Patent CA-2109994-A1 (CA)
Title: Herbicidal thiadiazabicyclooctanes
Inventor: BRUNNER HANS-GEORG
IPC: C07D513/04
Filed: 1993-11-25
Abstract: Herbicidal thiadiazabicyclooctanes Abstract:            Thiadiazabicyclooctanes of formula I             (I), wherein Z is oxygen or sulfur; R53 is hydrogen or C1-C6alkyl; R54 is C1-C6alkyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, hydroxy or C1-C6haloalkoxy; or R53 and R54, together with the carbon atom to which they are bonded, form an unsubstituted 3-, 4-, 5- or 6-membered satulated ring; W is a group of formulae W1 to W10         (W1);                (W2);              (W3);            (W4);                    (W5);                     (W6);                  (W7);                     (W8);                  (W9); or                  (W10);   wherein R1, R22, R23, R24, R27, R30, R33, R37, R38 and R41 are each independently of the others hydrogen or halogen; R2  is hydrogen, cyano, nitro, halogen, C1-C4alkyl, C1-C4haloalkoxy or C1-C4haloalkyl; A   is hydrogen, cyano, nitro, -COR3, -X3R4,   ,-COR8,   ,    ,                            ,-N(R13)-SO2-R14,      or  ;       A1  is cyano or -COR16; R3  is halogen, -X4-R5, amino, C1-C4alkylamino, di-C1-C4alkylamino, C2-C4haloalkyl-amino, di-C2-C4haloalkylamino, C1-C4alkoxyalkylamino, di-C1-C4alkoxyalkyl-amino, C3- or C4-alkenylamino, diallylamino, -N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperazino, -O-N=C(CH3)-CH3 or -O-CH2-CH2-O-N=C(CH3)-CH3; R4, R42 and R43 are each independently of the others hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, C1-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C8alkylcarbonyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl that is unsubstituted or is substituted at the phenyl ring by one to three identical or different substituents selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy and C1-C4alkoxy; C1-C6alkyl substituted by cyano, nitro, carboxy, C1-C8alkylthio-C1-C8alkoxycarbonyl, phenyl, halophenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, C1-C4haloalkylphenyl, C1-C4haloalkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkylthiocarbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, C1-C4alkyl-aminocarbonyl, di-C1-C4alkylaminocarbonyl; phenylaminocarbonyl that is unsubstituted or is substituted at the phenyl by one to three identical or different substituents selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy and C1-C4alkoxy or by one substituent selected from cyano and nitro; dioxolan-2-yl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; or dioxanyl that is unsubstituted or substituted by one or two C1-C4alkyl radicals; R5 is hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C2-C8haloalkyl, C1-C10alkyl-thio-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, cyano-C1-C8alkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8alkynyl, C3-C7cycloalkyl, C3-C7cycloalkyl-C1-C4alkyl, halo-C3-C7cycloalkyl, or benzyl that is unsubstituted or is substituted at the phenyl ring by one to three identical or different substituents selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy and C1-C4alkoxy; or is an alkali metal, an alkaline earth metal or an ammonium ion; or is the group --[CHR6(CH2)n4]-COOR7; R6, R20. R21. R26. R28. R32, R34, R39, R40, R46, R47, R49, R50, R51 and R52 are each independently of the others hydrogen or C1-C4alkyl; R7 and R48 are each independently of the other hydrogen, C1-C6alkyl, C3-C8alkenyl, C3-C8alkynyl, C1-C8alkoxy-C2-C8alkyl, C1-C8alkylthio-C1-C8alkyl or C3-C7cyclo-alkyl; R8 is hydrogen or C1-C4alkyl;     R44 and R45 are each independently of the other hydrogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy-C1-C4alkyl; R9 and R10 are each independently of the other C1-C4alkyl, C2-C4haloalkyl or C2-C8alkoxyalkyl; or R9 and R10 together are an ethano-, a propano- or a cyclohexane-1,2-diyl bridge, those groups either being unsubstituted or being substituted by one or two radicals selected from the group C1-C4alkyl, C1-C4haloalkyl and C1-C4hydroxyalkyl; R11 is hydrogen, C1-C5alkyl or C3-C7alkenyl;     R12 is C1-C8alkyl; R13 is hydrogen, C1-C5alkyl, benzyl, C1-C4haloalkyl, C3-C8alkenyl or C3-C8alkynyl; R14 is C1-C6alkyl, C1-C5haloalkyl or di-C1-C4alkylamino; R15 is hydrogen, fluorine, chlorine, bromine, C1-C4alkyl or trifluoromethyl; R16 is chlorine, -X5-R17, amino, C1-C4alkylamino, di-C1-C4alkylamino, C2-C4haloalkyl-amino, di-C2-C4haloalkylamino, C1-C4alkoxyalkylamino, di-C1-C4alkoxyalkyl-amino, C3-C4alkenylamino, diallylamino, -N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperazino, or the group -O-N=C(CH3)-CH3, -O-CH2-CH2-O-N=C(CH3)-CH3 or -N(OR46)-R6; R17 is hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C2-C8haloalkyl, C1-C10alkyl-thio-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, cyano-C1-C8alkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8alkynyl, C3-C7cycloalkyl, C3-C7cycloalkyl-C1-C4alkyl, halo-C3-C7cycloalkyl, or benzyl that is unsubstituted or is substituted at the phenyl ring by one to three identical or different substituents selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy and C1-C4alkoxy; or is an alkali metal, an alkaline earth metal or an ammonium ion, or is the group -[CHR47-(CH2)m]-COOR48 or -[CHR49-(CH2)t-Si(R18)3]; m   is 0,1,2,3 or 4; t   is 0,1,2,3 or 4;     R18 is C1-C4alkyl; R19 is hydrogen, C1-C6alkyl, C2-C4alkenyl or C2-C6alkynyl; halo-substituted C1-C6alkyl, C2-C4alkenyl or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, C1-C6alkyl substituted by cyano or by C3-C6cycloalkyl; carboxy-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, C2-C6haloalkoxycarbonyl-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cyclo-alkyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C5alkylaminocarbonyl-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, benzyl or halo-substituted benzyl, C1-C4alkylsulfonyl, C3-C6alkenyloxy-C1-C4alkyl, C1-C4alkoxycarbonyl, C1-C8alkylcarbonyl,             ,              ,   , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group -[CHR47-(CH2),n]COX6-CHR47-(CH2)m-COOR48; R25, R29, R31, R35 and R36 are each independently of the others hydrogen, C1-C4alkyl, C1-C6haloalkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8alkynyl, C1-C4alkoxy-C1-C8alkyl, cyano-C1-C4alkyl, C1-C8alkoxycarbonyl-C1-C4alkyl, C3-C7cycloalkyl, C3-C7cycloalkyl-C1-C4alkyl, benzyl, C1-C4alkyl substituted by -N-morpholino, -N-thiomorpholino or by -N-piperazino, di-C1-C4alkylamino-C1-C4alkyl, C1-C4alkylaminocarbonyl-C1-C4alkyl, di-C1-C4alkylaminocarbonyl-C1-C4alkyl, C1-C4alkoxycarbonyl or C1-C4alkylcarbonyl; X1, X2, X3, X4, X5 and X6 are each independently of the others oxygen or sulfur;n1, n2, n3 and n4 are each independently of the others 0, 1, 2, 3 or 4; with the provisos that at least one of R1, R2 and A is different from hydrogen; and that when R53 is hydrogen, R54 is different from C1-C4alkyl; and the salts and stereoisomers thereof have good selective pre- and post-emergence herbicidal properties.