STEVENSON THOMAS MARTIN (US)
PATEL KANU MAGANBHAI (US)
TAGGI ANDREW EDMUND (US)
STEVENSON THOMAS MARTIN (US)
PATEL KANU MAGANBHAI (US)
| WO2007088876A1 | 2007-08-09 | |||
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| US2891855A | 1959-06-23 |
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| CLAIMS > claimed is: 1. A compound selected from Formula 1, N-oxides and salts thereof, wherein A is a radical selected from the group consisting of B1 and B3 are each independently a radical selected from the group consisting of B2 is a radical selected from the group consisting of 20 Rl !S ; or R1 is -W^E^R2 , -W1LC(=E2)R25, -W!C(=E )LR26, -W1S(0)XNR 8C(=0)R27, -W1S(0)XNR28C(=0)LR27, -W1S(0)xNR28S02LR27 or -W!CN; or R1 is N(R40)R41; or R1 is -GA or -W2GA; each GA is a 4- to 7-membered carbocyclic ring including ring members selected from C(=0), C(=S), C(=NR29), C(=N-OR30) or C=NN(R 9)2; or a 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=S), C(=NR29), C(=N-OR30), or C=NN(R29)2, each ring or ring system optionally substituted with up to five substituents selected from R21 on carbon ring members and R22 on nitrogen ring members; or each GA is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to 2 substituents selected from R21 on carbon ring members and R22 on nitrogen ring members; each El, E2, and E3 is independently O, S, NR28, NOR28, NN(R 8)2, N-CN or N-N02; each L is independently O, N(R31) or S; provided when E3 is O, L is other than O; each R24, R25, R26 and R27 is independently hydrogen; or C1-C6 alkyl, C2-C6 alkenyl, C2-Cg alkynyl or C3-C6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N02, hydroxy, C1-C4 alkoxy, CJ-C4 alkylsulfinyl, 1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino and (C1-C4 alkyl)C3-Cg cycloalkylamino; each R28 is independently H, C1-Cg alkyl or C1-Cg haloalkyl; each R29 is independently H, C^-Cg alkyl, C1-Cg haloalkyl, C1-Cg alkylcarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; each Q1 and Q2 is independently O, S or N(R 1); Q3 is C1-C4 alkylene optionally substituted with up to 4 substituents selected from C1-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl and C3-C6 cycloalkyl; R30 is independently H, C1-Cg alkyl or C1-Cg haloalkyl; R31 is independently H, C1-C6 alkyl or CrCg haloalkyl; R32 is H or C1-Cg alkyl; each x is 0, 1 or 2; W5 is C1-C6 alkylene; W1 is i-C6 alkylene, C2-C6 alkenylene or C2-C6 alkynylene; or -(CH2)20CH2- or -(CH2)3OCH2-; W2 is C1-C6 alkylene; R2 is phenyl or -W3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R21; or -G or -W4G; or H, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH2, -C(=S)NH2, -C(=0)NHCN, -C(=0)NHOH, -SH, -S02NH2, -S02NHCN, -S02NHOH, -SF5, -NHCHO, -NHNH2, -NHOH, -NHCN, -NHC(=0)NH2, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C4-C10 alkylcycloalkyl, C4-Ci0 cycloalkylalkyl, Cg-C^ cycloalkylcycloalkyl, C^CJQ halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C -C8 alkoxyalkyl, C3-C10 alkoxyalkenyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C alkylaminoalkyl, C3-C]o dialkylaminoalkyl, C2-C8 haloalkylaminoalkyl, C4-C10 cycloalkylaminoalkyl, C2-C8 alkylcarbonyl, C2-C haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-CJ2 cycloalkylalkoxycarbonyl, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C2-C5 cyanoalkyl, C1-Cg hydroxyalkyl, C4-C10 cycloalkenylalkyl, C2-C8 haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C2-C8 haloalkoxyhaloalkyl, C4-C10 halocycloalkoxyalkyl, C4-C10 cycloalkenyloxyalkyl, C4-CK) halocycloalkenyloxyalkyl, C3-CJQ dialkoxyalkyl, C3-C10 alkoxyalkylcarbonyl, C3-C10 alkoxycarbonylalkyl, C2-C8 haloalkoxycarbonyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkoxy, C3-C halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C -C8 alkoxyalkoxy, C2-C8 alkylcarbonyloxy, C2-C haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C3-C1o alkylcarbonylalkoxy, C Cg alkylthio, C1-Cg haloalkylthio, C3-C8 cycloalkylthio, C1-Cg alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-Cg haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C3-C8 trialkylsilyl, C3-C8 cycloalkenyloxy, C3-C8 halocycloalkenyloxy, C2-C8 haloalkoxyalkoxy, C2-C8 alkoxyhaloalkoxy, C2-Cg haloalkoxyhaloalkoxy, C3-CJQ alkoxycarbonylalkoxy, C2-Cg alkyl(thiocarbonyl)oxy, C2-C8 alkylcarbonylthio, C2-C8 alkyl(thiocarbonyl)thio, C3-C8 cycloalkylsulfinyl, C1-C6 alkylaminosulfonyl, C2-C8 dialkylarninosulfonyl, C^-C^Q halotrialkylsilyl, C1-Cg alkylamino, C2-Cg dialkylamino, C^-Cg haloalkylamino, C2-Cg halodialkylamino, C3-C8 cycloalkylamino, C2-C8 alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-Cg alkylsulfonylamino, C1-Cg haloalkylsulfonylamino or C4-C10 cycloalkyl(alkyl)amino; or R2 is -W6C(=E4)R33, -W^C^E^R 4, -WSC^E^L!R35, -W6S(0)yNR 7C(=0)R36 or -W6S(0)yNR37C(=0)L!R36; each E4, E5, and E<> is independently O, S, NR37, NOR37, NN(R37)2, N-CN or N-N02; each L1 is independently O, N(R38) or S; each R33, R34, R35 and R36 is independently hydrogen; or C j-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl or C3-C6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N02, hydroxy, C1-C4 alkoxy, CJ-C4 alkylsulfinyl, C C4 alkylsulfonyl, C C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino and (CJ-C4 alkyl)C3-Cg cycloalkylamino; each R37 is independently H, C1-Cg alkyl or C1-Cg haloalkyl; each Q4 and Q5 is independently O, S or N(R38); Q6 is C]-C4 alkylene optionally substituted with up to 4 substituents selected from C1-Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl and C3-C6 cycloalkyl; R38 is independently H, C1-Cg alkyl or C1-C haloalkyl; R39 is H or C1-C6 alkyl; each y is 0, 1 or 2; W7 is C1-C6 alkylene; W6 is C1-C6 alkylene, C2-C6 alkenylene or C2-C6 alkynylene; or -(CH2)2OCH2- or -(CH2)3OCH2-; W3 is C1-Cg alkylene, C2-C6 alkenylene or C2-Cg alkynylene; W4 is C1-C6 alkylene; R3 is H, halogen, cyano, hydroxy, -0"M+, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH2, -C(=S)NH2, -SH, -S02NH2, -S02NHCN, -S02NHOH, -OCN, -SCN, -SF5, -NHNH2, -NHOH, -N=C=0, -N=C=S, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkoxy, C3-C8 halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C -Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C2-C8 alkoxyalkoxy, C2-Cg alkylcarbonyloxy, C2-Cg haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C3-CK) alkylcarbonylalkoxy, C1-Cg alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-Cg alkylsulfinyl, C1-Cg haloalkylsulfinyl, C1-Cg alkylsulfonyl, C1-Cg haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-Cg alkylsulfonyloxy, C1-Cg alkylamino, C2-Cg dialkylamino, C1-Cg haloalkylamino, C2-Cg halodialkylamino, C3-Cg cycloalkylamino, C2-Cg alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-Cg alkylsulfonylamino or C1-Cg haloalkylsulfonylamino; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenyl sulfonyloxy, benzylsulfonyloxy, phenylthio, benzylthio, phenylsulfinyl, benzylsulfinyl, phenylsulfonyl or benzylsulfonyl, each optionally substituted on ring members with up to five substituents selected from R21; M+ is an alkali metal cation or an ammonium cation; R4, R5, R6 and R7 are each independently H, halogen, hydroxy, C1-Cg alkyl, C2-Cg alkenyl, C2-C6 alkynyl, C1-Cg haloalkyl, C1-C6 alkoxy, C1-Cg haloalkoxy, C3-C8 cycloalkoxy or C3-C8 halocycloalkoxy; or phenyl or benzyl, each optionally substituted on ring members with up to five substituents selected from R21; R8 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-C8 cycloalkyl or C3-Cg halocycloalkyl; or benzyl optionally substituted on ring members with up to five substituents selected from R21; R9 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-C8 cycloalkyl, C3-Cg halocycloalkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C -C14 cycloalkylcycloalkyl, C4-CJQ halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl or C2-C8 alkylthioalkyl; R10 is H, halogen, cyano, hydroxy, amino, nitro, SH, -S02NH2, -S02NHCN, -S02NHOH, -OCN, -SCN, -SF5, -NHCHO, -NHNH2, -N3, -NHOH, -NHCN, -NHC(=0)NH2, -N=C=0, -N=C=S, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-Cg haloalkyl, C2-C haloalkenyl, C2-Cg haloalkynyl, C3-C cycloalkyl, C3-C halocycloalkyl, C^-C^Q alkylcycloalkyl, C4-CJQ cycloalkylalkyl, Cg-C14 cycloalkylcycloalkyl, C4-C!o halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, CyCiQ alkoxyalkoxyalkyl or C2-Cg alkylthioalkyl; R1 1 is H, halogen, cyano, hydroxy, amino, C1-Cg alkyl, C2-C6 alkenyl, C2-Cg alkynyl, C1-Cg haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C8 cycloalkyl, C3-Cg halocycloalkyl, C4-CK) alkylcycloalkyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-Cg cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfinylalkyl or C2-Cg alkylsulfonylalkyl; or phenyl optionally substituted with up to five substituents selected from R21; R12 is H, halogen, cyano, hydroxy, amino, C1-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C1-Cg haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, Cg-C14 cycloalkylcycloalkyl, C4-C10 halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-Cg cycloalkenyl, C3-Cg halocycloalkenyl or C2-Cg alkoxycarbonylamino; R13 is H, halogen, cyano, hydroxy, amino, nitro or C2-C alkoxycarbonyl; n is 0, 1, or 2; each R14, R15, R18 and R19 is independently H, halogen, cyano, hydroxy or C1 -Cg alkyl; or a pair of R14 and R18 is taken together as C2-Cg alkylene or C2-C6 alkenylene; R20 is H, C1-C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkoxy, C1-Cg alkyl, C2-C6 alkenyl, C2-Cg alkynyl or C3-Cg cycloalkyl; T is C1-Cg alkylene or C2-Cg alkenylene; each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or 10-membered fused bicyclic ring system, each ring or ring system optionally substituted with up to five substituents selected from R21 on carbon ring members and R22 on nitrogen ring members; each R21 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH2, -C(=S)NH2, -C(=0)NHCN, -C(=0)NHOH, -SH, -S02NH2, -S02NHCN, -S02NHOH, -OCN, -SCN, -SF5, C1-C6 alkyl, C2-C6 alkenyl, C2-Cg alkynyl, C1-Cg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C4-C10 alkylcycloalkyl, C4-CJQ cycloalkylalkyl, C3-Cg cycloalkenyl, C3-C halocycloalkenyl, C2-C alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-C alkylsulfinylalkyl, C2-C alkoxyhaloalkyl, C2-C5 cyanoalkyl, C1-C hydroxyalkyl, C1-Cg alkoxy, C1-Cg haloalkoxy, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-CK) cycloalkylalkoxy, C2-Cg alkenyloxy, C2-C haloalkenyloxy, C2-C alkoxyalkoxy, C2-Cg alkylcarbonyloxy, C1-Cg alkylthio, C1-Cg haloalkylthio, C3-Cg cycloalkylthio, C1-Cg alkylsulfinyl, C1-Cg haloalkylsulfinyl, C1-Cg alkylsulfonyl, C1-Cg haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylamino, C2-C8 dialkylamino, C1-C6 haloalkylamino, C2-Cg halodialkylamino or C3-C8 cycloalkylamino; each R22 is independently C1-Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C^-C^ haloalkyl, C3-C8 cycloalkyl or C2-Cg alkoxyalkyl R40 is C1-C6 alkyl; and R41 is C1-C6 alkyl; or R40 and R41 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or -(CH2)20(CH2)2-. 2. A compound of Claim 1 wherein A is A-l, A-3, A-4, A-5 or A-6; R1 is R1 is -WiC^E^R2 , -W!LC(=E )R25 or -W!C(=E3)LR26; or Rl is N(R40)R41; or R1 is GA or -W2GA; GA is a 9- to 11-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR30) or C=NN(R29), each ring or ring system optionally substituted with up to three substituents selected from R21 on carbon ring members and R22 on nitrogen ring members; or each GA is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring substituted with 1 substituent selected from R22 on one nitrogen ring member; each E1, E2 and E3 is independently O, NOR28 or N(R28)2; L is independently O or N(R31); each R24, R25 and R26 is independently hydrogen; or C1-C4 alkyl or C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, Ci -C2 alkoxy, C1-C2 alkylsulfinyl and C1-C4 alkylsulfonyl; each R28 is independently H, C1-C3 alkyl or haloalkyl; each R29 is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylcarbonyl, C1-C3 alkylsulfonyl or C1-C3 haloalkylsulfonyl; each Q1 and Q2 is independently O or N(R31); Q3 is C2-C3 alkylene optionally substituted with up to 2 substituents selected from CrC4 alkyl; R30 is independently H, C1-C3 alkyl or C 1 -C3 haloalkyl; R31 is independently H, C1-C3 alkyl or C1-C3 haloalkyl; R32 is H or CrC3 alkyl; W1 is C2-C4 alkylene, -(CH2)2OCH2- or -(CH2)3OCH2-; W2 is CrC3 alkylene; W5 is CrC4 alkylene; R2 is phenyl or -W3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R21; or -G; or C j-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C Cg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C4-CJ0 alkylcycloalkyl, C4-C 10 cycloalkylalkyl, C -C14 cycloalkylcycloalkyl, C4-C10 halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C3-C10 alkoxyalkenyl, C4-C10 cycloalkoxyalkyl, C4-C10 cycloalkoxylalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfinylalkyl, C2-Cg alkylsulfonylalkyl, C2-C§ alkylcarbonyl, C4-C J0 cycloalkenylalkyl, C2-Cg haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C2-Cg haloalkoxyhaloalkyl, C4-C10 halocycloalkoxyalkyl, C4-C JQ cycloalkenyloxyalkyl, ^-CJQ halocycloalkenyloxyalkyl, C3-CJQ dialkoxyalkyl, C1-Cg alkoxy, C1-Cg haloalkoxy, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-Cg alkynyloxy, C3-Cg haloalkynyloxy, C2-Cg alkoxyalkoxy, C2-Cg alkylcarbonyloxy, C2-Cg haloalkylcarbonyloxy, C^-C IQ cycloalkylcarbonyloxy, C3-CJQ alkylcarbonylalkoxy, C1-Cg alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-Cg haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-Cg haloalkylsulfonyl, C3-Cg cycloalkylsulfonyl, C3-Cg trialkylsilyl, C3-Cg cycloalkenyloxy, C3-Cg halocycloalkenyloxy, C2-Cg haloalkoxyalkoxy, C2-Cg alkoxyhaloalkoxy, C2-Cg haloalkoxyhaloalkoxy, C3-CJQ alkoxycarbonylalkoxy, C2-C8 alkyl(thiocarbonyl)oxy, C3-Cg cycloalkylsulfinyl or C3-CJQ halotrialkylsilyl; or R2 is -W6C(=E4)R33, -W6L!C(=E5)R34 or -W6C(=E6)L!R35; each E4, E5, and E6 is independently O, NOR37 or NN(R37)2; each L1 is independently O or N(R38); each R33, R34 and R35 is independently hydrogen; or C1-C4 alkyl, C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C!-C2 alkoxy, Ci-C2 alkylsulfinyl and C1-C2 alkylsulfonyl; each R37 is independently H, C1-C^ alkyl or C1-C3 haloalkyl; R38 is independently H, C1-C3 alkyl or C1-C3 haloalkyl; W3 is -CH2-; W6 is C2-C4 alkylene, -(CH2)2OCH2- or -(CH2)3OCH2-; R3 is hydroxy, -0"M+, C2-Cg alkylcarbonyloxy, C2-Cg haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy or C3-C10 alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R21; M+ is a sodium or potassium metal cation; R9 is C1-C6 alkyl; R10 is H, halogen or C1-C6 alkyl; R1 1 is H or C1-C6 alkyl; R12 is H, halogen, cyano, hydroxy, amino or C1-Cg alkyl; each R14, R15, R18 and R19 is H or CH3; R20 is H or CH3; T is -CH2CH2- or -CH=CH-; each G is G-l through G-20 (as depicted in Embodiment 116); r is 0, 1, 2 or 3; each R21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, C1-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C1-C6 haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C4-C10 alkylcycloalkyl, C4-CJQ cycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C§ alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C§ alkylsulfinylalkyl, C2-Cg alkoxyhaloalkyl, C2-C5 cyanoalkyl, C^-Cg hydroxyalkyl, C j-Cg alkoxy, C1-Cg haloalkoxy, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-CK) cycloalkylalkoxy, C2-Cg alkenyloxy, C2-C haloalkenyloxy, C2-Cg alkoxyalkoxy, C2-Cg alkylcarbonyloxy, C1-Cg alkylthio, C Cg haloalkylthio, C3-Cg cycloalkylthio, C1-Cg alkylsulfinyl, C1-Cg haloalkylsulfinyl, C1-Cg alkylsulfonyl, C1-Cg haloalkylsulfonyl or C3-Cg cycloalkylsulfonyl; each R22 is independently C1-Cg alkyl or C1-Cg haloalkyl; R40 is ethyl or /-propyl; and R 1 is ethyl or z'-propyl; or R40 and R41 are taken together as -(CH2)5-, -CH2CH=CHCH2- or -(CH2)20(CH2)2-. 3. A compound of Claim 2 wherein A is A-l, A-3 or A-5; Bl is C-1; B2 is C-3; B3 is C-l; R1 is -GA; each GA is selected from GA-1, GA-2, GA-3, GA-7, GA-8 and GA-9; or each GA is R2 is phenyl or -W3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R21; or -G; or C1-C6 alkyl or C3-C8 cycloalkyl; R3 is hydroxy or C2-C8 alkylcarbonyloxy; R9 is CH2CH3; R10 is H or CH3; T is -CH2CH2-; G is G-2, G-3 or G-15; and R21 is independently halogen, nitro, alkyl, C Cg haloalkyl, C1-Cg alkoxy, C1-Cg haloalkoxy or C1-C6 alkylthio; each R22 is independently CH3 or CH2CF3; and R40 and R41 are taken together as -(CH2)5-, -CH2CH=CHCH2- or -(CH2)20(CH2)2-. 4. A compound of Claim 3 wherein A is A-l; each GA is R2 is phenyl; R30 is H or methyl; R21 halogen or C1-C3 alkyl; and R22 is CH3. 5. A compound of Claim 3 wherein A is A-l; GA is GA-2; R2 is phenyl, 2-thienyl, 5-chloro-2-pyridinyl or cyclopropyl; R3 is hydroxy; and each R14, R15, R18 and R19 is H. 6. A compound of Claim 3 wherein A is A-l; A is A-3; GA is GA-2; R2 is phenyl, 2-thienyl 5-chloro-2-pyridinyl or cyclopropyl; and R3 is hydroxyl. 7. A compound of Claim 2 wherein A is A-l; R1 is each Q1 and Q2 is O; Q3 is C2-alkylene; R32 is H or methyl; W5 is C2-C3 alkylene; R2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl or 2-thienyl; R3 is hydroxy or -OC(=0)CH2CH(CH3)2; and each R14, R15, R18 and R19 is H or CH3. 8. A compound of Claim 7 wherein W5 is C2 alkylene or C3 alkylene; R2 is phenyl, 3-thienyl cyclopropropyl; and R3 is hydroxy. 9. A compound of Formula 1 in Claim 1 selected from -(l,4-Dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-phe nyl-4(3H)-pyrimidinone, -[(2-Hydroxy-6-oxo-l-cyolohexen-l-yl)carbonyl]-6-oxo-2-phenyl- (6H)-pyrimidineacetaldehyde l-(O-methyloxime) -(5-chloro-3-pyridinyl)-3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l- cyclohexen-l-yl)carbonyl]-4(3H)-pyrimidinone, -cyclopropyl-3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l-cyclohexen-l- yl)carbonyl] -4(3H)-pyrimidinone, 3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-4-oxobicyclo[3.2.1]oct-2-en-3- yl)carbonyl]-2-(2-thienyl)-4(3H)-pyrimidinone and 5-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-phenyl-3-(4,5,6,7-tetrahydro-2- methyl-2H-indazol-5-yl)-4(3H)-pyrimidinone. 10. A herbicidal mixture comprising (a) a compound of Formula 1 and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) AHAS inhibitors, (b3) ACCase inhibitors, (b4) auxin mimics, (b5) EPSP inhibitors, (b6) photosystem I electron diverters, (b7) PPO (protoporphyrinogen oxidase) inhibitors, (b8) GS (glutamine synthetase) inhibitors, (b9) VLCFA (very long chain fatty acid) elongase inhibitors, (blO) auxin transport inhibitors, (bl 1) PDS (phytoene desaturase) inhibitors, (bl2) HPPD (4-hydroxyphenyl-pyruvate-dioxygnase) inhibitors, (bl3) HST (homogentisate solenesyltransererase) inhibitors, (bl4) other herbicides including mitotic disruptors, organic arsenicals, asulam, difenzoquat, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, etobenzanid, fosamine, fosamine-ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb, and (bl ) herbicide safeners; and salts of compounds of (bl) through (bl5). 11. The herbicidal mixture of Claim 10 comprising (a) a compound of Claim 1 and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors. 12. The herbicidal mixture of Claim 11 wherein (b) is bromoxynil. 13. The herbicidal mixture of Claim 10 comprising (a) a compound of Claim 1 and (b) at least one additional active ingredient selected from (bl5) herbicide safeners. 14. A herbicidal composition comprising a compound of Claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. 15. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1. |
HERBICIDAL BIS-NITROGEN-CONTAINING OXO HETEROCYCLES
FIELD OF THE INVENTION
This invention relates to certain bis-nitrogen oxo heterocycles, their salts and compositions, and methods of their use for controlling undesirable vegetation. This invention also relates to certain intermediates and a method useful for prepaing these bis-nitrogen heterocycles and their salts.
BACKGROUND OF THE INVENTION
The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
International patent application publication WO 2007/088876 discloses pyridone compounds of Formula i
wherein inter alia R 1 is C 1 -C 6 alkyl; R 2 and R 3 are each independently hydrogen, cyano, or nitro; and A is a A- 1 through A-5 as defined therein as herbicides.
The bis-nitrogen containing oxo heterocycles of the present invention are not disclosed in this publication.
SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides:
wherein
A is a radical selected from the group consisting of
B 1 and B 3 are each independently a radical selected from the group consisting of
B 2 is a radical selected from the group consisting of
Rl is or
R 1 is -W 1 C(=E 1 )R 24 , -W!LC(=E 2 )R 25 , -W 1 C(=E 3 )LR 26 , -W 1 S(0) x NR 28 C(=0)R 27 ,
-W 1 S(0) X NR28C(=0)LR 27 , -W 1 S(0) x NR 8 S0 2 LR 27 or -W!CN; or
R 1 is N(R 40 )R 41 ; or
Rl is -G A or -W 2 G A ;
each G A is a 4- to 7-membered carbocyclic ring including ring members selected from
C(=0), C(=S), C(=NR 29 ), C(=N-OR 30 ) or C= (R 29 ) 2 ; or a 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=S), C(=NR 29 ), C(=N-OR 30 ), or C=NN(R 9 ) 2 , each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; or
each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to 2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each E 1 , E 2 , and E 3 is independently O, S, NR 28 , NOR 28 , NN(R 28 ) 2 , N-CN or N-N0 2 ; each L is independently O, N(R 31 ) or S;
provided when E 3 is O, L is other than O;
each R 24 , R 25 , R 26 and R 27 is independently hydrogen; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N0 2 , hydroxy, C 1 -C 4 alkoxy, CJ-C 4 alkylsulfinyl, Q-C 4 alkylsulfonyl, C1-C4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino and (C1-C 4 alkyl^-C 6 cycloalkylamino;
each R 28 is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
each R 29 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl;
each Q 1 and Q 2 is independently O, S or N(R 31 );
Q 3 is C1-C 4 alkylene optionally substituted with up to 4 substituents selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl and C 3 -C 6 cycloalkyl;
R 30 is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
R 31 is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
R 32 is H or C 1 -C 6 alkyl;
each x is 0, 1 or 2;
W 5 is C 1 -C 6 alkylene;
W 1 is C 1 -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene; or -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -; C 1 -C 6 alkylene;
henyl or -W 3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G or -W 4 G; or H, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -S0 2 NHCN, -S(¾NHOH, -SF 5 , -NHCHO, -NHNH 2 , -NHOH, -NHCN, -NHC(=0)NH 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C Cg haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -Q cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -CJ Q alkylcycloalkyl, C^CJ Q
cycloalkylalkyl, Cg-C 1 4 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 3 -C 10 alkoxyalkenyl, C 4 -CK) cycloalkoxyalkyl, C 3 -C20 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -C 8 alkylsulfinylalkyl, C 2 -C 8 alkylsulfonylalkyl, C 2 -C 8 alkylaminoalkyl, C 3 -CJQ dialkylaminoalkyl, C 2 -C 8 haloalkylaminoalkyl, C 4 -C 10 cycloalkylaminoalkyl, 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, C5-C 12 cycloalkylalkoxycarbonyl, C 2 -C 8
alkylaminocarbonyl, C^-CI Q dialkylaminocarbonyl, C 4 -C 10
cycloalkylaminocarbonyl, C 2 -C5 cyanoalkyl, C 1 -C 6 hydroxyalkyl, C 4 -CK ) cycloalkenylalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -C 8 alkoxyhaloalkyl, C 2 -C 8 haloalkoxyhaloalkyl, C 4 -C 1 g halocycloalkoxyalkyl, C 4 -C 10
cycloalkenyloxyalkyl, C4-C1Q halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C 3 -C 10 alkoxyalkylcarbonyl, C 3 -C 10 alkoxycarbonylalkyl, C 2 -C 8
haloalkoxycarbonyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, C^-C IQ cycloalkylalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 3 -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^- IQ alkylcarbonylalkoxy, 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 8 trialkylsilyl, C 3 -C 8 cycloalkenyloxy, C 3 ~C 8 halocycloalkenyloxy, C 2 -C 8 haloalkoxyalkoxy, C 2 -C 8 alkoxyhaloalkoxy, C 2 -C 8 haloalkoxyhaloalkoxy, C 3 -C 10 alkoxycarbonylalkoxy, C 2 -C 8
alkyl(thiocarbonyl)oxy, C 2 -C 8 alkylcarbonylthio, C 2 -C 8 alkyl(thiocarbonyl)thio, C 3 "C 8 cycloalkylsulfinyl, C Cg alkylaminosulfonyl, C 2 -C 8
dialkylaminosulfonyl, C 3 -C 10 halotrialkylsilyl, C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C 1 -Cg haloalkylamino, C 2 -C 8 halodialkylamino, C 3 -C 8 cycloalkylamino, C 2 -C 8 alkylcarbonylamino, C 2 -C 8 haloalkylcarbonylamino, C 1 -Cg alkylsulfonylamino, C 1 -Cg haloalkylsulfonylamino or C 4 -C 10
cycloalkyl(alkyl)amino; or or
2 is -W 6 C(=E 4 )R 33 , -WSIJC^ES^ 34 ν 6 0(=Εό)Ε^ 3 5, -W 6 S(0) y NR 37 C(=0)R 36 or -λν 6 8(0)^ 37 0(=0)Ε^36;
each E 4 , E 5 , and E 6 is independently O, S, NR 37 , NOR 37 , NN(R 37 ) 2 , N-CN or N-N0 2 ; each L 1 is independently O, N(R 38 ) or S;
each R 33 , R 34 , R 35 and R 36 is independently hydrogen; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N0 2 , hydroxy,
C1-C 4 alkoxy, CJ-C 4 alkylsulfinyl, C C 4 alkylsulfonyl, C C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino and (C1-C 4 alkyl)C 3 -Cg cycloalkylamino;
each R 37 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
each Q 4 and Q 5 is independently O, S or N(R 38 );
Q 6 is C1-C 4 alkylene optionally substituted with up to 4 substituents selected from C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl and C 3 -C 6 cycloalkyl;
R 38 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R59 is H or C 1 -C 6 alkyl;
each y is 0, 1 or 2;
W 7 is C 1 -C 6 alkylene;
W 6 is C 1 -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene; or -(CH 2 ) 2 OCH 2 - or
-(CH 2 ) 3 OCH 2 -;
W 3 is C Cg alkylene, C 2 -C 6 alkenylene or C 2 -Cg alkynylene;
W 4 is C 1 -C 6 alkylene;
R 3 is H, halogen, cyano, hydroxy, -OM + , amino, nitro, -CHO, -C(=0)OH,
-C(=0)NH 2 , -C(=S)NH 2 , -SH, -S0 2 H 2 , -S0 2 NHCN, -S0 2 NHOH, -OCN, -SCN, -SF 5 , -NHNH 2 , -NHOH, -N=C=0, -N=C=S, 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 -Cg alkenyloxy, C 2 -C haloalkenyloxy, C 3 -C5 alkynyloxy,
C 3 -C 6 haloalkynyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -C 8 alkylcarbonyloxy, C 2 -C § haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy, C 3 -C 10
alkylcarbonylalkoxy, C 1 -Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -C 8
cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg
alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -Cg alkylsulfonyloxy, C 1 -Cg alkylamino, C 2 -C 8 dialkylamino, C 1 -Cg
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 or C 1 -Cg haloalkylsulfonylamino; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenyl sulfonyloxy, benzylsulfonyloxy, phenylthio, benzylthio, phenylsulfinyl, benzylsulfinyl, phenylsulfonyl or benzylsulfonyl, each optionally substituted on ring members with up to five substituents selected from R 21 ;
M + is an alkali metal cation or an ammonium cation;
R 4 , R 5 , R 6 and R 7 are each independently H, halogen, hydroxy, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -C 8 cycloalkoxy or C 3 -C 8 halocycloalkoxy; or phenyl or benzyl, each optionally substituted on ring members with up to five substituents selected from R21;
R 8 is H, 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 -Cg haloalkynyl, C 3 -C 8 cycloalkyl or C 3 -C 8 halocycloalkyl; or benzyl optionally substituted on ring members with up to five substituents selected from R 21 ;
R 9 is H, 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 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, Cg-C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5-C22 alkylcycloalkylalkyl, C 3 -Cg cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl or C 2 -Cg alkylthioalkyl;
R 10 is H, halogen, cyano, hydroxy, amino, nitro, SH, -S0 2 NH 2 , -S0 2 NHCN,
-S0 2 NHOH, -OCN, -SCN, -SF 5 , -NHCHO, -NHNH 2 , -N 3 , -NHOH, -NHCN, -NHC(=0)NH 2 , -N=C=0, -N=C=S, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -Cg haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C20 cycloalkylalkyl, Cg-C 14 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5-C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl or C 2 -C 8 alkylthioalkyl;
R 1 1 is H, halogen, cyano, hydroxy, amino, C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 2 -C 6 haloalkenyl, C -C^ haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl or C 2 -Cg alkylsulfonylalkyl; or phenyl optionally substituted with up to five substituents selected from R 21 ;
R 12 is H, halogen, cyano, hydroxy, amino, C 1 -Cg alkyl, C 2 -C alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 2 -Cg 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 -C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5-CJ2 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl or C 2 -Cg alkoxycarbonylamino;
R 13 is H, halogen, cyano, hydroxy, amino, nitro or C 2 -C 8 alkoxycarbonyl;
n is 0, 1, or 2;
each R 14 , R 15 , R 18 and R 19 is independently H, halogen, cyano, hydroxy or C 1 -Cg alkyl; or
a pair of R 14 and R 18 is taken together as C 2 -Cg alkylene or C 2 -Cg alkenylene;
R 20 is H, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 8 cycloalkoxy, C 1 -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 8 cycloalkyl; T is C 1 -Cg alkylene or C 2 -C alkenylene;
each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or
10-membered fused bicyclic ring system, each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each R 21 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -SO2NHCN, -SO2NHOH, -OCN, -SCN, -SF 5 , C R C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl, C 1 -Cg haloalkyl, C 2 -C5 haloalkenyl, C 2 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10
cycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -Cg cycloalkoxy, C 3 ~Cg halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C alkenyloxy, C 2 -C haloalkenyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 1 -C alkylthio, C 1 -Cg haloalkylthio, C 3 -Cg cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 1 -Cg alkylamino, C 2 -Cg dialkylamino, C^-Cg haloalkylamino, C 2 -Cg halodialkylamino or C 3 -Cg cycloalkylamino; each R 22 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C¾ alkynyl, C 1 -Cg haloalkyl, C 3 -C 8 cycloalkyl or C 2 -Cg alkoxyalkyl;
R ° is C 1 -C 6 alkyl; and
R 41 is C 1 -C 6 alkyl; or
R 40 and R 41 are taken together as -(CH 2 ) 4 -, -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or
-(CH 2 ) 2 0(CH 2 ) 2 -.
This invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide, or a salt thereof. This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).
This invention also relates to a herbicidal mixture of (a) a compound of Formula 1 and (b) at least one additional active ingredient.
This invention is also directed to an intermediate compound of Formula 1Q (including all stereoisomers), N-oxides, and salts thereof:
Q
wherein A' is a radical selected from the group consisting of
; and
R 1 , R 2 , B 1 , B 2 , B 3 , T, R 9 and R 10 are as defined above for a compound of Formula 1 which is useful for preparing a compound of Formula 1.
This invention is also directed to a compound of Formula 1R (including all stereoisomers), N-oxides, and salts thereof:
wherein
R 1 is
R 1 is -W i C^E^R 24 , -W ! LC(=E )R 25 or -W ! C(=E )LR 26 ; or
R 1 is N(R 40 )R 41 ; or
R 1 is G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0), C(=N-OR 30 ) or C= N(R 29 ) 2 ; or a 9- to 11-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=N (R 29 ) 2 , each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; or each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to
2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each E 1 , E 2 and E 3 is independently O, NOR 28 or N(R 28 ) 2 ;
L is independently O or N(R 1 );
each R 24 , R 25 and R 26 is independently hydrogen; or CJ-C 4 alkyl or C 3 -C 5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C1-C 2 alkoxy, alkylsulfinyl and
C1-C 4 alkylsulfonyl;
each R 28 is independently H, alkyl or C1-C 3 haloalkyl;
each R 29 is independently H, C 1 -C 3 alkyl, C1-C 3 haloalkyl, C 1 -C 3 alkylcarbonyl,
C1-C 3 alkylsulfonyl or C 1 -C 3 haloalkylsulfonyl;
each Q 1 and Q 2 is independently O or N(R 31 );
Q 3 is C 2 -C 3 alkylene optionally substituted with up to 2 substituents selected from C r C 4 alkyl;
R 30 is independently H, C r C 3 alkyl or C r C 3 haloalkyl; R 31 is independently H, C 1 -C 3 alkyl or C1-C 3 haloalkyl;
R 32 is H or C r C 3 alkyl;
W 5 is C r C 4 alkylene;
W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
R 2 is phenyl or -W 3 (phenyl), each substituted on ring members with up to two
substituents selected from R 21 ; or -G; or C 1 -Cg alkyl or C 3 -C 8 cycloalkyl;
W 3 is C 1 -Cg alkylene, C 2 -C 6 alkenylene or C 2 -Cg alkynylene;
each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or
10-membered fused bicyclic ring system, each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each R 21 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -S0 2 NHCN, -S0 2 NHOH, -OCN, -SCN, -SF 5 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r Cg 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 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -CK) cycloalkoxyalkyl, C 3 -CJQ alkoxyalkoxyalkyl, C 2 -C alkylthioalkyl, C 2 -C 8 alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -Cg cycloalkoxy, C 3 -Cg halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -Cg haloalkenyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 1 -Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C^Cg haloalkylamino, C 2 -C 8 halodialkylamino or C 3 -C 8 cycloalkylamino;
each R 22 is independently C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, C^Cg
haloalkyl, C 3 -C cycloalkyl or C 2 -C 8 alkoxyalkyl;
R 40 is C 1 -Cg alkyl; and
R 41 is C 1 -Cg alkyl; or
R 40 and R 41 are taken together as -(CH 2 ) 4 -, -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or
-(CH 2 ) 2 0(CH 2 ) 2 -.
which is useful for preparing a compound of Formula 1.
This invention is also directed to a compound of Formula IS (including all stereoisomers), N-oxides, and salts thereof:
IS
wherein
R 1 is ; or
R 1 is -WiC^E^R 24 , -W!LC^E^S or -W!C(=E 3 )LR 6; or
R 1 is N(R 40 )R 41 ; or
R 1 is G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 29 ) 2 ; or a 9- to 11-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C= (R 29 )2, each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; or each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to 2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each E 1 , E 2 and E 3 is independently O, NOR 28 or N(R 28 ) 2 ;
L is independently O or N(R 31 );
each R 24 , R 25 and R 26 is independently hydrogen; or C1-C 4 alkyl or C 3 -C 5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C C 2 alkoxy, C 1 -C 2 alkylsulfinyl and C1-C 4 alkylsulfonyl;
each R 28 is independently H, C1-C3 alkyl or haloalkyl;
each R 29 is independently H, C1-C 3 alkyl, C1-C 3 haloalkyl, Ci-C^ alkylcarbonyl, C 1 -C 3 alkylsulfonyl or CJ-C 3 haloalkylsulfonyl;
each Q 1 and Q 2 is independently O or N(R 31 );
Q 3 is C 2 -C 3 alkylene optionally substituted with up to 2 substituents selected from C r C 4 alkyl;
R 30 is independently H, CJ-C 3 alkyl or C!-C 3 haloalkyl; R 31 is independently H, C 1 -C 3 alkyl or C1-C 3 haloalkyl;
R 32 is H or C r C 3 alkyl;
W 5 is C r C 4 alkylene;
W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
R 2 is phenyl or -W 3 (phenyl), each substituted on ring members with up to two
substituents selected from R 21 ; or -G; or C 1 -Cg alkyl or C 3 -C 8 cycloalkyl; W 3 is C 1 -Cg alkylene, C 2 -C 6 alkenylene or C 2 -Cg alkynylene;
each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or
10-membered fused bicyclic ring system, each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each R 21 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -S0 2 NHCN, -S0 2 NHOH, -OCN, -SCN, -SF 5 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r Cg 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 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -CK) cycloalkoxyalkyl, C 3 -CJQ alkoxyalkoxyalkyl, C 2 -C alkylthioalkyl, C 2 -C 8 alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -Cg cycloalkoxy, C 3 -Cg halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -Cg haloalkenyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 1 -Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C^Cg haloalkylamino, C 2 -C 8 halodialkylamino or C 3 -C 8 cycloalkylamino;
each R 22 is independently C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, C^Cg
haloalkyl, C 3 -C cycloalkyl or C 2 -C 8 alkoxyalkyl; and
R 23 is an optionally substituted carbon moiety;
R 40 is C 1 -Cg alkyl;
R 41 is C 1 -Cg alkyl; or
R 40 and R 41 are taken together as -(CH 2 ) 4 -, -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or
-(CH 2 ) 2 0(CH 2 ) 2 - which is useful for preparing a compound of Formula 1. DETAILS OF THE INVENTION
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains", "containing," "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
The transitional phrase "consisting of excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
The transitional phrase "consisting essentially of is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of occupies a middle ground between "comprising" and "consisting of.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms "consisting essentially of or "consisting of."
Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
As referred to herein, the term "seedling", used either alone or in a combination of words means a young plant developing from the embryo of a seed.
As referred to herein, the term "broadleaf used either alone or in words such as
"broadleaf weed" means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons. As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylating" does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for R 1 , R 2 and R 3 . The term "de-alkylating agent" refers to a reagent that cleaves a carbon-carbon or carbon-oxygen bond.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, «-propyl, z ' -propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene" denotes a straight-chain or branched alkanediyl. Examples of "alkylene" include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) and the different butylene isomers. "Alkenylene" denotes a straight-chain or branched alkenediyl containing one olefinic bond. Examples of "alkenylene" include CH=CH, CH 2 CH=CH, CH=C(CH 3 ) and the different butenylene isomers. When examples are provided for two variables being "taken together as a C 2 -Cg alkenylene", these examples are not limiting as to the point of attachment. For example when R 14 and R 18 are taken together as -CH=CHCH 2 - the attachment point of this examplary group is interpreted to be attached to either or the R 14 or R 18 variable (i.e. is equivalent to -CH 2 CH=CH-). "Alkynylene" denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of "alkynylene" include C≡C, CH 2 C≡C, C≡CCH 2 and the different butynylene isomers.
"Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H 2 C=CHCH 2 0, (CH 3 ) 2 C=CHCH 2 0, (CH 3 )CH=CHCH 2 0, (CH 3 )CH=C(CH 3 )CH 2 0 and CH 2 =CHCH 2 CH 2 0. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH 2 0, CH 3 C≡CCH 2 0 and CH 3 C≡CCH 2 CH 2 0. "Alkoxyalkenyl" includes straight-chain or branched alkenyl substituted by an alkoxy group. Examples of "alkoxyalkenyl" include CH 3 OCH=CH, CH 3 C(OCH 3 )=CH and CH 3 CH 2 OCH=CHCH 2 . "Alkoxyalkoxyalkyl" denotes alkoxyalkoxy substitution on alkyl. Examples of "alkoxyalkoxyalkyl" include CH 3 OCH 2 OCH 2 , CH 3 OCH 2 OCH 2 CH 2 , CH 3 CH 2 OCH 2 OCH 2 and CH 3 OCH3CH 2 OCH2CH 2 . "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfmyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH 3 S(0)-, CH 3 CH 2 S(0)-, CH 3 CH 2 CH 2 S(0)-, (CH 3 ) 2 CHS(0)- and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH 3 S(0) 2 -, CH 3 CH 2 S(0) 2 -, CH 3 CH 2 CH 2 S(0) 2 -, (CH 3 ) 2 CHS(0) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. The terms "cycloalkylsulfinyl" and "cycloalkylsulfonyl are defined analogously to the terms "alkylsulfinyl" and "alkylsulfonyl" above.
"Alkyl thioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 ; "alkylsulfinylalkyl" and "alkylsulfonylalkyl" include the corresponding sulfoxides and sulfones, respectively. "Alkylamino" includes an NH radical substituted with straight-chain or branched alkyl. Examples of "alkylamino" include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH. Examples of "dialkylamino" include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N. "Alkylaminoalkyl" denotes alkylamino substitution on alkyl. Examples of "alkylaminoalkyl" include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 , CH 3 CH 2 CH 2 CH 2 NHCH 2 and CH 3 CH 2 NHCH 2 CH 2 . Examples of "dialkylaminoalkyl" include ((CH 3 ) 2 CH) 2 NCH 2 , (CH 3 CH 2 CH 2 ) 2 NCH 2 and CH 3 CH 2 (CH 3 )NCH 2 CH 2 . The term "alkylcarbonylamino" denotes alkyl bonded to a C(=0)NH moiety. Examples of "alkylcarbonylamino" include CH 3 CH 2 C(=0)NH and CH 3 CH 2 CH 2 C(=0)NH.
"Alkylcarbonylthio" denotes a straight-chain or branched alkylcarbonyl attached to and linked through a sulfur atom. Examples of "alkylcarbonylthio" include CH 3 C(=0)S, CH 3 CH 2 CH 2 C(=0)S and (CH 3 ) 2 CHC(=0)S. The term "alkyl(thiocarbonyl)oxy" denotes an alkyl group bonded to a thiocarbonyl moiety attached to and linked through an oxygen atom. Examples of "alkyl(thiocarbonyl)oxy", include CH 3 CH 2 C(=S)0 and CH 3 CH 2 CH 2 C(=S)0. The term "alkyl(thiocarbonyl)thio" refers to an alkyl group bonded to a sulfur atom. Examples "alkyl(thiocarbonyl)thio" include CH 3 CH 2 C(=S)S.
"Trialkylsilyl" includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl. Examples of "halotrialkylsilyl" include CF 3 (CH 3 ) 2 Si-, (CF 3 ) 3 Si-, and CH 2 Cl(CH 3 ) 2 Si-. "Hydroxyalkyl" denotes an alkyl group substituted with one hydroxy group. Examples of "hydroxyalkyl" include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 CH 2 . "Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethyl cyclopropyl, z ' -propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term "cycloalkoxy" denotes cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety. Examples of "alkylcycloalkyl" include methylcyclopropyl, ethylcyclopentyl, and other straight-chain or branched alkyl groups bonded to cycloalkyl moiety. The term "alkoxycycloalkyl" denotes alkoxy substitution on a cycloalkyl moiety. Examples of "alkoxycycloalkyl" include methoxycyclopropyl, ethoxycyclopentyl and other straight -chain or branched alkoxy groups bonded to a cycloalkyl moiety. "Cycloalkylalkoxy" denotes cycloalkylalkyl linked through an oxygen atom attached to the alkyl chain. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. Examples of "cyanocycloalkyl" include 4-cyanocyclohexyl and 3-cyanocyclopentyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1 ,4-cyclohexadienyl.
The term "halogen", either alone or in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted with halogen" includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted with halogen" said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F 3 C-, C1CH 2 -, CF 3 CH 2 - and CF 3 CC1 2 -. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", haloalkylsulfmyl, haloalkylsulfonyl, "haloalkenyloxy", "haloalkynyloxy" "haloalkenyl", "haloalkynyl", "haloalkoxyalkyl", "haloalkoxyalkoxy" "haloalkoxyhaloalkoxy", "haloalkoxyhaloalkyl", "haloalkylamino", "haloalkylaminoalkyl" "halocycloalkoxy", "halocycloalkoxyalkyl", "halocycloalkylalkyl", "halocycloalkenyl", "halocycloalkenyloxy", "halocycloalkenyloxy", "halocycloalkenyloxyalkyl", "alkoxyhaloalkoxy", alkoxyhaloalkyl, haloalkylcarbonyloxy, and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CC1 3 CH 2 0-, HCF 2 CH 2 CH 2 0- and CF 3 CH 2 0-. Examples of "haloalkylthio" include CC1 3 S-, CF 3 S-, CC1 3 CH 2 S- and C1CH 2 CH 2 CH 2 S-. Examples of "haloalkylsulfmyl" include CF 3 S(0)-, CC1 3 S(0)-, CF 3 CH 2 S(0)- and CF 3 CF 2 S(0)-. Examples of "haloalkylsulfonyl" include CF 3 S(0) 2 -, CC1 3 S(0) 2 -, CF 3 CH 2 S(0) 2 - and CF 3 CF 2 S(0) 2 -. Examples of "haloalkenyl" include (C1) 2 C=CHCH 2 - and CF 3 CH 2 CH=CHCH . Examples of "haloalkynyl" include HCsCCHCl-, CF 3 CsC-, CC1 3 C≡C- and FCH 2 C≡CCH 2 -. Examples of "haloalkoxyalkoxy" include CF 3 OCH 2 0-, C1CH 2 CH 2 0CH 2 CH 2 0-, Cl 3 CCH 2 OCH 2 0- as well as branched alkyl derivatives. Examples of "haloalkylamino" include CF 3 (CH 3 )CHNH, (CF 3 ) 2 CHNH and CH 2 C1CH 2 NH. The term "halodialkyl", either alone or in compound words such as "halodialkylamino", means at least one of the two alkyl groups is substituted with at least one halogen atom, and independently each halogenated alkyl group may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "halodialkylamino" include (BrCH 2 CH 2 ) 2 N and BrCH 2 CH 2 (ClCH 2 CH 2 )N.
