HAAKE MANFRED (DE)
ZONDLER HELMUT (CH)
STOLLER ANDRE (FR)
HAAKE MANFRED (DE)
ZONDLER HELMUT (CH)
| EP0075117A2 | 1983-03-30 |
| 1. | A compound of the formula I in which Rj is C C20alkyl, C3C8cycloalkyl, C3C8cycloalkylCjC17alkyl, CjCj7alkylC3C8cycloalkyl, C2C17alkenyl, C3C8cycloalkylC C17alkenyl, C2C17alkenylC3C8cycloalkyl, C2C17alkynyl, C3C8cycloalkylC2C17alkynyl, C2Cj7alkynylC3C8cycloalkyl, C5C8cycloalkenyl, C5C8cycloalkenylCjC17alkyl, CjC 7alkylC5C8cycloalkenyl, C5C8cycloalkenylC2Cι7alkenyl, C2Cj7alkenylC5C8cycloalkenyl, C5CgcycloalkenylC2Cj7alkynyl, C2Cj7alkynylC5C8cycloalkenyl, C3C8cycloalkylC3Cgcycloalkyl, C5C8cycloalkenylC5CgCycloalkenyl, C3C8cycloalkylC5Cgcycloalkenyl, C5C8cycloalkenylC3C8cycloalkyl, C2C17alkynylC2Cj7alkenyl or C2Cj7alkenylC Cj7alkynyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O, OR5, S(O)nR6, COOR7, CONRgR^ NRJQRJJ, =NRJ2, =NNR13RJ4, phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NR10RJJ or CONR8R9, or R is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, OR5, S(O)nR6, COOR7, CONRgRc), NRJQRJ J, =NR12, =NNR13Rj4, CjCj7alkyl, C2Cj7alkenyl, C2C17alkynyl, C3Cgcycloalkyl, CsCgcycloalkenyl, phenyl, biphenyl, naphthyl, CjC17alkyl which is substituted by halogen, cyano, nitro, OR5, CONRgR9 or NR10Rj j, C2C17alkenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NR10Rjj, C2C17alkynyl which is substituted by halogen, cyano, nitro, OR5, CONRgR9 or NRj0Ru, C3C8cycloalkyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NR10RJJ, CsCgcycloalkenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, phenyl which is substimted by halogen, cyano, nitro, OR5, CONR8R9 or NR10RJJ, biphenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, or naphthyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NR10RJJ, or Rj is phenyl, biphenyl, naphthyl, CjCjQalkylphenyl, CjCjQalkylbiphenyl, CjCjQalkylnaphthyl, C CjQalkenylphenyl, C2CjQalkenylbiphenyl, C C10alkenylnaphthyl, C2CjQalkynylphenyl, GjCjoalkynylbiphenyl or C2C10alkynylnaphthyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, OR5, S(O)nR6, COOR7, CONR8R9 or NR10Rjj, in which R5 is hydrogen, CjC6alkyl, CjC6haloalkyl, C C6alkoxyalkyl, CrC6cyanoalkyl, phenyl, halophenyl, CjC4alkoxyphenyl, phenylC C4alkyl, CjC7alkylcarbonyl, benzoyl, halobenzoyl, CjC6alkylamino, C C8dialkylamino, N=CH2, N=CHCjC4alkyl, N=C(CjC4alkyl)2, C3C6trialkylsilyl, C3C7cycloalkyl, C2C7alkenyl or C3C7alkynyl, n is 0, 1 or 2, R6 is hydrogen or cyano if n is 0 or R6 is C C5alkyl, CjC5haloalkyl, CjC5hydroxyalkyl, phenyl, naphthyl, CjC alkylphenyl, CjC4alkylnaphthyl, halophenyl, halonaphthyl, heterocyclyl, haloheterocyclyl or C3C7cycloalkyl, R7 is hydrogen, CrC12alkyl, CjC1 haloalkyl, C C6nitroalkyl, CjC6cyanoalkyl, phenyl, naphthyl, halophenyl, halonaphthyl, C2C10alkoxyalkyl, CjCj0alkylcarbonyl, heterocyclyl, haloheterocyclyl, C3C7cycloalkyl, C3C7halocycloalkyl, N=CH2, N=CHCjC4alkyl, N=C(CjC4alkyl)2 or C2C6dialkylamino, Rg and R9 independently of one another are hydrogen, phenyl, naphthyl, halophenyl, halonaphthyl, CjC8alkyl, CjC8haloalkyl, CjC8alkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, CjC7cyanoalkyl, C3C7alkenyl, C3C7alkynyl or C2C8alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, Rjo and RJJ independently of one another are hydrogen, phenyl, naphthyl, halophenyl, halonaphthyl, CjC8alkyl, CjC8haloalkyl, CjCgalkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, CjGycyanoalkyl, C3C7alkenyl, C3C7alkynyl, C2C8 alkoxy alkyl, CjC6alkylamino, C2C6dialkylamino, formyl, C2C8alkylcarbonyl, phenylcarbonyl or naphthylcarbonyl, it being possible therein for the phenyl or naphthyl moiety to be substituted