Fungicidal pyrazoles
View Patent ↗Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, wherein Q 1 is a phenyl ring, naphthalenyl ring system, a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each as described with optional substituents as defined in the disclosure; Q 2 is a phenyl ring, a naphthalenyl ring system, a 5- to 6-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring, or an 8- to 10-membered heteroaromatic bicyclic ring system, each as described with optional substituents as defined in the disclosure; X is O, S(O) m , NR 4 , CR 15 R 16 , C(═O) or C(═S); and R 1 , R 1a , R 2 , R 4 , R 15 , R 16 and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention. Also disclosed are compounds of Formula 2, including all geometric and stereoisomers, and salts thereof, wherein X is NH; and Q 1 , Q 2 and R 2 are as defined for Formula 1; which are useful as intermediates for preparing compounds of Formula 1.
1. A compound selected from Formula 1, N-oxides and salts thereof,
wherein
Q 1 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 3 ;
Q 2 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 3 ;
X is;
R 1 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy or C 2 -C 5 alkoxyalkyl;
R 1a is H; or
R 1a and R 1 are taken together with the carbon atom to which they are attached to form a cyclopropyl ring optionally substituted with up to 2 substituents independently selected from halogen and methyl;
R 2 is CH 3 , CH 2 CH 3 , halogen, cyano, cyanomethyl, halomethyl, hydroxymethyl, methoxy or methylthio; or cyclopropyl optionally substituted with up to 2 substituents independently selected from halogen and methyl;
each R 3 is independently selected from halogen, cyano, nitro, amino, methylamino, dimethylamino, formylamino, C 2 -C 3 alkylcarbonylamino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 1 -C 2 alkylsulfonyloxy, C 1 -C 2 haloalkylsulfonyloxy, C 3 -C 4 cycloalkyl, C 3 -C 7 cycloalkoxy, C 4 -C 6 alkylcycloalkyl, C 4 -C 6 cycloalkylalkyl, C 3 -C 7 halocycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, hydroxy, formyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 alkylcarbonyloxy, —SF 5 , —SCN, C(═S)NR 19 R 20 or -U-V-T;
R 4 is H;
each R 19 and R 20 is independently H or CH 3 ;
each U is independently O, S(═O) w , NR 22 or a direct bond;
each V is independently C 1 -C 6 alkylene, C 2 -C 6 alkenylene, C 3 -C 6 alkynylene, C 3 -C 6 cycloalkylene or C 3 -C 6 cycloalkenylene, wherein up to 3 carbon atoms are independently selected from C(═O), each optionally substituted with up to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 haloalkoxy;
each T is independently cyano, NR 23a R 23b , OR 24 or S(═O) y R 25 ;
each R 22 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl);
each R 23a and R 23b is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl); or
a pair of R 23a and R 23b attached to the same nitrogen atom are taken together with the nitrogen atom to form a 3- to 6-membered heterocyclic ring, the ring optionally substituted with up to 5 substituents independently selected from R 26 ;
each R 24 and R 25 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl);
each R 26 is independently halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy;
each w is independently 0, 1 or 2; 1 and
each y is independently 0, 1 or 2;
provided that:
(a) when Q 2 is a phenyl ring substituted on at least one ortho position with a substituent selected from -U-V-T wherein U is a direct bond, V is a C(=O) and T is NR 23a R 23b or
(b) the compound of Formula 1 is other than
2. A compound of claim 1 wherein
Q 1 is phenyl substituted with from 1 to 4 substituents independently selected from R 3 ; provided that when an R 3 substituent is located at a meta position, then said R 3 substituent is selected from F, Cl, Br and cyano;
Q 2 is phenyl substituted with 1, 2 or 3 substituents independently selected from R 3 , provided that when an R 3 substituent is located at a meta position, then said R 3 substituent is selected from F, Cl, Br and cyano;
R 1 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy or C 2 C 5 alkoxyalkyl;
Rhu 1 a is H;
R 2 is CH 3 , CH 2 CH 3 , Cl or Br; and
each R 3 is independently selected from halogen, cyano, amino, methylamino, dimethylamino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 3 -C 4 cycloalkyl, C(═S)NH 2 and -U-V-T.
