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Title:
AROMATIC AMIDES HAVING A FUNGICIDAL ACTIVITY, THEIR AGRONOMIC COMPOSITIONS AND RELATIVE PREPARATION METHOD
Document Type and Number:
WIPO Patent Application WO/2019/087145
Kind Code:
A1
Abstract:
Aromatic amides are described, having general formula (I), suitably substituted and having a high fungicidal activity, together with their use for controlling phytopathogenic fungi of important agricultural crops.

Inventors:
GUSMEROLI MARILENA (IT)
BELLANDI PAOLO (IT)
MORMILE SILVIA (IT)
BOGGIO PAOLO (IT)
BRAVINI PAOLO (IT)
VAZZOLA MATTEO (IT)
BADARACCO CHRISTIAN (IT)
LIGUORI RICCARDO (IT)
Application Number:
PCT/IB2018/058629
Publication Date:
May 09, 2019
Filing Date:
November 02, 2018
Export Citation:
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Assignee:
ISAGRO SPA (IT)
International Classes:
C07D309/12; A01N37/00; A01N39/00; A01N43/16; C07C235/62; C07C237/30; C07C237/44; C07C321/24
Domestic Patent References:
WO1999027783A11999-06-10
Foreign References:
EP2277869A12011-01-26
Attorney, Agent or Firm:
DE GREGORI, Antonella et al. (IT)
Download PDF:
Claims:
Ci8 cycloalkoxy Ci-Ci2-alkylthioalkyl C1-C12, a C1-C12 aryloxy alky lthio alkyl d- C12, a C1-C12 benzyloxy alky lthio alkyl C1-C12, a C3-C18 cycloalkylthioalkyl C1-C12, a C1-C12 benzy lthio alkyl, a C1-C12 ary lthio alkyl, a C1-C12 heterocyclylthioalkyl, a C2- C12 alkanoylamino alkyl C1-C12, a C2-C12 halo alkanoylamino alkyl C1-C12, a C4-C18 cycloalkanoylaminoalkyl C1-C12, a C1-C12 aroylaminoalkyl, a C1-C12 benzoylamino alkyl, a C1-C12 heterocyclylcarbonylaminoalkyl, a C1-C12 hetero- cyclylaminoalkyl, a C4-C18 cycloalkylaminoalkyl C1-C12, a tetrahydropyranyl, a d- C12 trimethylsilyloxy alkyl, a C1-C12 trimethylsilyl-ethoxyalkyl;

R 1 and R 2 together with the carbon atoms to which they are bound can form a 1,3-oxazole ring;

R represents a hydrogen atom, a C1-C12 alkyl, a C3-C18 cycloalkyl;

R4 and R5, the same or different, represent a hydrogen atom, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a C1-C12 alkyl, a formyl, a C2-C13 acyl, a C2-C13 haloalkylcarbonyl, a benzyl group, an aroyl group, a C2-C13 alkoxycarbonyl, a C1-C12 alkoxyalkyl C1-C12; a d- C12 alkanoyloxy alkyl C1-C12, a C1-C12 halo alkanoyloxy alkyl C1-C12, a C3-C18 cycloalkanoyloxyalkyl C1-C12, a C1-C12 aroyloxyalkyl, a C1-C12 heterocyclylcarbonyloxyalkyl, a C1-C12 aryloxyalkyl, a C1-C12 heterocyclyloxyalkyl, a C1-C12 alkanoylthio alkyl C1-C12, a C1-C12 halo -alkanoylthio alkyl C1-C12, a C3-C18 cycloalkanoylthioalkyl C1-C12, a C1-C12 aroylthioalkyl, a C1-C12 heterocyclylthioalkyl, a C1-C12 arylthioalkyl a C1-C12 alkanoylamino alkyl C1-C12, a C1-C12 halo alkanoylamino alkyl C1-C12, a C3-C18 cycloalkanoylaminoalkyl C1-C12, a C1-C12 aroylaminoalkyl, a C1-C12 heterocyclylaminoalkyl;

A represents a direct bond or a C1-C12 alkyl;

Y represents an oxygen or sulfur atom;

Z represents an oxygen or sulfur atom; X represents a halogen atom, a CN group, a N02 group;

n represents a number ranging from 0 to 3;

G represents a C3-C18 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C3-C18 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C6-C2o bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C6-C2o bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C6 alkyl, C3-Ci2 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR3;

with the proviso that

if R1 represents a -NR4R5 group wherein R4 is a hydrogen atom and R5 is an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a formyl, a C2-Ci3 acyl, a C2-Ci3 alkoxycarbonyl, and R 2 and R 3 represent a hydrogen atom, and Y is an oxygen atom, G cannot be a C3-Ci2 cycloalkyl, a C3-Ci2 cycloalkenyl and a C3-C8 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S.

2. The amides according to claim 1, wherein:

- R1 represents a Ci-C6 alkoxyl, a Ci-C6 haloalkoxyl, a C3-Ci2 cycloalkoxyl, a - NR4R5 group;

R represents a hydrogen atom, a C2-C7 acyl, a C2-C7 alkanoyloxy alkyl Ci-C6, a C2-C7 haloalkanoyloxyalkyl Ci-C6, a Ci-C6 alkoxy-Ci-C6-alkanoyloxyalkyl Ci-C6, a Ci-C6 haloalkoxy-Ci-C6-alkanoyloxyalkyl Ci-C6, a C3-Ci2 cycloalkoxy-Ci-C6- alkanoyloxy alkyl Ci-C6, an aryloxy Ci-C6 alkanoyloxyalkyl Ci-C6, a benzyloxy d- C6 alkanoyloxyalkyl C1-C6, a C4-Ci2 cycloalkanoyloxyalkyl Ci-C6, a Ci-C6 aroyloxyalkyl, a Ci-C6 benzoyloxyalkyl, a Ci-C6 heterocyclylcarbonyloxyalkyl, a d- C6 alkyloxyalkyl Ci-C6, a Ci-C6 halo alky loxyalkyl Ci-C6, a Ci-C6 alkoxy- Ci-C6- alkyloxyalkyl Ci-C6, a Ci-C6 haloalkoxy-Ci-C6-alkyloxyalkyl Ci-C6, a C3-C12 cycloalkoxy Ci-C6-alkyloxyalkyl Ci-C6, an aryloxy Ci-C6-alkyloxyalkyl Ci-C6, a benzyloxy Ci-C6-alkyloxyalkyl Ci-C6, a C3-C12 cycloalkyloxyalkyl Ci-C6, a Ci-C6 aryloxyalkyl, a Ci-C6 benzyloxyalkyl; a Ci-C6 heterocyclyloxyalkyl, a C4-C6 alkanoylthioalkyl Ci-C6, a C2-C6 halo alkanoylthio alky 1 Ci-C6, a C4-C12 cycloalkanoylthioalkyl Ci-C6, a Ci-C6 aroylthioalkyl, a Ci-C6 benzoylthioalkyl; a Ci-C6 heterocyclylcarbonylthioalkyl, a Ci-C6 alky lthio alky 1 Ci-C6, a Ci-C6 halo alky lthio alky 1 Ci-C6, a Ci-C6 alkoxy-Ci-C6-alkylthioalkyl Ci-C6, a Ci-C6 haloalkoxy-Ci-C6-alkylthioalkyl Ci-C6, a C3-C12 cycloalkoxy Ci-C6 alky lthio alky 1 Ci-C6, a Ci-C6 aryloxy alky lthio alky 1 Ci-C6, a Ci-C6 benzyloxy alky lthio alky 1 d- C6, a C3-C12 cycloalkylthioalkyl Ci-C6, a Ci-C6 benzy lthio alky 1, a Ci-C6 arylthioalkyl, a Ci-C6 heterocyclylthioalkyl, a C2-C6 alkanoylaminoalkyl Ci-C6, a C2-C6 halo alkanoylaminoalkyl Ci-C6, a C4-C12 cycloalkanoylaminoalkyl Ci-C6, a d- C6 aroylaminoalkyl, a Ci-C6 benzoylaminoalkyl, a Ci-C6 heterocyclylcarbonylaminoalkyl, a Ci-C6 heterocyclylaminoalkyl, a C4-C12 cycloalkylaminoalkyl Ci-C6, a tetrahydropyranyl, a Ci-C6 trimethylsily loxyalkyl, a Ci-C6 trimethylsilyl-ethoxyalkyl;

R represents a hydrogen atom, a Ci-C6 alkyl, a C3-C12 cycloalkyl;

R4 and R5, the same or different, represent a hydrogen atom, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a Ci-C6 alkyl, a formyl, a C2-C7 acyl, a C2-C-7 haloalkylcarbonyl, a benzyl group, an aroyl group, a C2-C-7 alkoxycarbonyl, a Ci-C6 alkoxyalkyl Ci-C6; a Ci-C6 alkanoyloxy alkyl Ci-C6, a Ci-C6 haloalkanoyloxyalkyl C1-C12, a C3-C12 cycloalkanoyloxyalkyl Ci-C6, a Ci-C6 aroyloxyalkyl, a Ci-C6 heterocyclylcarbonyloxyalkyl, a Ci-C6 aryloxyalkyl, a Ci-C6 heterocyclyloxyalkyl, a Ci-C6 alkanoylthioalkyl Ci-C6, a Ci-C6 halo alkanoylthio alky 1 Ci-C6, a C3-C12 cycloalkanoylthioalkyl Ci-C6, a Ci-C6 aroylthioalkyl, a Ci-C6 heterocyclylthioalkyl, a Ci-C6 arylthioalkyl a Ci-C6 alkanoylaminoalkyl Ci-C6, a Ci-C6 halo alkanoylaminoalkyl Ci-C6, a C3-C12 cycloalkanoylaminoalkyl Ci-C6, a Ci-C6 aroylaminoalkyl, a Ci-C6 heterocyclylaminoalkyl;

A represents a direct bond or a Ci-C6 alkyl;

Y represents an oxygen or sulfur atom;

X represents a halogen atom, a CN group, a N02 group;

- n represents a number ranging from 0 to 1 ;

G represents a C3-C12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C3-C12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C6-Ci6 bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C6-Ci6 bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C6 alkyl, C3-C12 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR3.

3. The amides according to any of the previous claims, wherein:

R represents a C2-C6 acyl, a Ci-C6 alkoxy-Ci-C6-alkanoyloxyalkyl Ci-C6, a Ci-C6 haloalkoxy-Ci-C6-alkanoyloxyalkyl Ci-C6, a C3-C12 cycloalkoxy-Ci-C6- alkanoyloxy alkyl Ci-C6, a C3-C12 cycloalkyloxyalkyl Ci-C6, a C4-C12 alkanoylthioalkyl Ci-C6, a C2-C6 halo alkanoylthio alkyl Ci-C6, a C4-C12 cycloalkanoylthioalkyl Ci-C6, a C2-C6 alkanoylaminoalkyl Ci-C6, a C2-C6 halo alkanoylaminoalkyl Ci-C6, a Ci-C6 alkoxy-Ci-C6-alkyloxyalkyl Ci-C6, a Ci-C6 haloalkoxy-Ci-C6-alkyloxyalkyl Ci-C6, a C3-Ci2 cycloalkoxy Ci-C6-alkyloxyalkyl d- C6, a tetrahydropyranyl, a Ci-C6 trimethylsilyloxyalkyl, a Ci-C6 trimethylsilyl- ethoxyalkyl;

Y and Z both represent an oxygen atom;

G represents a C3-C12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C3-C12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C6-Ci6 bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C6-Ci6 bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C6 alkyl, C3-C12 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR3 .

4. The amides according to any of the claims 1 or 2, wherein:

R represents a hydrogen atom;

G represents a C3-C12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C3-C12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C6 alkyl, C3- C12 cycloalkyl, benzyl and incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR3.

5. The amides according to any of the previous claims, selected from compounds having general formula (I) wherein R 1 , R2 , R 3 , Y, Z, X, n, A, G have the meanings indicated in the following table 97

98

13. NHCHO H 0 0 0

0

14. NHCHO H 0 0 0 1

0

0

15. NHCHO H 0 0 0

0

16. NHCHO H 0 0 0 *

0

17. NHCHO H 0 0 0

*

0

18. NHCHO H 0 0 0 *

0 Θ 100

101

102

103

107

108

6. The amides according to any of the previous claims, selected from compounds having general formula (I) wherein R 1 , R2 , R 3 , Y, Z, X, n, A, G have the meanings indicated in the following table

7. The amides according to any of the previous claims, wherein R1 represents a

NR 2 CHO group, R 2 being equal to a hydrogen atom or having the meanings previously indicated, R preferably represents a NHCHO

8. The amides according to any of the previous claims, which are a) geometric isomers of the compounds having general formula (I); b) in the form of salts of the compounds having formula (I) obtained by the addition of inorganic or organic acids; c) hydrated forms of the compounds having formula (I).

9. Fungicidal compositions comprising at least one compound having formula (I) according to any of the claims from 1 to 8, a solvent and/or solid or liquid diluent, possibly a surfactant.

10. The compositions according to claim 9, comprising one or more further active ingredients such as fungicides other than those having general formula (I), phytoregulators, antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof, preferably comprising at least one other fungicide.

