N-hetaryl(thio)carbonyl-2-(benzocycloalken-1-yl)cyclamines and their use as fungicides

Abstract

The present invention relates to fungicidal N-hetarylcarbonyl-2-(benzocycloalken-1-yl)piperidines or pyrrolidines of formula (I), and their thiocarbonyl derivatives, wherein A represents a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R that can be the same or different; T represents 0 or S; n represents 1 or 2; m represents 1, 2 or 3; p represents 1, 2, 3 or 4, L.sup.1 and L.sup.2 independently represent CZ.sup.4Z.sup.5, NZ.sup.6, 0, S, S(O) or S(0).sub.2; and R and Z.sup.1-Z.sup.6 are as defined in the claims; 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.

Claims

1. A compound of formula (I) ##STR00042## wherein: A is a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R that can be the same or different; T is O or S; n is 1 or 2; m is 1, 2 or 3; p is 1, 2, 3 or 4; L.sup.1 and L.sup.2 are independently CZ.sup.4Z.sup.5, NZ.sup.6, O, S, S(O) or S(O).sub.2; Z.sup.1 is a hydrogen atom, or substituted or non-substituted C.sub.1-C.sub.8-alkyl; Z.sup.2 is a hydrogen atom, a halogen atom, hydroxyl group, cyano, substituted or non-substituted C.sub.1-C.sub.8-alkyl, substituted or non-substituted C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, amino or C.sub.1-C.sub.8-alkylamino; Z.sup.3 is a hydrogen atom; 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 having 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-halogenoalkenyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkynyl; C.sub.2-C.sub.8-halogenoalkynyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; C.sub.1-C.sub.8-halogenoalkoxy having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; C.sub.1-C.sub.8-halogenoalkylsulfanyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl; C.sub.1-C.sub.8-halogenoalkylsulfinyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl having 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 having 1 to 9 halogen atoms; substituted or non-substituted C.sub.3-C.sub.8-alkynyloxy; C.sub.2-C.sub.8-halogenoalkynyloxy having 1 to 9 halogen atoms; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogenocycloalkyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.4-C.sub.7-cycloalkenyl; C.sub.4-C.sub.7-halogenocycloalkenyl having 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.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 having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyloxy; C.sub.1-C.sub.8-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonylamino; C.sub.1-C.sub.8-halogenoalkylcarbonylamino having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkyloxycarbonyloxy; C.sub.1-C.sub.8-halogenoalkoxycarbonyloxy having 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 that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.1-C.sub.8-alkyl that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.2-C.sub.8-alkenyl that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.2-C.sub.8-alkynyl that can be substituted by up to 6 groups Q which can be the same or different; aryloxy that can be substituted by up to 6 groups Q which can be the same or different; arylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different; or arylamino that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.1-C.sub.8-alkyloxy that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.1-C.sub.8-alkylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different; aryl-C.sub.1-C.sub.8-alkylamino that can be substituted by up to 6 groups Q which can be the same or different; pyridinyl which can be substituted by up to 4 groups Q; pyridinyloxy which can be substituted by up to 4 groups Q; Z.sup.4 and Z.sup.5 are independently a hydrogen atom, 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 can be 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 can be the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, 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 can be the same or different, substituted or non-substituted C.sub.2-C.sub.8-alkynyl, C.sub.2-C.sub.8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl, substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl-C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, 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 can be 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 can be the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl, C.sub.1-C.sub.8-halogenoalkylsulfinyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl, or C.sub.1-C.sub.8-halogenoalkylsulfonyl comprising up to 9 halogen atoms that can be the same or different; Z.sup.6 is a hydrogen 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 that can be the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkoxy-C.sub.1-C.sub.8-alkyl, 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 can be the same or different, substituted or non-substituted C.sub.2-C.sub.8-alkynyl, C.sub.3-C.sub.8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl, substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl-C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, 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 can be the same or different, substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl, 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 can be the same or different, phenylsulfonyl can be substituted by up to 5 groups Q that can be the same or different, or benzyl that can be substituted by up to 5 groups Q that can be the same or different; each Q 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 can be 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 can be 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 can be 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; and each R is independently hydrogen atom; halogen atom; nitro; cyano; hydroxy; amino; sulfanyl; pentafluoro-.sup.6-sulfanyl; substituted or non-substituted (C.sub.1-C.sub.8-alkoxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted (benzyloxyimino)-C.sub.1-C.sub.8-alkyl; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-halogenoalkenyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.2-C.sub.8-alkynyl; C.sub.2-C.sub.8-halogenoalkynyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; C.sub.1-C.sub.8-halogenoalkoxy having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; C.sub.1-C.sub.8-halogenoalkylsulfanyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfinyl; C.sub.1-C.sub.8-halogenoalkylsulfinyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl