Fungicidal Heterocyclic Amines

Abstract

Disclosed are compounds of Formula 1, N-oxides, and salts thereof, wherein R 1 , R 2 , R 9a , R 9b , G, W, X, Y, and Z 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.

1 . A compound selected from Formula 1, an N-oxide and salt thereof, 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is H, halogen, cyano, hydroxy, amino, nitro, —CHO or —C(═O)NH 2 ; or C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 2 -C 8  alkylcarbonyl, C 2 -C 8  alkoxycarbonyl, C 2 -C 8  alkylaminocarbonyl, C 3 -C 10  dialkylaminocarbonyl, C 1 -C 6  alkoxy, C 3 -C 8  cycloalkoxy, C 2 -C 8  alkylcarbonyloxy, C 4 -C 10  cycloalkylcarbonyloxy, C 1 -C 6  alkylthio, C 3 -C 8  cycloalkylthio, C 1 -C 6  alkylsulfinyl, C 1 -C 6  alkylsulfonyl, C 3 -C 8  cycloalkylsulfonyl, C 1 -C 6  alkylamino, C 2 -C 8  dialkylamino, C 3 -C 8  cycloalkylamino, C 2 -C 8  alkylcarbonylamino, C 1 -C 6  alkylsulfonylamino, G A , G N  or naphthalenyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, —CHO, —C(═O)OH, —C(═O)NH 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 2 -C 8  alkylcarbonyl, C 2 -C 8  haloalkylcarbonyl, C 4 -C 10  cycloalkylcarbonyl, C 2 -C 8  alkoxycarbonyl, C 4 -C 10  cycloalkoxycarbonyl, C 2 -C 8  alkylaminocarbonyl, C 3 -C 10  dialkylaminocarbonyl, C 4 -C 10  cycloalkylaminocarbonyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 8  cycloalkoxy, C 3 -C 8  halocycloalkoxy, C 4 -C 10  cycloalkylalkoxy, C 2 -C 6  alkenyloxy, C 2 -C 6  haloalkenyloxy, C 2 -C 6  alkynyloxy, C 3 -C 6  haloalkynyloxy, C 2 -C 8  alkoxyalkoxy, C 2 -C 8  alkylcarbonyloxy, C 2 -C 8  haloalkylcarbonyloxy, C 4 -C 10  cycloalkylcarbonyloxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio, C 3 -C 8  cycloalkylthio, C 1 -C 6  alkylsulfinyl, C 1 -C 6  haloalkylsulfinyl, C 1 -C 6  alkylsulfonyl, C 1 -C 6  haloalkylsulfonyl, C 3 -C 8  cycloalkylsulfonyl, C 3 -C 10  trialkylsilyl, C 1 -C 6  alkylamino, C 2 -C 8  dialkylamino, C 1 -C 6  haloalkylamino, C 2 -C 8  halodialkylamino, C 3 -C 8  cycloalkylamino, C 2 -C 8  alkylcarbonylamino, C 2 -C 8  haloalkylcarbonylamino, C 1 -C 6  alkylsulfonylamino, C 1 -C 6  haloalkylsulfonylamino, G A , G N  and phenyl; 
 R 2  is H, cyano, hydroxy, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 2 -C 6  haloalkynyl, C 3 -C 8  cycloalkyl, C 3 -C 8  halocycloalkyl, C 4 -C 10  alkylcycloalkyl, C 4 -C 10  cycloalkylalkyl, C 5 -C 12  alkylcycloalkylalkyl, C 2 -C 8  alkoxyalkyl, C 4 -C 10  cycloalkoxyalkyl or C 3 -C 10  alkoxyalkoxyalkyl; or 
 R 1  and R 2  are taken together with the nitrogen to which they are attached to form a 3- to 7-membered ring, containing ring members in addition to the nitrogen selected from the group consisting of C(R 8 ) 2 , O, S, NR 3 , —C(R 8 )═C(CR 8 )—, —C(R 8 )═N—, —N═N—, C(≡O), C(═S), C(═NR 4 ), S(═O) p (═NR 4 ) q  and SiR 5a R 5b ; 
 each G A  is independently a benzoyl, phenoxy or phenylsulfonyl or a 5- or 6-membered heteroaromatic ring; 
 each G N  is independently a 3- to 7-membered nonaromatic carbocyclic or heterocyclic ring, containing ring members selected from the group consisting of C(R 8 ) 2 , O, S, NR 3 , —C(R 8 )≡C(CR 8 )—, —C(R 8 )≡N—, —N≡N—, C(≡O), C(≡S), C(≡NR 4 ), S(═O) p (═NR 4 ) q  and SiR 5a R 5b ; 