"Alkylcarbonyl" denotes a straight-chain or branched alkyl moieties bonded to a C(=0) moiety. Examples of "alkylcarbonyl" include CH 3 C(=0)-, CH 3 CH 2 CH 2 C(=0)- and (CH 3 ) 2 CHC(=0)-. Examples of "alkoxycarbonyl" include CH 3 OC(=0)-, CH 3 CH 2 OC(=0)-, CH 3 CH 2 CH 2 OC(=0)-, (CH 3 ) 2 CHOC(=0)- and the different butoxy- or pentoxycarbonyl isomers. The terms "haloalkylcarbonyl" "haloalkoxycarbonyl", "alkoxyalkylcarbonyl", "cycloalkoxycarbonyl", "cycloalkylalkoxycarbonyl" and "cycloalkylaminocarbonyl" are defined analogously.
The term "alkoxycarbonylamino" denotes a straight-chain or branched alkoxy moieties bonded to a C(=0) moiety of carbonylamino group. Examples of "alkoxycarbonylamino" include CH 3 OC(=0)NH- and CH 3 CH 2 OC(=0)NH-. Examples of "alkylaminocarbonyl" include CH 3 NHC(=0), CH 3 CH 2 NHC(=0), CH 3 CH 2 CH 2 NHC(=0), (CH 3 ) 2 CHNHC(=0) and the different butylamino- or pentylaminocarbonyl isomers. Examples of "dialkylaminocarbonyl" include (CH 3 ) 2 NC(=0), (CH 3 CH 2 ) 2 NC(=0), CH 3 CH 2 (CH 3 )NC(=0), (CH 3 ) 2 CH(CH 3 )NC(=0) and CH 3 CH 2 CH 2 (CH 3 )NC(=0). The term "alkylcarbonyloxy" denotes straight-chain or branched alkyl bonded to a C(=0)0 moiety. Examples of "alkylcarbonyloxy" include CH 3 CH 2 C(=0)0 and (CH 3 ) 2 CHC(=0)0. The term "alkylcarbonylalkoxy" denotes alkylcarbonyl bonded to an alkoxy moiety. Examples of "alkylcarbonylalkoxy" include CH 3 C(=0)CH 2 CH 2 0 and CH 3 CH 2 C(=0)CH 2 0. Examples of "alkoxycarbonyloxy" include CH 3 CH 2 CH 2 OC(=0)0 and (CH 3 ) 2 CHOC(=0)0. The term "cycloalkylcarbonyloxy" denotes a cycloalkylcarbonyl group bonded to oxygen. Examples of "cycloalkylcarbonyloxy" include cyclopropyl-C(0)0- and cyclohexyl-C(0)0-.
"Alkylsulfonylamino" denotes an NH radical substituted with alkylsulfonyl. Examples of "alkylsulfonylamino" include CH 3 CH 2 S(=0) 2 NH- and (CH 3 ) 2 CHS(=0) 2 NH-. The term "alkylsulfonyloxy" denotes an alkylsulfonyl group bonded to an oxygen atom. Examples of "alkylsulfonyloxy" include CH 3 S(=0) 2 0-, CH 3 CH 2 S(=0) 2 0-, CH 3 CH 2 CH 2 S(=0) 2 0-, (CH 3 )2CHS(=0)20-, and the different butylsulfonyloxy, pentylsulfonyloxy and hexylsulfonyloxy isomers.
The term "cycloalkoxyalkyl" denotes cycloalkoxy substitution on an alkyl moiety. Examples of "cycloalkoxyalkyl" include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy moieties bonded to straight-chain or branched alkyl groups. The term "cycloalkylthio" denotes cycloalkyl attached to and linked through a sulfur atom such as cyclopropylthio and cyclopentylthio; "cycloalkylsulfonyl" includes the corresponding sulfones. "Alkylcycloalkylalkyl" denotes an alkyl group substituted with alkylcycloalkyl. Examples of "alkylcycloalkylalkyl" include 1-, 2-, 3- or 4-methyl or -ethyl cyclohexylmethyl. The term "cycloalkoxyalkoxyalkyl" denotes a cycloalkoxy moiety attached to the alkoxy moiety of an alkoxyalkyl group. Examples of the term "cycloalkoxyalkoxyalkyl" include (cyclopropyl)OCH 2 OCH 2 -,
(cyclobutyl)OCH 2 CH 2 OCH 2 - or (cyclohexyl)OCH 2 OCH 2 CH 2 -. The term "cycloalkylcycloalkyl" denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (such as Ι,Γ-bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as Ι, -bicyclohexyl-l-yl), and the different cis- and fr «5-cycloalkylcycloalkyl isomers, (such as (1 ?,2S)-l, -bicyclopropyl-2-yl and ( 1 R,2R)- 1 , 1 '-bicyclopropyl-2-yl) .
"Dialkoxyalkyl" denotes two independent alkoxy groups substituted on same carbon of the alkyl group. Examples of "dialkoxyalkyl" include (CH 3 0) 2 CH- and CH 3 CH 2 0(CH 3 0)CH-. "Cycloalkylamino" denotes an NH radical substituted with cycloalkyl. Examples of "cycloalkylamino" include cyclopropylamino and cyclohexylamino. "Cycloalkyl(alkyl)amino" means a cycloalkylamino group where the hydrogen atom is replaced by an alkyl radical. Examples of "cycloalkyl(alkyl)amino" include groups such as cyclopropyl(methyl)amino, cyclobutyl(butyl)amino, cyclopentyl(propyl)amino, cyclohexyl(methyl)amino and the like. The term "cycloalkylaminoalkyl" denotes cycloalkylamino substitution on an alkyl group. Examples of "cycloalkylaminoalkyl" include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to straight-chain or branched alkyl groups.
"Cycloalkylcarbonyl" denotes cycloalkyl bonded to a C(=0) group including, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. The term "cycloalkoxycarbonyl" means cycloalkoxy bonded to a C(=0) group, for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. "Cycloalkylaminocarbonyl" denotes cycloalkylamino bonded to a C(=0) group, for example, cyclopentylaminocarbonyl and cyclohexylaminocarbonyl. "Cycloalkylalkoxycarbonyl" denotes cycloalkylalkoxy bonded to a C(=0) group. Examples of "cycloalkylalkoxycarbonyl" include cyclopropylethoxycarbonyl and cyclopentylmethoxycarbonyl. "Cycloalkylcarbonyloxy" denotes cycloalkylcarbonyl attached to and linked through an oxygen atom. Examples of "cycloalkylcarbonyloxy" include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy.
The term "cycloalkenylalkyl" denotes cycloalkenyl substitution on an alkyl moiety.
Examples of "cycloalkenylalkyl" include cyclobutenylmethyl, cyclopentenylethyl, and other cycloalkenyl moieties bonded to straight-chain or branched alkyl groups. The term "cycloalkenyloxy" denotes cycloalkenyl linked through an oxygen atom such as cyclopentenyloxy and cyclohexenyloxy. The term "cycloalkenyloxyalkyl" denotes cycloalkenyloxy substitution on an alkyl moiety. Examples of "cycloalkenyloxyalkyl" include cyclobutenyloxymethyl, cyclopentenyloxyethyl, and other cycloalkenyloxy moieties bonded to straight-chain or branched alkyl groups.
The term "alkylaminosulfonyl" denotes a straight-chain or branched alkylamino moiety bonded to a sulfonyl group. Examples of an "alkylaminosulfonyl" group include CH 3 NHS(0) 2 - or CH 3 CH 2 CH 2 NHS(0) 2 -. The term "dialkylaminosulfonyl" denotes a straight-chain or branched dialkylamino moiety bonded to a sulfonyl group. Examples of a "dialkylaminosulfonyl" group include (CH 3 ) 2 NS(0) 2 - or (CH 3 CH 2 CH 2 ) 2 NS(0) 2 -.
The total number of carbon atoms in a substituent group is indicated by the "C 1 -C j " prefix where i and j are numbers from 1 to 14. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C 2 alkoxyalkyl designates CH 3 OCH 2 -; C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 )-, CH 3 OCH 2 CH 2 - or CH 3 CH 2 OCH 2 -; and C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 - and CH 3 CH 2 OCH 2 CH 2 -.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R V ) R , r is 1, 2, 3, 4 or 5 in U-l of Exhibit 3. When a group contains a substituent which can be hydrogen, for example R 2 , R3, R4 R5, R6, R7 ? RS, R9 ? RW RU R 12 ? R H R14 R15 ; RIS, R19 OR R 20 ? THEN when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example (R V ) R in Q-29 of Exhibit 2 then hydrogen may be at the position (i.e. when r is 0) even if not recited in the variable group definition. When one or more positions on a group are said to be "not substituted" or "unsubstituted", then hydrogen atoms are attached to take up any free valency.
Unless otherwise indicated, a "ring" or "ring system" as a component of Formula 1 (e.g., substituent G A ) is carbocyclic or heterocyclic. The term "ring system" denotes two or more fused rings. The terms "bicyclic ring system" and "fused bicyclic ring system" denote a ring system consisting of two fused rings, in which either ring can be saturated, partially unsaturated, or fully unsaturated unless otherwise indicated. The term "spirocyclic ring system" denotes two rings fused at a single atom, and can be either carbospirocyclic or heterospirocyclic. The term "ring member" refers to an atom or other moiety (e.g., C(=0), C(=S), S(O) or S(0)2) forming the backbone of a ring or ring system.
The terms "carbocyclic ring", "carbocycle" or "carbocyclic ring system" denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Hiickel's rule, then said ring is also called an "aromatic ring". "Saturated carbocyclic" refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
The terms "heterocyclic ring", "heterocycle" or "heterocyclic ring system" denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogen atoms, no more than 2 oxygen atoms and no more than 2 sulfur atoms. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hiickel's rule, then said ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". Unless otherwise indicated, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
"Aromatic" indicates that each of the ring atoms is essentially in the same plane and has a ^-orbital perpendicular to the ring plane, and that (4n + 2) π electrons, where n is a positive integer, are associated with the ring to comply with Hiickel's rule. The term "aromatic ring system" denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic.
As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
As noted above, G A can be (among others) a 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members, each ring or ring system optionally substituted with up to five substituents as defined in the Summary of the Invention (i.e. R 21 or R 22 ). Examples of 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring systems optionally including ring members selected from C(=0), C(=S), C(=NR 29 ), C(=N-OR 30 ), or C=NN(R 29 )2 and optionally substituted with up to five substituents include the rings V-l through V-l 04 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for G A (i.e. R 21 or R 22 ), and r is typically an integer from 0 to 4. Note that when the attachment point on the V group is illustrated as floating, the V group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the V group by replacement of a hydrogen atom.
Exhibit 1
V-13 V-14 V-15 V-83 V-84
V-101 V-102
V-104
When G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring can be optionally substituted with up to 2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members. Exhibit 1A shows examples of examples of 9-membered partially saturated fused ring systems containing carbon ring members and 2 nitrogen ring members and are optionally substituted by R v (i.e. R 21 or R 22 ). Note that when the attachment point on the T group is illustrated as floating, the T group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the T group by replacement of a hydrogen atom.
T-5 T-6
When G is a 5- or 6-membered heterocyclic ring, it may be attached to the remainder of Formula 1 through any available carbon or nitrogen ring atom, unless otherwise described. When G is (among others) a 5- or 6-membered heterocyclic ring it may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. Examples of a 5- or 6-membered heterocyclic ring optionally substituted with from one or more substituents include the rings Q- 1 through Q-60 illustrated in Exhibit 2 wherein R v is the optional substituent and is any substituent as defined in the Summary of the Invention for R 21 on carbon ring members or R 22 on nitrogen ring members, and r is an integer from 0 to 4, limited by the number of available positions on each Q group. As Q-29, Q-30, Q-36, Q-37, Q-38, Q-39, Q-40, Q-41, Q-42 and Q-43 have only one available position, for these Q groups r is limited to the integers 0 or 1, and r being 0 means that the Q group is unsubstituted and a hydrogen is present at the position indicated by (R v ) r .
Note that when G is a 5- or 6-membered heterocyclic ring optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention for R 21 one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety. Examples of a 5- or 6-membered heterocyclic ring include the rings U-l through U-36 as illustrated in Exhibit 3. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. The optional substituents corresponding to R v can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these U rings, r is typically an integer from 0 to 4, limited by the number of available positions on each U group.
Note that when G comprises a ring selected from U-29 through U-36, U 2 is selected from O, S or N. Note that when U 2 is N, the nitrogen atom can complete its valence by substitution with either H or the substituents corresponding to R v as defined in the Summary of the Invention for U (i.e. R 22 ).
and
As noted above, G can be (among others) an 8-, 9- or 10-membered fused bicyclic ring system optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention (i.e. R 21 or R 22 ). Examples of 8-, 9- or 10-membered fused bicyclic ring system optionally substituted with from one or more substituents include the rings Q-81 through Q-123 illustrated in Exhibit 4 wherein R v is any substituent as defined in the Summary of the Invention for G (i.e. R 21 or R 22 ), and r is typically an integer from 0 to 4.
-121 Q-123
Although R v groups are shown in the structures Q-l through Q-60 and Q-81 through Q-123, it is noted that they do not need to be present since they are optional substituents. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the Q group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the Q group. Note that when the attachment point on the Q group is illustrated as floating, the Q group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the Q group by replacement of a hydrogen atom. Note that some Q groups can only be substituted with less than 4 R v groups (e.g., Q-l through Q-5, Q-7 through Q-48, and Q-52 through Q-60).
A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1 84 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
One skilled in the art will recognize that many of the compound of the invention, as well as intermediate compounds for their preparationcan exist in the form of multiple tautomers. For example, when a compound of Formula 1 is identified by A being A-l, A-2 or A-3, and the R 3 variable being hydroxy or O M + , then said compound of Formula 1 can exist as a "triketone" tautomer or a "di-keto enol" tautomer, or a combination thereof. Likewise, when a compound of Formula 1 is identified by A being A-l, A-2 or A-3, and the R 3 variable being -SH, then said compound of Formula 1 can exist as a "di-keto thioketo" tautomer, a "di-keto thioenol" tautomer or a "keto thioketo enol" tautomer, or a combination thereof. As a further example, a compound of Formula 1Q wherein A' is A'-l, A'-2 or A'-3 can be present as a "di-ketone" tautomer or two possible "keto enol" tautomers, or a combination thereof. Furthermore, acyclic enols (e.g., the fragment A-7 in the definition of the variable A) can exist as tautomers having E and Z configurations. In the context of the present invention, tautomers represent functionally equivalent species, and identification of a compound by one tautomer is to be considered reference to all possible tautomers of the compound unless otherwise indicated
Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides and salts thereof typically exist in more than one form, and Formula 1 thus includes all crystalline and non-crystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1. Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and /n-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as i-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of a compound of Formula 1 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
Embodiments of the present invention as described in the Summary of the Invention also include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):
Embodiment 1. A compound of Formula 1 as described in the Summary of the
Invention wherein A is A-l, A-3, A-4, A-5 or A-6.
Embodiment 2. A compound of Embodiment 1 wherein A is A-l, A-3, A-5 or A-6. Embodiment 3. A compound of Embodiment 2 wherein A is A-l, A-3 or A-5.
Embodiment 4. A compound of Embodiment 3 wherein A is A-l or A-3.
Embodiment 5. A compound of Embodiment 4 wherein A is A- 1.
Embodiment 6. A compound of Embodiment 4 wherein A is A-3.
Embodiment 7. A compound of Formula 1 or any one of Embodiments 1 through 4 wherein A is other than A-l .
Embodiment 8. A compound of Formula 1 or any one of Embodiments 1 through 7 wherein B 1 is C- 1.
Embodiment 9. A compound of Formula 1 or any one of Embodiments 1 through 7 wherein B 1 is C-2. Embodiment 10. A compound of Formula 1 or any one of Embodiments 1 through 9 wherein B 2 is C-3.
Embodiment 11. A compound of Formula 1 or any one of Embodiments 1 through 9 wherein B 2 is C-4.
Embodiment 12. A compound of Formula 1 or any one of Embodiments 1 through 11 wherein B 3 is C-l.
Embodiment 13. A compound of Formula 1 or any one of Embodiments 1 through 11 wherein B 3 is C-2.
Embodiment 14. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein R 1 is
R 1 is -W 1 C(=E 1 )R 24 , -W 1 LC(=E 2 )R 25 or -W!C(=E 3 )LR 26 ; or
R 1 is -G A or -W G A .
Embodiment 15. A compound of Formula 1 or any one of Embodiments 1 through 14 wherein R 1 is
Embodiment 16. A compound of Embodiment 15 wherein each Q 1 and Q 2 is
independently O or N(R 31 ).
Embodiment 17. A compound of Embodiment 16 wherein each Q 1 and Q 2 is O. Embodiment 18. A compound of Formula 1 or any one of Embodiments 1 through 17 wherein Q 3 is C 2 -C 3 alkylene optionally substituted with up to 4 substituents selected from C C 4 alkyl.
Embodiment 19. A compound of Embodiment 18 wherein Q 3 is C 2 -C 3 alkylene optionally substituted with up to 2 substituents selected from C J-C 2 alkyl. Embodiment 20. A compound of Embodiment 19 wherein Q 3 is C 2 -alkylene
optionally substituted with up to 2 substituents selected from C J-C 2 alkyl. Embodiment 21. A compound of Embodiment 20 wherein Q 3 is C 2 -alkylene
optionally substituted with up to 2 substituents selected from methyl.
Embodiment 22. A compound of Formula 1 or any one of Embodiments 1 through 21 wherein W 5 is C r C 4 alkylene.
Embodiment 22 A. A compound of Formula 1 or any one of Embodiments 1 through
22 wherein W 5 is C 2 -C 3 alkylene. Embodiment 22B. A compound of Embodiment 22 wherein W 5 is C 2 alkylene or C 3 alkylene.
Embodiment 23. A compound of Formula 1 or any one of Embodiments 1 through 22 wherein R 32 is H or CJ-C 3 alkyl.
Embodiment 23A. A compound of Embodiment 23 wherein R 32 is H or methyl.
Embodiment 24. A compound of Embodiment 23 wherein R 32 is H.
Embodiment 25. A compound of Embodiment 23 wherein R 32 is i-C^ alkyl.
Embodiment 26. A compound of Embodiment 25 wherein R 32 is methyl.
Embodiment 26 A. A compound of Formula 1 or any one of Embodiments 1 through 14 wherein R 1 is -W 1 C(=E 1 )R 24 , -W!LC(=E 2 )R 25 or -W!C(=E 3 )LR 26 .
Embodiment 27. A compound of Embodiment 26A wherein R 1 is -W 1 C(=E 1 )R 24 . Embodiment 28. A compound of Embodiment 26A wherein R 1 is -W 1 LC(=E 2 )R 25 . Embodiment 29. A compound of Embodiment 26A wherein R 1 is -W 1 C(=E 3 )LR 26 . Embodiment 29 A. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein R 1 is other than -N(R 40 )R 41 .
Embodiment 30. A compound of Formula 1 or any one of Embodiments 1 through 14 or 26A through 29 wherein each E 1 , E 2 , and E 3 is independently O, NOR 28 or
NN(R 28 ) 2 .
Embodiment 31. A compound of Embodiment 27 wherein E 1 is O.
Embodiment 32. A compound of Embodiment 27 wherein E 1 is NOR 28 .
Embodiment 33. A compound of Embodiment 27 wherein E 1 is NN(R 28 )2- Embodiment 34. A compound of Embodiment 28 wherein E 2 is O.
Embodiment 35. A compound of Embodiment 28 wherein E 2 is NOR 28 .
Embodiment 36. A compound of Embodiment 28 wherein E 2 is NN(R 8 ) 2 .
Embodiment 37. A compound of Embodiment 29 wherein E 3 is O.
Embodiment 38. A compound of Embodiment 29 wherein E 3 is NOR 28 .
Embodiment 39. A compound of Embodiment 29 wherein E 3 is NN(R 28 ) 2 .
Embodiment 39A. A compound of Formula 1 or any of Embodiments 1 through 39 wherein each R 28 is independently H, Ci -C 3 alkyl or C 1 -C 3 haloalkyl.
Embodiment 40. A compound of Formula 1 or any one of Embodiments 26A, 28, 29 or 34 through 39 wherein each L is independently O or N(R 31 ); provided when E 3 is O, L is other than O.
Embodiment 41. A compound of Embodiment 40 wherein L is O.
Embodiment 42. A compound of Embodiment 40 wherein L is N(R 31 ).
Embodiment 42 A. A compound of Embodiment 40 or 42 wherein R 31 is
independently H, C 1 -C 3 alkyl or C1-C 3 haloalkyl. Embodiment 42B. A compound of Formula 1 or any one of Embodiments 1 through 42 wherein W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -.
Embodiment 43. A compound Embodiments 42B wherein W 1 is C 1 -C 4 alkylene.
Embodiment 43 B. A compound of Formula 1 or any one of Embodiments 1 through 42 wherein W 2 is C 1 -C 3 alkylene.
Embodiment 44. A compound of Formula 1 or any one of Embodiments 1 through 14 or 27 through 39 wherein each R 24 , R 25 and R 26 is independently hydrogen; or C 1 -C 4 alkyl or C 3 -C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C 1 -C 2 alkoxy, C 1 -C 2 alkylsulfinyl and C j -C 4 alkylsulfonyl.
Embodiment 45. A compound of Embodiment 44 wherein each R 24 , R 25 and R 26 is independently hydrogen; or C 1 -C 2 alkyl or C 3 -C 4 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy and C 1 -C 2 alkoxy.
Embodiment 46. A compound of Formula 1 or any one of Embodiments 1 through 14 wherein R 1 is -G A .
Embodiment 47. A compound of Formula 1 or any one of Embodiments 1 through 14 wherein R 1 is -W 2 G A .
Embodiment 47 A. A compound of any one of Embodiments 46 or 47 wherein each G A is a 4- to 7-membered carbocyclic ring including ring members selected from
C(=0), C(=N-OR 30 ) or C=NN(R 29 ) 2 ; or a 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 9 ) 2 , each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 47B. A compound of any one of Embodiments 46 or 47 wherein each G A is a 4- to 6-membered carbocyclic ring including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 9 ) 2 ; or a 9- to 11-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 9 ) 2 , each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members. Embodiment 48. A compound of Embodiment 47A wherein G A is a 4- to 7-membered carbocyclic ring including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 29 ) 2j each ring optionally substituted with up to three substituents selected from R 21 . Embodiment 49. A compound of Embodiment 48 wherein G A is a 5- or 6-membered carbocyclic ring including ring members selected from C=0, C(=N-OR 30 ) or C=NN(R 29 ) 2 each ring optionally substituted with up to three substituents selected from R 21 .
Embodiment 49 A. A compound of any one of Embodiments 47 A through 49 wherein each R 29 is independently H, C1-C 3 alkyl, C1-C 3 haloalkyl, C1-C 3
alkylcarbonyl, C^C^ alkylsulfonyl or Q-C 3 haloalkylsulfonyl.
Embodiment 49B. A compound of Embodiment 49A wherein each R 29 is
independently C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkylcarbonyl.
Embodiment 49C. A compound of any one of Embodiments 47A through 49 wherein R 30 is independently H, C r C 3 alkyl or C r C 3 haloalkyl.
Embodiment 50. A compound of Formula 1 or Embodiment 47 A wherein G A is a 6- to 12-membered saturated or partially saturated carbospirocyclic or
heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 29 ), each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 50A. A compound of Embodiment 50 wherein G A is a 9- to
11-membered saturated or partially saturated carbospirocyclic or
heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C= N(R 29 ), each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 50B. A compound of Embodiment 50 wherein R 30 is independently H, C r C 3 alkyl or C r C 3 haloalkyl.
Embodiment 50C. A compound of Embodiment 50 wherein each R 29 is C Cg alkyl, C 1 -Cg haloalkyl, C 1 -Cg alkylcarbonyl.
Embodiment 51. A compound of Embodiment 50A wherein G A is selected from
wherein r is 0 to 3; and R v is selected from R 21 .
Embodiment 52. A compound of Embodiment 51 wherein G A is selected from G A -1, G A -2, G A -3, G A -7, G A -8 and G A -9.