11. The compositions according to claim 10, consisting of a compound having formula (I) and a further fungicide, selected from:

CI : compound 1 + tetraconazole;

C2: compound 1 + tebuconazole;

C3: compound 1 + epoxyconazole;

C4: compound 1 + prothioconazole;

C5: compound 1 + difenoconazole;

C6: compound 1 + penconazole;

C7: compound 1 + prochloraz;

C8: compound 1 + fenpropimorph;

C9: compound 1 + spiroxamine;

CIO: compound 1 + bixafen;

Cl l : compound 1 + boscalid; C12: compound '_ + carboxin;

C13: compound + fluopyram;

C14: compound + fluxapyroxad;

C15: compound + isopyrazam;

CI 6: compound + penthiopyrad;

C17: compound + sedaxane;

CI 8: compound + azoxystrobin;

CI 9: compound + dimoxystrobin;

C20: compound : + fluoxastrobin;

C21 : compound + kresoxim-methyl;

C22 compound 1 + picoxystrobin;

C23: compound + pyraclostrobin;

C24: compound + trifloxystrobin;

C25: compound + metrafenone;

C26: compound + proquinazid;

C21: compound + mepanipyrim;

C28: compound + cyprodinil;

C29: compound + iprodione;

C30: compound : + procymidone;

C31 : compound + carbendazim;

C32: compound + thiophanate-methyl;

C33: compound + fluindapyr;

C34: compound '. + benalaxyl-M;

C35: compound + fenpyrazamine;

C36: compound + fluazinam; C37: compound 1 + tolclofos-methyl;

C38: compound 1 + mandipropamid;

C39: compound 1 + copper oxychloridi

C40: compound 1 + copper salicylate;

C41: compound 1 + chlorothalonil;

C42: compound 1 + cimoxanil;

C43: compound 1 + dimetomorph;

C44: compound 1 + oxathiapiprolin;

C45: compound 1 + fluopicolide;

C46: compound 2 + tetraconazole;

C47: compound 2 + tebuconazole;

C48: compound 2 + epoxyconazole;

C49: compound 2 + prothioconazole;

C50: compound 2 + difenoconazole;

C51: compound 2 + penconazole;

C52: compound 2 + prochloraz;

C53: compound 2 + fenpropimorph;

C54: compound 2 + spiroxamine;

C55: compound 2 + bixafen;

C56: compound 2 + boscalid;

C57: compound 2 + carboxin;

C58: compound 2 + fluopyram;

C59: compound 2 + fluxapyroxad;

C60: compound 2 + isopyrazam;

C61: compound 2 + penthiopyrad; C62: compound 2 + sedaxane;

C63: compound 2 + azoxystrobin;

C64: compound 2 + dimoxystrobin;

C65: compound 2 + fluoxastrobin;

C66: compound 2 + kresoxim-methyl;

C67: compound 2 + picoxystrobin;

C68: compound 2 + pyraclostrobin;

C69: compound 2 + trifloxystrobin;

C70: compound 2 + metrafenone;

C71 : compound 2 + proquinazid;

C72: compound 2 + mepanipyrim;

C73: compound 2 + cyprodinil;

C74: compound 2 + iprodione;

C75: compound 2 + procymidone;

C76: compound 2 + carbendazim;

C77: compound 2 + thiophanate-methyl;

C78: compound 2 + fluindapyr;

C79: compound 2 + benalaxyl-M;

C80: compound 2 + fenpyrazamine;

C81 : compound 2 + fluazinam;

C82: compound 2 + tolclofos-methyl;

C83: compound 2 + mandipropamid;

C84: compound 2 + copper oxychloride;

C85: compound 2 + copper salicylate;

C86: compound 2 + chlorothalonil; C87: compound 2 + cimoxanil;

C88: compound 2 + dimetomorph;

C89: compound 2 + oxathiopiproline;

C90: compound 2 + fluopicolide;

C91 : compound 4 + tetraconazole;

C92: compound 4 + tebuconazole;

C93: compound 4 + epoxyconazole;

C94: compound 4 + prothioconazole;

C95: compound 4 + difenconazole; C96: compound 4 + penconazole;

C97: compound 4 + prochloraz;

C98: compound 4 + fenpropimorph;

C99: compound 4 + spiroxamine;

C IOO: compound 4 + bixafen;

ClOl : compound 4 + boscalid;

CI 02: compound 4 + carboxin;

C103: compound 4 + fluopyram;

C 104: compound 4 + fluxapyroxad;

C 105: compound 4 + isopyrazam; CI 06: compound 4 + penthiopyrad;

CI 07: compound 4 + sedaxane;

C108: compound 4 + azoxystrobin;

C 109: compound 4 + dimoxystrobin;

C I 10: compound 4 + fluoxastrobin; C 1 1 1 : compound 4 + kresoxim- methyl; CI 12: compound 4 + picoxystrobin; CI 13: compound 4 + pyraclostrobin; CI 14: compound 4 + trifloxystrobin; CI 15: compound 4 + metrafenone;

CI 16: compound 4 + proquinazid;

CI 17: compound 4 + mepanipyrim;

CI 18: compound 4 + cyprodinil;

CI 19: compound 4 + iprodione;

C120: compound 4 + procymidone;

C121: compound 4 + carbendazim;

CI 22: compound 4 + thiophanate-methyl; C123: compound 4 + fluindapyr;

CI 24: compound 4 + benalaxyl-M;

CI 25: compound 4 + fenpyrazamine; CI 25: compound 4 + fluazinam;

C126: compound 4 + tolclofos-methyl; CI 27: compound 4 + mandipropamid; C128: compound 4 + copper oxychloride; C129: compound 4 + copper salicylate; CI 30: compound 4 + chlorothalonil; C131: compound 4 + cimoxanil;

C132: compound 4 + dimetomorph; CI 33: compound 4 + oxathiopiproline; C134: compound 4 + fluopicolide;

CI 35: compound 1 + pyrachlostrobin; C136: compound 1 + zoxamide;

C137: compound 1 + ametoctradin;

C138: compound 1 + metiram;

C139: compound 1 + potassium phosphite;

C140: compound 1+ tetraconazole + azoxystrobin,

C141 : compound 1 + pyraclostrobin + tetraconazole;

C142: compound 1 + epoxyconazole + azoxystrobin;

C143: compound 1 + pyraclostrobin + epoxyconazole;

C144: compound 1 + azoxystrobin + fluindapyr;

C145: compound 1 + pyraclostrobin + fluindapyr;

C146: compound 1 + fosetyl-aluminium + copper oxychlorid

C147: compound 1 + fosetyl-aluminium + copper salicylate;

C148: compound 1 + fluindapyr+ tetraconazole;

C149: compound 4 + tetraconazole + azoxystrobin;

C150: compound 4 + pyraclostrobin + tetraconazole;

C151 : compound 4 + azoxystrobin + fluindapyr;

C152: compound 4+ fluindapyr + tetraconazole,

C153: compound 10 + tetraconazole;

C154: compound 10+ tebuconazole;

C155: compound 10+ epoxyconazole;

C156: compound 10 prothioconazole;

C157: compound 10+ difenoconazole;

C158: compound 10+ penconazole;

C159: compound 10+ prochloraz;

C160: compound 10+ fenpropimorph; C161 : compound 10+ spiroxamine;

C 162: compound 10 + bixafen;

CI 63: compound 10 + boscalid;

C164: compound 10 + carboxin;

CI 65: compound 10 + fluopyram;

C 166 compound 10 + fluxapyroxad;

CI 67: compound 10 + isopyrazam;

C168 compound 10 + penthiopyrad;

CI 69 compound 10 + sOedaxane;

C 170: compound 10 + azoxystrobin;

C171 : compound 10 + dimoxystrobin;

C172: compound 10 + fluoxastrobin;

C 173: compound 10 + kresoxim-methyl;

C174: compound 10 + picoxystrobin;

C175: compound 10 + pyraclostrobin;

C176: compound 10 + trifloxystrobin;

C 177: compound 10 + metrafenone;

C178: compound 10 + proquinazid;

C179: compound 10 + mepanipyrim;

C180: compound 10 + cyprodinil;

C 181 : compound 10 + iprodione;

C182: compound 10 + procymidone;

C183: compound 10 + carbendazim;

C184: compound 10 + thiophanate-methyl;

C 185: compound 10 + fluindapyr; C 186: compound 10 + benalaxyl-M;

C187: compound 10 + fenpyrazamine;

C188: compound 10 + fluazinam;

C 189: compound 10 + tolclofos-methyl;

C190: compound 10 + mandipropamid;

C191 : compound 10 + copper oxychlorid

C192: compound 10 + copper salicylate;

C 193: compound 10 + chlorothalonil;

C194: compound 10 + cimoxanil;

C195: compound 10 + dimetomorph;

C 196: compound 10 + oxathiopiproline;

C 197: compound 10 + fluopicolide;

C198: compound 106 + tetraconazole;

C199: compound 106 + tebuconazole;

C200: compound 106 + epoxyconazole;

C201 : compound 106 + prothioconazole;

C202: compound 106 + difenoconazole;

C203: compound 106 + penconazole;

C204: compound 106 + prochloraz;

C205: compound 106 + fenpropimorph;

C206: compound 106 + spiroxamine;

C208: compound 106 + bixafen;

C209: compound 106 + boscalid;

C210: compound 106 + carboxin;

C211 : compound 106 + fluopyram; C212: compound 106 + fluxapyroxad;

C213 compound 106 + isopyrazam;

C214: compound 106 + penthiopyrad;

C215: compound 106 + sedaxane;

C216: compound 106 + azoxystrobin;

C217: compound 106 + dimoxystrobin;

C218: compound 106 + fluoxastrobin;

C219: compound 106 + kresoxim-methyl;

C220: compound 106 + picoxystrobin; C221 : compound 106 + pyraclostrobin;

C222: compound 106 + trifloxystrobin;

C223: compound 106 + metrafenone;

C224: compound 106 + proquinazid;

C225: compound 106 + mepanipyrim;

C226: compound 106 + cyprodinil;

C227: compound 106 + iprodione;

C228: compound 106 + procymidone;

C229: compound 106 + carbendazim;

C230: compound 106 + thiophanate-methyl; C231 : compound 106 + fluindapyr;

C232: compound 106 + benalaxyl-M;

C233: compound 106 + fenpyrazamine;

C234: compound 106 + fluazinam;

C235: compound 106 + tolclofos-methyl; C236: compound 106 + mandipropamid; C237: compound 06 + copper oxychloride;

C238: compound 06 + copper salicylate;

C239: compound .06 + chlorothalonil;

C240: compound 106 + cimoxanil;

C241: compound L06 + dimetomorph;

C242: compound 106 + oxathiopiproline;

C243: compound 106 + f uopicolide;

C244: compound 107 + tetraconazole;

C245: compound 107 + tebuconazole;

C246: compound L07 + epoxyconazole;

C247: compound 107 + prothioconazole;

C248: compound 107 + difenoconazole;

C249: compound L07 + penconazole;

C250: compound L07 + prochloraz;

C251: compound 107 + fenpropimorph;

C252: compound 107 + spiroxamine;

C253: compound 107 + bixafen;

C254: compound 107 + boscalid;

C255: compound 107 + carboxin;

C256: compound 107 + fluopyram;

C257: compound 107 + fluxapyroxad;

C258: compound 107 + isopyrazam;

C259: compound 107 + penthiopyrad;

C260: compound 107 + sedaxane;

C261: compound 107 + azoxystrobin; C262: compound 07 + dimoxystrobin;

C263: compound 07 + fluoxastrobin;

C264: compound 101 + kresoxim-methyl;

C265: compound L07 + picoxystrobin;

C266: compound L07 + pyraclostrobin;

C267: compound 107 + trif oxystrobin;

C268: compound 107 + metrafenone;

C269: compound 107 + proquinazid;

C270: compound L07 + mepanipyrim;

C271 : compound L07 + cyprodinil;

C272: compound 107 + iprodione;

C273: compound 107 + procymidone;

C274: compound 107 + carbendazim;

C275: compound 107 + thiophanate-methyl;

C276: compound 107 + fluindapyr;

C277: compound 107 + benalaxyl-M;

C278: compound 107 + fenpyrazamine;

C279: compound 107 + fluazinam;

C280: compound 107 + tolclofos-methyl;

C281 : compound 107 + mandipropamid;

C282: compound 107 + copper oxychloride;

C283: compound 107 + copper salicylate;

C284: compound 107 + chlorothalonil;

C285: compound 107 + cimoxanil;

C286: compound 107 + dimetomorph; C287: compound L07 + oxathiopiproline;

C288: compound L07 + fluopicolil;

C289: compound 10+ tetraconazole + azoxystrobin,

C290: compound ίθ + pyraclostrobin + tetraconazole;

C291: compound 10 + epoxyconazole + azoxystrobin;

C292: compound Ι + pyraclostrobin + epoxyconazole;

C293: compound 10 + azoxystrobin + fluindapyr;

C294: compound 10 + pyraclostrobin + fluindapyr;

C295: compound 10 + fosetyl-aluminium + copper oxychloride;

C296: compound 10 + fosetyl-aluminium + copper salicylate;

C297: compound 10 + fluindapyr+ tetraconazole;

C298: compound 106 + tetraconazole + azoxystrobin,

C299: compound L06 + pyraclostrobin + tetraconazole;

C300: compound L06 + epoxyconazole + azoxystrobin;

C301: compound L06 + pyraclostrobin + epoxyconazole;

C302: compound 106 + azoxystrobin + fluindapyr;

C303: compound 106 + pyraclostrobin + fluindapyr;

C304: compound 106 + fosetyl-aluminium + copper oxychloride;

C305: compound 106 + fosetyl-aluminium + copper salicylate;

C306: compound 106 + fluindapyr+ tetraconazole;

C307: compound 107 + tetraconazole + azoxystrobin,

C308: compound L07 + pyraclostrobin + tetraconazole;

C309: compound L07 + epoxyconazole + azoxystrobin;

C310: compound L07 + pyraclostrobin + epoxyconazole;

C311: compound 107 + azoxystrobin + fluindapyr; C312: compound 107 + pyraclostrobin + fluindapyr;

C313: compound 107 + fosetyl-aluminium + copper oxychloride;

C314: compound 107 + fosetyl-aluminium + copper salicylate;

C315: compound 107 + fluindapyr+ tetraconazole;

wherein compounds 1, 2, 4, 10, 106, 107 are compounds having general formula (I) wherein the substituents have the meanings defined hereunder:

12. Use of amides according to one or more of the claims from 1 to 8 for the control of phytopathogenic fungi of agricultural crops, both curative and preventive, and for the control of phytopathogenic bacteria and viruses.

