-{1-[3-(3-thienyl)-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-1h-pyrazole-4-carboxamide (compound i.06)

(1) In a 5 mL microwave vial, 182 mg (0.40 mmol) of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide are added to a mixture of 102 mg (0.80 mmol) of 3-thienylboronic acid and 5 mg (0.008 mmol) of 1,10-bis(di-tert-butyl-phosphino)ferrocene palladium(II) dichloride in solution in 1.5 mL of acetonitrile and degassed with argon. 138 mg (1 mmol) of potassium carbonate in solution in 1.5 mL of water are further added and the mixture is heated under microwave at 130 C. for 20 minutes. To the cooled reaction mixture are added 1 mL of water and 2 mL of dichloromethane. The mixture is deposited of a ChemElut cartridge (3 g) and eluted three times by 6 mL of dichloromethane. The organic extracts are concentrated under vacuum and the residue (74 mg) is purified by preparative HPLC (gradient acetonitrile/water+0.1% HCO.sub.2H) to provide 22 mg (10% yield) of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[3-(3-thienyl)-5-(trifluoro-methyl)-pyridin-2-yl]propan-2-yl}-1H-pyrazole-4-carboxamide as an oil. Log P=4.03. (M+H)=503.

General Preparation Example 2: Thionation of Amide of Formula (I) on Chemspeed apparatus

(2) In a 13 mL Chemspeed vial is weighted 0.27 mmol of phosphorous pentasulfide (P.sub.2S.sub.5). 3 mL of a 0.18 M solution of the amide (I) (0.54 mmol) 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 cartridge (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 LC.

Example A: In Vivo Preventive Test on Alternaria Brassicae (Leaf Spot on Radish)

(3) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(4) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(5) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(6) The young plants of radish are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80. After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores. The contaminated radish plants are incubated for 6 days at 20 C. and at 100% relative humidity.

(7) The test is evaluated 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(8) In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: I.19

(9) In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: I.16; I.18

(10) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.14; I.15; I.17.

(11) Under the same conditions, high (at least 80%) protection was observed at a dose of 100 and 500 ppm of active ingredient with compound of example I.16, whereas poor (less than 50%) protection was observed with compound CMP1 (pyridyl analogue) disclosed in patent application WO-2011/151369 as in table A2:

(12) TABLE-US-00003 TABLE A2 Example dose (ppm) Efficacy I.16 from this patent 500 86 100 86 CMP1 from WO2011/151369 500 43 100 0

(13) Example CMP1 disclosed in international patent WO-2011/0151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[3-(pyridin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]propan-2-yl}-1H-pyrazole-4-carboxamide.

(14) These results showed that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2011/015369.

Example B: In Vivo Preventive Test on Puccinia Recondita (Brown Rust on Wheat)

(15) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(16) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(17) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(18) The young plants of wheat are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80.

(19) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores. 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 70-80% relative humidity.

(20) The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(21) In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: I.14; I.15; I.16; I.17; I.18.

(22) In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: I.01; I.03; I.08

(23) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.04; I.05; I.06; I.07; I.11; I.12.

(24) Under the same conditions, good (at least 70%) protection was observed at a dose of 500 ppm of active ingredient with compound of example I.16, whereas no protection was observed with compound CMP1 (pyridyl analogue) disclosed in patent application WO-2011/151369 as in table B2:

(25) TABLE-US-00004 TABLE B2 Example dose (ppm) Efficacy I.16 from this patent 500 78 CMP1 from WO2011/151369 500 0

(26) Example CMP1 disclosed in international patent WO-2011/0151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[3-(pyridin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]propan-2-yl}-1H-pyrazole-4-carboxamide.

(27) These results showed that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2011/015369.

(28) Under the same conditions, excellent (at least 90%) to total protection was observed at a dose of 100 and 500 ppm of active ingredient with compound of example I.05, whereas average (less than 70%) protection was observed with compound CMP2 (pyridyl analogue) disclosed in patent application WO-2011/151369 as in table B3:

(29) TABLE-US-00005 TABLE B3 Example dose (ppm) Efficacy I.05 from this patent 500 100 100 93 CMP2 from WO2011/151369 500 69 100 38

(30) Example CMP2 disclosed in international patent WO-2011/0151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[5-(trifluoromethyl)-3,3-bipyridin-2-yl]propan-2-yl}-1H-pyrazole-4-carboxamide.

(31) These results showed that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2011/015369.

Example C: In Vivo Preventive Test on Pyrenophora Teres (Net Blotch on Barley)

(32) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(33) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(34) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(35) The young plants of barley are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80.

(36) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. The contaminated barley plants are incubated for 48 hours at 20 C. and at 100% relative humidity and then for 12 days at 20 C. and at 70-80% relative humidity.

(37) The test is evaluated 14 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(38) In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: I.13; I.19

(39) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.14; I.15; I.16; I.17.

Example D: In Vivo Preventive Test on Septoria Tritici (Wheat)

(40) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(41) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(42) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(43) The young plants of wheat are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80.

(44) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Septoria tritici spores. The contaminated wheat plants are incubated for 72 hours at 18 C. and at 100% relative humidity and then for 21 days at 20 C. and at 90% relative humidity.

(45) The test is evaluated 24 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(46) In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: I.18; I.19

(47) In this test the following compounds according to the invention showed efficacy between 80% and 89% at a concentration of 500 ppm of active ingredient: I.16

(48) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.01; I.02; I.03; I.04; I.05; I.06; I.07; I.11; I.12; I.13; I.14; I.15; I.17.

Example E: In Vivo Preventive Test on Sphaerotheca Fuliginea (Powdery Mildew on Cucurbits)

(49) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(50) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(51) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(52) The young plants of gherkin are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80.

(53) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores. The contaminated gherkin plants are incubated for 72 hours at 18 C. and at 100% relative humidity and then for 12 days at 20 C. and at 70-80% relative humidity.

(54) The test is evaluated 15 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(55) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.01; I.02; I.03; I.04; I.05; I.06; I.07; I.08; I.11; I.12; I.13; I.14; I.15; I.16; I.17; I.18; I.19.

Example F: In Vivo Preventive Test on Uromyces Appendiculatus (Bean Rust)

(56) Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone

(57) Emulsifier: 1 L of Tween 80 per mg of active ingredient

(58) The active ingredients are made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone//Tween 80 and then diluted in water to the desired concentration.

(59) The young plants of bean are treated by spraying the active ingredient prepared as described above. Control plants are treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/Tween 80.

(60) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores. The contaminated bean plants are incubated for 24 hours at 20 C. and at 100% relative humidity and then for 10 days at 20 C. and at 70-80% relative humidity.

(61) The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease is observed.

(62) In this test the following compounds according to the invention showed efficacy between 70% and 79% at a concentration of 500 ppm of active ingredient: I.02

(63) In this test the following compounds according to the invention showed efficacy between 90% and 100% at a concentration of 500 ppm of active ingredient: I.04; I.05; I.06; I.07.

(64) Under the same conditions, total protection was observed at a dose of 500 ppm of active ingredient with compound of example I.05, whereas no protection was observed with compound CMP2 (pyridyl analogue) disclosed in patent application WO-2011/151369 as in table F2:

(65) TABLE-US-00006 TABLE F2 Example dose (ppm) Efficacy I.05 from this patent 500 100 CMP2 from WO2011/151369 500 0

(66) Example CMP2 disclosed in international patent WO-2011/0151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-{1-[5-(trifluoromethyl)-3,3-bipyridin-2-yl]propan-2-yl}-1H-pyrazole-4-carboxamide.

(67) These results showed that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2011/015369.