having 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; substituted or non-substituted C.sub.3-C.sub.8-alkynyloxy; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogenocycloalkyl having 1 to 9 halogen atoms; substituted or non-substituted tri(C.sub.1-C.sub.8)alkylsilyl; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyl; C.sub.1-C.sub.8-halogenoalkylcarbonyl having 1 to 9 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl having 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; phenoxy; phenylsulfanyl; phenylamino; benzyloxy; benzylsulfanyl; or benzylamino; 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, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, wherein A is selected from the group consisting of: a heterocycle of formula (A.sup.1) ##STR00043## wherein: R.sup.1, R.sup.2, and R.sup.3 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 can be 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 can be the same or different; a heterocycle of formula (A.sup.2) ##STR00044## wherein: R.sup.4, R.sup.5, and R.sup.6 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 can be 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 can be the same or different; a heterocycle of formula (A.sup.3) ##STR00045## 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 can be 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 can be the same or different; 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) ##STR00046## wherein: R.sup.9, R.sup.10, and R.sup.11 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A.sup.5) ##STR00047## wherein: R.sup.12 and R.sup.13 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A.sup.6) ##STR00048## wherein: R.sup.15 is a hydrogen atom; a halogen atom; a 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R.sup.16 and R.sup.18 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; 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) ##STR00049## wherein: R.sup.19 is a hydrogen atom or a C.sub.1-C.sub.5-alkyl R.sup.20, R.sup.21, and R.sup.22 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 can be the same or different; a heterocycle of formula (A.sup.8) ##STR00050## 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 can be the same or different; 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 can be the same or different; a heterocycle of formula (A.sup.9) ##STR00051## 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 can be the same or different; 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 can be the same or different; a heterocycle of formula (A.sup.10) ##STR00052## 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 can be the same or different; 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 can be the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be 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) ##STR00053## 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; 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 can be the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be 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) ##STR00054## 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 can be the same or different; R.sup.33 is a hydrogen atom; a halogen atom; a 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A.sup.13) ##STR00055## 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 can be 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 can be 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; a 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 can be the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be 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; 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) ##STR00056## wherein: R.sup.37 and R.sup.38 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 can be 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; 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) ##STR00057## wherein: R.sup.40 and R.sup.41 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 can be the same or different; a heterocycle of formula (A.sup.16) ##STR00058## wherein: R.sup.42 and R.sup.43 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 can be the same or different or amino; a heterocycle of formula (A.sup.17) ##STR00059## wherein: R.sup.44 and R.sup.45 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 can be the same or different; a heterocycle of formula (A.sup.18) ##STR00060## 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 can be the same or different; 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 can be the same or different or substituted or non-substituted C.sub.1-C.sub.5-alkylsulfanyl; a heterocycle of formula (A.sup.19) ##STR00061## wherein: R.sup.48 and R.sup.49 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A.sup.20) ##STR00062## wherein: R.sup.50 and R.sup.51 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 can be the same or different or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; a heterocycle of formula (A.sup.21) ##STR00063## 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 can be the same or different; a heterocycle of formula (A.sup.22) ##STR00064## 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 can be the same or different; a heterocycle of formula (A.sup.23) ##STR00065## wherein: R.sup.54 and R.sup.56 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 can be the same or different; 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) ##STR00066## wherein: R.sup.57 and R.sup.59 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 can be the same or different; 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) ##STR00067## wherein: R.sup.60 and R.sup.61 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 can be the same or different; 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) ##STR00068## 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 can be 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 can be 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; a 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 can be the same or different; C.sub.1-C.sub.5-halogenoalkoxy comprising up to 9 halogen atoms that can be 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; R.sup.64 is a hydrogen atom or substituted or non-substituted C.sub.1-C.sub.5-alkyl.