13. Use according to claim 12, for the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Puccinia Recondita, Erisiphae Graminis, Helminthosporium Teres, Septoria Nodorum, Septoria Tritici and Fusarium spp. on cereals, for the control of Phakopsora Pachyrhizi on soybeans, for the control of Uromyces Appendiculatus on beans, for the control of Venturia Inaequalis on apple trees, for the control of Sphaerotheca Fuliginea on cucumbers; for the control of Xanthomonas spp., Pseudomonas spp., Erwinia Amylovora.

14. Use of fungicidal compositions according to one or more of claims 9-11 for the control of phytopathogenic fungi in agricultural crops, both curative and preventive or eradicative, for the control of fungi of the soil and for the control of phytopathogenic bacteria and viruses.

15. Use according to claim 14, for the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Phytophtora infestans on potatoes, Puccinia Recondita, Erysiphe Graminis, Helminthosporium Teres, Septoria spp and Fusarium spp. on cereals, for the control of Phakopsora Pachyrhizi on soybeans, for the control of Uromyces Appendiculatus on beans, for the control of Venturia Inaequalis on apple trees, for the control of Sphaerotheca Fuliginea on cucumbers, for the control of Rhizoctonia Solani, Sclerotinia spp, Pythium Ultimum on horticultural plants, for the control of Xanthomonas spp., Pseudomonas spp., Erwinia Amylovora.

16. A method for controlling phytopathogenic fungi in agricultural crops, which consists in applying, on any part of the plants to be protected or on the ground, effective and non-phytotoxic doses of compounds having formula (I) according to any of the claims from 1 to 8, used as such or formulated in fungicidal compositions according to one or more of claims 9- 11.

17. A process for preparing a compound having formula (I) according to any of the claims from 1 to 8, according to the following reaction scheme:

(VII) (II)

wherein a compound having formula (VII) is obtained by the reaction of a compound R -Q with a mixture of a compound having formula (VI) dissolved in a solvent selected from ethyl acetate, Ν,Ν-dimethylformamide or acetone, at a temperature ranging from - 15°C to 0°C, in the presence of an organic or inorganic base, selected from potassium carbonate, sodium carbonate, sodium hydride, triethylamine or pyridine, optionally in the presence of a catalyst such as sodium iodide, potassium iodide or a crown ether, such as 15-crown-5 or 18-crown-6, wherein, in the compound R -Q, Q represents an outgoing group such as a halogen, or a mesylate or a triflate, preferably a halogen, more preferably an iodine atom, the other substituents having the meanings previously indicated.

Description:
AROMATIC AMIDES HAVING A FUNGICIDAL ACTIVITY, THEIR AGRONOMIC COMPOSITIONS AND RELATIVE PREPARATION METHOD

The present invention relates to aromatic amides having a high fungicidal activity; in particular, it relates to amides suitably substituted having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops. Aromatic amides having a fungicidal activity are already known and in particular are described in patent applications W099/27783, WO01/14339, WO01/12587 and WO01/05769.

The products described in these documents, however, are often unsatisfactory in terms of effectiveness with respect to various phytopathogenic fungi of interest in important agricultural crops.

The Applicant has now surprisingly found that the combination of specific substituents on the aromatic ring of these amides allows the spectrum of action already known previously on analogous compounds to be broadened, without demonstrating symptoms of phytotoxicity in the agricultural crops of interest.

The object of the present invention therefore relates to new amides having general formula (I):

wherein:

R 1 represents a Q-C 12 alkoxyl, a Q-C 12 haloalkoxyl, a C3-C18 cycloalkoxyl, -NR 4 R 5 group;

R represents a hydrogen atom, a C2-C13 acyl, a C2-C12 alkanoyloxyalkyl Ci Ci 2 , a C 2 -C 12 halo alkanoyloxy alkyl C 1 -C 12 , a C 1 -C 12 alkoxy-Ci-Ci 2 -alkanoyloxyalkyl C1-C12, a Ci-Ci2 haloalkoxy-Ci-Ci2-alkanoyloxyalkyl C1-C12, a C3-C18 cycloalkoxy- Ci-Ci 2 -alkanoyloxyalkyl C 1 -C 12 , an aryloxy C 1 -C 12 alkanoyloxy alky 1 C 1 -C 12 , a benzyloxy C 1 -C 12 alkanoyloxy alky 1 C 1 -C 12 , a C 4 -C 18 cycloalkanoyloxyalkyl C 1 -C 12 , a C 1 -C 12 aroyloxyalkyl, a C 1 -C 12 benzoyloxyalkyl, a C 1 -C 12 heterocyclylcarbonyloxyalkyl, a C 1 -C 12 alkyloxyalkyl C 1 -C 12 , a C 1 -C 12 halo alky loxy alky 1 C 1 -C 12 , a C 1 -C 12 alkoxy-Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a C 1 -C 12 haloalkoxy-Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a C 3 -C 18 cycloalkoxy Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , an aryloxy Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a benzyloxy Ci-Ci 2 -alkyloxyalkyl C1-C12, a C3-C18 cycloalkyloxyalkyl C1-C12, a C1-C12 aryloxyalkyl, a C1-C12 benzyloxyalkyl; a C 1 -C 12 heterocyclyloxyalkyl, a C 4 -C 12 alkanoylthioalkyl C 1 -C 12 , a C 2 -C 12 halo alkanoylthioalkyl C 1 -C 12 , a C 4 -C 18 cycloalkanoylthioalkyl C 1 -C 12 , a d- C 12 aroylthioalkyl, a C 1 -C 12 benzoylthioalkyl; a C 1 -C 12 heterocyclylcarbonylthioalkyl, a C1-C12 alky lthio alky 1 C1-C12, a C1-C12 halo alky lthio alky 1 C1-C12, a C1-C12 alkoxy- Ci-Ci 2 -alkylthioalkyl C 1 -C 12 , a Ci-Ci 2 haloalkoxy-Ci-Ci 2 -alkylthioalkyl C 1 -C 12 , a C 3 - Ci 8 cycloalkoxy Ci-Ci 2 -alkylthioalkyl C 1 -C 12 , a C 1 -C 12 aryloxy alky lthio alky 1 d- C12, a C1-C12 benzyloxy alky lthio alkyl C1-C12, a C 3 -Cis cycloalkylthioalkyl C1-C12, a C 1 -C 12 benzy lthio alkyl, a C 1 -C 12 ary lthio alkyl, a C 1 -C 12 heterocyclylthioalkyl, a C 2 - C12 alkanoylamino alkyl C1-C12, a C2-C12 halo alkanoylamino alkyl C1-C12, a C4-C18 cycloalkanoylaminoalkyl C 1 -C 12 , a C 1 -C 12 aroylaminoalkyl, a C 1 -C 12 benzoylamino alkyl, a C 1 -C 12 heterocyclylcarbonylaminoalkyl, a C 1 -C 12 hetero- cyclylaminoalkyl, a C 4 -C 18 cycloalkylaminoalkyl C 1 -C 12 , a tetrahydropyranyl, a d- C 12 trimethylsily loxy alkyl, a C 1 -C 12 trimethylsilyl-ethoxyalkyl;

1 2

R and R together with the carbon atoms to which they are bound can form a 1,3-oxazole ring;

R represents a hydrogen atom, a C 1 -C 12 alkyl, a C 3 -Cis cycloalkyl; R 4 and R 5 , the same or different, represent a hydrogen atom, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a C 1 -C 12 alkyl, a formyl, a C 2 -C 13 acyl, a C 2 -C 13 haloalkylcarbonyl, a benzyl group, an aroyl group, a C 2 -C 13 alkoxycarbonyl, a Q-C 12 alkoxyalkyl C 1 -C 12 ; a d- C12 alkanoyloxy alkyl C1-C12, a Q-C 12 halo alkanoyloxy alkyl C1-C12, a C3-C18 cycloalkanoyloxyalkyl C 1 -C 12 , a C 1 -C 12 aroyloxyalkyl, a C 1 -C 12 heterocyclylcarbonyloxyalkyl, a C 1 -C 12 aryloxyalkyl, a C 1 -C 12 heterocyclyloxyalkyl, a C1-C12 alkanoylthio alkyl C1-C12, a C1-C12 halo -alkanoylthio alkyl C1-C12, a C3-C18 cycloalkanoylthioalkyl C 1 -C 12 , a C 1 -C 12 aroylthioalkyl, a C 1 -C 12 heterocyclylthioalkyl, a C 1 -C 12 arylthioalkyl a C 1 -C 12 alkanoylamino alkyl C 1 -C 12 , a C 1 -C 12 halo alkanoylamino alkyl C 1 -C 12 , a C 3 -C 18 cycloalkanoylaminoalkyl C 1 -C 12 , a C 1 -C 12 aroylaminoalkyl, a C 1 -C 12 heterocyclylaminoalkyl;

A represents a direct bond or a C 1 -C 12 alkyl;

Y represents an oxygen or sulfur atom;

- Z represents an oxygen or sulfur atom;

X represents a halogen atom, a CN group, a NO 2 group;

n represents a number ranging from 0 to 3;

G represents a C 3 -C 18 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 3 -C 18 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C 6 -C 20 bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 6 -C 20 bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C 6 alkyl, C 3 -C 12 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure a group selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR 3 ; with the proviso that

if R 1 represents a -NR 4 R 5 group wherein R 4 is a hydrogen atom and R 5 is an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a formyl, a 2 3

C 2 -C 13 acyl, a C 2 -C 13 alkoxycarbonyl, and R and R represent a hydrogen atom, and Y is an oxygen atom, G cannot be a C 3 -C 12 cycloalkyl, a C 3 -C 12 cycloalkenyl and a C 3 -C8 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S.

Amides having formula (I) are preferred wherein:

R 1 represents a Ci-C 6 alkoxyl, a Ci-C 6 halohaloalkoxyl, a C 3 -C 12 cycloalkoxyl, a -NR 4 R 5 group;

R represents a hydrogen atom, a C 2 -C-7 acyl, a C 2 -C-7 alkanoyloxyalkyl Ci-C 6 , a C 2 -C-7 haloalkanoyloxyalkyl Ci-C 6 , a Ci-C 6 alkoxy-Ci-C 6 -alkanoyloxyalkyl Ci-C 6 , a Ci-C 6 haloalkoxy-Ci-C6-alkanoyloxyalkyl Ci-C 6 , a C3-C12 cycloalkoxy-Ci-C6- alkanoyloxyalkyl Ci-C 6 , an aryloxy Ci-C 6 alkanoyloxyalkyl Ci-C 6 , a benzyloxy d- C 6 alkanoyloxyalkyl C1-C6, a C4-C12 cycloalkanoyloxyalkyl Ci-C 6 , a Ci-C 6 aroyloxyalkyl, a Ci-C 6 benzoyloxyalkyl, a Ci-C 6 heterocyclylcarbonyloxyalkyl, a d- C 6 alkyloxyalkyl Ci-C 6 , a Ci-C 6 halo alky loxyalkyl Ci-C 6 , a Ci-C 6 alkoxy-Ci-C6- alkyloxyalkyl Ci-C 6 , a Ci-C 6 haloalkoxy-Ci-C 6 -alkyloxyalkyl Ci-C 6 , a C 3 -C 12 cycloalkoxy Ci-C 6 -alkyloxyalkyl Ci-C 6 , an aryloxy Ci-C 6 -alkyloxyalkyl Ci-C 6 , a benzyloxy Ci-C 6 -alkyloxyalkyl Ci-C 6 , a C 3 -C 12 cycloalkyloxyalkyl Ci-C 6 , a Ci-C 6 aryloxyalkyl, a Ci-C 6 benzyloxyalkyl; a Ci-C 6 heterocyclyloxyalkyl, a C 4 -C 6 alkanoylthioalkyl Ci-C 6 , a C 2 -C 6 halo alkanoylthio alky 1 Ci-C 6 , a C 4 -C 12 cycloalkanoylthioalkyl Ci-C 6 , a Ci-C 6 aroylthioalkyl, a Ci-C 6 benzoylthioalkyl; a Ci-C 6 heterocyclylcarbonylthioalkyl, a Ci-C 6 alky lthio alky 1 Ci-C 6 , a Ci-C 6 halo alky lthio alky 1 Ci-C 6 , a Ci-C 6 alkoxy-Ci-C 6 -alkylthioalkyl Ci-C 6 , a Ci-C 6 haloalkoxy-Ci-C 6 -alkylthioalkyl Ci-C 6 , a C 3 -C 12 cycloalkoxy Ci-C 6 alky lthio alky 1 Ci-C 6 , a Ci-C 6 aryloxy alky lthio alky 1 Ci-C 6 , a Ci-C 6 benzyloxy alky lthio alky 1 d- C6, a C3-C12 cycloalkylthioalkyl Ci-C 6 , a Ci-C 6 benzy lthio alky 1, a Ci-C 6 ary lthio alkyl, a Ci-C 6 heterocyclylthioalkyl, a C 2 -C 6 alkanoylaminoalkyl Ci-C 6, a C 2 -C 6 halo alkanoylaminoalkyl Ci-C 6 , a C 4 -C 12 cycloalkanoylaminoalkyl Ci-C 6 , a d- C 6 aroylaminoalkyl, a Ci-C 6 benzoylamino alkyl, a Ci-C 6 heterocyclylcarbonylaminoalkyl, a Ci-C 6 heterocyclylaminoalkyl, a C 4 -C 12 cycloalkylaminoalkyl Ci-C 6 , a tetrahydropyranyl, a Ci-C 6 trimethylsilyloxy alkyl, a Ci-C 6 trimethylsilyl-ethoxyalkyl;

R represents a hydrogen atom, a Ci-C 6 alkyl, a C 3 -C 12 cycloalkyl;

R 4 and R 5 , the same or different, represent a hydrogen atom, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a Ci-C 6 alkyl, a formyl, a C 2 -C-7 acyl, a C 2 -C 7 haloalkylcarbonyl, a benzyl group, an aroyl group, a C 2 -C-7 alkoxycarbonyl, a Ci-C 6 alkoxyalkyl Ci-C 6 ; a Ci-C 6 alkanoyloxy alkyl Ci-C 6 , a Ci-C 6 haloalkanoyloxyalkyl C1-C12, a C3-C12 cycloalkanoyloxyalkyl Ci-C 6 , a Ci-C 6 aroyloxyalkyl, a Ci-C 6 heterocyclylcarbonyloxyalkyl, a Ci-C 6 aryloxyalkyl, a Ci-C 6 heterocyclyloxyalkyl, a Ci-C 6 alkanoylthio alkyl Ci-C 6 , a Ci-C 6 halo alkanoylthio alkyl Ci-C 6 , a C3-C12 cycloalkanoylthioalkyl Ci-C 6 , a Ci-C 6 aroy lthio alkyl, a Ci-C 6 heterocyclylthioalkyl, a Ci-C 6 arylthioalkyl a Ci-C 6 alkanoylaminoalkyl Ci-C 6 , a Ci-C 6 halo alkanoylaminoalkyl Ci-C 6 , a C 3 -C 12 cycloalkanoylaminoalkyl Ci-C 6 , a Ci-C 6 aroylaminoalkyl, a Ci-C 6 heterocyclylaminoalkyl;

A represents a direct bond or a Ci-C 6 alkyl;

Y represents an oxygen or sulfur atom;

X represents a halogen atom, a CN group, a NO 2 group;

n represents a number ranging from 0 to 1;

G represents a C 3 -C 12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 3 -C 12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C 6 -Ci 6 bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 6 -Ci 6 bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C 6 alkyl, C 3 -C 12 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR 3 .