 each R 3  is independently H, cyano, hydroxy, —C(═O)NH 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 2 -C 6  haloalkynyl, C 3 -C 8  cycloalkyl, C 3 -C 8  halocycloalkyl, C 4 -C 10  alkylcycloalkyl, C 4 -C 10  cycloalkylalkyl, C 5 -C 12  alkylcycloalkylalkyl, C 3 -C 8  cycloalkenyl, C 2 -C 8  alkoxyalkyl, C 4 -C 10  cycloalkoxyalkyl, C 3 -C 10  alkoxyalkoxyalkyl, C 2 -C 8  alkylthioalkyl, C 2 -C 8  alkylsulfinylalkyl, C 2 -C 8  alkylsulfonylalkyl, C 2 -C 8  alkylaminoalkyl, C 4 -C 10  dialkylaminoalkyl, C 3 -C 8  haloalkylaminoalkyl, C 4 -C 10  cycloalkylaminoalkyl, C 2 -C 10  alkylcarbonyl, C 2 -C 10  haloalkylcarbonyl, C 4 -C 10  cycloalkylcarbonyl, C 2 -C 10  alkoxycarbonyl, C 4 -C 10  cycloalkoxycarbonyl, C 2 -C 10  alkylaminocarbonyl, C 3 -C 10  dialkylaminocarbonyl, C 4 -C 10  cycloalkylaminocarbonyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 8  cycloalkoxy, C 3 -C 8  halocycloalkoxy, C 4 -C 10  cycloalkylalkoxy, C 2 -C 8  alkoxyalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio, C 3 -C 8  cycloalkylthio, C 1 -C 6  alkylsulfonyl, C 1 -C 6  haloalkylsulfonyl, C 3 -C 8  cycloalkylsulfonyl, C 3 -C 5  trialkylsilyl or C 3 -C 5  halotrialkylsilyl; 
 each R 4  is independently H, cyano, amino, hydroxy, C 1 -C 6  alkyl, C 3 -C 10  cycloalkyl, C 2 -C 6  alkylcarbonyl, C 2 -C 6  haloalkylcarbonyl, C 1 -C 6  alkoxy, phenyl or benzoyl; 
 each R 5a  and R 5b  is independently C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 3 -C 8  cycloalkyl, C 3 -C 8  halocycloalkyl, C 4 -C 10  cycloalkylalkyl, C 4 -C 10  alkylcycloalkyl, C 5 -C 12  alkylcycloalkylalkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy or C 1 -C 6  haloalkoxy; 
 G is benzoyl, phenoxy, phenylethynyl, phenylsulfonyl or —(CR 6a R 6b ) n G B ; 
 G B  is a phenyl ring, naphthalenyl or 5- to 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 5 substituents independently selected from R 7 ; 
 each R 6a  and R 6b  is independently H, halogen, —C(═O)OH, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 3 -C 8  cycloalkyl, C 3 -C 8  halocycloalkyl, C 4 -C 10  cycloalkylalkyl, C 4 -C 8  alkylcycloalkyl, C 5 -C 12  alkylcycloalkylalkyl, C 1 -C 6  haloalkyl, C 2 -C 8  alkoxycarbonyl, C 1 -C 6  alkoxy or C 1 -C 6  haloalkoxy; or 
 R 6a  and R 6b  in geminal configuration are taken together with the carbon atom to which they are attached to form a 3- to 7-membered ring, containing ring members in addition to the carbon atom selected from the group consisting of C(R 8 ) 2 , O, S, NR 3 , —C(R 8 )═C(CR 8 )—, —C(R 8 )═N—, —N═N—, C(═O), C(═S), C(═NR 4 ), S(═O) p (═NR 4 ) q  and SiR 5a R 5b ; 
 R 7  is halogen, cyano, hydroxy, amino, nitro, —CHO, —C(═O)OH, —C(═O)NH 2 , —SO 2 NH 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 2 -C 8  alkylcarbonyl, C 2 -C 8  haloalkylcarbonyl, C 2 -C 8  alkoxycarbonyl, C 4 -C 10  cycloalkoxycarbonyl, C 5 -C 12  cycloalkylalkoxycarbonyl, C 2 -C 8  alkylaminocarbonyl, C 3 -C 10  dialkylaminocarbonyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 2 -C 8  alkylcarbonyloxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio, C 1 -C 6  alkylsulfinyl, C 1 -C 6  haloalkylsulfinyl, C 1 -C 6  alkylsulfonyl, C 1 -C 6  haloalkylsulfonyl, C 1 -C 6  alkylaminosulfonyl, C 2 -C 8  dialkylaminosulfonyl, C 3 -C 10  trialkylsilyl, C 1 -C 6  alkylamino, C 2 -C 8  dialkylamino, C 2 -C 8  alkylcarbonylamino, C 1 -C 6  alkylsulfonylamino, phenyl, pyridinyl or thienyl; 
 each R 8  is independently H, halogen, CN, C 1 -C 3  alkyl or C 1 -C 3  alkoxy; 
 X is N or CR 9e ; 
 Y is N or CR 9d ; 
 W is CR 9e ; 
 Z is CR 9f ; 
 each R 9a , R 9b , R 9e , R 9d , R 9e  and R 9f  is independently H, halogen, nitro, CN, C 1 -C 3  alkyl, C 1 -C 3  haloalkyl, C 3 -C 6  cycloalkyl, C 1 -C 3  alkoxy or C 1 -C 3  haloalkoxy; 
 n is an integer selected from 0 through 6; and 
 p and q are independently 0, 1 or 2 in each instance of S(═O) p (═NR 4 ) q , provided that the sum of p and q is 0, 1 or 2; 
 