by C C4alkyl, halogen, CjC4alkoxy, hydroxy, cyano, nitro or CjC6alkoxycarbonyl, or RJO and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, RJ2 is hydrogen, CrC8alkyl, CjCghaloalkyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, CjC4alkylphenyl, CjC4alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, Cj alkylnaphthyl, CjC alkoxynaphthyl, phenylCjC6alkyl or naphthylCjCgalkyl, and R13 and R14 independently of one another are hydrogen, CjC6alkyl, C C6alkylcarbonyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, CjC alkylphenyl, C C4alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, CjC4alkylnaphthyl or C j C4alkoxynaphthyl, R2 and R3 independently of one another are hydrogen, CjC6alkyl, CjC6alkyl which is substituted by halogen, cyano, nitro, CjC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triC C4alkylammonium, COOH, COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, C3C8cycloalkyl, CjCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CjC6alkylamino, CjC5alkoxycarbonyl, C2C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, CjC4alkylthio, CjC4alkylsulfonyl or CONR8R9 R and R3 independently of one another are C2C6alkenyl, C2C6alkenyl which is substituted by halogen, cyano, nitro, CjC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triCjC4alkylammonium, COOH, COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, C3C8cycloalkyl, C2C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CjC6alkylamino, C2C5alkoxycarbonyl, C2C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, CjC4alkylthio, CjC4alkylsulfonyl or CONR8R9 , or R2 and R3 independently of one another are C3C6alkynyl, C3C6alkynyl which is substituted by halogen, cyano, nitro, CjC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triCιC4alkylammonium, COOH, COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, C3C8cycloalkyl, CjC5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CjC6alkylamino, CjC5alkoxycarbonyl, C C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, CjC4alkylthio, CjC4alkylsulfonyl or CONR8R9 , or R2 and R3 independently of one another are formyl, CjC salkylcarbonyl, C2C15alkenylcarbonyl, C^cycloalkylcarbonyl, C6C9cycloalkenylcarbonyl or C3C8cycloalkylC C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, C C6alkylamino, C2C12dialkylamino, COOH, COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or CjC8alkoxycarbonyl, C C10cycloalkoxycarbonyl, CjC8alkylaminocarbonyl or C2C12dialkylaminocarbonyl, or R and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CjCsϋkyl, C Csalkoxy, CjC5alkylcarbonyl, CjCsalkylcarbonyloxy, CjC6alkoxycarbonyl, aminocarbonyl, CjC6alkylaminocarbonyl or C2Cjjdialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CjCsdkyl, CjC5alkoxy, CjCsalkylcarbonyl, CjC6alkoxycarbonyl, aminocarbonyl, CjC6alkylamino or CjCsalkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCjC6alkylcarbonyl, biphenylC1C6alkylcarbonyl, naphthylCjC6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylC C6alkenylcarbonyl, naphthylC2C6alkenylcarbonyl, phenylC3C6alkynylcarbonyl, biphenylC3C6alkynylcarbonyl or naphthylC3C6alkynylcarbonyl, it being possible for these substituents to be substituted by CjC5alkyl, CrC5alkoxy, CrC5alkylthio, CjC5haloalkyl, CjC5alkylcarbonyl, halogen, cyano, amino, nitro, COOR7, CjC8alkoxycarbonyl, hydroxyl, CjC5alkylsulfinyl, CjCsalkylsulfonyl, CjCgalkylaminocarbonyl or C2C12dialkylaminocarbonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, CjCsalkyl, C,C5alkoxy, CrC5alkylthio, COOH, CONH2, CjC6alkylaminocarbonyl, C2C10dialkylaminocarbonyl, CjC5alkylcarbonyl or C C5alkoxycarbonyl, or R