More preferred are amides having formula (I) wherein:

- R represents a C 2 -C 6 acyl, a Ci-C 6 alkoxy-Ci-C 6 -alkanoyloxyalkyl Ci-C 6 , a Ci-C 6 haloalkoxy-Ci-C6-alkanoyloxyalkyl Ci-C 6 , a C3-C12 cycloalkoxy-Ci-C6- alkanoyloxy alkyl Ci-C 6 , a C3-C12 cycloalkyloxyalkyl Ci-C 6 , a C4-C12 alkanoylthio alkyl Ci-C 6 , a C 2 -C 6 halo alkanoylthio alkyl Ci-C 6 , a C 4 -C 12 cycloalkanoylthioalkyl Ci-C 6 , a C 2 -C 6 alkanoylamino alkyl Ci-C 6 , a C 2 -C 6 halo alkanoylamino alkyl Ci-C 6 , a Ci-C 6 alkoxy- Ci-C6-alkyloxyalkyl Ci-C 6 , a Ci-C 6 haloalkoxy-Ci-C 6 -alkyloxyalkyl Ci-C 6 , a C 3 -Ci 2 cycloalkoxy Ci-C 6 -alkyloxyalkyl d- C 6 , a tetrahydropyranyl, a Ci-C 6 trimethylsylyloxyalkyl, a Ci-C 6 trimethylsylyl- ethoxyalkyl;

Y and Z both represent an oxygen atom;

- G represents a C 3 -C 12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 3 -C 12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, a C 6 -Ci 6 bicycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 6 -Ci 6 bicycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, adamantyl, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C 6 alkyl, C 3 -C 12 cycloalkyl, benzyl and with the possibility of incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR 3 .

Even more preferred are amides having formula (I) wherein:

R represents a hydrogen atom;

- G represents a C 3 -C 12 cycloalkyl containing from 0 to 3 heteroatoms selected from O, N, S, a C 3 -C 12 cycloalkenyl containing from 1 to 3 unsaturations and from 0 to 3 heteroatoms selected from O, N, S, said cyclic groups being optionally substituted with 1 to 3 groups, the same or different, selected from Ci-C 6 alkyl, C 3 - C 12 cycloalkyl, benzyl and incorporating in said cyclic structure one or more groups selected from: C=0, C(=0)0, C(=0)S, C(=S)0, C(=S)S, C(=0)NR 3 .

Said cyclic systems can also be condensed with an aromatic system with 5 and 6 terms possibly containing from 1 to 2 heteroatoms selected from O, N, S.

Said cyclic systems can be substituted by one or more groups selected from halogen atoms, C 1 -C 12 alkyl groups, C 1 -C 12 haloalkyl groups, C 3 -C 18 cycloalkyl groups, C 2 - C 12 alkenyl groups, C 3 -C 18 cycloalkenyl groups, C 2 -C 12 haloalkenyl groups, C 1 -C 12 alkoxyl groups, C 3 -C 18 cycloalkoxyl groups, C 1 -C 12 haloalkoxyl groups, a cyano group, a formyl, a C 1 -C 12 alky lthio alkyl C 1 -C 12 group, a C 1 -C 12 halo alky lthio alkyl C 1 -C 12 group, a C 3 -C 18 cycloalkylthioalkyl C 1 -C 12 group, an aryl group, a phenoxyl group, a thiophenoxyl group, a benzyl group, a C 4 -C 18 cycloalkylalkyl group, a d- C12 alkoxyalkyl C2-C12 group, a C1-C12 alky lthio alkyl C1-C12 group, a C2-C12 alkoxycarbonyl group, a C 4 -C 12 cycloalkoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, a C 2 -C 12 alkylaminocarbonyl group, a C 3 -C 12 dialkylaminocarbonyl group, a C 1 -C 12 alkylamine group, a C 3 -C 18 cycloalkylamine group, an arylamine group, a C2-C12 dialkylamine group, a N-Ci-Ci2alkyl-N-C3-Cis cycloalkylamine group, a diarylamine group;

or an R 6 group wherein R 6 represents a spiro-anular carbocyclic group with from 3 to 10 terms saturated or partially unsaturated.

C2-C12 alkanoyloxyalkyl C1-C12, C2-C12 halo alkanoyloxyalkyl C1-C12, C4-C18 cycloalkanoyloxyalkyl C 1 -C 12 , C 1 -C 12 aroyloxyalkyl, C 1 -C 12 benzo yloxy alkyl, C 1 -C 12 heterocyclylcarbonyloxyalkyl, refer to a radical having formula RaC(=0)ORb wherein Ra respectively has the meaning of C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 18 cycloalkyl, aryl, benzyl and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl. Examples of these groups are propanoyloxymethyl, cyclohexanoyloxymethyl, benzo ylo xy ethyl.

C1-C12 alkoxy C1-C12 alkanoyloxyalkyl C1-C12, C1-C12 haloalkoxy C1-C12- alkanoyloxyalkyl C 1 -C 12 , C 3 -C 18 cycloalkoxy C 1 -C 12 alkanoyloxyalkyl C 1 -C 12 , phenoxy C 1 -C 12 alkanoyloxyalkyl C 1 -C 12 , benzyloxy C 1 -C 12 alkanoyloxyalkyl C 1 -C 12 , refer to a radical having formula RcORbC(=0)ORa wherein Rc respectively has the meanings of C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 18 cycloalkyl, aryl and benzyl and heterocyclyl and Ra and Rb have the meaning of C 1 -C 12 alkyl.

Examples of these groups are 3-meth.oxy-propanoylox.ym.ethyl, 2-cyclopropoxy- bu lano ylox ymethyi.

C2-C12 alkano ylthioalkyl C1-C12, C2-C12 halo alkano ylthioalkyl C1-C12, C4-C18 cycloalkano ylthioalkyl C 1 -C 12 , C 1 -C 12 aroylthioalkyl, C 1 -C 12 benzo ylthioialkyl, C 1 -C 12 heterocyclylcarbonylthioalkyl, refer to a radical having formula RaC(=0)SRb wherein Ra respectively has the meaning of C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 18 cycloalkyl, aryl and benzyl and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl. Examples of these groups are propanoylthiomethyl, cyc!ohexanoyltliioniethyl, benzo ylthioeth y 1.

C1-C12 alkyloxyalkyl C1-C12, C1-C12 halo alky loxy alkyl C1-C12, a C3-C18 cycloalkyloxyalkyl C 1 -C 12 , a C 1 -C 12 aryloxyalkyl, a benzyloxy alkyl C 1 -C 12 ; a heterocyclyloxyalkyl C1-C12, refer to a radical having formula RaORb wherein Ra has the meaning of Q-C 12 alkyl, C1-C12 haloalkyl, C3-C18 cycloalkyl, aryl and benzyl and heterocyclyl and Rb has the meaning of Q-C 12 alkyl.

Examples of these groups are ethoxyniethyl, trifluoromethoxymethyl, phenoxyethyl. C1-C12 alkylthioalkyl C1-C12, C1-C12 halo alky lthio alkyl C1-C12, C 3 -Ci 8 cycloalkylthioalkyl C1-C12, a C1-C12 benzy lthio alkyl, a C1-C12 ary lthio alkyl, a C1-C12 heterocyclylthioalkyl, refer to a radical having formula RaSRb wherein Ra has the meaning of C1-C12 alkyl, C1-C12 haloalkyl, C 3 -Ci 8 cycloalkyl, aryl and benzyl and heterocyclyl and Rb has the meaning of C1-C12 alkyl.

Examples of these groups are ethylthioethyl, cyclopropylthiomethyl, phenylthioethyl. C1-C12 alkoxy C1-C12 alkyloxyalkyl C1-C12, Ci-Ci2 haloalkoxy C1-C12- alkyloxyalkyl C1-C12, C 3 -Cis cycloalkoxy C1-C12 alkyloxyalkyl C1-C12, C1-C12 aryloxy C1-C12 alkyloxyalkyl, C1-C12 benzyloxy C1-C12 alkyloxyalkyl, refer to a radical having formula RcORbORa wherein Rc has the meaning of C1-C12 alkyl, C1-C12 haloalkyl, C 3 -Ci 8 cycloalkyl, aryl, and benzyl and Ra and Rb have the meaning of C1-C12 alkyl. Examples of these groups are l-methoxy-propy!-2-oxy-methyl, cyclopentoxy-2- ethoxy-methyl.

C1-C12 alkoxy C1-C12 alkylthioalkyl C1-C12, C1-C12 haloalkoxy-Ci-Ci2- alkylthioalkyl C1-C12, C 3 -Cis cycloalkoxy Ci-Ci2-alkylthioalkyl C1-C12, aryloxy C1-C12 - alkylthioalkyl C1-C12, benzyloxy C1-C12 alkylthioalkyl C1-C12, refer to a radical having formula RcORbSRa wherein Rc has the meaning of C1-C12 alkyl, C1-C12 haloalkyl, C 3 -Ci 8 cycloalkyl, aryl, and benzyl and Ra and Rb have the meaning of C1-C12 alkyl.

Examples of these groups are l-methoxy-propyl-2-thio-methyl, cyclopentoxy-2- ethvlthio-methvl. C2-C12 alkanoylaminoalkyl C1-C12, C2-C12 halo alkanoylamino alkyl C1-C12, C4-C18 cycloalkanoylaminoalkyl C 1 -C 12 , C 1 -C 12 aroylamino-alkyl, C 1 -C 12 heterocyclylcarbonylaminoalkyl, refer to a radical having formula RaC(=0)NHRb wherein Ra has the meaning of C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 18 cycloalkyl, aryl and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl.

Examples of these groups are propanoylammomethyl, cyclohexanoylammomethyl, benzoylaminoethy] .

C 2 -C 12 alkoxyalkyl, C 4 -C 12 cycloalkyl-oxyalkyl, C 1 -C 12 aryloxyalkyl and C 1 -C 12 heterocyclyloxyalkyl, refer to a radical RaORb wherein Ra respectively has the meaning of C 1 -C 12 alkyl, C 3 -C 18 cycloalkyl, aryl and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl.

Examples of these groups are cyclopentyloxymethyl, 2-thiadiazoles-oxymethyl.

C 2 -C 12 alky lthio alkyl, C 1 -C 12 cycloalkylthioalkyl, C 1 -C 12 arylthio alkyl, C 1 -C 12 heterocyclylthioalkyl, refer to a radical RaSRb wherein Ra respectively has the meaning of C 1 -C 12 alkyl, C 3 -C 18 cycloalkyl, aryl and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl.

Examples of these groups are cyclopenty!thiomethyl, 2-thiadiazoly!-thiomethyl.

C 1 -C 12 cycloalkylaminoalkyl, and C 1 -C 12 heterocyclylaminoalkyl, refer to a radical RaNHRb wherein Ra respectively has the meaning of C 3 -C 18 cycloalkyl, and heterocyclyl and Rb has the meaning of C 1 -C 12 alkyl.

Examples of these groups are N-cyclopentyl-N-methylamino, N-2-lhiadiazol-N- methylamino.

Examples of halogen are fluorine, chlorine, bromine, iodine.

Examples of C 1 -C 12 alkyl are methyl, ethyl, n -propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl. Examples of Q-C 12 haloalkyl are fiuoromethyl, difluoromethyl, trifluoromethyl, chloro methyl, dichloro methyl, 2,2,2-trifluoroethyl, 1 , 1 ,2,2-tetrafluoroethyl, pentafiuoroethyl, heptafluoropropvL 4,4,4-trichl.oro-butyl , 4,4-difluoropentyl, 5,5- difluorohexyl.

Examples of C 3 -C 18 cycloalkyl are cyc!opropyl, cyclobutyl, cyclopentyl, cyclohexyl, (2E, 6E, 10E) -2,6,9,9-tetramethyl-2,6, 10-cycloundecatrienyl.

Examples of C6-C 20 bicycloaikyl are bicyclo[2.2.1 Jheptane, bicyclo[4.3.0] nonane, bicyclo[3.2.1] octane.

Examples of C 2 -C 12 alkenyl are: ethenyl, propenyl, butenyl.