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

4. The compound according to claim 3, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, wherein A is A.sup.13, wherein 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 can be 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.

5. The compound 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, wherein A is A.sup.13, wherein R.sup.34 is C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-halogenoalkyl comprising up to 3 halogen atoms that can be the same or different; R.sup.35 is a hydrogen atom; a chlorine atom; or a fluorine atom, and R.sup.36 is a methyl.

6. The compound 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, wherein T is O.

7. The compound 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, wherein m is 1 or 2.

8. The compound 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, wherein L.sup.1 is CZ.sup.4Z.sup.5.

9. The compound 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, wherein L.sup.2 is CZ.sup.4Z.sup.5, O or S.

10. The compound according to claim 9, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, wherein L.sup.2 is CZ.sup.4Z.sup.5.

11. The compound 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, wherein L.sup.2 is O.

12. The compound 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, wherein Z.sup.1 or Z.sup.2 or both are a hydrogen atom.

13. The compound 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, wherein Z.sup.3 is a hydrogen atom, a halogen atom, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkoxy or C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.

14. The compound 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, wherein Z.sup.4 and Z.sup.S are independently a hydrogen atom or C.sub.1-C.sub.8-alkyl.

15. The compound according to claim 14, or a salt, an N-oxide, a metal complex, a metalloid complex, an optically active isomer, or a geometric isomer thereof, wherein Z.sup.4 and Z.sup.5 both are a hydrogen atom.

16. A fungicide composition comprising, as an active ingredient, an effective amount of a 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.

17. A fungicide composition according to claim 16, comprising at least one further active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners, biologicals and semiochemicals.

18. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of a compound 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.

19. A process for producing compositions for controlling phytopathogenic harmful fungi, comprising mixing a 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.

20. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of a compound 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 plants, seeds, transgenic plants or transgenic seeds.

21. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of a composition according to claim 16, 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.

Description

EXAMPLE 1

Preparation of [2-(5,7-difluoro-2,3-dihydro-1H-inden-1-yl)pyrrolidin-1-yl][5-(difluoromethyl)-2-methyl-2H-1,2,3-triazol-4-yl]methanone (Compounds 1.14 and 1.15)

(1) At ambient temperature, a solution of 77 mg (0.40 mmol) of 5-(difluoromethyl)-2-methyl-2H-1,2,3-triazole-4-carbonyl chloride in 1 mL of tetrahydrofurane is added dropwise to a solution of 121 mg (0.36 mmol) of 2-(5,7-difluoro-2,3-dihydro-1H-inden-1-yl)pyrrolidine trifluoroacetate (1:1) and 76 mg (0.75 mmol) of triethylamine in 5 mL of tetrahydrofurane. The reaction mixture is stirred for 1 hour at room temperature. The mixture is poured over a basic alumina cartridge (2 g) and eluted with tetrahydrofurane to give after concentration 147 mg of crude material. The two diastereoisomers of [2-(5,7-difluoro-2,3-dihydro-1H-inden-1-yl)pyrrolidin-1-yl][5-(difluoromethyl)-2-methyl-2H-1,2,3-triazol-4-yl]methanone are separated by preparative HPLC (gradient acetonitrile/water+0.1% of formic acid): diastereoisomer 1: isomer with the highest Rf by TLC on silica gel: 33 mg (22%) (log P=3.63); diastereoisomer 2: isomer with the lowest Rf by TLC on silica gel: 56 mg (38%) (log P=3.41).