Embodiment 53. A compound of Embodiment 52 wherein G A is selected from G A -2 and G A -3.
Embodiment 53 A. A compound of Embodiment 53 wherein G A is G A -2.
Embodiment 53B. A compound of Formula 1 or any one of Embodiments 1 throuh 53A wherein each G A is other than a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to 2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 53C. A compound of Formula 1 or any one of Embodiments 1 through 47 wherein each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring substituted with 1 substituent selected from R 22 on one nitrogen ring member.
Embodiment 53D. A compound of Embodiment 53C wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the remainder of the compound of Formula 1.
Embodiment 53E. A compound of Embodiment 53D wherein each G A is
Embodiment 54. A compound of Formula 1 or any one of Embodiments 1 through 53E wherein R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G; or C 1 -Cg 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 -CJ0 cycloalkylalkyl, Cg-C^ cycloalkylcycloalkyl, C 4 -C 10
halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C alkoxyalkyl, C 3 -CK ) alkoxyalkenyl, C 4 -C 10 cycloalkoxyalkyl, C 4 -C 10 cycloalkoxylalkoxyalkyl, C 3 -C J0 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -C § alkylsulfonylalkyl, C 2 -Cg alkylcarbonyl, C 4 -C 10 cycloalkenylalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -C 8 alkoxyhaloalkyl, C 2 -C 8 haloalkoxyhaloalkyl, C 4 -C JQ halocycloalkoxyalkyl, C 4 -CJ0 cycloalkenyloxyalkyl, C 4 -C 10 halocycloalkenyloxyalkyl, C 3 -CJ0 dialkoxyalkyl, C^-Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -Cg halocycloalkoxy, C 4 -C JQ cycloalkylalkoxy, C 2 -C alkenyloxy, C 2 -Cg haloalkenyloxy, C 3 -Cg alkynyloxy, C 3 -C5 haloalkynyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -C alkylcarbonyloxy, C 2 -Cg haloalkylcarbonyloxy, C -C\ §
cycloalkylcarbonyloxy, C- $ -Ci § alkylcarbonylalkoxy, C 1 -Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -C alkylsulfinyl, C 1 -Cg
haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -C cycloalkylsulfonyl, C 3 -C 8 trialkylsilyl, C 3 -C 8 cycloalkenyloxy, C 3 -Cg halocycloalkenyloxy, C 2 -Cg haloalkoxyalkoxy, C 2 -Cg alkoxyhaloalkoxy, C 2 -C 8 haloalkoxyhaloalkoxy, C 3 -C J0 alkoxycarbonylalkoxy, C 2 -Cg
alkyl(thiocarbonyl)oxy, C 3 -Cg cycloalkylsulfinyl or C 3 -C 10 halotrialkylsilyl; or
-W 6 C(=E 4 )R 33 , -W 6 L!C(=E 5 )R 34 or -\ν 6 0(=Ε 6 )Ε^ 35 .
Embodiment 54 A. A compound of Embodiment 54 wherein R 2 is phenyl or
-W 3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R 21 ; or -G; or C 1 -Cg alkyl or C 3 -Cg cycloalkyl. Embodiment 55. A compound of Embodiment 54 wherein R 2 is -W 6 C(=E )R 24 ,
-W 6 L 1 C(=E 5 )R25 or -W 6 C(=E 6 )L ! R 26 .
Embodiment 56. A compound of Embodiment 55 wherein R 2 is -W 6 C(=E 4 )R 24 . Embodiment 57. A compound of Embodiment 55 wherein is R 2 is -W 6 L 1 C(=E 5 )R 25 . Embodiment 58. A compound of Embodiments 55 wherein R 2 is - ν 6 ϋ(=Ε 6 )1_,¾ 26 .
Embodiment 59. A compound of Formula 1 or any one of Embodiments 1 through 58 wherein each E 4 , E 5 and E 6 is independently O, NOR 37 or N(R 37 )2.
Embodiment 60. A compound of Formula 1 or any one of Embodiments 1 through 56 wherein E 4 is O.
Embodiment 61. A compound of Formula 1 or any one of Embodiments 1 through 56 wherein E 4 is NOR 37 .
Embodiment 62. A compound of Embodiment Formula 1 or any one of Embodiments
1 through 56 wherein E 4 is NN(R 37 ) 2 .
Embodiment 63. A compound of Formula 1 or any one of Embodiments 1 through 55 or 57 wherein E 5 is O.
Embodiment 64. A compound of Formula 1 or any one of Embodiments 1 through 55 or 57 wherein E 5 is NOR 37 .
Embodiment 65. A compound of Formula 1 or any one of Embodiments 1 through 55 or 57 wherein E 5 is NN(R 37 ) 2 .
Embodiment 66. A compound of Formula 1 or any one of Embodiments 1 through 55 or 58 wherein E 6 is O.
Embodiment 67. A compound of Formula 1 or any one of Embodiments 1 through 55 or 58 wherein E 6 is NOR 37 .
Embodiment 68. A compound of Formula 1 or any one of Embodiments 1 through 55 or 58 wherein E6 is NN(R 37 ) 2 .
Embodiment 68 A. A compound of Formula 1 or any one of Embodiments 1 through 68 wherein W 6 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -.
Embodiment 69. A compound of Formula 1 or any one of Embodiments 1 through 68 wherein W 6 is C 2 -C 4 alkylene.
Embodiment 70. A compound of Formula 1 or any one of Embodiments 1 through 55 or 57 through 59 or 63 through 69 wherein each L 1 is independently O or N(R 8).
Embodiment 70A. A compound of any one of Embodiments 59, 61, 64 through 65 or 68 wherein each R 37 is independently H, C1-C 3 alkyl or C1-C 3 haloalkyl.
Embodiment 71. A compound of Formula 1 or any one of Embodiments 1 through 70 wherein each R 33 , R 34 and R 35 is independently hydrogen; or C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, CJ-C 4 alkoxy, C 1 -C 4 alkylsulfinyl and CJ-C 4 alkylsulfonyl.
Embodiment 7 IB. A compound of Embodiment 71 wherein each R 33 , R 34 and R 35 is independently hydrogen; or C1-C 4 alkyl, C 3 -C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C1-C 2 alkoxy, C1-C 2 alkylsulfinyl and C1-C 2
alkylsulfonyl.
Embodiment 72. A compound of Embodiment 7 IB wherein each R 33 , R 34 and R 35 is independently hydrogen; or C J-C 2 alkyl or C 3 -C 4 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy and C J-C 2 alkoxy.
Embodiment 73. A compound of Formula 1 or any one of Embodiments 1 through 72 wherein R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R 21 ; or -G; or C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl.
Embodiment 74. A compound of Embodiment 73 wherein R 2 is phenyl optionally substituted on ring members with up to two substituents selected from R 21 ; or
-G; or C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl.
Embodiment 74 A. A compound of Embodiment 73 wherein R 2 is phenyl; or -G; or C 3 -C 8 cycloalkyl.
Embodiment 74B. A compound of Embodiment 74A wherein R 2 is phenyl, 2-thienyl
5-chloro-2-pyridinyl or cyclopropyl.
Embodiment 74C. A compound of Embodiment 74A wherein R 2 is phenyl, 3-thienyl or cyclopropropyl.
Embodiment 75. A compound of Embodiment 74 wherein R 2 is phenyl,
2- methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 76. A compound of Embodiment 74 wherein R 2 is phenyl,
3- bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 76A. A compound of Embodiment 74A wherein R 2 is 5-chloro-2- pyridinyl.
Embodiment 77. A compound of Embodiment 74 wherein R 2 is phenyl.
Embodiment 78. A compound of Formula 1 or any one of Embodiments 1 through 76 wherein R 2 is other than phenyl.
Embodiment 79. A compound of Embodiment 74 wherein R 2 is 3-thienyl, 2-thienyl or
3-pyridinyl.
Embodiment 79A. A compound of Embodiment 79 wherein R 2 is 2-thienyl. Embodiment 80. A compound of Embodiment 79 wherein R 2 is 3-pyridinyl.
Embodiment 81. A compound of Embodiment 76 wherein R 2 is w-propyl, «-butyl or cyclopropyl.
Embodiment 81 A. A compound of Embodiment 81 wherein R 2 is cyclopropyl.
Embodiment 82. A compound of Formula 1 or any one of Embodiments 1 through 75 wherein W 3 is -CH2-.
Embodiment 83. A compound of Formula 1 or any one of Embodiments 1 through 75 wherein W 4 is -CH 2 -.
Embodiment 84. A compound of Formula 1 or any one of Embodiments 1 through 83 wherein R 3 is hydroxy, -OM + , C 2 -C alkylcarbonyloxy, C 2 -Cg
haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy or C 3 -C 10
alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy,
phenylcarbonyloxy, phenyl sulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R 21 . Embodiment 85. A compound of Embodiment 84 wherein R 3 is hydroxy, -0 ~ M + or C 2 -Cg alkylcarbonyloxy; or phenylsulfonyloxy optionally substituted with up to two substituents selected from R 21 .
Embodiment 86. A compound of Embodiment 85 wherein M + is a sodium or
potassium metal cation.
Embodiment 87. A compound of Embodiment 86 wherein R 3 is hydroxy or C 2 -Cg alkylcarbonyloxy.
Embodiment 88. A compound of Embodiment 87 wherein R 3 is hydroxy or
-OC(=0)CH 2 CH(CH 3 ) 2 .
Embodiment 89. A compound of Formula 1 or any one of Embodiments 1, 7 and 14 through 88 wherein R 4 , R 5 , R 6 and R 7 are each independently H or C 1 -C alkyl.
Embodiment 90. A compound of Formula 1 or any one of Embodiments 1 or 7
wherein R 8 is C 1 -Cg alkyl or C 3 -Cg cycloalkyl.
Embodiment 91. A compound of Embodiment 90 wherein R 8 is CH3, CH2CH3 or cyclopropyl.
Embodiment 92. A compound of Formula 1 or any one of Embodiments 1 through 3 or
14 through 91 wherein R 9 is C 1 -Cg alkyl.
Embodiment 93. A compound of Embodiment 92 wherein R 9 is CH2CH3.
Embodiment 94. A compound of Formula 1 or any one of Embodiments 1 through 3 or 14 through 93 wherein R 10 is H, halogen or C 1 -Cg alkyl.
Embodiment 95. A compound of Embodiment 94 wherein R 10 is H or CH3.
Embodiment 96. A compound of Formula 1 or any one of Embodiments 1, 2 or 14 through 95 wherein R 11 is H or C 1 -C 6 alkyl. Embodiment 97. A compound of Embodiment 96 wherein R 1 1 is H.
Embodiment 98. A compound of Formula 1 or any one of Embodiments 1, 2 or 14 through 97 wherein R 12 is H, halogen, cyano, hydroxy, amino or C 1 -C 6 alkyl. Embodiment 99. A compound of Embodiment 98 wherein R 12 is H, halogen, cyano, C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl.
Embodiment 100. A compound of Embodiment 99 wherein R 12 is CH3, CH2CH3 or cyclopropyl.
Embodiment 101. A compound of Formula 1 or any one of Embodiments 1 or 14 through 100 wherein R 13 is H, halogen, cyano or nitro.
Embodiment 102. A compound of Embodiment 101 wherein R 13 is cyano or nitro.
Embodiment 103. A compound of Formula 1 or any one of Embodiments 1 through
102 wherein when instances of R 14 and R 18 are taken alone (i.e. R 14 and R 18 are not taken together as alkylene or alkenylene), then independently said instances of R 14 and R 18 are H or C 1 -C 6 alkyl.
Embodiment 104. A compound of Embodiment 103 wherein when instances of R 14 and R 18 are taken alone, then independently said instances of R 14 and R 18 are H or CH 3 .
Embodiment 105. A compound of Embodiment 104 wherein when instances of R 14 and R 18 are taken alone, then independently said instances of R 14 and R 18 are H. Embodiment 106. A compound of Formula 1 or any one of Embodiments 1 through
105 wherein when instances of R 14 and R 18 are taken together, then said instances of R 14 and R 18 are taken together as -CH 2 CH 2 CH 2 - or -CH=CHCH 2 -.
Embodiment 107. A compound of Formula 1 or any one of Embodiments 1 through
105 wherein all instances of R 14 and R 18 are taken alone.
Embodiment 108. A compound of Formula 1 or any one of Embodiments 1 through
106 wherein independently each R 15 and R 19 is H or C 1 -Cg alkyl.
Embodiment 109. A compound of Embodiment 108 wherein independently each R 15 and R 19 is H or CH 3 .
Embodiment 110. A compound of Embodiment 109 wherein independently each R 15 and R 19 is H.
Embodiment 110A. A compound of any one of Embodiments 104 and 109 wherein each R 14 , R 15 , R 18 and R 19 is H or CH 3 .
Embodiment 110B. A compound of Embodiment 110A wherein each R 14 , R 15 , R 18 and R 19 is H.
Embodiment 111. A compound of Formula 1 or any one of Embodiments 1 through
110B wherein R 2 ° is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 3 -C 8 cycloalkyl.
Embodiment 112. A compound of Embodiment 111 wherein R 20 is H or CH 3 . Embodiment 113. A compound of Formula 1 or any one of Embodiments 1 through 4, 6, 10, 11 and 14 through 51 wherein T is -CH 2 CH 2 - or -CH=CH-.
Embodiment 114. A compound of Embodiment 113 wherein T is -CH 2 CH 2 -.
Embodiment 115. A compound of Formula 1 or any one of Embodiments 1 through 54, 75 or 84 through 114 wherein each G is independently a 5- or 6-membered heterocyclic ring optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 116. A compound of Embodiment 115 wherein G is
wherein r is 0, 1, 2 or 3.
Embodiment 117. A compound of Embodiment 116 wherein G is G-2, G-3 or G-15. Embodiment 118. A compound of Embodiment 117 wherein G is G-2 or G-3.
Embodiment 119. A compound of Embodiment 118 wherein G is G-2.
Embodiment 120. A compound of Embodiment 118 wherein G is G-3.
Embodiment 120A. A compound of Embodiment 116 wherein G is G-15. Embodiment 121. A compound of Formula 1 or any one of Embodiments 1 through 120 wherein each R 21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, 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 -Cg haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -CJ Q alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -CK) cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C 5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C 1 -Cg alkoxy, C^-Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, C 4 -C 10
cycloalkylalkoxy, C 2 -C 6 alkenyloxy, C 2 -Cg haloalkenyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg alkylcarbonyloxy, C 1 -Cg alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 8 cycloalkylthio, C Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C^-C 6 haloalkylsulfonyl or C 3 -C 8 cycloalkylsulfonyl.
Embodiment 121 A. A compound of Embodiment 121 wherein each R 21 is
independently halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -Cg haloalkoxy or C1-C 6 alkylthio.
Embodiment 122. A compound of Embodiment 121 A wherein each R 21 is
independently fluorine, chlorine, bromine, CH 3 , CF 3 , OCH 3 , OCF 3 or SCH 3 .
Embodiment 123. A compound of Formula 1 or any one of Embodiments 1 through 122 wherein each R 22 is independently C Cg alkyl or C 1 -C 6 haloalkyl.
Embodiment 124. A compound of Embodiment 123 wherein each R 22 is
independently CH 3 or CH 2 CF 3 .
Embodiment 124A. A compound of Embodiment 124 wherein R 22 is CH3.
Embodiment 124B. A compound of Formula 1 or any one of Embodiments 1 through 124A wherein R 40 is ethyl or z ' -propyl.
Embodiment 124C. A compound of Fromula 1 or any one of Embodiments 1 through 124A wherein R 41 is ethyl or z ' -propyl.
Embodiment 124D. A compound of Formula 1 or any one of Embodiments 1 through 124A wherein R 4 and R 41 are taken together as -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 124E. A compound of Embodiment 124D wherein R 40 and R 41 are taken together as -(CH 2 ) 5 - or -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 124F. A compound of Embodiment 124E wherein R 40 and R 41 are taken together as -(CH 2 ) 2 0(CH 2 ) 2 -.
This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (blO) auxin transport inhibitors, (bl l) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl -pyruvate dioxygenase (HPPD) inhibitors, (bl3) homogentisate solenesyltransererase (HST) inhibitors, (bl4) other herbicides including mitotic disruptors, organic arsenicals, asulam, difenzoquat, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, etobenzanid, fosamine, fosamine-ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb, and (bl5) herbicide safeners; and salts of compounds of (bl) through (bl5).
Embodiment 125. A herbicidal mixture comprising (a) a compound of Formula 1 or any one of Embodiments 1 through 125E, and (b) at least one additional active ingredient selected from (bl), (b2), (b3), (bl2), (bl3) and (bl5).
Embodiment 126. A herbicidal mixture of Embodiment 125 wherein component (b) comprises at least one additional active ingredient selected from (bl), (bl2),
(bl3) and (bl5).
Embodiment 127. A herbicidal mixture of Embodiment 126 wherein component (b) comprises at least one additional active ingredient selected from (bl).
Embodiment 128. A herbicidal mixture of Embodiment 127 wherein component (b) comprises bromoxynil.
Embodiment 129. A herbicidal mixture of Embodiment 127 wherein component (b) comprises dimethametryn.
Embodiment 130. A herbicidal mixture of Embodiment 126 wherein component (b) comprises at least one additional active ingredient selected from (bl3).
Embodiment 131. A herbicidal mixture of Embodiment 130 wherein component (b) comprises haloxydine.
Embodiment 132. A herbicidal mixture of Embodiment 126 wherein component (b) comprises at least one additional active ingredient selected from (bl5).
Embodiment 133. A herbicidal mixture of Embodiment 132 wherein component (b) comprises at least one additional active ingredient selected from allidochlor, benoxacor, 1 -bromo-4-[(chloromethyl)sulfonyl]benzene, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, 4-(dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660),
2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride and oxabetrinil.
Embodiment 134. A herbicidal mixture of Embodiment 133 wherein component (b) comprises at least one additional active ingredient selected from benoxacor, cloquintocet-mexyl, cyprosulfamide, diamuron, fenchlorazole-ethyl, mefenpyr-diethyl, mephenate and oxabetrinil.
Embodiment 135. A herbicidal mixture of Embodiment 134 wherein component (b) comprises at least one additional active ingredient selected from
cloquintocet-mexyl, mefenpyr-diethyl and oxabetrinil.
Embodiment 136. A herbicidal mixture of Embodiment 135 wherein component (b) comprises at least one additional active ingredient selected from
cloquintocet-mexyl .
Embodiment 137. A herbicidal mixture of Embodiment 135 wherein component (b) comprises at least one additional active ingredient selected from oxabetrinil.
Embodiments of this invention, including Embodiments 1-124F above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds, including compounds of Formulae 1Q, 1R and IS, useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-124E or 125—137 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
Combinations of Embodiments 1-124F are illustrated by:
Embodiment A. A compound of Formula 1 wherein
A is A-l, A-3, A-4, A-5 or A-6;
R 1 is
R 1 is -WiC^E^R 24 , -W!LC(=E 2 )R 2 5 or -W 1 C(=E3)LR 2 6; or
R 1 is N(R 40 )R 41 ; or
R 1 is G A or -W 2 G A ;
G A is a 9- to 11-membered saturated or partially saturated carbospirocyclic or
heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=NN(R 29 ), each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; or
each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring substituted with 1 substituent selected from R 22 on one nitrogen ring member;
each E 1 , E 2 and E 3 is independently O, NOR 28 or N(R 28 ) 2 ;
L is independently O or N(R 31 );
each R 24 , R 25 and R 26 is independently hydrogen; or C1-C 4 alkyl or C 3 -C 5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, ^-0 2 alkoxy, C 1 -C 2 alkylsulfinyl and
C1-C 4 alkylsulfonyl;
each R 28 is independently H, C1-C 3 alkyl or C1-C 3 haloalkyl;
each R 29 is independently H, C1-C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkylcarbonyl,
C]-C 3 alkylsulfonyl or C 1 -C 3 haloalkylsulfonyl;
each Q 1 and Q 2 is independently O or N(R 31 );
Q 3 is C 2 -C 3 alkylene optionally substituted with up to 2 substituents selected from
C r C 4 alkyl;
R 30 is independently H, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
R 31 is independently H, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
R 3 is H or C r C 3 alkyl;
W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
W 2 is C r C 3 alkylene;
W 5 is C 1-C 4 alkylene;
R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -Cg halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10
cycloalkylalkyl, C5-CJ4 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5"C 12 alkylcycloalkylalkyl, C 3 -Cg cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 3 -C 10 alkoxyalkenyl, C 4 -C 10 cycloalkoxyalkyl, C 4 -C 10 cycloalkoxylalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -C 8 alkylsulfonylalkyl, C 2 -Cg alkylcarbonyl, C 4 -C 10 cycloalkenylalkyl, C 2 -Cg haloalkoxyalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -Cg haloalkoxyhaloalkyl, C 4 -C 10 halocycloalkoxyalkyl, C 4 -CJQ
cycloalkenyloxyalkyl, C 4 -CJ Q halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C 1 -Cg 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 3 -C5 alkynyloxy, C 3 -C 6 haloalkynyloxy, C 2 -C alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 2 -C 8 haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy, C 3 -C 10 alkylcarbonylalkoxy, C 1 -Cg alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg
alkylsulfonyl, C^-Cg haloalkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 3 -Cg trialkylsilyl, C 3 -C 8 cycloalkenyloxy, C 3 -C halocycloalkenyloxy, C 2 -Cg haloalkoxyalkoxy, C 2 -Cg alkoxyhaloalkoxy, C 2 -Cg haloalkoxyhaloalkoxy, C 3 -C 10 alkoxycarbonylalkoxy, C 2 -Cg alkyl(thiocarbonyl)oxy, C 3 -C
cycloalkylsulfinyl or C 3 -CJQ halotrialkylsilyl; or
R 2 is -W 6 C(=E 4 )R 33 , -W 6 L!C(=E 5 )R 34 or -WSC^E^l R 35 ;
each E 4 , E 5 , and E 6 is independently O, NOR 37 or NN(R 37 ) 2 ;
each L 1 is independently O or N(R 8 );
each R 33 , R 34 and R 35 is independently hydrogen; or C1-C 4 alkyl, C 3 -C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, C 1 -C 2 alkoxy, C C 2 alkylsulfinyl and C 1 -C 2 alkylsulfonyl;
each R 37 is independently H, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
R 38 is independently H, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
W 3 is -CH 2 -;
W 6 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
R 3 is hydroxy, -OM + , C 2 -Cg alkylcarbonyloxy, C 2 -C haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy or C 3 -CJQ alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R 21 ;
M + is a sodium or potassium metal cation;
R 9 is C 1 -C 6 alkyl;
R 10 is H, halogen or C 1 -C 6 alkyl;
R 1 1 is H or C 1 -C 6 alkyl;
R 12 is H, halogen, cyano, hydroxy, amino or C 1 -Cg alkyl;
each R 14 , R 15 , R 18 and R 19 is H or CH 3 ;
R 20 is H or CH 3 ;
T is -CH 2 CH 2 - or -CH=CH-;
each G is G-l through G-20 (as depicted in Embodiment 116);
r is 0, 1, 2 or 3;
each R 21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -Cg cycloalkyl, C 3 -Cg halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -CJ Q cycloalkylalkyl, C 3 -Cg cycloalkenyl, C 3 -Cg halocycloalkenyl, C 2 -C alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C j0 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -C alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C 1 -C hydroxyalkyl, C j -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -C cycloalkoxy, C 3 -C halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -Cg haloalkenyloxy, C 2 -Cg alkoxyalkoxy, C 2 -C
alkylcarbonyloxy, C 1 -C alkylthio, C 1 -Cg haloalkylthio, C 3 -C cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl or C 3 -C cycloalkylsulfonyl;
each R 22 is independently C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R 40 is ethyl or /-propyl; and
R 41 is ethyl or z ' -propyl; or
R 40 and R 41 are taken together as -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or -(CH 2 ) 2 0(CH 2 ) 2 -. Embodiment B. A compound of Embodiment A wherein
A is A-l, A-3 or A-5;
B 1 is C-l;
B 2 is C-3;
B 3 is C-l;
R 1 is -G A ;
each G A is selected from G A -1, G A -2, G A -3, G A -7, G A -8 and G A -9; or
each G A is
R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R 21 ; or -G; or C 1 -Cg alkyl or C 3 -C cycloalkyl; R 3 is hydroxy or C 2 -C alkylcarbonyloxy;
R 9 is CH 2 CH 3 ;
R 10 is H or CH 3 ;
T is -CH 2 CH 2 -;
G is G-2, G-3 or G- 15; and
R 1 is independently halogen, nitro, C 1 -Cg alkyl, C 1 -Cg haloalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy or C 1 -Cg alkylthio;
each R 22 is independently CH 3 or CH 2 CF 3 ; and
R 40 and R 41 are taken together as -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or -(CH 2 ) 2 0(CH 2 ) 2 -. Embodiment C. A compound of Embodiment B wherein A is A-l or A-3;
each G A is selected from G A -2 and G A -3; or
each G A is
R 2 is phenyl; or -G; or C 3 -C 8 cycloalkyl; and
R 40 and R 41 are taken together as -(CH 2 ) 5 - or -(CH 2 )20(CH 2 )2-. Embodiment D. A compound of Embodiment C wherein
A is A-l;
each G A is
R 2 is phenyl;
R 30 is H or methyl;
R 21 halogen or C 1-C 3 alkyl; and
R 22 is CH 3 .