Examples of C 2 -C 12 haloalkenyl are: 2,2-dichloro-propenyl, 1,2,2-trichloro propenyl, Examples of C 3 -C 18 cycloalkenyl are cyclobiUenyl, cyclopentenyl, cyclohexenyl, Examples of bicycloalkenyl are 2,3,4A,5,8,8a-hexahydronaphthyl, norbornyl.

Examples of C4-C18 cycloalkylalkyl are: 2-ethylcyclopropyl, cyclopentylmethyl, 3- propylhexyl.

Examples of C 2 -C 13 acyl groups are acetyl, propanoyl, isopropanoyl.

Examples of C 2 -C 12 haloalkylcarbonyl are: iluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, dichloromethylecarbonyl, 2,2,2- trifluoroethylcarbonyl.

Examples of C 2 -C 12 alkoxycarbonyl are methoxycarbonyl, propoxycarbonyl, hexyloxycarbonyl.

Examples of C 4 -C 12 cycloalkoxycarbonyl are cyclopropoxicarbonyl, eye lo hexyloxycarbonyl.

Examples of C 2 -C 12 alkylaminocarbonyl are N-methylaminocarbonyl, N- propylaminocarbonyl, N-decylaminocarbonyl.

Examples of C 3 -C 12 dialkylaminocarbonyl are , N-dimethylaminocarbonyl, N- propyl- N-methylaminocarbonyl, N-decyl-N-propylaminocarbonyl.

Examples of Q-C^ alkylamino are methylamino, isopropylamino, dodecylamino. Examples of C 3 -C 18 cycloalkylamino are cyclopentylamino, cyclohexyiamino, eye looctylammo .

Examples of C 2 -C 18 dia!ky! amino are Ν,Ν-dimethylamino, N-ethyl-N-butylamino, N- hexyl-N-nonylamino .

Examples of N-C1-C12 alkyl-N-C 3 -C 18 cyclo-alkylammo C3-C18 are N-methyl-N- cyclopropylamino; N-propyl-N-cyclohexylarmno, N-octyl-N-cyclopropylammo. Examples of Q-C^ alkoxyl are methoxyl, ethoxyl.

Examples of Q-C 12 haloalkoxyl are trifluoromethoxyl, 1,1,2,2-tetrafluoroethoxyl, 1 , 1 ,2,3,3,3-hexafluoro-propyloxyl.

Examples of C 3 -C 18 cycloalkoxyl are cyclopropoxyl, eyclopentloxyl.

Examples of Q-C 12 thioalkyl are thiomethyl, thioethyl.

Examples of C 1 -C 12 thiohaloalkyl are trifluorothiomethyl, 1,1,2,2-tetrafluorothioethyl. Examples of C3-C 18 thiocycloalkyl. are thiocyclopropyl, thiocyclopentyl.

Examples of heterocyclic rings, which refer to 5 or 6-term cyclical systems, aromatic or non-aromatic, possibly benzocondensed, containing from 1 to 3 beteroatoms selected from O, N, S, are: thiazole, 1,3,4 thiadiazole, pyrrolidine, piperidine, morpholine, pyrazole etc.

Examples of aryl, which refer to mono, bi or tricyclic aromatic systems, consisting of only carbon atoms, are phenyl, naphthyl, phenanthrenyl, anthracenyi.

All of the aryl, benzyl, phenoxy, thiophenoxyl and heterocyclic systems can be substituted by one or more groups selected from halogens, Q-C 12 alkyl, C 1 -C 12 haioalkyl, C 3 -C 18 cycloalkyl, C C^ alkoxyl, C 4 -C 18 cycloalkoxyl, Q-Qs haloalkoxyl. The following also fall within the spirit of the present invention: a) all the possible geometric isomers of the compounds having general formula (I) deriving from particular meanings of the substituents R^-R 6 Z, A and G;

b) the salts of the compounds having formula (I) obtained by the addition of inorganic or organic acids;

5 c) possible hydrated forms of the compounds having formula (I).

Examples of preferred compounds having general formula (I) are compounds wherein

R 1 , Y, Z, X, n, A, G have the meanings indicated in Table 1:

Table 1





21

22







1 2 2

Amides Slaving general formula (I) wherein R represents an NR CHO group, R being equal to a hydrogen atom or having the meanings previously indicated for R in Table 1, are particularly preferred, R 1 preferably represents an NHCHO group.

The compounds having general formula (I) can be obtained using various synthesis methods; for example, for exemplifying but non-exhaustive purposes, the compounds having general formula (I) wherein Z has the meaning of O, can be prepared from the compounds having general formula (II) by reaction with a suitable amine having formula (III) according to the reaction scheme 1.

Scheme 1

(II) (III) (I)

The reaction is carried out by activating the acid by means of the corresponding chloride, for example with thionyl chloride in dichloromethane or chloroform or using a condenser such as N, N'-dicyclohexylcarbodiimide or N- (3- dimethylaminopropyl) -N'-ethylcarbodiimide in tetrahydrofuran or ethyl acetate, or using 1, 1-carbonyIdiimidazole in tetrahydrofuran or methylene chloride at a temperature ranging from 0°C to the reflux temperature of the solvent used, as widely described in R. Larock "Comprehensive Organic Transformations". The activated acid form is then reacted with the amine having formula (III) in a suitable solvent such as methylene chloride, or dichloroethane, or chloroform at a temperature ranging from 0°C to the reflux temperature of the solvent in the presence or absence of a base such as, for example, triethylamine or 4-dimethylaminopyridine according to what is known in literature in R. Larock "Comprehensive Organic Transformation " .

The compounds having formula (III), when they are not commercial and A has the meaning of a direct bond and R is hydrogen, can be prepared, for example, from the corresponding cyclic ketones having formula. (IV) by reaction in a solvent such as ethanol or methanol, at room temperature, with hydroxy lamines having formula NH 2 OR' wherein R' represents a hydrogen atom or a methyl according to the reaction scheme 2.

Scheme 2

The corresponding oximes having formula (V) can be converted to amines having general formula (III) by reduction with sodium in ethanol or with platinum, platinum oxide or nickel as catalysts in the presence of hydrogen, as described in WO2010010458.

Alternatively, the methyloximes can be reduced with sodium borohydride and trifluoro acetic acid in a solvent such as tetrahydrofuran or with sodium borohydride and zirconium chloride in tetrahydrofuran at temperatures ranging from 0°C to the reflux temperature of the solvent, as described in N. Umino et al. in "Chem. Pharm. Bull " 1978,26,2897.

Alternatively, the compounds having formula (III), when they are not commercial and A has the meaning of C1-C12 alkyl and R is hydrogen, can he obtained, for example, from the corresponding aldehyde or nitrile or azide or amide according to methods well known in literature and described in E.P. Kyba et al. "Tetrahedron Letters" (1977) 2737-2740, in Chen Feng et al. "Journal American Chemical Society" (2016) vol. 138 8781-8788, in Srinivasa, Nalina et al. in "Journal of Chemical Research" part S (2003) 630-631 or in G. Beamson et al. in "Journal of Catalysis" (2010) vol.269 93- 102.

Again, the compounds having formula (III), when they are not commercial and A has the meaning of Q-C 12 alkyl and R is different from hydrogen, can be obtained either by reduction of the corresponding N-alkylamide or N-cycloalkylamide, for example with lithium aluminium hydride in tetrahydrofuran at temperatures ranging from 0 C C to the reflux temperature of the solvent as described in WO2010035032 or by- reaction of the aldehyde having formula G-A-CHO with an appropriate alkylamine or cycloalkylamine having formula R " NH 2 and subsequent reduction of the imino- derivative thus obtained with methods known from literature, as described for example in WO2006100036.

The compounds having formula (II), as indicated in scheme 3, can be prepared by hydrolysis of the compound having formula (VII) wherein W has the meaning of methyl or ethyl or, if W has the meaning of a benzyl group, by hydrogeno lysis with hydrogen in the presence of catalysts such as palladium on coal, using the methods indicated for example in Theodora W. Greene "Protective Groups in Organic Synthesis" Third Edition.

As is well known to skilled persons in the field, in order to obtain the compound having formula (VII) wherein R is different from H, the alkylation of compound (V I ) is carried out as indicated in scheme 3.

When R 1 represents the -NHCHO group, however, the Applicant has surprisingly discovered that the alkylation reaction of the -YH group leads to the formation of significant quantities of dialkylated product.

A further object of the present invention therefore relates to a process for the preparation of the compound having formula. (I), comprising the preparation of the compound having formula (VII), wherein a compound R -Q is added to a. mixture of the compound having formula. (VI) dissolved in a suitable solvent, such as ethyl acetate, Ν,Ν-dimethylformamide or acetone, wherein Q represents an outgoing group such as a halogen or a mesylate or a triflate, preferably a halogen, more preferably an iodine atom at a temperature ranging from -15 ° C to 0 0 C, in the presence of an organic or inorganic base such as potassium carbonate, sodium carbonate, sodium hydride, triethylamine or pyridine, optionally in the presence of a catalyst such as sodium iodide, potassium iodide or a crown ether such as 15-crown-5 or 18-crown-6 according to the reaction scheme 3.

Scheme 3

(VII) (II)

(VI) (VII)

The compounds having general formula (I) can, alternatively, be obtained from the compounds having general formula (VIII) by alkylation reaction with a compound having formula R 2 -Q wherein R 2 is different from H and Q represents a leaving group such as halogen, a mesylate or a triflate in ethyl acetate or N, N-dimethylformamide or acetone at a temperature ranging from -15°C to 70°C, in the presence of an organic or inorganic base such as potassium carbonate, or sodium carbonate, or triethylamine or pyridine or sodium hydride in the presence or absence of a catalyst such as sodium iodide, potassium iodide and a crown ether such as 15-crown-5 or 18-crown-6 according to the reaction scheme 4.

Scheme 4

The compounds having general formula (VIII) wherein R represents an H atom, can, in turn, be prepared from the compounds having general formula (IX) by reaction with a suitable amine R -NH-A-G having formula (III) according to the reaction scheme s.

Scheme 5

The reaction is carried out by activating the earhoxylic acid through the corresponding chloride, for example with thionyl chloride in dichloro methane or chloroform or using a condenser such as Ν,Ν'-dicyclohexylcarbodiimide or N- (3- dimethylaminopropyl) -N'-ethylcarbodiimide in tetrahydrofuran or ethyl acetate, or using 1,1-carbonyldiimidazole in tetrahydrofuran or methylene chloride a temperatures ranging from 0°C to the reflux temperature of the solvent used, as amply described in R. Larock "Comprehensive Organic Transformations".

The activated acid form is then reacted with the amine having formula (III) in a suitable solvent such as methylene chloride, or dichloroethane. or chloroform at a temperature ranging from 0°C to the reflux temperature of the solvent, in the presence or absence of a base such as, for example, triethylamine or 4-dimethylaminopyridine, according to what is known in literature in R. Larock "Comprehensive Organic Transformations " .

The acids having general formula (IX) and the corresponding esters having formula (VI) are either commercial or can be synthesized according to methods known in literature and are easily available in the Reaxys Database (w w w .reaxy s .com) .

The compounds wherein Z has the meaning of S, can be prepared from the corresponding oxygenated compounds by reaction with phosphorus peniasulfide, or using the Lawesson reagent, in solvents such as toluene or dioxane at a temperature ranging from room temperature to the reflux temperature of the solvent as described in "Bioorganic and Medicinal Chemistry, 2018, vol.26, pages 1547-1559". A further object of the present invention relates to the use of the compounds having formula (I) for the control of phvtopathogenic fungi of agricultural crops.

The compounds having general formula (I) are in fact provided with a very high fungicidal activity which is exerted with respect to numerous phytopathogenic fungi that attack important agricultural crops.

Examples of phytopathogenic fungi that can be effectively treated and fought with compounds having general formula (I) are those belonging to the classes of Basidiomycetes, Ascomycetes, Deuteromycetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Eryiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. {Mycosphaerella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.

The main crops that can be protected with the compounds according to the present invention include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit- trees (apples, pears, plums, peaches, almonds, cherries, bananas, vines, strawberries, raspberries, blackberries, etc.), citrus fruits (oranges, lemons, mandarins, grapefruit, etc.), legumes (beans, peas, lentils, soybeans, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, eggplants, peppers, etc.), cucurbits (pumpkins, courgettes, cucumbers, melons, watermelons, etc.), oleaginous plants (sunflower, rapeseed, peanut, castor, coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton. In particular, the compounds having formula (I) have proved to be extremely effective in the control of Plasmopara viticola on grapevines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Puccinia Recondita, Erisiphae Graminis, Helminthosporium Teres, Seploria Nodorum, Septoria Tritici and Fusarium. spp. on cereals, in the control of Phakopsora Pachyrhiz.i on soybeans, in the control of Uromyces Appendiculatus on beans, in the control of Venturia Inaequalis on apple trees, in the control of Sphaerotheca Fuliginea on cucumbers.

Furthermore, the compounds having general formula. (I) are also effective in the control of phytopathogenic bacteria and viruses, such as for example Xanthomonas spp., Pseudomonas spp., Etwinia Amylovora, the tobacco mosaic virus.

The compounds having formula (I) are capable of exerting a fungicidal action of both a curative and preventive nature and show an extremely low or zero phytotoxicity with respect to the crops treated.

For practical uses in agriculture, it is often preferable to use fungicidal compositions containing the compounds according to the present invention suitably formulated.

A further object of the present invention relates to fungicidal compositions comprising one or more compounds having formula (I), a solvent and/or solid or liquid diluent, possibly a surfactant.

The above-mentioned fungicidal compositions can be in the form of dry powders, wettable powders, emulsifiable concentrates, emulsions, micro-emulsions, pastes, granules, granules dispersible in water, solutions, suspensions, etc.: the selection of the type of composition depends on the specific use.

The fungicidal compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent medium and/or a solid or liquid diluent, possibly in the presence of surfactants.

Silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, seppiolite, can be used, for example, as solid diluents, or carriers.

Solvents or liquid diluents that can be used for example, in addition to water, are aromatic organic solvents (xylols or blends of alkyl benzenes, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, hutanol, octanol, glycerin, etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, alkyl esters of adipic acid, alkyl esters of glutaric acid, alkyl esters of succinic acid, alkyl esters of lactic acid, etc.), vegetable oils (rapeseed oil, sunflower oil, soybean oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone, etc.), amides (N,N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides and sulfones (dimethyl sulfoxide, dimethyl- sulfone, etc.), and mixtures thereof.

Propellant gases such as butane, propane, halogenated hydrocarbons, nitrogen or carbon dioxide can be used as liquefied diluents or liquefied substances which gasify at room temperature and pressure.

Surfactants that can be used are sodium, calcium, potassium, triethylamine or triethanoiamine salts of alkylnaphthalenesulfonates, poly-naphthalenesulfonates, alkylsulfonates, arylsiilfonates, alkylarylsulfonates, polycarboxylates, suifo succinates, alkyl- sulfosuccinates, lignin sulfonates, alkyl sulfates; and furthermore poiyethoxylated fatty alcohols, polyethoxylated alkylphenols, polyethoxylated or poiypropoxy-poiyethoxylated arylphenols or polyethoxylated esters of sorbitol, polyproproxy-polyethoxylates (block polymers), can also be used.

The fungicidal compositions can also contain special additives for particular purposes, for example antifreeze agents such as propylene glycol, or adhesion agents such as arable gum, polyvinyl alcohol, polyvinylpyrrolidone, dispersing agents, for example lignin and its salts, cellulose derivatives or alginates, or stabilizers, for example antioxidants or ultraviolet-ray absorbents.

The concentration of active compound having formula (I) in the above compositions can vary within a wide range and depends on various factors. It varies in relation to the active compound having formula. (I), the applications for which said compositions are destined, the environmental conditions and type of formulation adopted, in genera], the concentration of active compound having formula (I) ranges from 0.1 to 90% by weight with, respect to the total weight of the composition, preferably from 0.5 to 90% by weight.

If desired, it is possible to add to the fungicidal compositions containing the compounds having general formula (I), other active ingredients compatible with the same, such as fungicides other than those having general formula (I), phytoregulators, antibiotics, herbicides, insecticides, fertilizers, bio stimulants and/or mixtures thereof. Examples of fungicides different from those having general formula (I) which can be included in the fungicidal compositions object of the present invention are: fluindapyr, acibenzolar, aldimorph, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azithiram, azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthoxazin, benzamacril, benzamorf, benzovindiflupyr, binapacryl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, chinomethionat, chlobenthiazone, chlorfenazole, chloroneb, chlorothalonil, chlorquinox, chlozolinate, cufraneb, cyazofamid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dichlofluanid, dichlone, dichlorophen, dichlozoline, diclobutrazol, diclomezine, dicloran, diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis, furophanate, guazatine, griseofulvin, halacrinate, hexaconazole, hexylthiofos, hymexazol, hydroxyquinoline sulfate, imazalil, imibenconazole, iminoctadine, inpyrfluxam, ipconazole, iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metam, metconazole, methasulfocarb, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, myclozolin, nabam, natamycin, nicobifen, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorofenol and its salts, penthiopyrad, phthalide, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrapropoyne, pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiophanate, thiophanate- methyl, thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziram, sulfur, zoxamide. A further object of the present invention therefore relates to fungicidal compositions comprising at least one compound having general formula (I) and at least another fungicide different from the compounds having formula (I).

Fungicidal compositions containing at least one amide having formula (i) and one or more known fungicides, particularly preferred for the particularly wide spectrum of action and a marked synergistic effect, are those in which one or more compounds having general formula (I) are combined with one or more known fungicides belonging to the following classes:

a) azoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; b) amines, ergosterol biosynthesis inhibitors selected from aldimorph, dodemorph, fenpropimorph, fenpropidin, spiroxamine, tridemorph;

c) succinate-dehydrogenase inhibitors (SDHI) selected from benzovindiflupyr, bixafen, boscalid, carboxin, fluindapyr, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamide;

d) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxostrobin, trifloxystrobin;

e) specific antioidic compounds selected from cyflufenamid, flutianil, metrafenone, proquinazid, pyriofenone, quinoxyfen;

f) aniline-pyramidines selected from pyrimethanil, mepanipyrim, cyprodinil; g) benzimidazoles and analogues thereof selected from carbendazim, benomyl, thiabendazole, thiophanate-methyl;

h) dicarboxyimides selected from iprodione, procymidone;

i) phtalimides selected from captafol, captan, folpet;

1) systemic acquired resistance (SAR) inducers selected from acibenzolar, probenazole, isotianil, tiadinil;

m) phenylpyrroles selected from fenpiclonil, fludioxonil;

n) acylalanines selected from benalaxyl, benalaxyl-M, furalaxyi, metalaxyl, metalaxyl-M;

o) other specific antiperonosporic compounds selected from ametoctradin, amisulbrom, benthiavalicarb, cyazofamid, cymoxanil, dimethomorph, ethaboxam, famoxadone, fenamidone, flumetover, flumorph, fluopicolide, iprovalicarb, mandipropamid, oxathiapiproline, valifenalate, zoxamide;

p) dithiocarbamates selected from maneb, mancozeb, propineb, zineb, metiram; q) phosphorus acid and its inorganic or organic salts, fosetyl- aluminium r) cupric compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulfate, copper salicylate;

s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, silthiofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine, tolclofos-methyl.

The fungicidal compounds are indicated in the present description with their international ISO name; the chemical structures and their CAS and I UPAC names are reported in Alan Wood's Website (www.alanwood.net), Compendium of Pesticide Common Names; the chemical-physical data and biological characteristics of most of these compounds are indicated in the "Pesticide Manual", C.D.S. Tomlin, 15th edition, 2(309, British Crop Production Council.

The compound Fluindapyr has been described in patent application WO 2012/084812.

Preferred compositions containing at least one compound having formula (I) (component A) and at least one other known fungicide are those consisting of:

CI: compound 1 + tetraconazole;

C2: compound 1 + tebuconazole;

C3: compound 1 + epoxyconazole;

C4: compound 1 + prothioconazole;

C5: compound 1 + difenoconazole;

C6: compound 1 + penconazole;

C7: compound 1 + prochloraz;

C8: compound 1 + fenpropimorph;

C9: compound 1 + spiroxamine;

CIO: compound 1 + bixafen;

Cl l: compound 1 + boscalid;

C12: compound 1 + carboxin;

C13: compound 1 + fluopyram;

C14: compound 1 + fluxapyroxad;

C15: compound 1 + isopyrazam;

CI 6: compound 1 + penthiopyrad;

C17: compound 1 + sedaxane; C18: compound + azoxystrobin;

C19: compound + dimoxystrobin;

C20: compound + fluoxastrobin;

C21 : compound + kresoxim-methyl;

C22: compound + picoxystrobin;

C23: compound + pyraclostrobin;

C24: compound + trifloxystrobin;

C25: compound + metrafenone;

C26: compound + proquinazid;

C27: compound + mepanipyrim;

C28: compound + cyprodinil;

C29: compound + iprodione;

C30: compound + procymidone;

C31 : compound + carbendazim;

C32: compound + thiophanate-methyl;

C33 compound . + fluindapyr;

C34: compound + benalaxyl-M;

C35 compound . + fenpyrazamine;

C36: compound + fluazinam;

C37: compound + tolclofos-methyl;

C38: compound + mandipropamid;

C39: compound + copper oxychloride;

C40: compound + copper salicylate;

C41 : compound + chlorothalonil;

C42: compound + cimoxanil; C43: compound 1 + dimetomorph;

C44: compound 1 + oxathiopiproline;

C45: compound 1 + fluopicolide;

C46: compound 2 + tetraconazole;

C47: compound 2 + tebuconazole;

C48: compound 2 + epoxyconazole;

C49: compound 2 + prothioconazole;

C50: compound 2 + difenoconazole;

C51 : compound 2 + penconazole;

C52: compound 2 + prochloraz;

C53: compound 2 + fenpropimorph;

C54: compound 2 + spiroxamine;

C55: compound 2 + bixafen;

C56: compound 2 + boscalid;

C57: compound 2 + carboxin;

C58: compound 2 + fluopyram;

C59: compound 2 + fluxapyroxad;

C60: compound 2 + isopyrazam;

C61 : compound 2 + penthiopyrad;

C62: compound 2 + sedaxane;

C63: compound 2 + azoxystrobin;

C64: compound 2 + dimoxystrobin;

C65: compound 2 + fluoxastrobin;

C66: compound 2 + kresoxim-methyl;

C67: compound 2 + picoxystrobin; C68: compound 2 + pyraclostrobin;

C69: compound 2 + trifloxystrobin;

C70: compound 2 + metrafenone;

C71 : compound 2 + proquinazid;

C72: compound 2 + mepanipyrim;

C73: compound 2 + cyprodinil;

C74: compound 2 + iprodione;

C75: compound 2 + procymidone;

C76: compound 2 + carbendazim;

C77: compound 2 + thiophanate-methyl;

C78: compound 2 + fluindapyr;

C79: compound 2 + benalaxyl-M;

C80: compound 2 + fenpyrazamine;

C81 : compound 2 + fluazinam;

C82: compound 2 + tolclofos-methyl;

C83: compound 2 + mandipropamid;

C84: compound 2 + copper oxychloride;

C85: compound 2 + copper salicylate;

C86: compound 2 + chlorothalonil;

C87: compound 2 + cimoxanil;

C88: compound 2 + dimetomorph;

C89: compound 2 + oxathiopiproline;

C90: compound 2 + fluopicolide;

C91 : compound 4 + tetraconazole;

C92: compound 4 + tebuconazole; C93: compound 4 + epoxyconazole; C94: compound 4 + prothioconazole; C95: compound 4 + difenconazole; C96: compound 4 + penconazole; C97: compound 4 + prochloraz;

C98: compound 4 + fenpropimorph; C99: compound 4 + spiroxamine;

CIOO: compound 4 + bixafen;

ClOl: compound 4 + boscalid;

C102: compound 4 + carboxin;

CI 03: compound 4 + fluopyram;

CI 04: compound 4 + fluxapyroxad; CI 05: compound 4 + isopyrazam; C106: compound 4 + penthiopyrad; CI 07: compound 4 + sedaxane;

C108: compound 4 + azoxystrobin; C109: compound 4 + dimoxystrobin; CI 10: compound 4 + fluoxastrobin; CI 11: compound 4 + kresoxim- methyl; CI 12: compound 4 + picoxystrobin; CI 13: compound 4 + pyraclostrobin; CI 14: compound 4 + trifloxystrobin; CI 15: compound 4 + metrafenone; CI 16: compound 4 + proquinazid; CI 17: compound 4 + mepanipyrim; CI 18: compound 4 + cyprodinil;

CI 19: compound 4 + iprodione;

C120: composto 4 + procymidone;

C121: compound 4 + carbendazim;

C122: compound 4 + thiophanate-methyl;

C123: compound 4 + fluindapyr;

C124: compound 4 + benalaxyl-M;

CI 25: compound 4 + fenpyrazamine;

CI 25: compound 4 + fluazinam;

C126: compound 4 + tolclofos-methyl;

CI 27: compound 4 + mandipropamid;

C128: compound 4 + copper oxychloride;

C129: compound 4 + copper salicylate;

CI 30: compound 4 + chlorothalonil;

C131: compound 4 + cimoxanil;

C132: compound 4 + dimetomorph;

C133: compound 4 + oxathiopiproline;

C134: compound 4 + fluopicolide;

C135: compound 1 + pyrachlostrobin;

CI 36: compound 1 + zoxamide;

CI 37: compound 1 + ametoctradin;

C138: compound 1 + metiram;

C139: compound 1 + potassium phosphite;

C140: compound 1+ tetraconazole + azoxystrobin,

C141: compound 1 + pyraclostrobin + tetraconazole; C142: compound 1 + epoxyconazole + azoxystrobin;

C143: compound 1 + pyraclostrobin + epoxyconazole;

C144: compound 1 + azoxystrobin + fluindapyr;

C145: compound 1 + pyraclostrobin + fluindapyr;

C146: compound 1 + fosetyl-aluminium + copper oxychloride;

C147: compound 1 + fosetyl-aluminium + copper salicylate;

C148: compound 1 + fluindapyr+ tetraconazole;

C149: compound 4 + tetraconazole + azoxystrobin;

C150: compound 4 + pyraclostrobin + tetraconazole;

C151: compound 4 + azoxystrobin + fluindapyr;

C152: compound 4+ fluindapyr + tetraconazole;

C153: compound 10 + tetraconazole;

C154: compound 10+ tebuconazole;

C155: compound 10+ epoxyconazole;

C156: compound 10 prothioconazole;

C157: compound 10+ difenoconazole;

C158: compound 10+ penconazole;

C159: compound 10+ prochloraz;

C160: compound 10+ fenpropimorph;

C161: compound 10+ spiroxamine;

C162: compound 10 + bixafen;

C163: compound 10 + boscalid;

C164: compound 10 + carboxin;

C165: compound 10 + fluopyram;

C166: compound 10 + fluxapyroxad; C167: compound 0 + isopyrazam;

C168: compound [0 + penthiopyrad;

C169: compound 10 + sedaxane;

C 170: compound 10 + azoxystrobin;

C171 : compound [0 + dimoxystrobin;

C172: compound 10 + fluoxastrobin;

C173: compound 10 + kresoxim-methyl;

C 174: compound 10 + picoxystrobin;

C175: compound 10 + pyraclostrobin;

C176: compound 10 + trifloxystrobin;

C 177: compound 10 + metrafenone;

C 178: compound 10 + proquinazid;

C179: compound 10 + mepanipyrim;

