Heteroarylpiperidine and-piperazine derivatives as fungicides
Heteroarylpiperidine and -piperazine derivatives of the formula (I) in which the symbols are each as defined in the description, and agrochemically active salts thereof, and use thereof for controlling phytopathogenic harmful fungi, and also processes for preparing compounds of the formula (I).
1. A compound of formula (I), or a salt, a metal complex or a N-oxide thereof
in which
A is pyrazol-1-yl which is bonded to L 1 and may contain up to four further substituents, where the substituents on carbon are each independently selected from Z A-2 and the substituents on nitrogen are each independently selected from Z A-3 ,
Z A-2 and R G1 are the same or different and are each independently hydrogen, halogen, hydroxyl, thioxy, nitro, cyano, —C(═O)H, —CO(═O)H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, hydroxyalkyl, formylalkyl, alkoxyalkyl, alkylcarbonylalkyl, alkylcycloalkyl, alkoxy, alkylcycloalkylalkyl, alkylthio, haloalkylthio, alkynylthio, alkenyloxy, alkynyloxy, haloalkoxy, alkoxyalkoxy, alkylcarbonyloxy, halo alkylcarbonyloxy, cycloalkylcarbonylamino, alkylsulphonylamino, haloalkylsulphonylamino, phenylsulphonylamino, cycloalkylalkyl, halocycloalkylalkyl, cycloalkylcycloalkyl, alkoxycarbonyloxy, alkylcarbonylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyloxy, —C(═O)NR 3 R 4 or —NR 3 R 4 ,
Z A-3 are the same or different and are each independently hydrogen, —C(═O)H, —C(═O)NR 3 R 4 , alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, phenylsulphonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, cycloalkoxycarbonyl, phenyl or benzyl,
R 3 , R 4 and R 7 are the same or different and are each independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, benzyl or phenyl,
L 1 is NR L12 or C(R L11 ) 2 ,
R L11 is the same or different and is independently hydrogen, halogen, hydroxyl, cyano, —C(═O)H, —CO(═O)H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxy, alkylthio, haloalkylthio, haloalkoxy, alkylcarbonyloxy, alkylcarbonylamino, alkylcarbonylthio, alkylsulphonyl, haloalkylsulphonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, trialkylsilyloxy, —NR 3 R 4 or —C(═O)NR 3 R 4 ,
or the two R L11 radicals, together with the carbon atom to which they are bonded, form a cyclopropyl ring, or
the two R L11 radicals are ═CH 2 , ═COR 3 , ═NOR 3 or ═CHN(R 3 ) 2 ,
R L12 is hydrogen, —C(═O)H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkylaminocarbonyl, haloalkylaminocarbonyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, cycloalkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, phenyl or benzyl,
Y 1 is oxygen,
X is carbon,
R X2 is hydrogen,
R 2 is oxo, alkyl, alkenyl, haloalkyl, alkoxy, halogen, cyano or hydroxyl,
p is 0, 1 or 2,
G is G 1 or G 3
where the bond identified by “v” is bonded directly to X and where the bond identified by “w” is bonded directly to Q 1 ,
Q 1 is
where the bond identified by “x” is bonded directly to G, and where the bond identified by “y” is bonded directly to —C(═Y 2 )—Y 3 —R 1 ,
R Q1 is bonded to carbon of the 5-membered heterocyclyl of Q 1 :
hydrogen, oxo, halogen, cyano, hydroxyl, nitro, —CHO, —CO(═O)H, —C(═O)NH 2 , —C(═O)NR 3 R 4 , —NR 3 R 4 , alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkylcycloalkyl, halocycloalkylalkyl, alkylcycloalkylalkyl, cycloalkenyl, halocycloalkenyl, alkoxyalkyl, haloalkoxyalkyl, cycloalkoxyalkyl, alkoxyalkoxyalkyl, alkylthioalkyl, formylalkyl, alkylcarbonylalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, haloalkylaminoalkyl, cycloalkylaminoalkyl, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkoxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, cycloalkylaminocarbonyl, hydroxyalkyl, alkoxy, haloalkoxy, cycloalkoxy, halocycloalkoxy, cycloalkylalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkoxyalkoxy, alkylcarbonyloxy, haloalkylcarbonyloxy, cycloalkylcarbonyloxy, alkylcarbonylalkoxy, alkylthio, haloalkylthio, cycloalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, halo