Embodiment E. A compound of Embodiment B wherein
A is A-l;
G A is G A -2;
R 2 is phenyl, 2-thienyl, 5-chloro-2-pyridinyl or cyclopropyl; R 3 is hydroxy; and
each R 14 , R 15 , R 18 and R 19 is H.
Embodiment F. A compound of Embodiment B wherein
A is A-3;
G A is G A -2;
R 2 is phenyl, 2-thienyl 5-chloro-2-pyridinyl or cyclopropyl; and R 3 is hydroxy.
Embodiment G. A compound of Embodiment A wherein
A is A-l;
R 1 is
each Q 1 and Q 2 is O; Q 3 is C 2 -alkylene;
R 32 is H or methyl;
W 5 is C 2 -C 3 alkylene;
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl,
4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl or 2-thienyl;
R 3 is hydroxy or -OC(=0)CH 2 CH(CH 3 ) 2 ; and
each R 14 , R^, Rl8 and R 19 is H or CH 3 .
Embodiment H. A compound of Embodiment G wherein
W 5 is C 2 alkylene or C 3 alkylene;
R 2 is phenyl, 3-thienyl cyclopropropyl; and
R 3 is hydroxy.
Specific embodiments include a compound of Formula 1 selected from:
3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l-cycloh exen-l-yl)carbonyl]-2- phenyl-4(3H)-pyrimidinone (Compound 1),
5-[(2-hydroxy-6-oxo-l-cyolohexen-l-yl)carbonyl]-6-oxo-2-phen yl- l(6H)-pyrimidineacetaldehyde l-(O-methyloxime) (Compound 2), 2-(5-chloro-3-pyridinyl)-3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[ (2-hydroxy-6-oxo-l- cyclohexen-l-yl)carbonyl]-4(3H)-pyrimidinone (Compound 7),
2- cyclopropyl-3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6- oxo-l-cyclohexen-l- yl)carbonyl]-4(3H)-pyrimidinone (Compound 10),
3- (l,4-dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-4-oxobicyclo[3.2 .1]oct-2-en-3- yl)carbonyl]-2-(2-thienyl)-4(3H)-pyrimidinone (Compound 15) and 5-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-phenyl-3-( 4,5,6,7-tetrahydro-2- methyl-2H-indazol-5-yl)-4(3H)-pyrimidinone (Compound 19).
Embodiments of the present invention as described in the Summary of the Invention also include (where Formula 1Q from the Summary of the Invention as used in the following Embodiments includes N-oxides and salts thereof):
Embodiment 1Q. A compound of Formula 1Q wherein A' is A'-l, A'-3 or A'-5.
Embodiment 2Q. A compound of Embodiment 1Q wherein A' is A'-l or A'-3.
Embodiment 3Q. A compound of Embodiment 2Q wherein A' is A'-l.
Embodiment 4Q. A compound of Embodiment 2Q wherein A' is A'-3.
Embodiment 5Q. A compound of Formula 1Q or any one of Embodiments 1Q through
4Q wherein B 1 is C-l .
Embodiment 6Q. A compound of Formula 1Q or any one of Embodiments 1Q through
4Q wherein B 1 is C-2.
Embodiment 7Q. A compound of Formula 1Q or any one of Embodiments 1Q through
6Q wherein B 2 is C-3. Embodiment 8Q. A compound of Formula 1Q or any one of Embodiments 1Q through
6Q wherein B 2 is C-4.
Embodiment 9Q. A compound of Formula 1Q or any one of Embodiments 1Q through
8Q wherein B 3 is C-1.
Embodiment 10Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 8Q wherein B 3 is C-2.
Embodiment 11Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 10Q wherein R 1 is
R 1 is -W 1 C(=E 1 )R 24 , -W 1 LC(=E 2 )R25 or -W!C(=E )LR 2 6; or
R 1 is -G A or -W 2 G A .
Embodiment 12Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 11Q wherein R 1 is
Embodiment 13Q. A compound of Embodiment 12Q wherein each Q 1 and Q 2 is O. Embodiment 14Q. A compound of Embodiment 12Q wherein Q 3 is C 2 -alkylene optionally substituted with up to 2 substituents selected from C j-C 2 alkyl. Embodiment 15Q. A compound of Embodiment 14Q wherein Q 3 is C 2 -alkylene optionally substituted with up to 2 substituents selected from methyl.
Embodiment 16Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 15Q wherein W 5 is C1-C 4 alkylene.
Embodiment 17Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 16Q wherein R 32 is H or CJ-C 3 alkyl.
Embodiment 17QA. A compound of Embodiment 17Q wherein R 32 is H or methyl. Embodiment 18Q. A compound of Embodiments 17Q wherein R 32 is methyl.
Embodiment 19Q. A compound of Formula 1Q or any one of Embodiments 1Q
through HQ wherein R 1 is -W 1 C(=E 1 )R 24 , -W 1 LC(=E 2 )R 25 or
-W ! C(=E 3 )LR 26 .
Embodiment 12QA. A compound of Formula 1Q or any one of Embodiments 1Q through 19Q wherein W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -. Embodiment 20Q. A compound of Formula 1Q or any one of Embodiments 1Q through 11Q or 19Q wherein each E 1 , E 2 , and E 3 is independently O, NOR 28 or NN(R 28 ) 2 .
Embodiment 20QA. A compound of Formula 1Q or any of Embodiments 1Q through 20Q wherein each R 28 is independently H, CJ-C 3 alkyl or C1-C 3 haloalkyl
Embodiment 20QB. A compound of Formula 1Q or any one of Embodiments 1Q through 10Q wherein R 1 is other than -N(R 40 )(R 41 ).
Embodiment 21 Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 11Q or 19Q wherein each L is independently O or N(R 3 ! );
provided when E 3 is O, L is other than O;
Embodiment 22Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 21Q wherein W 1 is CJ-C 4 alkylene.
Embodiment 23Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 11Q or 19Q wherein each R 24 , R 25 and R 26 is independently hydrogen; or C j -C 2 alkyl or C 3 -C 4 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxyl and Ci-C 2 alkoxy.
Embodiment 24Q. A compound of Formula 1Q or any one of Embodiments 1Q
through HQ wherein R 1 is -G A .
Embodiment 25Q. A compound of Embodiment 24Q wherein G A is a 5- or
6-membered carbocyclic ring including ring members selected from C=0,
C(=N-OR 30 ) or C= N(R 29 ) 2 ,each ring optionally substituted with up to two substituents selected from R 21 .
Embodiment 26Q. A compound of Embodiment 25Q wherein R 29 is independently H, C ! -C 3 alkyl, C l -C 3 haloalkyl or C 1 -C 3 alkylcarbonyl.
Embodiment 26QA. A compound of Embodiment 25Q wherein R 30 is independently
H, C r C 3 alkyl or C r C 3 haloalkyl
Embodiment 27Q. A compound of Embodiment 24Q wherein G A is a 9- to
10-membered saturated heterospirocyclic ring system optionally including ring members selected from C(=0) or C(=N-OR 30 ), each ring or ring system optionally substituted with up to two substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
Embodiment 28Q. A compound of Embodiment 27Q wherein R 30 is independently H,
C1-C 3 alkyl or C r C 3 haloalkyl;
Embodiment 29Q. A compound of Embodiment 27Q or 28Q wherein G A is selected from G A -1, G A -2, G A -3, G A -7, G A -8 and G A -9 (as described in Embodiment Embodiment 30Q. A compound of Embodiment 29Q wherein G A is selected from G A -2 and G A -3.
Embodiment 30QA. A compound of Embodiment 30Q wherein G A is G A -2.
Embodiment 30QB. A compound of Formula 1Q or any one of Embodiments 1Q
through 30QA wherein each G A is other than a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring optionally substituted with up to 2 substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
Embodiment 30QC. A compound of Formula 1 or any one of Embodiments 1Q
through 24Q wherein each G A is a 9-membered partially saturated fused ring system containing carbon ring members and 2 nitrogen ring members, the ring substituted with 1 substituent selected from R 22 on one nitrogen ring member.
Embodiment 30QD. A compound of Embodiment 30QC wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the remainder of the compound of Formula 1.
Embodiment 30QE. A compound of Embodiment 30QD wherein each G A is
Embodiment 31Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 30Q wherein R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R 21 ; or -G or; or C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl.
Embodiment 32Q. A compound of Embodiment 31Q wherein R 2 is phenyl optionally substituted on ring members with up to two substituents selected from R 21 ; or -G; or C 1 -Cg alkyl, C 3 -C 8 cycloalkyl.
Embodiment 32QA. A compound of Embodiment 32Q wherein R 2 is phenyl; or -G; or C 3 -C 8 cycloalkyl.
Embodiment 32QB. A compound of Embodiment 32QA wherein R 2 is phenyl,
2- thienyl 5-chloro-2-pyridinyl or cyclopropyl.
Embodiment 32QC. A compound of Embodiment 32QA wherein R 2 is phenyl,
3- thienyl or cyclopropropyl. Embodiment 33Q. A compound of Embodiment 32Q wherein R 2 is phenyl,
2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl,
4-chlorophenyl, 3 -fluorophenyl or 3,5-difluorophenyl.
Embodiment 33QA. A compound of Embodiment 32Q wherein R 2 is phenyl, 3-thienyl or cyclopropropyl.
Embodiment 34Q. A compound of Embodiment 33Q wherein R 2 is phenyl.
Embodiment 35Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 31Q wherein R 2 is other than phenyl.
Embodiment 36Q. A compound of Embodiment 35Q wherein R 2 is 3-thienyl,
2-thienyl or 3-pyridinyl.
Embodiment 36Qa. A compound of Embodiment 36Q wherein R 2 is 3-pyridinyl. Embodiment 37Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 36Q wherein W 3 is -CH2-.
Embodiment 38Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 3Q, 7Q and 11Q through 37Q wherein R 9 is C 1 -C 6 alkyl.
Embodiment 39Q. A compound of Embodiments 38Q wherein R 9 is CH2CH3.
Embodiment 40Q. A compound of Formula 1Q or any one of Embodiments 1Q or
11Q through 39Q wherein R 10 is H, halogen or C 1 -C 6 alkyl.
Embodiment 41Q. A compound of Embodiment 40Q wherein R 10 is H or CH 3 .
Embodiment 42Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 41Q wherein when instances of R 14 and R 18 are taken alone (i.e. R 14 and R 18 are not taken together as alkylene or alkenylene), then independently said instances of R 14 and R 18 are H or C 1 -C 6 alkyl.
Embodiment 43Q. A compound of Embodiment 42Q wherein when instances of R 14 and R 18 are taken alone, then independently said instances of R 14 and R 18 are H or CH 3 .
Embodiment 44Q. A compound of Embodiment 43Q wherein when instances of R 14 and R 18 are taken alone, then independently said instances of R 14 and R 18 are H.
Embodiment 45Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 44Q wherein independently each R 15 and R 19 is H or CH3.
Embodiment 46Q. A compound of Embodiment 45Q wherein independently each R 15 and R 19 is H.
Embodiment 47Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 46Q wherein R 20 is H, C^- ^ alkyl, C 2 -C 6 alkenyl or C 3 -C 8 cycloalkyl. Embodiment 48Q. A compound of Embodiment 47Q wherein R 20 is H or CH3.
Embodiment 49Q. A compound of Formula 1Q or any one of Embodiments 1Q, 2Q, 4Q, 7Q, 8Q and 11Q through 48Q wherein T is -CH 2 CH 2 - or -CH=CH-. Embodiment 50Q. A compound of Embodiment 49Q wherein T is -CH2CH2-.
Embodiment 51Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 50Q wherein G is G-2, G-3 or G-15 (as depicted in Embodiment 51). Embodiment 52Q. A compound of Embodiment 51Q wherein G is G-2 (as depicted in
Embodiment 51).
Embodiment 53Q. A compound of Embodiment 51Q wherein G is G-3 (as depicted in Embodiment 51).
Embodiment 54Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 54Q wherein each R 21 is independently halogen, nitro, C 1 -Cg alkyl, C 1 -Cg haloalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy or C 1 -Cg alkylthio. Embodiment 55Q. A compound of Embodiment 54Q wherein each R 21 is
independently fluorine, chlorine, bromine, CH 3 , CF 3 , OCH 3 , OCF3 or SCH3. Embodiment 56Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 55Q wherein each R 22 is independently C 1 -C 6 alkyl or C 1 -C 6 haloalkyl. Embodiment 57Q. A compound of Embodiment 56Q wherein each R 22 is
independently CH 3 or CH 2 CF 3 .
Embodiment 58Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 57Q wherein R 40 is ethyl or /-propyl.
Embodiment 59Q. A compound of Formula 1Q or any one of Embodiments 1Q
through 58Q wherein R 41 is ethyl or z-propyl.
Embodiment 60Q. A compound of Formula 1Q or any one of Embodiments 1 through
57Q wherein R 40 and R 41 are taken together as -(CH 2 ) 5 -, -CH 2 CH=CHCH 2 - or
-(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 61Q. A compound of Embodiment 60Q wherein R 40 and R 1 are taken together as -(CH 2 ) 5 - or -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 62Q. A compound of Embodiment 61Q wherein R 40 and R 41 are taken together as -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiments of the present invention as described in the Summary of the Invention also include (where Formula 1R from the Summary of the Invention as used in the following Embodiments include N-oxides and salts thereof):
Embodiment 1R. A compound of Formula 1R wherein R 1 is
each Q 1 and Q 2 is O;
Q 3 is C 2 -alkylene;
R 32 is H or methyl; W 5 is C 2 -C 3 alkylene;
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl,
4- chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl, 2-thienyl or 3-pyridinyl; and
each R 14 , R 15 , R 18 and R 19 is H.
Embodiment IRA. A compound of Formula 1R or Embodiment 1 wherein R 1 is other than -N(R 40 )(R 41 ).
Embodiment 1RB. A compound of Formula 1R wherein R 2 is phenyl; or -G; or C 3 -C 8 cycloalkyl.
Embodiment IRC. A compound of Embodiment 1RB wherein R 2 is phenyl, 2-thienyl
5- chloro-2-pyridinyl or cyclopropyl.
Embodiment 1RD. A compound of Embodiment 1RB wherein R 2 is phenyl, 3-thienyl or cyclopropropyl.
Embodiment 2R. A compound of Embodiment 1R wherein R 2 is phenyl,
2-methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 3R. A compound of Embodiment 1R wherein R 2 is phenyl, 3-thienyl or cyclopropropyl.
Embodiment 3RA. A compound of Embodiment 1R wherein R 2 is phenyl,
3-bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 4R. A compound of Embodiment 1R wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 5R. A compound of Embodiment 1R wherein R 2 is phenyl.
Embodiment 6R. A compound of Formula 1R wherein
R 1 is -W!C(=El)R 2 4;
E 1 is NOR 28 ;
R 28 is H or methyl; and
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 7R. A compound of Embodiment 6R wherein R 2 is phenyl,
2-methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 8R. A compound of Embodiment 6R wherein R 2 is phenyl,
3-bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 9R. A compound of Embodiment 6R wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl. Embodiment 10R. A compound of Embodiment 6R wherein R 2 is phenyl.
Embodiment 11R. A compound of Formula 1R wherein
Rl is -G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0) or C(=N-OR 30 ); or a 9- to 10-membered saturated
heterospirocyclic ring system optionally including ring members selected from C(=0) or C(=N-OR 30 ), each ring or ring system optionally substituted with up to two substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
R 30 is H or methyl;
R 21 halogen or C r C 3 alkyl;
R 22 is C r C 3 alkyl.
Embodiment 12R. A compound of Embodiment 11R wherein G A is selected from G A -1, G a -2, G a -3, G A -7, G a -8 and G A -9 (as depicted in Embodiment 51), and R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl 2-thienyl or 3-pyridinyl;
Embodiment 13R. A compound of Embodiment 11R wherein R 2 is phenyl,
2- methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 14R. A compound of Embodiment 11R wherein R 2 is phenyl,
3- bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 15R. A compound of Embodiment 11R wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 16R. A compound of Embodiment 11R wherein R 2 phenyl.
Embodiment 16RA. A compound of Formula 1R wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the remainder of the compound of Formula 1R.
Embodiment 16RB. A compound of Embodiment 16RA wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the
remainder of a compound of Formula 1. Embodiment 17R. A compound of Formula 1R or any one of Embodiments 1R through 16R wherein R 40 is ethyl or /-propyl.
Embodiment 18R. A compound of Formula 1R or any one of Embodiments 1R
through 16R wherein R 41 is ethyl or /-propyl.
Embodiment 19R. A compound of Formula 1R or any one of Embodiments 1R
through 16R wherein R 40 and R 41 are taken together as -(CH 2 ) 5 -,
-CH 2 CH=CHCH 2 - or -(CH 2 ) 2 0(CH 2 ) .
Embodiment 20R. A compound of Embodiment 19R wherein R 40 and R 41 are taken together as -(CH 2 ) 5 - or -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 21 R. A compound of Embodiment 20R wherein R 40 and R 41 are taken together as -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiments of the present invention as described in the Summary of the Invention also include (where Formula IS from the Summary of the Invention as used in the following Embodiments includes N-oxides and salts thereof):
Embodiment IS. A compound of Formula IS wherein
R 1 is
each Q 1 and Q 2 is O;
Q 3 is C 2 -alkylene;
R 32 is H or methyl;
W 5 is C 2 -C 3 alkylene;
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl, 3,5-difluorophenyl, 3-thienyl, 2-thienyl or 3-pyridinyl;
each R 14 , R^, Rl8 and R 19 is H; and
R 23 is methyl or ethyl.
Embodiment ISA. A compound of Formula IS or Embodiment IS wherein R 1 is other than -N(R 40 )(R 41 ).
Embodiment 1SB. A compound of Formula IS or Embodiment IS wherein R 2 is phenyl; or -G; or C 3 -C 8 cycloalkyl.
Embodiment ISC. A compound of Embodiment 1SB wherein R 2 is phenyl, 2-thienyl
5-chloro-2-pyridinyl or cyclopropyl.
Embodiment 1SD. A compound of Embodiment 1SB wherein R 2 is phenyl, 3-thienyl or cyclopropropyl. Embodiment 2S. A compound of Embodiment IS wherein R 2 is phenyl,
2- methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 2SA. A compound of Embodiment IS wherein R 2 is phenyl, 3-thienyl or cyclopropropyl.
Embodiment 3S. A compound of Embodiment IS wherein R 2 is phenyl,
3- bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 4S. A compound of Embodiment IS wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 5S. A compound of Embodiment IS wherein R 2 is phenyl.
Embodiment 6S. A compound of Formula IS wherein
R 1 is -W 1 C(=E 1 )R 24 ;
E 1 is NOR 28 ;
R 28 is H or methyl; and
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl,
4-chlorophenyl, 3 -fluorophenyl, 3,5-difluorophenyl, 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 7S. A compound of Embodiment 6S wherein R 2 is phenyl,
2- methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 8S. A compound of Embodiment 6S wherein R 2 is phenyl,
3- bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 9S. A compound of Embodiment 6S wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 9SA. A compound of Embodiment 6S wherein R 2 is 2-thienyl.
Embodiment 10S. A compound of Embodiment 6S wherein R 2 is phenyl.
Embodiment 1 IS. A compound of Formula IS wherein
R 1 is -G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0) or C(=N-OR 30 ); or a 9- to 10-membered saturated
heterospirocyclic ring system optionally including ring members selected from C(=0) or C(=N-OR 30 ), each ring or ring system optionally substituted with up to two substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; or
R 30 is H or methyl;
R 21 halogen or C r C 3 alkyl;
R 22 is C r C 3 alkyl. Embodiment 12S. A compound of Embodiment 1 IS wherein G A is selected from G A -1, G A -2, G A -3, G A -7, G A -8 and G A -9; and
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl, 3,5-difluorophenyl, 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 12SA. A compound of Embodiment 12S wherein G A is selected from G A -2; and
R 2 is phenyl or 2-thienyl.
Embodiment 13S. A compound of Embodiment 1 IS wherein wherein R 2 is phenyl,
2- methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3,5-difluorophenyl.
Embodiment 14S. A compound of Embodiment 1 IS wherein R 2 is phenyl,
3- bromophenyl, 3-chlorophenyl or 2-methylphenyl.
Embodiment 15S. A compound of Embodiment 1 IS wherein R 2 is 3-thienyl, 2-thienyl or 3-pyridinyl.
Embodiment 16S. A compound of Formula IS wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the remainder of the compound of Formula IS.
Embodiment 17S. A compound of Embodiment 16S wherein each G A is
wherein the bond projecting to the left represents the point of attachment to the remainder of a compound of Formula 1.
Embodiment 17SA. A compound of Formula IS or any one of Embodiments IS
through 16S wherein R 40 is ethyl or z ' -propyl.
Embodiment 18S. A compound of Formula IS or any one of Embodiments IS through
16S wherein R 41 is ethyl or z ' -propyl.
Embodiment 19S. A compound of Formula IS or any one of Embodiments IS
through 16S wherein R 40 and R 41 are taken together as -(CH 2 )5-,
-CH 2 CH=CHCH 2 - or -(CH 2 ) 2 0(CH 2 ) 2 -.
Embodiment 20S. A compound of Embodiment 19S wherein R 40 and R 41 are taken together as -(CH 2 ) 5 - or -(CH 2 ) 2 0(CH 2 ) 2 -. Embodiment 21 S. A compound of Embodiment 20S wherein R 40 and R 41 are taken together as -(CH 2 )20(CH 2 ) 2 -.