3. A compound of claim 2 wherein Q 1 is phenyl substituted with 1, 2 or 3 substituents independently selected from R 3 ;
R 1 is H or C 1 -C 6 alkyl;
R 2 is CH 3 , Cl or Br;
each R 3 is independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy and -U-V-T;
each U is independently O or NH;
each V is independently C 2 -C 4 alkylene;
each T is independently NR 23a R 23b or OR 24 ;
each R 23a and R 23b is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl; and
each R 24 is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl.
4. A compound of claim 3 wherein
at least one of Q 1 and Q 2 is phenyl substituted with 2 or 3 substituents independently selected from R 3 ;
R 1 is H or CH 3 ;
R 2 is CH 3 ; and
each R 3 is independently selected from halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy and C 1 -C 3 haloalkoxy.
5. A compound of claim 4 wherein
Q 1 is phenyl substituted at the 2-, 4- and 6-positions with substituents independently selected from R 3 ; or phenyl substituted at the 2- and 4-positions with substituents independently selected from R 3 ; or phenyl substituted at the 2- and 6-positions with substituents independently selected from R 3 ;
Q 2 is phenyl substituted at the 2-, 4- and 6-positions with substituents independently selected from R 3 ; or phenyl substituted at the 2- and 4-positions with substituents independently selected from R 3 ; or phenyl substituted at the 2- and 6-positions with substituents independently selected from R 3 ;
R 1 is H; and
each R 3 is independently selected from F, Cl, Br, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy and C 1 -C 2 haloalkoxy.
6. A compound of claim 5 wherein
each R 3 is independently selected from F, Cl, Br, cyano, methyl, C 1 -C 2 alkoxy and fluoromethoxy.
7. A compound of claim 6 wherein
each R 3 is independently selected from F, Cl, Br, cyano and methoxy.
8. A compound of claim 1 which is selected from the group:
4-(2-chloro-4-fluorophenyl)-1,3 -dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,
N-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2,6-difluoro-4-methoxyphenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2,6-difluoro-4-methoxyphenyl)-1,3 -dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,
N-(2,6-difluoro-4-methoxyphenyl)-4-(3,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2,4-difluorophenyl)-1,3 -dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5 -amine,
4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N,4-bis(2-chloro-4-fluorophenyl)- 1,3 -dimethyl- 1H-pyrazol-5-amine,
N-(2-chloro-4-fluorophenyl)-4-(2-chloro-6-fluorophenyl)-1,3 -dimethyl-1H-pyrazol-5-amine,
N-(2-chloro-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3- dimethyl-1H-pyrazol-5-amine,
N-(2-chloro-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3- dimethyl-1H-pyrazol-5-amine,
N-(4-chloro-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3- dimethyl-1H-pyrazol-5-amine,
N-(4-chloro-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]amino]-3,5-difluoro-benzonitrile,
N-(2-chloro-4-fluorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine,
N-(2-chloro-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2,6-dichloro-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
3-chloro-4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile,
3-chloro-4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile,
N-(2-bromo-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2-chloro-4-fluorophenyl)-N-(2,4-dichloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2-chloro-4-fluorophenyl)-N-(2,6-dichloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2-bromo-4-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,
N-(4-bromo-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
4-(2-bromo-4-fluorophenyl)-N-(2-chloro-4,6-difluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine,
4-(2-bromo-4-fluorophenyl)-N-(4-chloro-2,6-difluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine,
N-(4-bromo-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine,
N-(2,4-dichloro-6-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2,6-dichloro-4-fluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2-bromo-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine,
N-(4-bromo-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2-bromo-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,
N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-6-fluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine,
4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl- 1H-pyrazol-4-yl]-3-fluorobenzonitrile, and
4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl- 1H-pyrazol-4-yl]-3-fluorobenzonitrile.
9. The compound of claim 1 which is 4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine.
10. A fungicidal composition comprising (a) a compound of claim 1 or
and (b) at least one other fungicide.