alkylsulphonyl, cycloalkylsulphonyl, trialkylsilyl, alkylsulphonylamino, haloalkylsulphonylamino, phenyl or a 5- or 6-membered heteroaryl radical, where the phenyl or the 5- or 6-membered heteroaryl radical may bear up to two further substituents which are each independently selected from: alkenyl, alkenylamino, alkenyloxy, alkenylthio, alkynyl, alkynylamino, alkynyloxy, alkynylthio, alkoxy, alkoxyalkenyl, alkoxyalkynyl, alkoxyalkoxy, alkoxyalkoxyalkyl, alkoxyalkoxycarbonyl, alkoxyalkyl, alkoxyalkylaminocarbonyl, alkoxyalkylcarbonyl, alkoxyamino, alkoxycarbonyl, alkoxycarbonylalkoxy, alkoxycarbonylalkyl, alkoxycarbonylamino, alkoxyhaloalkoxy, alkoxyhaloalkyl, alkyl, alkylamino, alkylaminoalkyl, alkylaminocarbonyl, alkylaminocarbonylalkylamino, alkylaminocarbonylamino, alkylaminosuiphonyl, alkylaminothiocarbonyl, alkylaminothiocarbonylamino, alkylcarbonyl, alkylcarbonylalkoxy, alkylcarbonylamino, alkylcarbonyloxy, alkylcarbonylthio, alkylcycloalkyl, alkylcycloalkylalkyl, alkylsulphinyl, alkylsulphinylalkyl, alkylsulphonyl, alkylsulphonylalkyl, alkylsulphonylamino, alkylsulphonylaminocarbonyl, alkylthio, alkylthioalkyl, alkylthiocarbonyl, alkylthiocarbonyloxy, amino, aminocarbonyl, C(═N—OR 7 )R 8 , C(═O)NHCN, C(═O)OH, cyano, cyanoalkoxy, cyanoalkyl, cycloalkenyl, cycloalkenyloxyalkyl, cycloalkoxy, cycloalkoxyalkyl, cycloalkoxycarbonyl, cycloalkyl, cycloalkylalkoxy, cycloalkylalkoxycarbonyl, cycloalkylalkyl, cycloalkylalkylamino, cycloalkylalkylaminoalkyl, cyclo alkyl amino, cycloalkylaminoalkyl, cycloalkylaminocarbonyl, cycloalkylcarbonyl, cycloalkylcarbonyloxy, cycloalkylcycloalkyl, cycloalkylsulphonyl, cycloalkylthio, dialkoxyalkyl, dialkylamino, dialkylaminoalkyl, dialkylaminocarbonyl, dialkylaminocarbonylamino, dialkylaminosulphonyl, dialkylaminothiocarbonyl, dialkylaminothiocarbonylamino, halogen, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, haloalkoxy, haloalkoxyalkoxy, haloalkoxyalkyl, haloalkoxyamino, haloalkoxycarbonyl, haloalkoxycarbonylamino, haloalkoxyhaloalkoxy, halo alkoxyhaloalkyl, haloalkyl, haloalkylamino, haloalkylaminoalkyl, haloalkylcarbonyl, haloalkylcarbonylamino, haloalkylcarbonyloxy, haloalkylsulphinyl, haloalkylsulphonyl, haloalkylsulphonylamino, haloalkylsulphonylaminocarbonyl, haloalkylthio, halocycloalkenyl, halocycloalkenyloxyalkyl, halocycloalkoxy, halocycloalkoxyalkyl, halocycloalkyl, halocycloalkylalkyl, halocycloalkylcarbonyloxy, halodialkylamino, halodialkylaminoalkyl, hydroxyl, hydroxyalkyl, NHCHO, NHCN, nitro, phenylsulphonylamino, SH, SF 5 , SO 2 NHCN, thioxy, trialkylsilyl, hydrogen; or
R Q1 is bonded to nitrogen of the 5-membered heterocyclyl of Q 1 :
hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, phenyl, benzyl, alkylsulphonyl, phenylsulphonyl, —C(═O)H, alkoxycarbonyl, benzyloxycarbonyl, alkylcarbonylalkyl or alkylcarbonyl,
R 8 is hydrogen, alkyl, alkenyl, haloalkyl, alkoxy, halogen, cyano or hydroxyl,
Y 2 is oxygen,
Y 3 is oxygen, sulphur or —(NR Y3 )—,
R Y3 is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkylalkyl, halocycloalkyl, benzyl, phenyl, NR 3 R 4 , alkylcarbonyl, alkyloxycarbonyl, alkylaminocarbonyl, trialkylsilyl, benzyloxycarbonyl, alkoxy, haloalkoxy, phenoxy or benzyloxy,
R 1 is substituted C 3 -C 7 -cycloalkyl,
where the substituents are each independently selected from -Q 2 , Z 1d , oxo and/or thioxo,
Q 2 is a phenyl ring which bears up to two substituents each independently selected from Z 1f ,
or
Q 2 is a 5- or 6-membered heteroaryl radical which may contain up to two substituents, where the substituents are each independently selected from the following list:
substituents on carbon: hydrogen, halogen, cyano, hydroxyl, formyl, SH, nitro, NR 6 R 7 , alkyl, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkylcycloalkyl, alkylcycloalkylalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxyalkyl, alkoxy, haloalkoxy, alkylcarbonyloxy, alkylcarbonylthio, alkylthio, haloalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, trialkylsilyl or phenyl,
substituents on nitrogen: hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl, cycloalkylalkyl, phenyl, benzyl, alkylsulphonyl, phenylsulphonyl, C(═O)H, alkoxycarbonyl, benzyloxycarbonyl, alkylaminocarbonyl, alkylcarbonylalkyl or alkylcarbonyl,
R 6 are the same or different and are each independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, benzyl, phenyl, alkylsulphonyl, phenylsulphonyl, alkoxycarbonyl, halo alkoxycarbonyl, benzyloxycarbonyl, alkylaminocarbonyl, alkylcarbonylalkyl, alkylcarbonyl, haloalkylcarbonyl or trialkylsilyl,
Z 1d is cyano, halogen, nitro, NR 6 R 7 , alkyl, haloalkyl, cycloalkyl, cycloalkylcycloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, trialkylsilyl, phenyl, hydroxyl, SH, oxo, alkoxy, alkoxyalkoxy, haloalkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkylalkyloxy, halocycloalkyloxy, halocycloalkylalkyloxy, alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonyl, alkylthio or haloalkylthio, or phenoxy,
Z 1f is hydrogen, alkenyl, alkenylamino, alkenyloxy, alkenylthio, alkynyl, alkynylamino, alkynyloxy, alkynylthio, alkoxy, alkoxyalkenyl, alkoxyalkynyl, alkoxyalkoxy, alkoxyalkoxyalkyl, alkoxyalkoxycarbonyl, alkoxyalkyl, alkoxyalkylaminocarbonyl, alkoxyalkylcarbonyl, alkoxyamino, alkoxycarbonyl, alkoxycarbonylalkoxy, alkoxycarbonylalkyl, alkoxycarbonylamino, alkoxyhaloalkoxy, alkoxyhaloalkyl, alkyl, alkylamino, alkylaminoalkyl, alkylaminocarbonyl, alkylaminocarbonylalkylamino, alkylaminocarbonylamino, alkylaminosulphonyl, alkylaminothiocarbonyl, alkylaminothiocarbonylamino, alkylcarbonyl, alkylcarbonylalkoxy, alkylcarbonylamino, alkylcarbonyloxy, alkylcarbonylthio, alkylcycloalkyl, alkylcycloalkylalkyl, alkylsulphinyl, alkylsulphinylalkyl, alkylsulphonyl, alkylsulphonylalkyl, alkylsulphonylamino, alkylsulphonylaminocarbonyl, alkylthio, alkylthioalkyl, alkylthiocarbonyl, alkylthiocarbonyloxy, amino, aminocarbonyl, C(═N—OR 7 )R 8 , C(═O)H, C(═O)NHCN, CO(═O)H, cyano, cyanoalkoxy cyanoalkyl, cycloalkenyl, cycloalkenyloxyalkyl, cycloalkoxy, cycloalkoxyalkyl, cycloalkoxycarbonyl, cycloalkyl, cycloalkylalkoxy, cycloalkylalkoxycarbonyl, cycloalkylalkyl, cycloalkylalkylamino, cycloalkylalkylaminoalkyl, cycloalkyl amino, cycloalkylaminoalkyl, cycloalkylaminocarbonyl, cycloalkylcarbonyl, cycloalkylcarbonyloxy, cycloalkylcycloalkyl, cycloalkylsulphonyl, cycloalkylthio, dialkoxyalkyl, dialkylamino, dialkylaminoalkyl, dialkylaminocarbonyl, dialkylaminocarbonylamino, dialkylaminosulphonyl, dialkylaminothiocarbonyl, dialkylaminothiocarbonylamino, halogen, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, haloalkoxy, haloalkoxyalkoxy, haloalkoxyalkyl, haloalkoxyamino, haloalkoxycarbonyl, haloalkoxycarbonylamino, haloalkoxyhaloalkoxy, haloalkoxyhaloalkyl, haloalkyl, haloalkylamino, haloalkylaminoalkyl, haloalkylcarbonyl, haloalkylcarbonylamino, haloalkylcarbonyloxy, haloalkylsulphinyl, haloalkylsulphonyl, haloalkylsulphonylamino, haloalkylsulphonylaminocarbonyl, halo alkylthio, halocycloalkenyl, halocycloalkenyloxyalkyl, halocycloalkoxy, halocycloalkoxyalkyl, halocycloalkyl, halocycloalkylalkyl, halocycloalkylcarbonyloxy, halodialkylamino, halodialkylaminoalkyl, hydroxyl, hydroxyalkyl, NHCHO, NHCN, nitro, phenylsulphonylamino, SH, SF 5 , SO 2 NHCN, thioxy, or trialkylsilyl,
under the condition that the following compounds are excluded:
2. The compound of formula (I) according to claim 1 ,
in which
A is pyrazol-1-yl which is bonded to L 1 and may contain up to two substituents, where the substituents are each independently methyl, ethyl, chlorine, bromine, fluorine, difluoromethyl or trifluoromethyl.