GENERAL PREPARATION EXAMPLE 2

Preparation of Amide of Formula (I) on Chemspeed Apparatus

(2) In a 13 mL Chemspeed vial is distributed 4 mL of a 0.15 M solution of the amine (II) (0.60 mmol) in dichloromethane followed by 0.72 mmol of triethylamine. At a rate of 1 mL/min, 2 mL of a 0.30 M solution of the acyl chloride (III) (0.60 mmol) are added and the mixture is then stirred at room temperature overnight. 1 mL of water is then added and the mixture is poured over a basic alumina cartridge (2 g) and eluted with dichloromethane. The solvents are removed and the crude amide derivative is analyzed by HPLC-MS and NMR. Insufficiently pure compounds are further purified by preparative LC.

GENERAL PREPARATION EXAMPLE 3

Thionation of Amide of Formula (I) on Chemspeed Apparatus

(3) 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 HPLC-MS and NMR. Insufficiently pure compounds are further purified by preparative LC.

EXAMPLE A

In Vivo Preventive Test on Alternaria brassicae (Leaf Spot on Radish)

(4) TABLE-US-00004 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone 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.

(7) 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.

(8) 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.

(9) 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.25

(10) 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.19

(11) 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.03; I.08; I.09; I.10; I.11; I.13; I.17; I.18; I.21; I.26; I.27

EXAMPLE B

In Vivo Preventive Test Botrytis cinerea (Grey Mould)

(12) TABLE-US-00005 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(13) 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.

(14) 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.

(15) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores. The contaminated gherkin plants are incubated for 4 to 5 days at 17 C. and at 90% relative humidity.

(16) The test is evaluated 4 to 5 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.

(17) 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.13

(18) 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.03; I.21

(19) 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.10; I.18; I.26; I.34.

EXAMPLE C

In Vivo Preventive Test on Puccinia recondita (Brown Rust on Wheat)

(20) TABLE-US-00006 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(21) 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.

(22) 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.

(23) 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.

(24) 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.

(25) 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.32; I.34; I.36

(26) 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.10; I.11; I.17; I.20; I.24; I.27; I.28

(27) 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.02; I.03; I.12; I.13; I.15; I.16; I.18; I.21; I.25; I.26; I.31

(28) Under the same conditions, excellent (at least 90%) to average (at least 60%) protection is observed at a dose of 500 and 100 ppm of active ingredient with compound of example I.31, whereas average protection, is observed at a dose of 500 and 100 ppm of active ingredient with the uncyclized analogue 136 disclosed in patent application WO-2012/052489, as in table C1:

(29) TABLE-US-00007 TABLE C1 Example dose (ppm) Efficacy I.31 from this patent 500 93 100 64 136 from WO-2012/052489 500 65 100 50

(30) Example 136 disclosed in international patent WO-2012/052489, corresponds to [3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl][2-(1-phenylpropyl)piperidin-1-yl]methanone.

(31) These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds claimed in WO-2012/052489.

(32) Under the same conditions, excellent (at least 90%) to high (at least 80%) protection is observed at a dose of 500 and 100 ppm of active ingredient with compound of example I.26, whereas poor (less than 40%) to no protection, is observed in very similar conditions at a dose of 500 and 100 ppm of active ingredient with the uncyclized analogues 11 and 13 disclosed in patent application WO-2011/151369, as in table C2:

(33) TABLE-US-00008 TABLE C2 Example dose (ppm) Efficacy I.26 from this patent 500 98 100 88 11 from WO-2011/151369 500 10 .sup.(a) 100 0 .sup.(a) 13 from WO-2011/151369 500 40 .sup.(a) 100 10 .sup.(a) Note .sup.(a) formulated in DMF with 2% of alkylarylpolyglycolether

(34) Example 11 disclosed in international patent WO-2011/151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-(2-phenylethyl)-1H-pyrazole-4-carboxamide,

(35) Example 13 disclosed in international patent WO-2011/151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-(2-phenylpropyl)-1H-pyrazole-4-carboxamide.

(36) These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds claimed in WO-2011/151369.

EXAMPLE D

In Vivo Preventive Test on Pyrenophora teres (Net Blotch on Barley)

(37) TABLE-US-00009 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(38) 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.

(39) 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.

(40) 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.

(41) 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.