and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CjCsalkyl, CjC5alkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, CjC6alkylamino, C2C8dialkylamino, phenylamino, naphthylamino, CrC6alkylcarbonylamino, C Cj0alkoxycarbonylamino, hydroxyl, C C6alkoxy, CjC6alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, X is O or S(O)x , in which x is 0, 1 or 2, and R is C C8alkyl, C2C8alkenyl, C3C8alkynyl, C3C8cycloalkyl, C5C cycloalkenyl, C3C8cycloalkylC1C alkyl or CjC4alkylC3C8cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O or OR5 , or R4 is phenyl, biphenyl, naphthyl, heterocyclyl, CrC4alkylphenyl, CjC4alkylnaphthyl, phenylC alkyl or naphthylCrC alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, CjC Qalkyl, CjCjQalkyloxy, CjC6alkylamino, diC2C8alkylamino, CjCjQalkylthio, CjCjohaloalkyl, C Cjohaloalkoxy, CjCjohaloalkylthio, C2CjQalkoxycarbonylalkoxy, C C6alkylsulfinyl, CjC6alkylsulfonyl, CjC6alkyloxycarbonyl, C C6alkylcarbonyl, CONH2, formyl, C C7alkylaminocarbonyl, Cjjdialkylaminocarbonyl, C3C6trialkylsilyl, CjC10alkylcarbonylamino, C CjQalkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cj alkyl, CjC4alkoxy, cyano, nitro or amino, or. |
| 2. | adjacent substituents on the phenyl or naphthyl ring R4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, COOH, =O, CjCjQalkyl, C C Qalkoxy, CjCj0alkylthio, CjCjohaloalkyl, hydroxyl, C3C10alkoxycarbonylalkoxy, CjC6alkylsulfinyl, CjC6alkylsulfonyl, C2C6alkyloxycarbonyl, C2C6alkylcarbonyl, CONH2, formyl, C2C7alkylaminocarbonyl, C3Cjjdialkylaminocarbonyl, C3C6trialkylsilyl, C2Cj0alkylcarbonylamino, C C10alkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, CjC4alkyl, CjC4alkoxy, cyano, nitro or amino, and salts of the compounds of the formula I, the compounds of the formulae la, Iaj, Ia2, Ia3 and Ia4 being excluded: OPhenyl 2 A compound according to claim 1, in which RJ is CjCj0alkyl, C3C8cycloalkyl, C3C8cycloalkylCjC6alkyl, CjC8alkylC3C8cycloalkyl, C2C10alkenyl, C3C8cycloalkylC2C6alkenyl, C2C8alkenylC3C8cycloalkyl, C2C10alkynyl, C3C8cycloalkylC2C6alkynyl, C2C8alkynylC3C8cycloalkyl, C5C8cycloalkenyl, C5C8cycloalkenylCjC6alkyl, C C8alkylC5Cgcycloalkenyl, C5C8cycloalkenylC2C6alkenyl, C2C8alkenylC5C8cycloalkenyl, C5C8cycloalkenylC2C6alkynyl, C2C8alkynylC5C8cycloalkenyl, C3C8cycloalkylC3C8cycloalkyl, C5C8cycloalkenylC5C8cycloalkenyl, C3C8cycloalkylC5C8cycloalkenyl, C5C8cycloalkenylC3C8cycloalkyl, C2C8alkynylC2C6alkenyl or C2C8alkenylC2C6alkynyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O, OR5, S(O)nR6, COOR7, CONR8R9, NRJQRJJ, =NRJ2, phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ or CONRgR,) , or R is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, OR5, S(O)nR6, COOR7, CONRg^, NR10RJJ, =NRj2, =NNRj3R14, CjCgalkyl, C2C8alkenyl, C2C8alkynyl, C3C8cycloalkyl, C5C8cycloalkenyl, phenyl, biphenyl, naphthyl, CjC8alkyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQR J, C C8alkenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, C C8alkynyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, C3C8cycloalkyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJ J, CsCgcycloalkenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NR10RJJ, phenyl which is substimted by halogen, cyano, nitro, CjC6alkyl, CjC6haloalkyl, OR5, CONR8R9 or NR10RJJ, biphenyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, or naphthyl which is substituted by halogen, cyano, nitro, OR5, CONR8R9 or NRJQRJJ, or RJ is phenyl, biphenyl, naphthyl, CjC4alkylphenyl, CjC4alkylbiphenyl, CjC4alkylnaphthyl, C2C alkenylphenyl, C2C4alkenylbiphenyl, C2C alkenylnaphthyl, C2C4alkynylphenyl, C2C alkynylbiphenyl or C2C alkynylnaphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, OR5, S(O)nR6, COOR7, CONR8R9 or NRJQRJJ , in which R5 is hydrogen, C C6alkyl, CjC6haloalkyl, C2C6alkoxyalkyl, CjC6cyanoalkyl, phenyl, halophenyl, CjC alkoxyphenyl, phenylC C alkyl, CjC4alkylcarbonyl, benzoyl, halobenzoyl, CjC alkylamino, C2C6dialkylamino, C3C6trialkylsilyl, C3C6cycloalkyl, C2C alkenyl or C3C4alkynyl, n is 0, 1 or 2, R6 is hydrogen or cyano if n is 0, or R6 is CjC alkyl, C C4haloalkyl, phenyl, CjC4alkylphenyl, halophenyl, heterocyclyl, haloheterocyclyl or C3C6cycloalkyl, R7 is hydrogen, CjC4alkyl, CjC haloalkyl, C C4cyanoalkyl, phenyl, halophenyl, C2C4alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R9 independently of one another are hydrogen, phenyl, halophenyl, C1C4alkyl, CjC haloalkyl, CjC4cyanoalkyl, C3C4alkenyl, C3C alkynyl or C2C alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, R O and RJJ independently of one another are hydrogen, phenyl, halophenyl, CjC4alkyl, CjC4haloalkyl, CjC4cyanoalkyl, C3C alkenyl, C3C4alkynyl, C2C4alkoxyalkyl, formyl, C1C4alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substimted by CjC4alkyl, halogen, CjC4alkoxy, hydroxyl, cyano, nitro or CjC4alkoxycarbonyl, or RJO and RJJ together with the nitrogen atom to which they are bonded to form a heterocycle which can be halogenated, and R12 is hydrogen, CjC4alkyl, CjC4haloalkyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, CjC4alkylphenyl, CjC alkoxyphenyl or phenylCjC4alkyl. |
| 3. | 3 A compound according to claim 2, in which Rj is CjCjQalkyl, C3C8cycloalkyl, C3C8cycloalkylCrC6alkyl, CjC8alkylC3C8cycloalkyl, C2C10alkenyl, C3C8cycloalkylC2C6alkenyl, C2C8alkenylC3C8cycloalkyl, C2C10alkynyl, C3C8cycloalkylC2C6alkynyl, C C8alkynylC3C8cycloalkyl, C5C8cycloalkenyl, C5C8cycloalkenylCjC6alkyl, CjC8alkylC5C8cycloalkenyl, C5CgcycloalkenylC2C6alkenyl, C C8alkenylC5C8cycloalkenyl, C5C8cycloalkenylC2C6alkynyl, C C8alkynylC5C8cycloalkenyl, C3C8cycloalkylC3C8cycloalkyl, C5Cgcycloa]_kenylC5Cgcycloalkenyl, C3C8cycloalkylC5C8cycloalkenyl, C5C8cycloalkenylC3C8cycloalkyl, C2C8alkynylC C6alkenyl or C2C8alkenylC2C6alkynyl, it being possible for these substituents to be unsubstimted or substituted by halogen, cyano, =O, OR5, COOR7, CONR8R9, NR10Rj or phenyl, it being possible for this phenyl ring to be unsubstituted or substimted by halogen, or Rj is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, =O, OR5, S(O)nR6, COOR7, CONRgRcj, NRJQRJJ, CjC8alkyl, C2C8alkenyl, C C8alkynyl, C3C8cycloalkyl, C5C8cycloalkenyl, phenyl, CjC8alkyl which is substituted by halogen, cyano, OR5, CONR8R9 or NR10RJJ, C2C8alkenyl which is substituted by halogen, cyano, OR5, CONRgRς, or NRJQRJJ, C2C8alkynyl which is substituted by halogen, cyano, OR5, CONR8Rc, or NRJQRJJ, C3C8cycloalkyl which is substituted by halogen, cyano, OR5, CONRgR^ or NRJQRJJ, C5C8cycloalkenyl which is substituted by halogen, cyano, OR5, CONR8Rc) or NRJQRJJ, phenyl which is substituted by halogen, cyano, nitro, CjC4alkyl, CrC6haloalkyl, OR5, CONR8R$, or NRJQRJJ, or Rj is phenyl, biphenyl, naphthyl, C C4alkylphenyl, C C4alkylbiphenyl, C C4alkylnaphthyl, C2C4alkenylphenyl, C2C4alkenylbiphenyl, C2C alkenylnaphthyl, C2C4alkynylphenyl, C2C4alkynylbiphenyl or C2C4alkynylnaphthyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, OR5, S(O)nR6, COOR7, CONRgRc, or NRJQRJJ, in which R5 is hydrogen, CjC6alkyl, CjC6haloalkyl, C2C6alkoxyalkyl, CjC6cyanoalkyl, phenylCjC alkyl, CjC alkylcarbonyl, benzoyl, halobenzoyl, CjCgtrialkylsilyl, C3C6cycloalkyl, C2C alkenyl or C3C4alkynyl, n is 0, 1 or 2, R6 is hydrogen or cyano if n is 0 or R6 is CjC4alkyl, CjC4haloalkyl, phenyl or