C180: compound 10 + cyprodinil;

C 181 : compound 10 + iprodione;

C182: compound 10 + procymidone;

C183: compound 10 + carbendazim;

C184: compound 10 + thiophanate-methyl;

C 185: compound 10 + fluindapyr;

C186: compound 10 + benalaxyl-M;

C187: compound 10 + fenpyrazamine;

C 188: compound 10 + fluazinam;

C 189: compound 10 + tolclofos-methyl;

CI 90: compound 10 + mandipropamid;

C191 : compound 10 + copper oxychloride; CI 92: compound 10 + copper salicylate;

CI 93: compound 10 + chlorothalonil;

C194: compound 10 + cimoxanil;

CI 95: compound 10 + dimetomorph;

CI 96: compound 10 + oxathiopiproline;

CI 97: compound 10 + fluopicolide;

C198: compound 106 + tetraconazole;

CI 99: compound 106 + tebuconazole;

C200: compound 106 + epoxyconazole;

C201 : compound 106 + prothioconazole;

C202: compound 106 + difenoconazole;

C203: compound 106 + penconazole;

C204: compound 106 + prochloraz;

C205: compound 106 + fenpropimorph;

C206: compound 106 + spiroxamine;

C208: compound 106 + bixafen;

C209: compound 106 + boscalid;

C210: compound 106 + carboxin;

C211 : compound 106 + fluopyram;

C212: compound 106 + fluxapyroxad;

C213 compound ; 06 + isopyrazam;

C214: compound 106 + penthiopyrad;

C215: compound 106 + sedaxane;

C216: compound 106 + azoxystrobin;

C217: compound 106 + dimoxystrobin; C218: compound 106 + fluoxastrobin;

C219: compound 106 + kresoxim-methyl;

C220: compound 106 + picoxystrobin;

C221 : compound 106 + pyraclostrobin;

C222: compound 106 + trifloxystrobin;

C223: compound 106 + metrafenone;

C224: compound 106 + proquinazid;

C225: compound 106 + mepanipyrim;

C226: compound 106 + cyprodinil;

C227: compound 106 + iprodione;

C228: compound 106 + procymidone;

C229: compound 106 + carbendazim;

C230: compound 106 + thiophanate-methyl;

C231 compound 106 + fluindapyr;

C232: compound 106 + benalaxyl-M;

C233 compound 106 + fenpyrazamine;

C234: compound 106 + fluazinam;

C235: compound 106 + tolclofos-methyl;

C236: compound 106 + mandipropamid;

C237: compound 106 + copper oxychloride;

C238: compound 106 + copper salicylate;

C239: compound 106 + chlorothalonil;

C240: compound 106 + cimoxanil;

C241 : compound 106 + dimetomorph;

C242: compound 106 + oxathiopiproline; C243: compound -06 + fluopicolide;

C244: compound 07 + tetraconazole;

C245: compound 107 + tebuconazole;

C246: compound 107 + epoxyconazole;

C247: compound 107 + prothioconazole;

C248: compound 107 + difenoconazole;

C249: compound 107 + penconazole;

C250: compound 107 + prochloraz;

C251 : compound L07 + fenpropimorph;

C252: compound L07 + spiroxamine;

C253: compound 107 + bixafen;

C254: compound 107 + boscalid;

C255: compound 107 + carboxin;

C256: compound 107 + fluopyram;

C257: compound 107 + fluxapyroxad;

C258: compound 107 + isopyrazam;

C259: compound 107 + penthiopyrad;

C260: compound 107 + sedaxane;

C261 : compound 107 + azoxystrobin;

C262: compound 107 + dimoxystrobin;

C263: compound 107 + fluoxastrobin;

C264: compound 107 + kresoxim-methyl;

C265: compound 107 + picoxystrobin;

C266: compound 107 + pyraclostrobin;

C267: compound 107 + trifloxystrobin; C268: compound 07 + metrafenone;

C269: compound 07 + proquinazid;

C270: compound 07 + mepanipyrim;

C271: compound 07 + cyprodinil;

C272: compound 07 + iprodione;

C273: compound 07 + procymidone;

C274: compound 07 + carbendazim;

C275: compound 07 + thiophanate-methyl;

C276: compound 07 + fluindapyr;

C277: compound 07 + benalaxyl-M;

C278: compound 107 + fenpyrazamine;

C279: compound 07 + fluazinam;

C280: compound 07 + tolclofos-methyl;

C281: compound 07 + mandipropamid;

C282: compound 07 + copper oxychloride;

C283: compound 07 + copper salicylate;

C284: compound 07 + chlorothalonil;

C285: compound 07 + cimoxanil;

C286: compound 07 + dimetomorph;

C287: compound 07 + oxathiopiproline;

C288: compound 107 + fluopicolil;

C289: compound 10+ tetraconazole + azoxystrobin, C290: compound L0 + pyraclostrobin + tetraconazole; C291: compound [0 + epoxyconazole + azoxystrobin; C292: compound 10+ pyraclostrobin + epoxyconazole; C293: compound 10 + azoxystrobin + fluindapyr;

C294: compound 10 + pyraclostrobin + fluindapyr;

C295: compound 10 + fosetyl-aluminium + copper oxychloride;

C296: compound 10 + fosetyl-aluminium + copper salicylate;

C297: compound 10 + fluindapyr+ tetraconazole;

C298: compound 106 + tetraconazole + azoxystrobin,

C299: compound 106 + pyraclostrobin + tetraconazole;

C300: compound 106 + epoxyconazole + azoxystrobin;

C301: compound 106 + pyraclostrobin + epoxyconazole;

C302: compound 106 + azoxystrobin + fluindapyr;

C303: compound 106 + pyraclostrobin + fluindapyr;

C304: compound 106 + fosetyl-aluminium + copper oxychloride;

C305: compound 106 + fosetyl-aluminium + copper salicylate;

C306: compound 106 + fluindapyr+ tetraconazole;

C307: compound 107 + tetraconazole + azoxystrobin,

C308: compound 107 + pyraclostrobin + tetraconazole;

C309: compound 107 + epoxyconazole + azoxystrobin;

C310: compound 107 + pyraclostrobin + epoxyconazole;

C311 : compound 107 + azoxystrobin + fluindapyr;

C312: compound 107 + pyraclostrobin + fluindapyr;

C313: compound 107 + fosetyl-aluminium + copper oxychloride;

C314: compound 107 + fosetyl-aluminium + copper salicylate;

C315: compound 107 + fluindapyr+ tetraconazole

Component A, i.e. the compounds having general formula (I), of the pre\ compositions C1-C315 ai e described and exemplified in Table 1 and specifically these are the following compounds having general formula (I) wherein the substituents have the meanings indicated hereunder:

The synergistic effect of the compositions containing a compound having general formula (I) (component A) and a known fungicide (component B), can be evaluated by applying the Colby formula ("Weeds, 1967, 15, pages 20-22):

Et = EA + EB - (EA x EB): 100

wherein Et is the percentage of expected effectiveness for the composition containing compounds A and B at the doses dA + dB, EA is the percentage of effectiveness observed for component A at the dose dA, EB is the percentage of effectiveness observed for component B at the dose dB.

When the effectiveness observed for the composition A + B (EA + B) is higher than the expected effectiveness according to the Colby formula (EA + B/Et> 1), there is a synergistic effect.

In the case of ternary combinations, the Colby formula, has the form:

Et = EA + EB 1 + EB2 - (EAxEB 1 + EAxEB2 + EB lxEB2)/100 wherein Et is the percentage of expected effectiveness for the composition containing compounds A, B l and B2 at the doses dA + dB l + dB2, EA is the percentage of effectiveness observed for component A at the dose dA, EB l is the percentage of effectiveness observed for component B l at the dose dB l, EB2 is the percentage of effectiveness observed for component B2 at the dose dB2.

When the effectiveness observed for the composition A + B l + B2 (EA + B l + B2) is higher than the expected effectiveness according to the Colby formula (EA + B l + B2 / Et> 1 ), there is a synergistic effect.

A further object of the present invention therefore relates to the use of the compositions comprising at least one amide having general formula (I) for the control of phytopathogenic fungi in agricultural crops.

The main crops which can be protected with the compositions comprising at least one compound having formula (I), alone or combined with at least one other known active ingredient, comprise cereals (wheat, bailey, rye, oats, rice, corn, sorghum, etc.), fruit-trees (apples, pears, plums, peaches, almonds, cherries, bananas, grapevines, strawberries, raspberries, blackberries, etc.), citrus fruit (oranges, lemons, mandarins, grapefruit, etc.), legumes (beans, peas, lentils, soybeans, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, eggplants, peppers, etc.), cucurbits (pumpkins, zucchini, cucumbers, melons, watermelons, etc.), oleaginous plants (sunflower, rapeseed, peanut, castor, coconut, etc.); tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton, nuts.

In particular, the compositions of the present invention have proved to be extremely effective in the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Phytophtora infestans on potatoes, Puccinia Recondita, Erysiphe Graminis, Helminthosporium Teres, Septoria spp and Fusarium spp. on cereals, in the control of Phakopsora Pachyrhizi on soybeans, in the control of Uromyces Appendiculatus on beans, in the control of Venturia Inaequalis on apple trees, in the control of Sphaerotheca F liginea on cucumbers.

Furthermore, the compositions of the present invention are also effective in the control of soil fungi, such as, for example, Rhizoctonia Solani, Sclerotinia spp, Pythium Ultimum on horticultural plants.

The compositions of the present invention are also effective in the control of phytopathogenic bacteria and viruses, preferably Xanthomonas spp., Pseudomonas spp., Erwinia Amylovora, the tobacco mosaic virus.

The compositions object of the present invention are capable of exerting a fungicidal action which can be of a curative, preventive or eradicative nature, and, in general, exhibit a very low or zero phytotoxicity on the crops treated.

If the compositions comprise a compound having general formula (I) and at least one known active ingredient, the weight ratios in the above compositions vary according to the compounds selected and can normally range from 1: 100 to 100: 1, preferably from 1 : 10 to 10: 1.

The total concentration of the active components in the above compositions can vary within a wide range; they generally range from 1% to 99% by weight with respect to the total weight of the composition, preferably from 5 to 90% by weight with respect to the total weight of the composition.

The application of these compositions can take place on any part of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the soil in which the plant grows.

A further object of the present invention therefore relates to a method for controlling phytopathogenic fungi in agricultural crops, which consists in applying effective and non-phytotoxic doses of compounds comprising at least one compound having formula (I), and, optionally, one or more known active ingredients compatible with the same, on any part of the plant to be protected or on the soil.

The concentration of the amide compounds having general formula (I) in the above- mentioned compositions can vary within a wide range; in general, it ranges from 1% to 90% by weight with respect to the total weight of the composition, preferably from 5 to 50% by weight with respect to the total weight of the composition.

The application of these compositions can take place on any part of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the soil in which the plant grows.

A further object of the present invention therefore relates to a method for the control of phytopathogenic fungi in agricultural crops, which consists in applying effective doses of the compounds having formula (I), used as such or formulated in fungicidal compositions as described above.

The quantity of compound to be applied for obtaining the desired effect can vary according to various factors such as, for example, the compound used, the crop to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the method of application, the formulation adopted.

Doses of compound ranging from 10 g to 5 kg per hectare of agricultural crop generally provide a sufficient control.

The following examples are provided for a better understanding of the invention, and should be considered illustrative and non-limitative of the same.

EXAMPLE 1

Preparation of 3-formylamino-2 hydroxy-N- (3,3,5,5-tetramethylcyclohexyl) benzamide.

A solution, prepared separately, obtained by dissolving 4.25 g of N— (3- dimethylaminopropyl)-N'-ethylcarbodiimide chlorohydrate (22.2 mmoles) and 3.10 ml of triethylamine (22.2 mmoles) in 100 ml of dichloromethane, was added dropwise on an ice bath, at about 0°C, to a suspension of 2.68 g of 3-formylamino salicylic acid (14.8 mmoles), 2.30 g of 3,3,5,5-tetramethylcyclohexylamine (14,8 mmol) and 3.40 g of 1 -hydro xybenzotriazole (22.2 mmoles) in 100 ml of dichloromethane. After an hour, the reaction mixture was left to return to room temperature and was left under stirring at this temperature for 24 hours.

After GC-MS and LC-MS control, the reaction mixture was washed with water and the phases were separated. The aqueous phase was re-extracted using dichloromethane and the organic phase was joined and washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 5.12 g of product.

The product thus obtained was purified by silica gel chromatography, eluting with heptane/ethyl acetate 9: 1. 4.19 g of the desired product were obtained.

Yield 88.5%. LC-MS : M + = 318

EXAMPLE 2

Preparation of 3-formylamino-2~[(2-methyl-propanoyl-oxy)methoxy]-N- (3,3,5,5-tetramethylcyclohexyl)benzamide [Compound nr. 1].

4.19 g of 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl) benzamide (13.2 mmoles) dissolved in 45 ml of anhydrous Ν,Ν-dimethylformamide, were added, at - 10°C, to a suspension of 0.58 g of sodium hydride (14.5 mmoles) at 60% in hexane, in 75 ml of anhydrous Ν,Ν-dimethylformamide. The reaction mixture was left at this temperature for 10 minutes, and 4.53 g of iodomethyl isobutyrate (19.80 mmoles) in 30 ml of Ν,Ν-dimethylformamide were then added dropwise and the reaction mixture was left at this temperature for about 1 hour.

After GC-MS and LC-MS control, the reaction mixture was poured into water and ice, recovered with ethyl acetate, washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 5.1 of raw product.

The product thus obtained was purified by means of silica gel chromatography, eluting with heptane/ethyl acetate 9: 1. 3.95 g of the desired product were obtained. Yield 71.6%

LC-MS: M + = 418

EXAMPLE 3

Preparation of 3-(N'-formyl-N'-[(2-methylpropanoyl-oxy)methyl]amino)-2-[(2- methylpropanoyloxy)methoxy]-N-(3,3,5,5-tetramethylcyclohexyl )- benzamide [Compound nr. 4].