3. The compound of formula (I) according to claim 1 or 2 ,
in which
L 1 is CHR L1 ,
R L11 is hydrogen, methyl, ethyl or cyclopropyl.
4. The compound of formula (I) according to claim 1 or 2 ,
in which
R Q1 is hydrogen, fluorine, cyano, methyl, trifluoromethyl, difluoromethyl or methoxymethyl, or
R Q1 is a phenyl ring which is bonded to the carbon atom of Q 1 and which bears up to two substituents each independently selected from the group consisting of hydrogen, fluorine, chlorine, nitro, trifluoromethyl, C(═O)H, methyl, ethyl, methoxy, ethoxy, prop-2-yn-1-yloxy, but-2-yn-1-yloxy, pent-2-yn-1-yloxy, but-3-yn-1-yloxy, but-3-en-1-yloxy, 3-chloroprop-2-yn-1-yloxy, cyanomethoxy, and allyloxy.
5. The compound of formula (I) according to claim 1 or 2 ,
in which
Y 2 is oxygen,
Y 3 is oxygen and —(NR Y3 )—,
R Y3 is hydrogen, methyl or cyclopropyl.
6. The compound of formula (I) according to claim 1 or 2 ,
in which
R 1 is substituted cyclopropyl or cyclohexyl, where the substituents are each independently fluorine, chlorine, bromine, cyano, methyl, ethyl or phenyl.
7. A composition for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I) according to claim 1 or 2 , and an agriculturally acceptable inert extender and/or a surfactant.
8. A method for controlling phytopathogenic harmful fungi, comprising applying a compound of formula (I) according to claim 1 or 2 to the phytopathogenic harmful fungi and/or their habitat.
9. A process for preparing a compound of formula (I) according to claim 1 , characterized in that
(A) a compound of formula (II) or (CII) is reacted with a substrate of formula (III) in the presence of a coupling reagent to give a compound of formula (Ia) or (CIa) according to the following scheme:
in which E is A-L 1 (Y 1 ) or acetyl, C 1 -C 4 -alkoxycarbonyl, benzyl or benzyloxycarbonyl and
R 1 , R 2 , G, Q 1 , R 2 , R X2 , Y 3 and p each is defined above, or
(B) a C 1 -C 2 -alkyl ester of formula (IV) or (CIV) is hydrolysed to a carboxylic acid of formula (II) or (CII) according to the following scheme:
in which E is A-L 1 (Y 1 ) or acetyl, C 1 -C 4 -alkoxycarbonyl, benzyl or benzyloxycarbonyl and
G, Q 1 , R 2 , R X2 and p each is defined above, or
(C) a compound of formula (XXVa) or (CXXVa) is reacted with a compound of formula (XXVIc) to give a compound of formula (Ii) and (CIi) according to the following scheme:
in which E is A-L 1 (Y 1 ) or acetyl, C 1 -C 4 -alkoxycarbonyl, benzyl or benzyloxycarbonyl and W vi is chlorine, bromine, iodine, toluenesulphonyloxy, and
X, R Q1 , Q 1 , R 1 , R 2 , R X2 , Y 2 , Y 3 and p each is defined above.
10. A process for producing a composition for controlling phytopathogenic harmful fungi, comprising mixing a compound of formula (I) according to claim 1 or 2 with an agriculturally acceptable inert extender and/or a surfactant.