11. A fungicidal composition comprising: (a) a compound of claim 1 or
and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
12. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of claim 1 or
13. A composition comprising a compound of claim 1 , and at least one invertebrate pest control compound or agent.
14. A compound of Formula 2 or a salt thereof
wherein
Q 1 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 3 ;
Q 2 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 3 ;
X is NH;
R 2 is CH 3 , CH 2 CH 3 , halogen, cyano, cyanomethyl, halomethyl, hydroxymethyl, methoxy or methylthio; or cyclopropyl optionally substituted with up to 2 substituents independently selected from halogen and methyl;
each R 3 is independently selected from halogen, cyano, nitro, amino, methylamino, dimethylamino, formylamino, C 2 -C 3 alkylcarbonylamino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 1 -C 2 alkylsulfonyloxy, C 1 -C 2 haloalkylsulfonyloxy, C 3 -C 4 cycloalkyl, C 3 -C 7 cycloalkoxy, C 4 -C 6 alkylcycloalkyl, C 4 -C 6 cycloalkylalkyl, C 3 -C 7 halocycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, hydroxy, formyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 alkylcarbonyloxy, —SF 5 , —SCN, C(═S)NR 19 R 20 and -U-V-T;
each R 19 and R 20 is independently H or CH 3 ;
each U is independently O, S(═O) W , NR 22 or a direct bond;
each V is independently C 1 -C 6 alkylene, C 2 -C 6 alkenylene, C 3 -C 6 alkynylene, C 3 -C 6 cycloalkylene or C 3 -C 6 cycloalkenylene, wherein up to 3 carbon atoms are independently selected from C(═O), each optionally substituted with up to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 haloalkoxy;
each T is independently cyano, NR 23a R 23b , OR 24 or S(═O) y R 25 ;
each R 22 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl);
each R 23a and R 23b is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl);
or a pair of R 23a and R 23b attached to the same nitrogen atom are taken together with the nitrogen atom to form a 3- to 6-membered heterocyclic ring, the ring optionally substituted with up to 5 substituents independently selected from R 26 ;
each R 24 and R 25 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 (alkylthio)carbonyl, C 2 -C 6 alkoxy(thiocarbonyl), C 4 -C 8 cycloalkylcarbonyl, C 4 -C 8 cycloalkoxycarbonyl, C 4 -C 8 (cycloalkylthio)carbonyl or C 4 -C 8 cycloalkoxy(thiocarbonyl);
each R 26 is independently halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy;
each w is independently 0, 1 or 2; and
each y is independently 0, 1 or 2;
provided that:
(a) when Q 2 is a phenyl ring substituted on at least one ortho position with a substituent selected from -U-V-T wherein U is a direct bond and T is NR 23a R 23b or OR 24 , then V is other than C(═O); and
(b) when Q 1 is phenyl and Q 2 is 4-(trifluoromethyl)phenyl, then R 2 is other than methyl.
15. A compound of claim 1 wherein
Q 1 is phenyl substituted at the 2- and 4-positions with substituents independently selected from R 3 ;
Q 2 is phenyl substituted at the 2- and 6-positions with substituents independently selected from R 3 ;
R 1 is H;
R 2 is CH 3 ; and
each R 3 is independently selected from F, Cl, Br, cyano and methoxy.
16. A composition of claim 10 wherein component (b) includes at least one compound selected from prothioconazole, metconazole, penthiopyrad and chlorothalonil.
17. A composition of claim 10 wherein component (b) includes at least one compound selected from azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin, pyrametostrobin, pyraoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin, carbendazim, chlorothalonil, quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph, bromuconazole, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, flusilazole, fluxapyroxad, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, proquinazid, prothioconazole, pyriofenone, tebuconazole, triticonazole, famoxadone, prochloraz, penthiopyrad and boscalid.
18. A composition of claim 10 wherein component (a) is a compound of Formula 1 wherein
Q 1 is phenyl substituted at the 2- and 4-positions with substituents independently selected from R 3;
Q 2 is phenyl substituted at the 2- and 6-positions with substituents independently selected from R 3;
R 1 is H;
R ia l is H;
R 2 is CH 3 ; and
each R 3 is independently selected from F, Cl, Br, cyano and methoxy;
and component (b) includes at least one compound selected from prothioconazole, metconazole, penthiopyrad and chlorothalonil.