(42) 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.09

(43) 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.06; I.14; I.17; I.20; I.27; I.28

(44) 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.03; I.05; I.07; I.08; I.10; I.11; I.12; I.13; I.15; I.16; I.18; I.21; I.25; I.26; I.29; I.30; I.34.

EXAMPLE E

In Vivo Preventive Test on Septoria tritici (Wheat)

(45) TABLE-US-00010 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(46) 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.

(47) 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.

(48) 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.

(49) 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.

(50) 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.32

(51) 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.02; I.06; I.18

(52) 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.03; I.05; I.07; I.08; I.09; I.10; I.11; I.12; I.13; I.14; I.15; I.16; I.17; I.19; I.20; I.21; I.25; I.26; I.28; I.29; I.30; I.31; I.34; I.35; I.36

EXAMPLE F

In Vivo Preventive Test on Sphaerotheca fuliginea (Powdery Mildew on Cucurbits)

(53) TABLE-US-00011 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(54) 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.

(55) 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.

(56) 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.

(57) 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.

(58) 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.06; I.20

(59) 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.09; I.25; I.36

(60) 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.08; I.10; I.11; I.12; I.14; I.15; I.17; I.18; I.19; I.21; I.26; I.27; I.30; I.31; I.34.

(61) Under the same conditions, total protection is observed at a dose of 500 and 100 ppm of active ingredient with compound of example I.26, whereas average (at least 60%) to poor (less than 10%) protection, is observed in very similar conditions at a dose of 500 and 100 ppm of active ingredient with the uncyclized analogue 13 disclosed in patent application WO-2011/151369, as in table F1:

(62) TABLE-US-00012 TABLE F1 Example dose (ppm) Efficacy I.26 from this patent 500 100 100 100 13 from WO-2011/151369 500 63 .sup.(a) 100 3 .sup.(a) Note .sup.(a) formulated in DMF with 2% of alkylarylpolyglycolether

(63) Example 13 disclosed in international patent WO-2011/151369 corresponds to N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-(2-phenylpropyl)-1H-pyrazole-4-carboxamide.

(64) These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds claimed in WO-2011/151369.

EXAMPLE G

In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

(65) TABLE-US-00013 Solvent: 5% by volume of Dimethyl sulfoxide 10% by volume of Acetone Emulsifier: 1 L of Tween 80 per mg of active ingredient

(66) 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.

(67) 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.

(68) 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.

(69) 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.

(70) 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.02; I.08; I.12; I.16; I.23

(71) 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.03; I.09; I.10; I.13; I.18; I.19; I.22; I.24; I.25; I.26; I.27

(72) Under the same conditions, total protection is observed at a dose of 500 and 100 ppm of active ingredient with compound of example I.26, whereas good (at least 70%) to no protection, is observed at a dose of 500 and 100 ppm of active ingredient with the uncyclized analogue 53 disclosed in patent application WO-2012/052491, as in table G1:

(73) TABLE-US-00014 TABLE G1 Example dose (ppm) Efficacy I.26 from this patent 500 100 100 100 53 from WO2012/052491 500 77 100 0

(74) Example 53 disclosed in international patent WO2012/052491 corresponds to [3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl][2-(1-phenylpropyl)pyrrolidin-1-yl]methanone.

(75) These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds claimed in WO2012/052491.

(76) Under the same conditions, total to average (at least 50%) protection is observed at a dose of 500 and 100 ppm of active ingredient with compounds of examples 1.26 and 1.27, whereas high (at least 80%) to no protection, is observed at a dose of 500 and 100 ppm of active ingredient with the uncyclized analogue 1.2 disclosed in patent application WO-2010/086311, as in table G2:

(77) TABLE-US-00015 TABLE G2 Example dose (ppm) Efficacy I.26 from this patent 500 100 100 100 I.27 from this patent 500 100 100 56 I.2 from WO-2010/086311 500 88 100 0

(78) Example I.2 disclosed in international patent WO-2010/086311 corresponds to N-cyclopropyl-5-fluoro-1,3-dimethyl-N-[1-(1,2,3,4-tetrahydronaphthalen-1-yl)ethyl]-1H-pyrazole-4-carboxamide.

(79) These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds claimed in WO-2010/086311.