This invention is also directed to compounds of Formula IP (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides:
wherein
A is a radical selected from the group consisting of
B 1 and B 3 are each independently a radical selected from the group consisting of
B 2 is a radical selected from the group consisting of R 1 is
o r
R 1 is -W!C(=El)R24 -W!LC^^S, -W!C(=E )LR26 5 -W 1 S(0) X NR 2 8C(=0)R 2 7, -W 1 S(0) X NR 28 C(=0)LR27, -W 1 S(0) X NR 28 S0 2 LR27 or -W^CN; or
R 1 is -G A or -W 2 G A ;
each G A is a 4- to 7-membered carbocyclic ring including ring members selected from C(=0), C(=S), C(=NR 29 ), C(=N-OR 30 ) or C=NN(R 29 ) 2 ; or a 6- to 12-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=S), C(=NR 29 ), C(=N-OR 30 ), or C=NN(R 29 ) 2 , each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each E 1 , E 2 , and E 3 is independently O, S, NR 28 , NOR 28 , NN(R 28 ) 2 , N-CN or N-N0 2 ; each L is independently O, NR 31 or S;
provided when E 3 is O, L is other than O;
each R 24 , R 25 , R 26 and R 27 is independently hydrogen; or C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N0 2 , hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfinyl, i-C 4 alkylsulfonyl, Ci-C 4 alkylamino, C 2 -Cg dialkylamino, C 3 -C5 cycloalkylamino and (CJ-C 4 alkyl)C 3 -Cg cycloalkylamino;
each R 28 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R 29 is independently H, C 1 -Cg alkyl, C C haloalkyl, C 1 -Cg alkylcarbonyl, C 1 -Cg alkylsulfonyl, or C 1 -C haloalkylsulfonyl;
each Q 1 and Q 2 is independently O, S or -NR 31 ;
Q 3 is C j -C 4 alkylene optionally substituted with up to 4 substituents selected from C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl and C 3 -C 6 cycloalkyl;
R 30 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R 31 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R 32 is H or C 1 -C 6 alkyl;
each x is 0, 1 or 2;
W 5 is C 1 -C 6 alkylene;
W 1 is C 1 -Cg alkylene, C 2 -C 6 alkenylene or C 2 -Cg alkynylene; or -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
W 2 is C 1 -C 6 alkylene; phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G or -W 4 G; or H, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -S0 2 NHCN, -S0 2 NHOH, -SF 5 , -NHCHO, -NHNH 2 , -NHOH, -NHCN, -NHC(=0)NH 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 2 -Cg haloalkenyl, C 2 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10
cycloalkylalkyl, Cg-C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 3 -C 10 alkoxyalkenyl, C 4 -CJQ cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -C 8 alkylsulfonylalkyl, C 2 -C 8 alkylaminoalkyl, C 3 -C 10 dialkylaminoalkyl, C 2 -Cg haloalkylaminoalkyl, C 4 -CJ Q cycloalkylaminoalkyl, 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 5 -C 12 cycloalkylalkoxycarbonyl, C 2 -C 8
alkylaminocarbonyl, C 3 -C 10 dialkylaminocarbonyl, C 4 -CK )
cycloalkylaminocarbonyl, C 2 -C 5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C^-CIQ cycloalkenylalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -Cg haloalkoxyhaloalkyl, C 4 -C 10 halocycloalkoxyalkyl, C 4 -C 10
cycloalkenyloxyalkyl, C 4 -CJ Q halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C 3 -C 10 alkoxyalkylcarbonyl, C 3 -C 10 alkoxycarbonylalkyl, C 2 -C 8
haloalkoxycarbonyl, C 1 -C 6 alkoxy, C 1 -Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C 6 alkenyloxy, C 2 -Cg haloalkenyloxy, C 2 -Cg alkynyloxy, C 3 -C5 haloalkynyloxy, C 2 -Cg alkoxyalkoxy, C 2 -C 8 alkylcarbonyloxy, C 2 -C 8 haloalkylcarbonyloxy, C 4 -C 10
cycloalkylcarbonyloxy, C 3 -C 10 alkylcarbonylalkoxy, C 1 -C 6 alkylthio, C 1 -Cg haloalkylthio, C 3 -Cg cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg
haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 3 -Cg trialkylsilyl, C 3 -Cg cycloalkenyloxy, C 3 -C 8 halocycloalkenyloxy, C 2 -Cg haloalkoxyalkoxy, C 2 -C 8 alkoxyhaloalkoxy, C 2 -Cg haloalkoxyhaloalkoxy, C 3 -C 10 alkoxycarbonylalkoxy, C 2 -C 8
alkyl(thiocarbonyl)oxy, C 2 -C § alkylcarbonylthio, C 2 -C 8 alkyl(thiocarbonyl)thio, C 3 -Cg cycloalkylsulfinyl, C 1 -Cg alkylaminosulfonyl, C 2 -Cg
dialkylaminosulfonyl, C 3 -CK ) halotrialkylsilyl, C 1 -Cg alkylamino, C 2 -Cg dialkylamino, C^-Cg haloalkylamino, C 2 -Cg halodialkylamino, C 3 -Cg cycloalkylamino, C 2 -C 8 alkylcarbonylamino, C 2 -C 8 haloalkylcarbonylamino, C 1 -Cg alkylsulfonylamino, C 1 -Cg haloalkylsulfonylamino or C 4 -C 10
cycloalkyl(alkyl)amino; or . or
2 is -W 6 C(=E 4 )R 33 , -WSIJC^ES^ 34 ν 6 0(=Εό)Ε^ 3 5, -W 6 S(0) x NR 37 C(=0)R 36 or -λν 6 8(0)^ 37 0(=0)Ε^36;
each E 4 , E 5 , and E 6 is independently O, S, NR 37 , NOR 37 , NN(R 37 ) 2 , N-CN or N-N0 2 ; each L 1 is independently O, NR 38 or S;
each R 33 , R 34 , R 35 and R 36 is independently hydrogen; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N0 2 , hydroxy,
C1-C 4 alkoxy, CJ-C 4 alkylsulfinyl, C C 4 alkylsulfonyl, C C 4 alkylamino, C 2 -Cg dialkylamino, C 3 -C 6 cycloalkylamino and (C1-C 4 alkyl)C 3 -Cg cycloalkylamino;
each R 37 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
each Q 4 and Q 5 is independently O, S or NR 38 ;
Q 6 is C1-C 4 alkylene optionally substituted with up to 4 substituents selected from C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl and C 3 -C 6 cycloalkyl;
R 38 is independently H, C 1 -Cg alkyl or C 1 -Cg haloalkyl;
R59 is H or C 1 -C 6 alkyl;
each x is 0, 1 or 2;
W 7 is C 1 -C 6 alkylene;
W 6 is C 1 -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene; or -(CH 2 ) 2 OCH 2 - or
-(CH 2 ) 3 OCH 2 -;
W 3 is C Cg alkylene, C 2 -C 6 alkenylene or C 2 -Cg alkynylene;
W 4 is C 1 -C 6 alkylene;
R 3 is H, halogen, cyano, hydroxy, -OM + , amino, nitro, -CHO, -C(=0)OH,
-C(=0)NH 2 , -C(=S)NH 2 , -SH, -S0 2 H 2 , -S0 2 NHCN, -S0 2 NHOH, -OCN, -SCN, -SF 5 , -NHNH 2 , -NHOH, -N=C=0, -N=C=S, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -Cg cycloalkoxy, C 3 -C 8 halocycloalkoxy, C 4 -C 10
cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -C haloalkenyloxy, C 2 -Cg alkynyloxy,
C 3 -C 6 haloalkynyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -C 8 alkylcarbonyloxy, C 2 -C § haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy, C 3 -C 10
alkylcarbonylalkoxy, C 1 -Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -Cg
cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg
alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -Cg alkylsulfonyloxy, C 1 -Cg alkylamino, C 2 -Cg dialkylamino, C 1 -Cg
haloalkylamino, C 2 -Cg halodialkylamino, C 3 -C 8 cycloalkylamino, C 2 -Cg alkylcarbonylamino, C 2 -C 8 haloalkylcarbonylamino, C 1 -C 6 alkylsulfonylamino or C 1 -Cg haloalkylsulfonylamino; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenyl sulfonyloxy, benzylsulfonyloxy, phenylthio, benzylthio, phenylsulfinyl, benzylsulfinyl, phenylsulfonyl or benzylsulfonyl, each optionally substituted on ring members with up to five substituents selected from R 21 ;
M + is an alkali metal cation or an ammonium cation;
R 4 , R 5 , R 6 and R 7 are each independently H, halogen, hydroxy, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -C 8 cycloalkoxy or C 3 -C 8 halocycloalkoxy; or phenyl or benzyl, each optionally substituted on ring members with up to five substituents selected from R21;
R 8 is H, 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 or C 3 -C 8 halocycloalkyl; or benzyl optionally substituted on ring members with up to five substituents selected from R 21 ;
R 9 is H, 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 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 6 -C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 22 alkylcycloalkylalkyl, C 3 -Cg cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl or C 2 -Cg alkylthioalkyl;
R 10 is H, halogen, cyano, hydroxy, amino, nitro, SH, -S0 2 NH 2 , -S0 2 NHCN,
-S0 2 NHOH, -OCN, -SCN, -SF 5 , -NHCHO, -NHNH 2 , -N 3 , -NHOH, -NHCN, -NHC(=0)NH 2 , -N=C=0, -N=C=S, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -Cg haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 20 cycloalkylalkyl, Cg-C 14 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl or C 2 -C 8 alkylthioalkyl;
R 1 1 is H, halogen, cyano, hydroxy, amino, C 1 -Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -Cg halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl or C 2 -Cg alkylsulfonylalkyl; or phenyl optionally substituted with up to five substituents selected from R 21 ;
R 12 is H, halogen, cyano, hydroxy, amino, C 1 -Cg alkyl, C 2 -C alkenyl, C 2 -C 6 alkynyl, C 1 -Cg haloalkyl, C 2 -Cg 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 -C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5-C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl or C 2 -Cg alkoxycarbonylamino;
R 13 is H, halogen, cyano, hydroxy, amino, nitro or C 2 -C 8 alkoxycarbonyl;
n is 0, 1, or 2;
each R 14 , R 15 , R 18 and R 19 is independently H, halogen, cyano, hydroxy or C 1 -Cg alkyl; or
a pair of R 14 and R 18 is taken together as C 2 -Cg alkylene or C 2 -Cg alkenylene;
R 20 is H, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 8 cycloalkoxy, C 1 -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 8 cycloalkyl; T is C 1 -Cg alkylene or C 2 -C alkenylene;
each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or
10-membered fused bicyclic ring system, each ring or ring system optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
each R 21 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=0)OH, -C(=0)NH 2 , -C(=S)NH 2 , -C(=0)NHCN, -C(=0)NHOH, -SH, -S0 2 NH 2 , -SO2NHCN, -SO2NHOH, -OCN, -SCN, -SF 5 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl, C 1 -Cg haloalkyl, C 2 -C5 haloalkenyl, C 2 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10
cycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C10 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C 1 -Cg hydroxyalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -Cg cycloalkoxy, C 3 ~Cg halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C alkenyloxy, C 2 -C haloalkenyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 1 -C alkylthio, C 1 -Cg haloalkylthio, C 3 -Cg cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 1 -Cg alkylamino, C 2 -Cg dialkylamino, C^-Cg haloalkylamino, C 2 -Cg halodialkylamino or C 3 -Cg cycloalkylamino; and each R 22 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C¾ alkynyl, C 1
haloalkyl, C 3 -C 8 cycloalkyl or C 2 -Cg alkoxyalkyl.
Embodiments of a compound of Formula IP include:
Embodiment PA is A-l, A-3, A-4, A-5 or A-6;
R 1 is
R 1 is -W!C^E^R 24 , -W!LC(=E )R 25 or -W^E^LR 26 ; or
Rl is G A or -W G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0), C(=N-OR 30 ) or C= N(R 29 ) 2 ; or a 9- to 11-membered saturated or partially saturated carbospirocyclic or heterospirocyclic ring system optionally including ring members selected from C(=0), C(=N-OR 30 ) or C=N (R 9 )2, each ring or ring system optionally substituted with up to three substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members; each E 1 , E 2 and E 3 is independently O, NOR 28 or NN(R 28 ) 2 ;
L is independently O or NR 31 ;
each R 24 , R 25 and R 26 is independently hydrogen; or C1-C 4 alkyl or C 3 -C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, i-C 2 alkoxy, C 1 -C 2 alkylsulfinyl and C1-C 4 alkylsulfonyl;
each R 28 is independently H, C 1 -C 3 alkyl or CJ-C 3 haloalkyl;
R 29 is independently H, C C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkylcarbonyl, C r C 3 alkylsulfonyl or CJ-C 3 haloalkylsulfonyl;
each Q 1 and Q 2 is independently O or N(R 31 );
Q 3 is C 2 -C 3 alkylene optionally substituted with up to 2 substituents selected from C r C 4 alkyl;
R 30 is independently H, C C 3 alkyl or C r C 3 haloalkyl;
R 31 is independently H, CJ-C 3 alkyl or C1-C 3 haloalkyl;
R 32 is H or C r C 3 alkyl;
W 1 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
W 2 is C r C 3 alkylene
W 5 is C r C 4 alkylene;
R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G; or C -C^ alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl, C 1 -C 6 haloalkyl, C 2 -Cg haloalkenyl, C 2 -Cg haloalkynyl, C 3 -C53 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10
cycloalkylalkyl, Cg-C^ cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 1 2 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C 3 -C 10 alkoxyalkenyl, C 4 -C 10 cycloalkoxyalkyl, C 4 -C 10 cycloalkoxylalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -Cg alkylsulfonylalkyl, C 2 -Cg alkylcarbonyl, C 4 -C 10 cycloalkenylalkyl, C 2 -Cg haloalkoxyalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -Cg haloalkoxyhaloalkyl, C 4 -C 10 halocycloalkoxyalkyl, C 4 -C ]Q
cycloalkenyloxyalkyl, C 4 -CJ Q halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -Cg halocycloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -Cg alkynyloxy, C 3 -C 6 haloalkynyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C 2 -Cg haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy, C 3 -CJ Q alkylcarbonylalkoxy, C 1 -Cg alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C haloalkylsulfinyl, C 1 -C 6
alkylsulfonyl, C 1 -Cg haloalkylsulfonyl, C 3 -Cg cycloalkylsulfonyl, C 3 -Cg trialkylsilyl, C 3 -C cycloalkenyloxy, C 3 -C halocycloalkenyloxy, C 2 -Cg haloalkoxyalkoxy, C 2 -C alkoxyhaloalkoxy, C 2 -Cg haloalkoxyhaloalkoxy, C 3 -CJ Q alkoxycarbonylalkoxy, C 2 -Cg alkyl(thiocarbonyl)oxy, C 3 ~C
cycloalkylsulfinyl or C 3 -C 10 halotrialkylsilyl; or
R 2 is -W 6 C(=E 4 )R 33 , -W 6 L!C(=E 5 )R 34 or -\ν 6 ( (=Ε 6 )Ε^ 35 ;
each E 4 , E 5 , and E 6 is independently O, NOR 37 or NN(R 37 ) 2 ;
each L 1 is independently O or NR 38 ;
each R 33 , R 34 and R 35 is independently hydrogen; or C j-C 4 alkyl, C 3 -C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, hydroxy, Ci~C 2 alkoxy, C C 2 alkylsulfinyl, or C 1 -C 2 alkylsulfonyl;
each R 37 is independently H, C 1 -C 3 alkyl or C1-C 3 haloalkyl;
R 38 is independently H, C 1 -C 3 alkyl or haloalkyl;
W 3 is -CH 2 -;
W 6 is C 2 -C 4 alkylene, -(CH 2 ) 2 OCH 2 - or -(CH 2 ) 3 OCH 2 -;
R 3 is hydroxy, -OM + , C 2 -Cg alkylcarbonyloxy, C 2 -Cg haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy or C 3 -C 10 alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R 21 ;
M + is a sodium or potassium metal cation; R 9 is C 1 -C 6 alkyl;
R 10 is H, halogen or C 1 -C 6 alkyl;
R 1 1 is H or C 1 -C 6 alkyl;
R 12 is H, halogen, cyano, hydroxy, amino or C 1 -Cg alkyl;
each R 14 , R 15 , R 18 and R 19 is H or CH 3 ;
R 14 and R 18 are taken together as -CH 2 CH 2 CH 2 - or -CH=CHCH 2 -;
R 20 is H or CH 3 ;
T is -CH 2 CH 2 - or -CH=CH-;
each G is G-l through G-20 (as depicted in Embodiment 116);
r is 0, 1, 2 or 3;
each R 21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, C 1 -Cg haloalkyl, C 2 -Cg haloalkenyl, C 2 -Cg haloalkynyl, C 3 -Cg cycloalkyl, C 3 -Cg halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C § alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -Cg alkylsulfinylalkyl, C 2 -Cg alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, -C hydroxyalkyl, C j-Cg alkoxy, C 1 -Cg haloalkoxy, C 3 -Cg cycloalkoxy, C 3 -Cg halocycloalkoxy, C 4 -CK) cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -C haloalkenyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg
alkylcarbonyloxy, C^-Cg alkylthio, C 1 -Cg haloalkylthio, C 3 -Cg cycloalkylthio, C 1 -Cg alkylsulfinyl, C 1 -Cg haloalkylsulfinyl, C 1 -Cg alkylsulfonyl, C 1 -Cg haloalkylsulfonyl or C 3 -Cg cycloalkylsulfonyl; and
each R 22 is independently C 1 -Cg alkyl or C 1 -Cg haloalkyl.
Embodiment PB. A compound of Embodiment PA wherein
A is A-l, A-3 or A-5;
Bl is C-l;
B 2 is C-3;
B 3 is C-l;
R 2 is phenyl or -W 3 (phenyl), each optionally substituted on ring members with up to two substituents selected from R 21 ; or -G; or C 1 -Cg alkyl or C 3 -Cg cycloalkyl; R 3 is hydroxy or C 2 -Cg alkylcarbonyloxy;
R 9 is CH 2 CH 3 ;
R 10 is H or CH 3 ;
G is G-2, G-3 or G-l 5; and
R 21 is independently halogen, nitro, C 1 -Cg alkyl, C 1 -Cg haloalkyl, C 1 -Cg alkoxy, C 1 -Cg haloalkoxy or C 1 -Cg alkylthio.
Embodiment PC. A compound of Embodiment PB wherein A is A-l;
R 1 is
each Q 1 and Q 2 is O;
Q 3 is C 2 -alkylene;
R 32 is H or methyl;
W 5 is C 3 -C 4 alkylene;
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl or 2-thienyl;
R 3 is hydroxy or -OC(=0)CH 2 CH(CH 3 ) 2 ;
each R 14 , R 15 , R 18 and R 19 is H or CH 3 .
Embodiment PD. A compound of Embodiment B wherein
A is A-l;
R 1 is -WiC^E^R 24 ;
E 1 is NOR 28 ;
R 28 is H or methyl;
R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 3-bromophenyl, 3-chlorophenyl, 4-chlorophenyl, 3 -fluorophenyl 3,5-difluorophenyl, 3-thienyl 2-thienyl or 2-pyridinyl;
R 3 is hydroxy or -OC(=0)CH 2 CH(CH 3 ) 2 ; and
each R 14 , R!S, RIS and R 19 is H.
Embodiment PE. A compound of Embodiment PB wherein
A is A-l;
R 1 is -G A ;
each G A is a 5- to 6-membered carbocyclic ring including ring members selected from C(=0) or C(=N-OR 30 ); or a 9- to 10-membered saturated heterospirocyclic ring system optionally including ring members selected from C(=0) or C(=N-OR 30 ), each ring or ring system optionally substituted with up to two substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
R 30 is R 30 is H or methyl;
R 21 halogen or C r C 3 alkyl;
R 22 is C r C 3 alkyl;
Embodiment PF. A compound of Embodiment PE wherein G A is selected from G A -1, G A -2, G A -3, G A -7, G A -8 and G A -9. R 2 is phenyl, 2-methylphenyl, 3-methylphenyl, 4-chlorophenyl, 3 -fluorophenyl or
3 ,5-difluorophenyl;
R 3 is hydroxy; and
each R 14 , R 15 , R 18 and R 19 is H.
Specific embodiments include a compound of Formula IP selected from:
3-(l,4-Dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l-cycloh exen-l-yl)carbonyl]-2-phe nyl-4(3H)-pyrimidinone (Compound 1) and
5-[(2-Hydroxy-6-oxo-l-cyolohexen-l-yl)carbonyl]-6-oxo-2-phen yl-
1 (6H)-pyrimidineacetaldehyde l-(O-methyloxime) (Compound 2). This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the compounds of embodiments described above.
As mentioned above, this invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3 -phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (blO) auxin transport inhibitors, (bl 1) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (bl3) homogentisate solenesyltransferase (HST) inhibitors, (bl4) other herbicides including mitotic disrupters, organic arsenicals, asulam, difenzoquat, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, etobenzanid, fosamine, fosamine-ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb, and (bl5) herbicide safeners; and salts of compounds of (bl) through (bl5).
"Photosystem II inhibitors" (bl) are chemical compounds that bind to the D-l protein at the Qg-binding niche and thus block electron transport from to Qg in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The Qg-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, atrazine, cyanazine, desmetryne, dimethametryn, prometon, prometryne, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryne, trietazine, hexazinone, metamitron, metribuzin, amicarbazone, bromacil, lenacil, terbacil, chloridazon, desmedipham, phenmedipham, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, propa il, pentanochlor, bromofenoxim, bromoxynil, ioxynil, bentazon, pyridate and pyridafol.
"AHAS inhibitors" (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for DNA synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl (including sodium salt), foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron-methyl (including sodium salt), mesosulfuron-methyl, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl, tritosulfuron, imazapic, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazethapyr, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, bispyribac-sodium, pyribenzoxim, pyriftalid, pyrithiobac-sodium, pyriminobac-methyl, thiencarbazone, flucarbazone-sodium and propoxycarbazone-sodium.
"ACCase inhibitors" (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. Examples of ACCase inhibitors include clodinafop, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, propaquizafop, quizalofop, alloxydim, butroxydim, clethodim, cycloxydim, pinoxaden, profoxydim, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P -ethyl.
Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimics" (b4) are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Examples of auxin mimics include but are not limited to aminocyclopyrachlor, aminopyralid benazolin-ethyl, chloramben, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, mecoprop, MCPA, MCPB, 2,3,6-TBA, picloram, triclopyr, quinclorac and quinmerac.
"EPSP (5-enol-pyruvylshikimate-3-phosphate) synthase inhibitors" (b5) are chemical compounds that inhibit the enzyme, 5 -enol-pyruvylshikimate-3 -phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).
"Photosystem I electron diverters" (b6) are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles "leak", leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include paraquat and diquat.
"PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out. Examples of PPO inhibitors include acifluorfen-sodium, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, oxyfluorfen, fluazolate, pyraflufen-ethyl, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, fluthiacet-methyl, thidiazimin, oxadiazon, oxadiargyl, saflufencil, azafenidin, carfentrazone, carfentrazone-ethyl, sulfentrazone, pentoxazone, benzfendizone, butafenacil, pyraclonil, profluazol and flufenpyr-ethyl.
"GS (glutamine synthase) inhibitors" (b8) are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P and bilanaphos.
"VLCFA (very long chain fatty acid) elongase inhibitors" (b9) are herbicides having a wide variety of chemical structures, which inhibit the elongase. Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs. In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, butachlor, dimethachlor, dimethanamid, metazachlor, metolachlor, pethoxamid, pretilachlor, propachlor, propisochlor, pyroxasulfone, thenylchlor, diphenamid, napropamide, naproanilide, fenoxasulfone, flufenacet, indanofan, mefenacet, fentrazamide, anilofos, cafenstrole, piperophos including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.
"Auxin transport inhibitors" (blO) are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include but are not limited to naptalam (also known as N-(l-naphthyl)phthalamic acid and 2-[(l-naphthalenylamino)carbonyl]benzoic acid) and diflufenzopyr.
"PDS (phytoene desaturase inhibitors) (bl l) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include norflurzon, diflufenican, picolinafen, beflubutamide, fluridone, flurochloridone and flurtamone.
"HPPD (4-hydroxyphenyl-pyruvate-dioxygenase) inhibitors" (bl2) are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxy- phenyl-pyruvate-dioxygenase. Examples of HPPD inhibitors include, but are not limited to mesotrione, sulcotrione, topramezone, tefuryltrione, tembotrione, isoxachlortole, isoxaflutole, benzofenap, pyrasulfatole, pyrazolynate, pyrazoxyfen, bicyclopyrone and benzobicyclon.
"HST" (homogentisate solenesyltransferase) inhibitors (bl3) disrupt a plant's ability to convert homogentisate to 2-methyl-6-solanyl-l,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include haloxydine, pyriclor and the compounds of Formulae A, B and C
B C
HST inhibitors also include the compounds of Formulae D and E
E
wherein R dl is H, CI or CF 3 ; R* 12 is H, CI or Br; R d3 is H or CI; R d4 is H, CI or CF 3 ; R d5 is CH 3 , CH 2 CH 3 or CH 2 CHF 2 ; and R d6 is OH, or -OC(=0)-i-Pr; and R el is H, F, CI, CH 3 or CH 2 CH 3 ; R e2 is H or CF 3 ; R e3 is H, CH 3 or CH 2 CH 3 ; R^ is H, F or Br; R e5 is CI, CH 3 , CF 3 , OCF 3 or CH 2 CH 3 ; R e6 is H, CH 3 , CH 2 CHF 2 or C≡CH; R e7 is OH, -OC(=0)Et, -OC(=0)-z-Pr or -OC(=0)-t-Bu; and A e8 is N or CH.