4.19 g of 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl) benzamide (13.2 mmoles) dissolved in 45 ml of Ν,Ν-dimethylformamide were added at - 10°C to a suspension of 1.32 g of sodium hydride (33.0 mmoles) at 60% in hexane, in 75 ml of anhydrous N,N-dimethylformamide.

The reaction mixture was left for ten minutes at this temperature, and 9.06 g of iodomethyl isobutyrate (39.60 mmoles) in 30 ml of anhydrous N,N- dimethylformamide were then added dropwise and the reaction mixture was left to return to room temperature and left under stirring for 3 hours.

After GC-MS and LC-MS control, the reaction mixture was poured into water and ice, recovered with ethyl acetate, washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 7.21 of raw product.

The product thus obtained was purified by means of silica gel chromatography, eluting with heptane/ethyl acetate 9: 1. 5.82 g of the desired product were obtained. Yield 85.1%

LC-MS: M + = 518

EXAMPLE 4

Preparation of 2-hydroxy-3-nitro-N-(3,3,5,5-tetramethylcyclohexyl)-benzamid e.

A solution, prepared separately, obtained by dissolving 4.25 g of N— (3- dimethylaminopropyl)-N'-ethylcarbodiimide chlorohydrate (22.2 mmoles) and 3.10 ml of triethylamine (22.2 mmoles) in 100 ml of dichloromethane, was added dropwise on an ice bath, at about 0°C, to a suspension of 2.72 g of 3-nitro salicylic acid (14.8 mmoles), 2.30 g of 3,3,5,5-tetramethylcyclohexylamine (14.8 mmoles) and 3.40 g of 1 -hydro xybenzotriazole (22.2 mmoles) in 100 ml of dichloromethane. After an hour, the reaction mixture was left to return to room temperature and was left under stirring at this temperature for 24 hours.

After GC-MS and LC-MS control, the reaction mixture was washed with water and the phases were separated. The aqueous phase was re-extracted with dichloromethane and the organic phase was joined and washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 4.95 g of product which was used as such for the subsequent reaction.

LC-MS : M + = 320

EXAMPLE 5

Preparation of 3-amino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl)- benzamide.

0.45 g of Pd/C at 10% (0.10% w/w) were added, under a nitrogen atmosphere, to a solution of 4.95g of 2-hydroxy-3-nitro-N-(3,3,5,5-tetramethylcyclohexyl)benzamide (14.8 mmoles theoretical) in 220 ml of ethyl acetate and the reaction mixture was hydrogenated in an autoclave at 3 bars and 30°C for 24 hours.

After GC-MS and LC-MS control, the reaction mixture was filtered on celite to eliminate the catalyst, washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 4.02 g of raw product which was used as such for the subsequent reaction. Yield 93.6%. LC-MS : M + = 290

EXAMPLE 6

Preparation of 3-(N',N'-bis(2-methylpropanoyloxy) methyl]amino)-2-[(2- methylpropanoyloxy)methoxy]-N-(3,3,5,5-tetramethylcyclohexyl ) benzamide [Compound nr. 7].

4.02 g of 3-amino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl)benzamide (13.8 mmoles theoretical) dissolved in 45 ml of Ν,Ν-dimethylformamide were added, at - 10°C, to a suspension in 75 ml of anhydrous Ν,Ν-dimethylformamide, of 2.21 g of sodium hydride (55.20 mmoles) al 60% in hexane. The reaction mixture was left for 10 minutes at this temperature and 12.64 g of iodomethyl isobutyrate (55.20 mmoles) in 60 ml of Ν,Ν-dimethylformamide were then added dropwise and the reaction mixture was left to return to room temperature and left under stirring for 4 hours. After GC-MS and LC-MS control, the reaction mixture was poured into water and ice, recovered with ethyl acetate, washed twice with water and then with a saturated solution of sodium chloride, anhydrified on sodium sulfate, filtered and evaporated to give 9.62 g of raw product.

The product thus obtained was purified by means of silica gel chromatography, eluting with heptane/ethyl acetate 9: 1. 7.53 g of the desired product were obtained. Yield 92.5%.

LC-MS : M + = 590

EXAMPLE 7

Preparation of 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl) benzamide.

A suspension of 4.02 g of 3-amino-2-hydroxy-N-(3, 3,5,5- tetramethylcyclohexyl)benzamide (13.8 mmoles theoretical) in 11.5 ml of formamide was stirred and heated to 150°C for an hour.

After GC-MS and LC-MS control, the reaction mixture was poured into water, extracted twice with ethyl acetate, then anhydrified on sodium sulfate, filtered and evaporated to give 4.40 g of raw product which was purified on silica gel, eluting with a mixture of heptane/ethyl acetate 6:4, obtaining 3.5 g of the desired product. Yield 80.1 %

LC-MS : M + = 318

EXAMPLE 8

Preparation of compounds nr. 2, 3, 5, 6, 8-107.

Compounds nr. 2, 3, 5, 6, 8- 107 having formula (I) indicated in Table 2, were obtained by operating analogously to what is described in the previous examples. Table 2 66



13. NHCHO H 0 0 0

0

14. NHCHO H 0 0 0

0

0

15. NHCHO H 0 0 0

0

16. NHCHO H 0 0 0 *

0

17. NHCHO H 0 0 0

*

0

18. NHCHO H 0 0 0 *

0 Θ 

70

71

74

76

81

Table 3 shows the results of the GC-MS analyses on the samples 2, 3, 5, 6, 8-107. Table 3

Compound Nr. LC-MS: M+

2. 432

3. 416

5. 546

6. 514

8. 632

9. 584

10. 432

11. 446

12. 390

13. 414

14. 398

15. 482

16. 404

17. 418

18. 416

19. 418

20. 446

21. 460

22. 428

23. 430

24. 436

25. 450

26. 389

27. 338

28. 420

29. 448

30. 402 31. 546

32. 446

33 425

34. 470

35. 436

36. 448

37. 432

38. 462

39. 391

40. 405

41. 407

42. 421

43. 347

44. 363

45. 375

46. 363

47. 417

48. 433

49. 445

50. 433

51. 345

52. 387

53. 407

54. 421

55. 435

56. 435

57. 419

58. 447

59. 419

60. 447 61. 419

62. 447

63. 435

64. 449

65. 404

66. 403

67. 435

68. 473

69. 417

70. 419

71. 337

72. 379

73. 409

74. 425

75. 437

76. 353

77. 395

78. 425

79. 441

80. 453

81. 339

82. 381

83. 411

84. 427

85. 439

86. 350

87. 450

88. 392

89. 422

90. 438 91. 435

92. 449

93. 433

94. 449

95. 421

96. 433

97. 435

98. 463

99. 463

100. 451

101. 395

102. 453

103. 411

104. 469

105. 466

106. 377

107. 391

EXAMPLE 9

Determination of the preventive fungicidal activity (5 days) against Puccinia Recondita on wheat,.

Leaves of wheat plants of the Salgemma variety, grown in pots in a conditioned environment at 20°C and 70% of Relative Humidity (RH) were treated by spraying both sides of the leaves with the compound under examination (see Table 4 hereunder) dispersed in a hydroacetone solution at 20% by volume of acetone.

After remaining 5 days in a conditioned environment, the plants were sprayed on both sides of the leaves with an aqueous suspension of conidia of Puccinia Recondita (2 mg of inoculum per 1 ml of solution for infection).

After spraying, the plants were kept in a humidity- saturated environment at a temperature ranging from 18 to 24°C for the incubation period of the fungus (1 day). At the end of this period, the plants were put in a greenhouse with a relative humidity (RH) of 70% and at a temperature of 18-24°C for 14 days.

At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the visual evaluation of the intensity of the infection, both on the parts treated directly with the products (T) and on the parts developed during the implementation of the test (NT).

The fungicidal activity is expressed as a percentage of the reduction, with respect to non-treated seedlings (comparison), in the area of the leaf affected by the disease (100 = full effectiveness; 0 = zero effectiveness).

All of the compounds 1, 2, 3, 5 showed full activity (100%) at the dosage of 250 ppm. At the same time, an evaluation of the phytotoxicity was effected (percentage of leaf necrosis) induced on the wheat seedlings by the application of the products: in this case the evaluation scale ranges from 0 (completely healthy plant) to 100 (completely necrotic plant).

Table 4 indicates the results obtained by carrying out the test described with compounds 1, 2, and 4 compared with compound 504 described in W09927783: CR1: 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl)ben zamide

Table 4

Compound Nr. ppm P5 activity

T NT

1 125 70 60

250 75 65

2 125 60 55

250 70 65

4 125 70 65

250 80 70 CR1 125 50 35

250 65 50

EXAMPLE 10

Determination of the preventive activity (7 days) of the compounds having formula (I) against Plasmopara viticola on vines.

Leaves of vine plants of the Merlot variety, grown in pots, in a conditioned environment, (20+1 °C, 70% of R.H.) were treated by spraying both sides with the compound under examination.

7 days after the treatment, the plants were inoculated with an aqueous suspension of spores of Plasmopara viticola (200,000 spores/cc) by spraying both sides of the leaves with a compressed air gun.

After remaining 24 hours in a humidity- saturated environment, at 21°C the plants were transferred for an incubation period (7 days) in a conditioned environment at 70% of R H. and at 24°C.

At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the infection.

The fungicidal activity was expressed as the reduction percentage, with respect to non-treated seedlings, in the area of the leaf affected by the disease (100 = full effectiveness; 0 = zero effectiveness).

Table 5 indicates the results obtained by carrying out the test described with compounds nr. 1, 2 and 4 compared with compound 504 described in W09927783. CR1: 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl)ben zamide

Table 5

Compound Nr ppm P7 activity

1 30 100 125 100

2 30 95

125 100

4 30 100

125 100

CR1 30 50

125 65

EXAMPLE 11

Determination of the fungicidal activity of the compounds having Formula (I) against Helmintosporium teres on barley.

Leaves of barley plants (cultivar Gemini), grown in pots in a conditioned environment (20+1 °C, 70% of R.H.), were treated by spraying both sides of the leaves with the compounds under examination, dispersed in a hydro-acetate solution at 20% by volume of acetone.

After remaining 5 days in a conditioned environment, the plants were sprayed on both sides of the leaves with an aqueous suspension of conidia of Helmintosporium teres (50,000 conidia per cm 3 (adding Tween 20 - 1 drop/ 100 ml).

The plants were then kept in a controlled environment during the incubation period of the fungus (1 day wet room for infection, 3 days in a cell with R.H. 70% and 0°C for the incubation period, 3 days for wet room evasion, 12 days biological cycle).

At the end of this period (12 days), the fungicidal activity was evaluated according to an evaluation percentage scale from 0 (plant completely infected) to 100 (healthy plant).

Table 6 indicates the results obtained by carrying out the test described with compound nr. 1 compared with compound 504 described in W09927783.

CR1: 3-formylamino-2-hydroxy-N-(3,3,5,5-tetramethylcyclohexyl)ben zamide Table 6

Compound Nr ppm P7 activity

1 125 75

250 80

CR1 125 5

250 15

CLAIMS

1. Amides having general formula (I):

wherein:

R 1 represents a Q-C 12 alkoxyl, a Q-C 12 haloalkoxyl, a C 3 -C 18 cycloalkoxyl, a -NR 4 R 5 group;

R represents a hydrogen atom, a C 2 -C 13 acyl, a C 2 -C 12 alkanoyloxyalkyl d- C 12 , a C 2 -C 12 halo alkanoyloxyalkyl C 1 -C 12 , a C 1 -C 12 alkoxy-Ci-Ci 2 -alkanoyloxyalkyl C1-C12, a Ci-Ci2 haloalkoxy-Ci-Ci2-alkanoyloxyalkyl C1-C12, a C3-C18 cycloalkoxy- Ci-Ci 2 -alkanoyloxyalkyl C 1 -C 12 , an aryloxy C 1 -C 12 alkanoyloxyalkyl C 1 -C 12 , a benzyloxy C 1 -C 12 alkanoyloxyalkyl C 1 -C 12 , a C 4 -C 18 cycloalkanoyloxyalkyl C 1 -C 12 , a C 1 -C 12 aroyloxyalkyl, a C 1 -C 12 benzoyloxyalkyl, a C 1 -C 12 heterocyclylcarbonyloxyalkyl, a C 1 -C 12 alkyloxyalkyl C 1 -C 12 , a C 1 -C 12 halo alky loxy alky 1 C 1 -C 12 , a C 1 -C 12 alkoxy- Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a C 1 -C 12 haloalkoxy-Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a C 3 -C 18 cycloalkoxy Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , an aryloxy Ci-Ci 2 -alkyloxyalkyl C 1 -C 12 , a benzyloxy Ci-Ci 2 -alkyloxyalkyl C1-C12, a C3-C18 cycloalkyloxyalkyl C1-C12, a C1-C12 aryloxyalkyl, a C1-C12 benzyloxyalkyl; a C 1 -C 12 heterocyclyloxyalkyl, a C 4 -C 12 alkanoylthioalkyl C 1 -C 12 , a C 2 -C 12 halo alkanoylthioalkyl C 1 -C 12 , a C 4 -C 18 cycloalkanoylthioalkyl C 1 -C 12 , a d- C 12 aroylthioalkyl, a C 1 -C 12 benzoylthioalkyl; a C 1 -C 12 heterocyclylcarbonylthioalkyl, a C1-C12 alky lthio alky 1 C1-C12, a C1-C12 halo alky lthio alky 1 C1-C12, a C1-C12 alkoxy- Ci-Ci 2 -alkylthioalkyl C 1 -C 12 , a Ci-Ci 2 haloalkoxy-Ci-Ci 2 -alkylthioalkyl C 1 -C 12 , a C 3 -