       provided that:
 (a) when R 1  is hydroxy, then R 2  is other than hydroxy; and 
 (b) at least one of X or Y is N. 
 
     
     
         2 . A compound of  claim 1  wherein
 R 1  is C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl or G N , each optionally substituted with one or more substituents selected from the group consisting of halogen, cyano, hydroxy, amino, nitro, —CHO, —C(═O)OH, —C(═O)NH 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 8  cycloalkoxy, C 3 -C 8  halocycloalkoxy, C 4 -C 10  cycloalkylalkoxy, C 2 -C 6  alkenyloxy, C 2 -C 6  haloalkenyloxy, C 2 -C 6  alkynyloxy, C 3 -C 6  haloalkynyloxy, C 2 -C 8  alkoxyalkoxy and G N ; 
 R 2  is H or C 1 -C 6  alkyl; 
 G is G B ; and 
 X is N and Y is CH. 
 
     
     
         3 . A compound of  claim 2  wherein
 R 1  is 2-methoxy-1-methylethyl, 2-ethoxy-1-methylethyl, 2-methoxy-1-ethylethyl, 2-ethoxy-1-ethylethyl, 3-methoxy-1-methylpropyl, 3-ethoxy-1-methylpropyl, 1-ethyl-3-methoxypropyl, 3-ethoxy-1-ethylpropyl or tetrahydro-2H-pyran-4-yl; 
 R 2  is H; and 
 G B  is naphthalenyl or a phenyl or pyridinyl ring, each optionally substituted with up to 3 substituents independently selected from halogen, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl and C 1 -C 6  alkoxy. 
 
     
     
         4 . A compound of  claim 3  wherein
 R 1  is 2-methoxy-1-methylethyl or tetrahydro-2H-pyran-4-yl; and 
 G B  is phenyl optionally substituted at the 3 and 5 positions with halogen. 
 
     
     
         5 . A compound of  claim 4  wherein
 G B  is phenyl optionally substituted at the 3 position with halogen. 
 
     
     
         6 . The compound of  claim 1  selected from the group consisting of:
 4-[2-[3-chlorophenyl)amino]-4-pyridinyl]-N-(2-methoxy-1-methylethyl)-2-pyrimidinamine; and 
 4-[2-[2-chloro-6-methylphenyl)amino]-4-pyridinyl]-N-(tetrahydro-2H-pyran-4-yl)-2-pyrimidinamine. 
 
     
     
         7 . A method for controlling plant diseases caused by Ascomycete or Basidiomycete fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a compound having a formula corresponding to of Formula 1 of  claim 1 . 
     
     
         8 . A fungicidal composition comprising (a) a compound having a formula corresponding to of Formula 1 of  claim 1 ; and (b) at least one other fungicide. 
     
     
         9 . A fungicidal composition comprising (1) a fungicidally effective amount of a compound having a formula corresponding to of Formula 1 of  claims 1 ; and (2) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. 
     
     
         10 . The compound of  claim 1  selected from the group consisting of:
 4-[2-[(3-fluorophenyl)amino]-4-pyridinyl]-N-[(1S)-2-methoxy-1-methylethyl]-2-pyrimidinamine; and 
 4-[2-[(3-fluorophenyl)amino]-4-pyridinyl]-N-(tetrahydro-2H-pyran-4-yl)-2-pyrimidinamine.