Other herbicides (bl4) include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and fiamprop-M-isopropyl) organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors. Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (bl) through (bl2) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, clomezone, fluometuron, difenzoquat, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, methiozolon, ipfencarbazone, etobenzanid, fosamine, fosamine-ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb.
"Herbicide safeners" (bl5) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include but are not limited to allidochlor, benoxacor, l-bromo-4-[(chloromethyl)sulfonyl]benzene, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, 4-(dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660),
2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride and oxabetrinil.
One or more of the following methods and variations as described in Schemes 1-18 can be used to prepare the compounds of Formula 1. The definitions of A, B 1 , B 2 , B 3 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 and R 13 in the compounds of Formulae 1-34 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae la-lh are various subsets of the compounds of Formula 1, and all substituents for Formulae la-lh are as defined above for Formula 1.
Compounds of Formula la, lb or lc (where R 3 is hydroxy) can be prepared via the two-step process shown in Schemes la, lb and lc respectively. Intermediate 4a, 4b or 4c can be prepared by reacting dione 2 with intermediate 3 where G 1 is a nucleophilic reaction leaving group (e.g., G 1 is a halogen, alkoxycarbonyl, haloalkylcarbonyloxy, haloalkoxycarbonyloxy, pyridinyl or imidazoyl group). Reaction of intermediate 4a, 4b or 4c with the appropriate cyano compound (e.g., acetone cyanohydrin, potassium cyanide, sodium cyanide) in the presence of a base such as triethylamine or pyridine leads to a compound of Formula la, lb or lc. Alternativly a fluoride anion source such as potassium fluoride or cesium fluoride and optionally in the presence of a phase transfer catalyst (e.g. tetrabutyl ammonium bromide, etc.) can be used in this transformation. A solvent such as dimethylsulfoxide, N,N-dimethylformamide, acetonitrile or dichloromethane at ambient temperature to the reflux temperature of the solvent can lead to a compound of Formula la, lb or lc. (Formula la is Formula 1 wherein A is A-l; Formula lb is Formula 1 wherein A is A-2; Formula lc is Formula 1 wherein A is A-3.) Alternatively, compounds of Formula la, lb or lc can be prepared by Process 2 (in Schemes la, lb and lc respectively) by reacting dione 2 a, 2b or 2c with intermediate 3 in the presence of a cyano compound or a fluoride anion source along with a base. For additional reaction conditions for this general coupling methodology, see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 and references cited therein.
Scheme la
me lb
Compounds of Formula la, lb or lc can also be prepared as shown in Scheme 2, by reacting dione 2a, 2b or 2c with intermediate 3 a in the presence of a base or Lewis acid. For reaction conditions for this general coupling methodology, see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 and references cited therein.
Scheme 2
As shown in Scheme 3, intermediate 4a, 4b or 4c can also be prepared by allowing dione 2a, 2b or 2c to react with acid 6 in the presence of a dehydrating condensation agent such as 2-chloro-l-pyridinium iodide (known as the Mukaiyama coupling agent), dicyclohexyl carbodiimide (DCC) or the like and optionally in the presence of a base. For additional reaction conditions for this general enol ester coupling methodology, see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley Weinheim, 2007; Chapter 4.3 and references cited therein.
Scheme 3
Intermediate 4 a, 4b or 4c can also be made by the palladium-catalyzed carbonylation reaction of a compound of Formula 7 in the presence of dione 2a, 2b or 2c (Scheme 4). For reaction conditions for this general enol ester forming methodology, see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 and references cited therein.
Scheme 4
O
Pd, CO
Hal is CI, Br o I
Compounds of Formula la, lb or lc (where R 3 is bonded through oxygen) are prepared by reacting compounds of Formula la, lb or lc with intermediate 8 where X is a nucleophilic reaction leaving group, also known as a nucleofuge in the presence of a base as shown in Scheme 5. Alternatively, compounds of Formula la, lb and lc (where R 3 is bonded through nitrogen, sulfur or carbon) can be prepared using the appropriate halogenating agent followed by nucleophilic addition. For reaction conditions for this general functionalization method, see Edmunds, A. or Almisick A. V. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 or Chapter 4.4, and references cited therein. Scheme 5
As shown in Scheme 6, compounds of Formula Id (i.e. Formula 1 wherein A is A-4 and R 3 is OH) can be prepared by the reaction of intermediate 9 with intermediate 3 in the presence of a Lewis base, for example ra-butyllithium or lithium diisopropylamide in an appropriate solvent such as tetrahydrofuran or diethyl ether. For reaction conditions for this type of transformation, see JP 2003327580.
Scheme 6
Compounds of Formula le (i.e. Formula 1 wherein A is A-5 and R 3 is OH) can be prepared via a two-step process as shown in Scheme 7. Intermediate 12 can be prepared by reacting pyrazole 11 with intermediate 3 where G 1 is a nucleophilic reaction leaving group (i.e. G 1 is a halogen atom, alkoxycarbonyl, haloalkylcarbonyloxy, benzoyloxy, pyridinyl or imidazoyl group). Reaction of intermediate 12 with the appropriate cyano compound in the presence of a base leads to a compound of Formula le. Alternatively, a compound of Formula le can be prepared directly by reacting intermediate 11 with intermediate 3 (Process 2, Scheme 7) in the presence of a cyano compound or a fluoride anion source with a base. For reaction conditions for this general coupling methodology, see Almisick A. V. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.4, and references cited therein. Scheme 7
Compounds of Formula If (i.e. Formula 1 wherein A is A-5) wherein R 3 is bonded through oxygen can be prepared by reacting a compound of Formula le with intermediate 8 (where X is a nucleophilic reaction leaving group, also known as a nucleofuge) in the presence of a base as shown in Scheme 8. Alternatively compounds of Formula If wherein R 3 is bonded through nitrogen, sulfur or carbon can be prepared using the appropriate halogenating agent followed by nucleophilic displacement. For reaction conditions for these general functionalization methods, see Almisick A. V. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.4, and references cited therein.
Scheme 8
Compounds of Formula 17 can be prepared by reacting intermediate 3 with a compound Formula 16 in an appropriate solvent in the presence of a base. Thereafter intermediate 17 can be rearranged into the compound of Furmula lg (i.e. Formula 1 wherein A is A-7) in the presence of a cyano compound and a base as shown in Scheme 9. For reaction conditions for this general coupling methodology, see Almisick A. V. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.4, and references cited therein. Scheme 9
Compounds of Formula 19 can be prepared from corresponding compounds of Formula lg wherein R 13 is an alkoxycarbonyl in the presence of an acid such as hydrogen chloride, sulfuric or acetic acid and optionally in the presence of a solvent such as tetrahydrofuran, diethyl ether or dichloromethane as shown in Scheme 10. Intermediate 19 is then reacted with an orthoformate ester or N,N-dimethylformamide dimethylacetal (DMF-DMA) in the presence of an acid to obtain intermediate 20. Reaction of intermediate 20 with hydroxylamine hydrochloride salt in a solvent such as ethanol, acetonitrile, water or acetic acid provides isoxazole compounds of Formula lh (i.e. Formula 1 wherein A is A-6 and R 1 1 is H). For reaction conditions for this general cyclization methodology, see Almisick A. V. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.4, and references cited therein.
Scheme 10
As illustrated in Scheme 11, sulfoxides and sulfones of Formula 1 wherein R 2 is a substituent bonded through a sulfoxide or sulfone radical can be prepared by oxidation of the compounds of Formula 1 wherein R 2 is a substituent bonded through a sulfide radical. In a typical procedure, an oxidizing agent in an amount from 1 to 4 equivalents depending on the oxidation state of the product desired is added to a solution of the compound of Formula 1 in a solvent. Useful oxidizing agents include Oxone® (potassium peroxymonosulfate), hydrogen peroxide, sodium periodate, peracetic acid and 3-chloroperbenzoic acid. The solvent is selected with regard to the oxidizing agent employed. Aqueous ethanol or aqueous acetone is preferably used with potassium peroxymonosulfate, and dichloromethane is generally preferable with 3-chloroperbenzoic acid. Useful reaction temperatures typically range from 0 to 90 °C. Particular procedures useful for oxidizing sulfides to sulfoxides and sulfones are described by Brand et al., J. Agric. Food Chem. 1984, 32, 221-226 and references cited therein.
Scheme 11
One skilled in the art will realize that acid chlorides of Formula 3d (i.e. Formula 3 wherein G 1 is CI) are easily prepared from the acid of Formula 6 (Scheme 12) by numerous well-known methods. For example reacting the acid with a chlorinating reagent such as oxalyl chloride or thionyl chloride in a solvent such as dichloromethane or toluene and optionally in the presence of a catalytic amount of NN-dimethylformamide can provide the corresponding acid chloride of Formula 3d.
Scheme 12
Compounds of Formula 6 can be prepared from esters of Formula 23 by numerous well-known methods, for example standard saponification procedures using aqueous bases such as LiOH, NaOH or KOH in a solvent such methanol or ethanol as described in Scheme 13. Alternatively, a dealkylating agent such as lithium iodide or trimethylsilyl iodide can be used in the presence of a base in a solvent such as pyridine or ethyl acetate. Additional reaction procedures for deesterification can be found in PCT Patent Publication WO 2006/133242. Boron tribromide (BB^) can alternatively be used to to prepare a compound of Formula 6 from a compound of Formula 23 in a solovent such as dichloromethane. Procedures using boron tribromide can be found in Bioorg. & Med. Chem. Lett. 2009, 19(16), 4733-4739. Scheme 13
Pyrimidinone esters of Formula 23a (i.e. Formula 23 whererin Alk is ethyl, X is CH and Y is C(O)) are prepared as illustrated in Scheme 14 by N-alkylation of pyridones of Formula 26 with agents such as alkyl halides in the presence of a base such as sodium hydride or potassium carbonate in a solvent such as N,N-dimethylformamide, tetrahydrofuran or diethyl ether.
Scheme 14
Pyrimidinone esters of Formula 23a can be made by the method of Scheme 15. In this method an methylene malonate of Formula 28 is cyclized with an amidine salt of Formula 29 wherein X is a halogen or sulfonate counter ion in the presence of excess base such as sodium alkoxide or potassium carbonate in an appropriate solvent such as ethanol (generally at the reflux temperature of the solvent) to give the corresponding pyrimidinone of Formula 3f. Examples of this synthetic method are reported in PCT Patent Publication WO 2006/133242 and Tetrahedron 2001, 57, 2689.
Scheme 15
Pyrimidinone esters of Formula 26 can be prepared by the method of Scheme 16. In this method, an ethylene malonate of Formula 28 is cyclized with an amidine salt Formula 29a wherein X is a halogen or sulfonate counter ion in the presence of excess base such as sodium alkoxide or potassium carbonate in an appropriate solvent such as methanol (generally at the reflux temperature of the solvent) to give the corresponding pyrimidinone of Formula 26. Examples of this synthetic procedure are reported in PCT Patent Publication WO 2006/133242 and Tetrahedron 2001, 57, 2689.
Scheme 16
Pyrimidone esters of Formula 23-Xl can be transformed to pyrimidone esters of Formula 23-X3 and 23-X4 by the method of Scheme 17. In this method 23-Xl is contacted with an acid such as HC1 or H2SO4 in an aprotic solvent such as dioxane, or a protic solvent such as methanol or ethanol at a temperature between 0° C and the boiling point of that solvent to yield aldehydes or ketones of Formula 23-X2. Subsequently, or concurrently, aldehydes or ketones of Formula 23-X2 can be reacted with substituted hydroxylamines or hydrazines in the presence of an acid catalyst such as HC1 or H2SO4 in an aprotic solvent such as dioxane, or a protic solvent such as methanol or ethanol at a temperature between 0° C and the boiling point of that solvent to yield compounds of Formula 23-X3 and 23-X4 which can be further reacted by methods described in Schemes 1 - 16. One skilled in the art will recognize that aldehydes and ketones of Figure 23-X2 can be further converted to many other functionalities by a myriad of methods known in the chemical literature.
Scheme 17
Amidines of Formula 29 can be prepared from amines of Formula 29X and nitriles of Formula 29Y according to many methods, including, but not limited to, those described in: European Patent Application EP 80592; J. Org. Chem. 2010, 75, 945-947; Chemistry - A European Journal 2009, 15, 7292-7296; Organic Process Research & Development 2008, 12, 1201-1208; Org. Lett, 2008, 10, 445-448.
Scheme 18
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1.
One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. l H NMR spectra are reported in CDCI3 in ppm downfield from tetramethylsilane at 400 MHz unless otherwise noted; "s" means singlet, "m" means multiplet, "br s" means broad singlet, "d" means doublet, "dd" means doublet of doublets, "t" means triplet, "td means triplet of doublets, "dt" means doublet of triplets and "q" means quartet.
EXAMPLE 1
Preparation of
3-(l,4-Dioxaspiro[4.5]dec-8-yl)-5-[(2-hydroxy-6-oxo-l-cycloh exen-l-yl)carbonyl]-2-phenyl-4
(3H)-pyrimidinone (Compound 1)
Step A: Preparation of
1 -( 1 ,4-dioxaspiro[4.5]dec-8-yl)- 1 ,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecar boxylic acid methyl ester
To ethylbenzimidate hydrochloride (1.1 g, 5.9 mmol) dissolved in 15 ml of methanol was added l,4-dioxa-spiro[4.5]dec-8-ylamine (1.0 g, 6.8 mmol). The mixture was stirred at ambient temperature for 16 h, after which time a 25% w/w solution of sodium methoxide (1.3 g, 6.1 mmol) was then added, and stirring was continued for 20 minutes. The mixture was concentrated to dryness, and the residual
N-l,4-dioxaspiro[4.5]dec-8-ylbenzenecarboximidamide hydrochloride was suspended in 20 ml acetonitrile and treated with dimethyl methoxymethylenemalonate (1.13 g, 6.5 mmol), followed by DBU (0.9 g, 5.9 mmol). The reaction mixture was refluxed for 16 h and then concentrated under reduced pressure, and purified by medium pressure liquid chromatography on silica gel eluting with 30%- 100% ethyl acetate in hexanes to provide 1.2 g of the title compound as an oil.
in NMR (CDCI3) 6 8.61 (d, 1H), 7.49-7.61 (m, 3 H), 7.42-7.48 (m, 2H), 3.98^1.08 (m, 1H), 3.86-3.94 (m, 7H), 3.09 (m, 2H), 1.76 (d, 2H), 1.64 (d, 2H), 1.27-1.34 (m, 2H).
Step B: Preparation of l-(l,4-Dioxaspiro[4.5]dec-8-yl)-l,6-dihydro6-oxo-2- phenyl-5-pyrimidinecarboxylic acid
To a solution of (l-(l,4-dioxaspiro[4.5]dec-8-yl)-l,6-dihydro-6-oxo-2-phenyl- 5-pyrimidinecarboxylic acid methyl ester (the product of Example 1, Step A) (0.40 g, 1.1 mmol) in 10 ml of ethyl acetate was added lithium iodide (0.43 g, 3.2 mmol). The reaction mixture was refluxed for 16 h and then cooled to ambient temperature and diluted with water. The mixture was made acidic with IN HC1 and extracted three times with ethyl acetate. The combined organic layers were then extracted with IN NaOH. The resulting aqueous layer was made acidic with concentrated HC1 and extracted three times with dichloromethane. The combined organic layers were then dried with MgSC>4, filtered and concentrated under reduced pressure to yield 0.39 g of the title compound as a solid.
!H NMR (CDCI3) 6 8.95 (s, 1H), 7.59 (m, 3H), 7.51 (s, 2H), 4.19 (m, 1H), 3.99 (s, 2H), 3.92 (s, 2H), 3.06 (m, 2H), 1.82 (d, 2H), 1.73 (d, 2H), 1.34 (m, 2H). Step C: Preparation of 3-(l,4-dioxaspiro[4.5]dec-8-yl)-5-[2-hydroxy-6-oxo-l- cyclohexen-l-yl]carbonyl]-2-phenyl-4(3H)-pyrimidinone (Compound 1) A solution of l-(l,4-Dioxaspiro[4.5]dec-8-yl)-l,6-dihydro-6-oxo-2-p enyl- 5-pyrimidinecarboxylic acid (the product of Example 1, Step B) (0.39 g, 1.1 mmol) in 10 ml dichloromethane was treated with oxalyl chloride (196μ1, 2.3 mmol) and 1 drop of N,N- dimethylformamide. The reaction was stirred for 1 h then concentrated and redissolved in 10ml dichloromethane. 1,3-cyclohexanedione (0.14 g, 1.2mmol) and triethylamine (310 μΐ, 2.2 mmol) were added and the reaction mixture was stirred at ambient temperature for 20 min and then treated with additional triethylamine (310 μΐ, 2.2 mmol) followed by 2 drops acetone cyanohydrin. The reaction mixture was stirred at ambient temperature for 16 h and then concentrated under reduced pressure and purified by medium pressure liquid chromatography on silica gel eluting with 0% - 3% methanol in chloroform to yield 0.060 g of the title compound, a compound of the present invention.
lH NMR (CDCI3) 5 16.58 (s, 1H), 7.98 (s, 1H), 7.50 (m, 5H), 3.99 (s, 1H), 3.89 (m, 4H), 2.95 (d, 2H), 2.72 (t, 2H), 2.50 (m, 2H), 2.08 (m, 2H), 1.72 (m, 4H), 1.29 (m, 2H).
EXAMPLE 2
Preparation of 5-[(2-hydroxy-6-oxo-l-cyolohexen-l-yl)carbonyl]-6-oxo-2-phen yl- l(6H)-pyrimidineacetaldehyde l-(O-methyloxime) (Compound 2) Step A: Preparation of N-(2,2-dimethoxyethyl)benzenecarboximidamide
Sodium methoxide (0.75 g, 14.56 mmol) was added portionwise to a stirred solution of benzonitrile (15.0 g, 145.6 mmol) in MeOH (150 mL) under nitrogen atmosphere at room temperature and stirred for 12 h. Acetic acid (0.5 mL) was added, the resulting mixture stirred for 20 minutes, followed by the addition of 2,2-dimethoxyethylamine (18.34 g, 174.75 mmol) The reaction mixture was stirred overnight, concentrated under reduced pressure, the residue dissolved in methylene chloride and washed with water. The organic layer was dried and concentrated under reduced pressure to afford the the title compound as a white solid (15.5 g).
! H NMR (CDCI3) δ 7.49-7.61 (m, 5H), 4.64 (m, 1H), 3.55 (m, 2H), 3.44 (s, 6H).
Step B: Preparation of Methyl l-(2,2-dimethoxyethyl)-l,6-dihydro-6-oxo- 2-phenyl-5 -pyrimidinecarboxylate
To a stirred solution of N-(2,2-Dimethoxyethyl)benzenecarboximidamide (15 g, 72.1 mmol) in acetonitrile (150 mL) was added dimethyl methoxymethylenemelonate (13.8 g, 79.3 mmol) followed by DBU (3.28 g, 21.6 mmol). The reaction mixture heated it at 120 °C for 6 h, cooled to room temperature and concentrated under reduced pressure. The residue was purified by column chromatography (60% ethyl acetate in hexane) to afford the title product (6 g). in NMR (CDCI3) 5 8.73 (s, 1H), 7.49-7.57 (m, 5H), 4.87 (m, 1H), 4.16 (m, 2H), 3.94 (s, 3H), 3.31 (s, 6H).
Step C: Preparation of l,6-dmydro-l-[2-(methoxyimino)ethyl]-6-oxo-2-phenyl-5- pyrimidinecarboxylic acid methyl ester
To a stirred solution of methyl l-(2,2-dimethoxyethyl)-l,6-dihydro-6- oxo-2-phenyl-5-pyrimidinecarboxylate (3.5 g, 11.0 mmol) in ethanol (10 mL), added catalytic amount of ?-toluenesulfonic acid and O-methylhydroxylamine hydrochloride (2.0 g, 24.2 mmol). The reaction mixture was warmed to reflux for 4 h then concentrated under reduced pressure. The residue was dissolved in dichloromethane (100 mL) and washed with saturated sodium bicarbonate solution (20 mL). The organic layer was dried (MgS0 4 ) and concentrated under reduced pressure and the residue was purified by column chromatography (100% of ethyl acetate in hexane to afford the title product (1.0 g)
!H NMR (CDCI3) δ 8.65 (s, 1H), 7.40-7.51 (m, 5H), 6.72 (m, 1H), 4.73 (m, 1H), 4.61 (m, 1H), 3.86 (s, 3H), 3.72 (s, 3H).
Step D: Preparation of l,6-dihydro-l-[2-(methoxyimino)ethyl]-6-oxo-2-phenyl-5- pyrimidinecarboxylic acid
To a stirred solution of l,6-dihydro-l-[2-(methoxyimino)ethyl]-6-oxo- 2-phenyl-5-pyrimidinecarboxylic acid methyl ester (0.8 g, 2.6 mmol) in ethyl acetate (10 mL) was added lithium iodide (0.88 g, 6.6 mmol). The reaction mixture was warmed to reflux and stirred for 4 h. The reaction mixture was concentrated and the residue was dissolved in water and added IN hydrochloric acid until the pH = 4 then extracted with dichloromethane (100 mL). The organic layer was dried (MgSO an d concentrated under reduced pressure to afford the the title compound as a white solid (0.7 g).
!H NMR (CDCI3) δ 8.93 (s, 1H), 7.45-7.55 (m, 5H), 6.72 (m, 1H), 4.84 (m, 1H), 4.22 (m, 1H), 3.68 (s, 3H).
Step E: Preparation of 3-oxo-l-cyclohexen-l-yl
l,6-dihydro-l-[2-(methoxyimino)ethyl]6-oxo- 2-phenyl-5 -pyrimidinecarboxylate
To a stirred solution of l,6-dihydro-l-[2-(methoxyimino)ethyl]-6-oxo- 2-phenyl-5-pyrimidinecarboxylic acid (0.25 g, 0.87 mmol) in dichloromethane (10 mL) eas added N-methyl 2-chloropyridimnium iodide (0.33 g, 1.3 mmol) and the resulting mixture stirred for 15 min. at room temperature. Cyclohexanedione (0.14 g, 1.3 mmol) followed by triethylamine (0.21 g, 2.17 mmol) were added and the reaction mixture stirred for 12 h at room temperature. The reaction mixture was diluted with dichloromethane (30 mL) and washed with ice water (20 mL), dichloromethane layer was separated and washed with brine (20 mL), dried over (MgS0 4 ) and concentrated under reduced pressure and the residue was purified by column chromatography (75% ethyl acetate in hexane) to afford the title compound ( 0.2 g). LC S: 382 (M +1).
Step F: Preparation 5-[(2-hydroxy-6-oxo-l-cyolohexen-l-yl)carbonyl]-6-oxo-2- phenyl- 1 (6H)-pyrimidineacetaldehyde l-(O-methyloxime)
To a stirred solution of 3-oxo-l-cyclohexen-l-yl l,6-dihydro-l-[2-(methoxyimino)ethyl]-6-oxo-2-phenyl-5-pyrim idinecarboxylate (0.2 g, 0.52 mmol) in acetonitrile (5 mL) added triethylamine (0.07 g, 0.78 mmol), followed by acetone cyanohydrin (3 drops, cat) and stirred for 6 h at room temperature. Reaction mixture was concentrated under reduced pressure and the residue diluted with methylene chloride (30 mL) and washed with water (20 mL). The dichloromethane layer was dried over (MgSO^ and concentrated under reduced pressure and the residue was purified by column chromatography (100% of ethyl acetate in hexanes to afford the title compound (20 mg)). in NMR (CDCI3) δ 8.93 (s, 1H), 7.45-7.59 (m, 5H), 6.68 (m, 1H), 4.70 (m, 1H), 4.57 (m, 1H), 3.68 (s, 3H), 2.96 (m, 2H), 2.49 (m, 2H), 0.94 (m, 2H).
EXAMPLE 3
Preparation of 2-cyclopropyl-5-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl ]-3-(4- mo holinyl)-4(3H)-pyrimidinone (Compound 22) Step A: Preparation of methyl 2-cyclopropyl-l,6-dihydro-l-(4-morpholinyl)-6-oxo-5- pyrimidinecarboxylate
N-aminomorpholine (1.37 g, 13.4 mmol) was added to a solution of ethyl cyclopropylimidate hydrochloride salt (2.0 g, 13.4 mmol) in methanol (19 mL), which was then stirred at room temperature for 16 h. Sodium methoxide solution (25% w/w in methanol, 3.18 g, 14.7 mmol) was added and the solution was stirred for 30 min. The solution was concentrated in vacuo and dissolved in acetonitrile (20 mL). Dimethyl methoxymethylenemalonate (2.56 g, 14.7 mmol) and l,8-diazabicyclo[5.4.0]undec-7-ene (0.83 g, 5.3 mmol) were added and the mixture was heated to reflux for 4 h before being concentrated under reduced pressure and purified by medium pressure liquid chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to provide 1.14 g of the title compound as a yellow oil.
lH NMR (500 MHz) δ ppm 8.46 (s, 1H), 4.31 (td, 2H), 3.97 (m, 2H), 3.89 (s, 3H), 3.71 (td, 2H), 2.97 (m, 1H), 2.83 (m, 2H), 1.25 (s, 2H), 1.17 (m, 2H).
Step B: Preparation of 2-cyclopropyl-l,6-dihydro-l-(4-morpholinyl)-6-oxo-5- pyrimidinecarboxylic acid
2-Cyclopropyl-l,6-dihydro-l-(4-morpholinyl)-6-oxo-5-pyrimidi necarboxylate (i.e. the product from Step A) (1.14 g, 4.1 mmol) was dissolved in acetonitrile (2% water by volume) and treated with lithium bromide (powder, 1.77 g, 20.4 mmol) and triethylamine (0.63 g, 6.1 mmol) and stirred at room temperature for 16 h. The crude reaction mixture was diluted with aqueous hydrochloric acid (1 N, 20 mL) and the aqueous layer was extracted with dichloromethane (2 x 40 mL). The organic layers were combined, dried (Ts^SO- , filtered and concentrated under reduced pressure resulting in 0.942 g of title compound as a white solid.
lH NMR (500 MHz) 5 ppm 12.68 (br s, 1H), 8.71 (s, 1H), 4.25 (td, 2H), 4.02 (m, 2H), 3.74 (d, 2H), 3.02 (m, 1H), 2.91 (m, 2H), 1.34 (d, 2H), 1.27 (d, 2H).
Step C: Preparation of 2-cyclopropyl-5-[(2-hydroxy-6-oxo-l-cyclohexen-l- yl)carbonyl]-3-(4-morpholinyl)-4(3H)-pyrimidinone (Compound 22)
To 2-cyclopropyl-l,6-dihydro-l-(4-morpholinyl)-6-oxo-5-pyrimidi necarboxylic acid (i.e. the product from Step B) (0.5 g, 1.9 mmol) in 6 mL of dichloromethane was added 2-chloro-l-methylpyridinium iodide (0.72 g, 2.8 mmol) and cyclohexanedione (0.32 g, 2.8 mmol). Triethylamine (0.48 g, 4.7 mmol) was added dropwise and the solution was stirred for 16 h under an atmosphere of N 2 . The solution was then diluted with dichloromethane (50 mL) and washed with distilled water and brine. The organic layer was dried (N 2S04), filtered and concentrated in vacuo. The crude material was filtered through a plug of silica gel eluting with ethyl acetate. The organic layer was concentrated in vacuo. The crude material was taken up in acetonitrile (10 mL) and 2-hydroxy-2-methyl-propanenitrile (0.015 g, 0.15 mmol) and triethylamine (0.48 g, 4.7 mmol) were added. The solution was stirred at ambient temperature for 16 h. The reaction mixture was then concentrated under reduced pressure and purified by medium pressure liquid chromatography on silica gel eluting with 0 to 5% methanol in dichloromethane to provide 0.95 g of the title compound as a solid.
1H NMR (500 MHz) δ ppm 16.47 (s, 1H), 7.88 (s, 1H), 4.19 (m, 2H), 3.95 (dd, 2H), 3.71 (m, 2H), 2.94 (m, 1H), 2.87 (d, 2H), 2.69 (t, 2H), 2.48 (t, 2H), 2.06 (m, 2H), 1.22 (m, 2H), 1.12 (m, 2H).
EXAMPLE 4
Preparation of 2-cyclopropyl-5-[(2-hydroxy-4-oxobicyclo[3.2.1]oct-2-en-3-yl )carbonyl]-
3-(4-morpholinyl)-4(3H)-pyrimidinone (Compound 23)
Step A: Preparation of 2-cyclopropyl-5-[(2-hydroxy-4-oxobicyclo[3.2.1]oct-2-en-3- yl)carbonyl]-3-(4-morpholinyl)-4(3H)-pyrimidinone (Compound 23)
To 2-cyclopropyl-l,6-dihydro-l-(4-morpholinyl)-6-oxo-5-pyrimidi necarboxylic acid (i.e. the product from Example 3, Step B) (0.5 g, 1.9 mmol) in 6 mL of dichloromethane was added 2-chloro-l-methylpyridinium iodide (0.72 g, 2.8 mmol) and bicyclo[3.2.1]octane-2,4- dione (0.39 g, 2.8 mmol). Triethylamine (0.48 g, 4.7 mmol) was added dropwise and the solution was stirred for 16 h under an atmosphere of nitrogen. The solution was then diluted with dichloromethane (50 mL) and washed with distilled water and brine. The organic layer was dried (T^SC^), filtered and concentrated in vacuo. The crude material was filtered through a plug of silica gel eluting with ethyl acetate. The organic layer was concentrated in vacuo. The crude material was taken up in acetonitrile (10 mL) and 2-hydroxy-2-methyl- propanenitrile (0.015 g, 0.15 mmol) and triethylamine (0.481 g, 4.7 mmol) were added. The solution was stirred at ambient temperature for 16 h. The reaction mixture was then concentrated under reduced pressure and purified by medium pressure liquid chromatography on silica gel eluting with 0 to 5% methanol in dichloromethane to provide 0.199 g of the title compound as a solid.
!H NMR (500 MHz) 5 ppm 16.64 (s, 1H), 7.82 (s, 1H), 4.21 (m, 2H), 3.96 (dd, 2H), 3.71 (m, 2H), 3.07 (m, 1H), 2.93 (m, 2H), 2.88 (d, 2H), 2.22 (d, 1H), 2.13 (m, 2H), 2.00 (m, 1H), 1.85 (m, 1H), 1.71 (m, 1H), 1.20 (m, 2H), 1.11 (m, 2H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 12 can be prepared. The following abbreviations are used in the Tables which follow: Me means methyl, Et means ethyl, «-Pr means normal propyl, z-Pr means isopropyl, c-Pr means cyclopropyl, «-Bu means normal butyl, z-Bu means isobutyl, s-Bu means secondary butyl, c-Bu means cyclobutyl, t-Bu means tertiary butyl, «-pent means normal pentyl, c-Pent means cyclopentyl, «-Hex means normal hexyl, hept means hetpyl, c-Hex means cyclohexyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, thp means tetrahydropyran, thtp means tetrahydrothiopyran, thf means tetrahydrofuran, -CN means cyano, - O2 means nitro, S(0)Me means methylsulfinyl, S0 2 means sulfonyl and S(0) 2 Me means methylsulfonyl.
The present disclosure also includes Tables 1A through 101 A, each of which is constructed the same as Table 1 above except that the row heading in Table 1 (i.e. "R 2 is Ph") is replaced with the respective row headings shown below. For example, in Table 1 A the row heading is "R 2 is Me", and R 1 is as defined in Table 1 above. Thus, the first entry in Table 1 A specifically discloses a compound of Formula 1 wherein R 1 is
R 2 is Me; R 3 is OH; A is A-l; B 1 is C-l; B 2 is C-3; B 3 is C-l; and each R 14 , R 15 , R 18 and R 19 is H. Tables 2A through 101A are constructed similarly.
TABLE 2
Table 2 is constructed the same as Table 1 , except the structure is replaced with
The present disclosure also includes Tables IB through 101B, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 3
Table 3 is constructed the same as Table 1 , except the structure is replaced with
The present disclosure also includes Tables 1C through 101C, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 4
Table 4 is constructed the same as Table 1 , except the structure is replaced with
The present disclosure also includes Tables ID through 10 ID, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 5
Table 5 is constructed the same as Table 1 , except the structure is replaced with
O O O
The present disclosure also includes Tables IE through 10 IE, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 6
Table 6 is constructed the same as Table 1 , except the structure is replaced with
O O O
The present disclosure also includes Tables IF through 101F, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 7
Table 7 is constructed the same as Table 1 , except the structure is replaced with
O O
The present disclosure also includes Tables 1G through 101G, which have row headings for R 2 which are identical to those in Tables 1A through 101 A. TABLE 8
Table 8 is constructed the same as Table 1 , except the structure is replaced with
O O
The present disclosure also includes Tables 1H through 101H, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 9
Table 9 is constructed the same as Table 1 , except the structure is replaced with
O
The present disclosure also includes Tables II through 1011, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 10
Table 10 is constructed the same as Table 1, except the structure is replaced with
The present disclosure also includes Tables 1J through 101 J, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 11
Table 11 is constructed the same as Table 1 except the structure is replaced with
The present disclosure also includes Tables IK through 10 IK, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 12
Table 12 is constructed the same as Table 1 except the structure is replaced with
The present disclosure also includes Tables 1L through 101L, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 13
Table 13 is constructed the same as Table 1 except the structure is replaced with
The present disclosure also includes Tables 1M through 101M, which have row headings for R 2 which are identical to those in Tables 1A through 101 A.
TABLE 14
Table 14 is constructed the same as Table 1 except the structure is replaced with
The present disclosure also includes Tables IN through 10 IN, which have row headings for R 2 which are identical to those in Tables 1A through 101 A. Formulation/Utility
A compound of Formula 1 of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
Sprayable formulations are typically extended in a suitable medium before spraying.
Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N^N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, «-propanol, isopropyl alcohol, fl-butanol, isobutyl alcohol, «-hexanol, 2-ethylhexanol, «-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C 2 2), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface-active agents") generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Em.ulsifi.ers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μπι can be wet milled using media mills to obtain particles with average diameters below 3 μηι. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 um range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, "The
Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-B. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated. Example A
High Strength Concentrate
Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%
Example B
Wettable Powder
Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
Example C
Granule
Compound 1 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)
Example D
Extruded Pellet
Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
Example E
Emulsifiable Concentrate
Compound 1 10.0% polyoxyethylene sorbitol hexoleate 20.0%
C 6 -C 10 fatty acid methyl ester 70.0%
Example F
Microemulsion
Compound 1 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0%
Water 20.0% These compounds generally show highest activity for early postemergence weed control (i.e. applied when the emerged weed seedlings are still young) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Compounds of the invention are particularly useful for selective control of weeds in wheat, barley, and particularly maize, soybean, cotton and perennial plantation crops such as sugarcane and citrus. Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.
As the compounds of the invention have both postemergent and preemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.
A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of a compound of this invention is about 0.001 to 20 kg/ha with a typical range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyr idine- carboxylic acid and its esters (e.g., methyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P -butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, indaziflam, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, IR6396, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB -sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyr idinecarboxylic acid (CAS number 943832-60-8), 4-amino-3-chloro-6-
(4-chloro-2-fluoro-3methoxyphenyl)2-pyridinecarboxylic acid methyl ester (CAS number 943831-98-9) pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P -ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiocarbazil, topramezone, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron and vernolate. Other herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.
General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.
For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1 :3000 and about 3000:1. Of note are weight ratios between about 1 :300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.
Table Al lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 1 in the Component (a) column is identified in Index Table A, The second column of Table Al lists the specific Component (b) compound (e.g., "2,4-D" in the first line). The third, fourth and fifth columns of Table Al lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b). Thus, for example, the first line of Table Al specifically discloses the combination of Component (a) (i.e. Compound 1 in Index Table A) with 2,4-D is typically applied in a weight ratio between 1 : 192 to 6:1. The remaining lines of Table Al are to be construed similarly.
Table A2 is constructed the same as Table Al above except that entries below the "Component (a)" column heading are replaced with the respective Component (a) Column Entry shown below. Compound 2 in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2 the entries below the "Component (a)" column heading all recite "Compound 2" (i.e. Compound 2 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 2 with 2,4-D. Tables A3 through A34 are constructed similarly.
Table Number Component (a) Column Entries Table Number Component (a) Column Entries
A2 Compound 2 A19 Compound 19
A3 Compound 3 A20 Compound 20
A4 Compound 4 A21 Compound 21
A5 Compound 5 A22 Compound 22
A6 Compound 6 A23 Compound 23
A7 Compound 7 A24 Compound 24
A8 Compound 8 A25 Compound 25
A9 Compound 9 A26 Compound 26
A10 Compound 10 A27 Compound 27
Al l Compound 1 1 A28 Compound 28
A12 Compound 12 A29 Compound 29
A13 Compound 13 A30 Compound 30
A14 Compound 14 A31 Compound 31
A15 Compound 15 A32 Compound 32
A16 Compound 16 A33 Compound 33
A17 Compound 17 A34 Compound 34 A18 Compound 18
In certain instances, combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.
Of note is a combination of a compound of the invention with at least one other herbicidal active ingredient. Of particular note is such a combination where the other herbicidal active ingredient has different site of action from the compound of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.
Compounds of this invention can also be used in combination with herbicide safeners such as allidochlor, benoxacor, BCS (l-bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cyometrinil, cyprosulfonamide, dichlormid,
4-(dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660),
2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dicyclonon, dietholate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone ((4-methoxy-3-methylphenyl)(3-methyl- phenyl)methanone), naphthalic anhydride (1,8-naphthalic anhydride) and oxabetrinil to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.
Table Bl lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. The second column of Table Bl lists the specific Component (b) compound (e.g., "Allidochlor" in the first line). The third, fourth and fifth columns of Table Bl lists ranges of weight ratios for rates at which the Component (b) compound is typically applied to a field-grown crop relative to Component (a). Thus, for example, the first line of Table Bl specifically discloses the combination of Component (a) (i.e. Compound 1 identified in Index Table A) with Allidochlor is typically applied in a weight ratio between 1 :48 to 6:1. The remaining lines of Table Bl are to be construed similarly.
Table B2 is constructed the same as Table Bl above except that entries below the "Component (a)" column heading are replaced with the respective Component (a) Column Entry shown below. Thus, for example, in Table B2 the entries below the "Component (a)" column heading all recite "Compound 2" (i.e. Compound 2 in Index Table A), and the first line below the column headings in Table B2 specifically discloses a mixture of Compound 2 with Allidochlor. Tables B2 through B34 are constructed similarly.
Of note is a composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group consisting of 2,4-D, ametryne, aminocyclopyrachlor, aminopyralid, atrazine, bromacil, bromoxynil, bromoxynil octanoate, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron, clopyralid, clopyralid-olamine, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, diflufenican, dimethenamid, dimethenamid-P, diuron, florasulam, flufenacet, flumetsulam, flumioxazin, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluroxypyr, glyphosate (particularly glyphosate-isopropylammonium, glyphosate-sodium, glyphosate-potassium, glyphosate-trimesium), hexazinone, imazamethabenz-methyl, imazaquin, imazethapyr, iodosulf ron-methyl, lactofen, lenacil, linuron, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, MCPA-thioethyl, mesosulfuron-methyl, S-metolachlor, metribuzin, metsulfuron-methyl, nicosulfuron, oxyfluorfen, pendimethalin, pinoxaden, pronamide, prosulfuron, pyroxasulfone, pyroxsulam, quinclorac, rimsulfuron, saflufenacil, sulfentrazone, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, and triclopyr-trietliylammonium.
The following Tests demonstrate the herbicidal eddect of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to the plant species tested. See Index Tables A for compound descriptions. The following abbreviations are used in the Index Tables which follow: "Cmpd." means Compound, Me is methyl, Ph is phenyl, thien means thiophene and c-Pr means cyclopropyl. in NMR spectra are reported in CDCI3 in ppm downfield from tetramethylsilane at 400 MHz unless otherwise noted; "s" means singlet, "m" means multiplet, "br s" means broad singlet, "d" means doublet, "dd" means doublet of doublets, "t" means triplet, "td means triplet of doublets, "dt" means doublet of triplets, and "q" means quartet. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. In the following Index Tables:
dioxaspiro[4.5]dec-8-yl" means
itetrahydro-2-methyl-indazol-5-yl" means
A- IB" means:
1 -( 1 ,3 -dioxolan-2-yl)propan-3 -yl" means ; and '2-(l,3-dioxolan-2-yl)pent-5-yl" means
INDEX TABLE A
INDEX TABLE B
INDEX TABLE C
INDEX TABLE D
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
Seeds of plant species selected from barnyardgrass (Echinochloa crus-galli), large (Lg) crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), and corn {Zea mays) were planted into a blend of loam soil and sand and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time these species were also treated with postemergence applications of test compounds formulated in the same manner.
Plants ranged in height from 2 to 10 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
TEST B
Seeds of plant species selected from blackgrass (Alopecurus myosuroides), downy bromegrass {Bromus tectorum), green foxtail {Setaria viridis), Italian ryegrass {Lolium multiflorum), winter wheat {Triticum aestivum), wild oat (Avena fatua), galium (catchweed bedstraw, Galium aparine), bermudagrass (Cynodon dactylon), Surinam grass (Brachiaria decumbens), cocklebur (common cocklebur, Xanthium strumarium), corn {Zea mays), large crabgrass {Digitaria sanguinalis), woolly cupgrass {Eriochloa villosa), giant foxtail {Setaria faberii), goosegrass {Eleusine indica), johnsongrass {Sorghum halepense), kochia {Kochia scoparia), lambsquarters {Chenopodium album), morningglory {Ipomoea coccinea), nightshade (eastern black nightshade, Solarium ptycanthum), yellow nutsedge {Cyperus esculentus), pigweed {Amaranthus retroflexus), ragweed (common ragweed, Ambrosia elatior), soybean {Glycine max), common (oilseed) sunflower {Helianthus annuus), Russian thistle {Salsola kali), and velvetleaf (Abutilon theophrasti) were planted into a blend of loam soil and sand and treated preemergence with test compounds formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these crop and weed species and also winter barley {Hordeum vulgare), canarygrass {Phalaris minor), chickweed (common chickweed, Stellaria media), windgrass {Apera spica-venti), and deadnettle (henbit deadnettle, Lamium amplexicaule) were planted in pots containing Redi -Earth ® planting medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) comprising spaghnum peat moss, vermiculite, wetting agent and starter nutrients and treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
Plant species in the flooded paddy test consisted of rice {Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test.
Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
TEST C
Seeds of plant species selected from bermudagrass {Cynodon dactylori), Surinam grass {Brachiaria decumbens), large crabgrass (Digiiaria sanguinalis), green foxtail {Setaria viridis), goosegrass {Eleusine indica , johnsongrass {Sorghum halepense), kochia {Kochia scoparia), morningglory (pitted morningglory, Ipomoea lacunosa), purple nutsedge {Cyperus rotundus), ragweed (common ragweed, Ambrosia elatior), black mustard (Brassica nigra), guineagrass {Panicum maximum), barnyardgrass {Echinochloa crus-galli), sandbur (southern sandbur, Cenchrus echinatus), prickly sida (Sida spinosa), Italian ryegrass {Lolium multiflorum), purslane (common purslane, Portulaca oleracea), signalgrass (broadleaf signalgrass, Brachiaria platyphylla), groundsel (common groundsel, Senecio vulgaris), chickweed (common chickweed, Stellaria media), dayflower (Virginia (VA) dayflower, Commelina virginica), bluegrass (annual bluegrass, Poa annua), itchgrass {Rottboellia cochinchinensis), quackgrass (Elytrigia repens), field bindweed {Convolvulus arvensis), spanishneedles {Bidens bipinnata), mallow (common mallow, Malva sylvestris), and Russian thistle {Salsola kali) were planted into a blend of loam soil and sand and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, plants from these weed species were treated with postemergence applications of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm ( 1 - to 4-leaf stage) for postemergence treatments.
Treated plants and controls were maintained in a greenhouse for 14 to 21 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (— ) response means no test result.
TEST D
Seeds of plant species selected from bird's-eye speedwell (Veronica persica), bluegrass (annual bluegrass, Poa annua), blackgrass (Alopecurus myosuroides), canarygrass (Phalaris minor), chickweed (common duckweed, Stellaria media), galium (catchweed bedstraw, Galium aparine), downy bromegrass (Bromus tectorum), field poppy (Papaver rhoeas), field violet (Viola arvensis), green foxtail (Setaria viridis), deadnettle (henbit deadnettle, Lamium amplexicaule), Italian ryegrass (Lolium multiflorum), kochia (Kochia scoparia), lambsquarters (Chenopodium album), oilseed rape (Brassica napus), pigweed (Amaranthus retroflexus), Russian thistle (Salsola iberica), scentless chamomile (Matricaria inodora), spring barley (Hordeum vulgare), spring wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua), wild radish (Raphanus raphanistrum), windgrass (Apera spica-venti), winter barley (Hordeum vulgare), and winter wheat (Triticum aestivum) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, plants from these crop and weed species were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage).
Treated plants and controls were maintained in a controlled growth environment for 14 to 21 days after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table D, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (— ) response means no test result.
TEST E
Seeds of plant species selected from corn (Zea mays), soybean (Glycine max), velvetleaf (Abutilon theophrasti), lambsquarters (Chenopodium album), wild poinsettia (Euphorbia heterophylla), palmer pigweed (Amaranthus palmeri), common waterhemp (Amaranthus rudis), resistant common waterhemp (ALS & HPPD resistant, Amaranthus rudis), ladysthumb smartweed (Polygonum persicaria), Surinam grass (Brachiaria decumbens), large crabgrass (Digitaria sanguinalis), Brazilian crabgrass (Digitaria horizontalis), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), ragweed (common ragweed, Ambrosia elatior), barnyardgrass (Echinochloa crus-galli), sandbur (southern sandbur, Cenchrus echinatus), arrowleaf sida (Sida rhombifolia), Italian ryegrass (Lolium multiflorum), dayflower (Virginia (VA) dayflower, Commelina virginica), field bindweed (Convolvulus arvensis), cocklebur (common cocklebur, Xanthium strumarium), morningglory (Ipomoea coccinea), nightshade (eastern black nightshade, Solanum ptycanthum), kochia (Kochia scoparia), yellow nutsedge (Cyperus esculentus), and hairy beggarticks (Bidens pilosa), were planted into a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, plants from these crop and weed species were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
Treated plants and controls were maintained in a greenhouse for 14 to 21 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table E, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
TEST F
Three plastic pots (ca. 1 -cm diameter) per rate were partially filled with sterilized Tama silt loam soil comprising a 35:50:15 ratio of sand, silt and clay and 2.6% organic matter. Separate plantings for each of the three pots were as follows. Seeds from the U.S. of monochoria {Monochoria vaginalis), smallflower umbrella sedge {Cyperus difformis), ricefield bulrush (Scirpus mucronatus), and purple redstem (Ammannia coccinea), were planted into one 16-cm pot for each rate. Seeds from the U.S. of rice flatsedge {Cyperus iria), bearded sprangletop (Leptochloa fascicularis), one stand of 9 or 10 water seeded rice seedlings (Oryza sativa cv. 'Japonica - M202'), and two stands of 3 or 4 transplanted rice seedlings {Oryza sativa cv. 'Japonica - M202') were planted into one 1 -cm pot for each rate. Seeds from the U.S. of barnyardgrass {Echinochloa crus-galli), and late watergrass {Echinochloa oryzicola) were planted into one 16-cm pot for each rate. Plantings were sequential so that crop and weed species were at the 2.0 to 2.5-leaf stage at time of treatment.
Potted plants were grown in a greenhouse with day/night temperature settings of 30/27 °C, and supplemental balanced lighting was provided to maintain a 16-hour photoperiod. Test pots were maintained in the greenhouse until test completion.
At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Effects of treatments on rice and weeds were visually evaluated by comparison to untreated controls after 21 days. Plant response ratings, summarized in Table F, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (— ) response means no test result.