CjC4alkylphenyl, R7 is hydrogen, CjC4alkyl, CjC haloalkyl, CjC4cyanoalkyl, phenyl, halophenyl, C2C4alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R9 independently of one another are hydrogen, phenyl, halophenyl, CjC4alkyl, Cj haloalkyl, CjC4cyanoalkyl, C3C4alkenyl, C3C4alkynyl or C2C4alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, RJO and Rjj independently of one another are hydrogen, phenyl, halophenyl, CjC alkyl, CjC haloalkyl, CjC cyanoalkyl, C3C4alkenyl, C3C4alkynyl, C2C4alkoxy alkyl, formyl, CjC alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substituted by CrC4alkyl, halogen, CjC alkoxy, hydroxyl, cyano, nitro or CjC4 alkoxycarbonyl, or R10 and Rj together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated. |
| 4. | A compound according to claim 3, in which Rj is CjCjQalkyl, C3C8cycloalkyl, C3C8cycloalkylCjC6alkyl, CjC8alkylC3C8cycloalkyl, C2C10alkenyl, C3C8cycloalkylC2C6alkenyl, C2C8alkenylC3C8cycloalkyl, C2C10alkynyl, C3C8cycloalkylC C6alkynyl, C2C8alkynylC3C8cycloalkyl, C5C8cycloalkenyl, C5C8cycloalkenylC C6alkyl, C]C8alkylC5C8cycloalkenyl, C5C8cycloalkenylC2C6alkenyl, C2C8alkenylC5C8cycloalkenyl, C5C8cycloalkenylC2C6alkynyl, C2C8alkynylC5C8cycloalkenyl, C3C8cycloalkylC3C8cycloalkyl, C5C8cycloalkenylC5C8cycloalkenyl, C3C8cycloalkylC5C8cycloalkenyl, C5C8cycloalkenylC3Cgcycloalkyl, C C8alkynylC2C6alkenyl or C2C8alkenylC2C6alkynyl, it being possible for these substituents to be unsubstimted or substituted by halogen, cyano, =O, OR5, COOR7, CONR8R9, NRJQRJJ or phenyl, it being possible for this phenyl ring to be unsubstituted or substituted by halogen, or RJ is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, =O, CjC alkoxy, CrC8alkyl, C2C8alkenyl, C C8alkynyl, phenyl, CrC8alkyl which is substituted by halogen, C2Cgalkenyl which is substituted by halogen, C2Cgalkynyl which is substituted by halogen, phenyl which is substituted by halogen, cyano, nitro, CjC4alkyl or CjC4 alkoxy, or RJ is phenyl, biphenyl, naphthyl, CjC4alkylphenyl, CrC alkylbiphenyl, CjC alkylnaphthyl, C C4alkenylphenyl or C2C4alkynylphenyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, OR5, S(O)nR6, COOR7, CONR8R9 or NRIQRJJ , in which R5 is hydrogen, CjC6alkyl, C C6haloalkyl, C2C6alkoxyalkyl, CjC6cyanoalkyl, phenylCjC4alkyl, CjC4alkylcarbonyl, benzoyl, halobenzoyl, C3C6trialkylsilyl, C3C6cycloalkyl, C2C4alkenyl or C3C4alkynyl, n is 0, 1 or 2, R6 is hydrogen or cyano if n is 0, or R6 is CjC alkyl, CrC4haloalkyl, phenyl or CjC alkylphenyl, R7 is hydrogen, CjC alkyl, CjC4haloalkyl, CjC4cyanoalkyl, phenyl, halophenyl, C2C alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R9 independently of one another are hydrogen, phenyl, halophenyl, CjC4alkyl, CjC4haloalkyl, CjC4cyanoalkyl, C3C4alkenyl, C3C4alkynyl or C2C4alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, RJO and R independently of one another are hydrogen, phenyl, halophenyl, CjC4alkyl, CjC4haloalkyl, CjC cyanoalkyl, C3C alkenyl, C3C4alkynyl, C2C4alkoxy alkyl, formyl, CjC4alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be unsubstituted or substituted by CjC4alkyl, halogen, CjC alkoxy, hydroxyl, cyano, nitro or CjC alkoxycarbonyl, or R10 and RJJ together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated. |
| 5. | A compound according to claim 1, in which R2 and R3 independendy of one another are hydrogen, CrC6alkyl, CjC6alkyl which is substituted by halogen, cyano, nitro, C C4alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triCjC4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C3Cgcycloalkyl, CjC5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, CjC6alkylamino, C Csalkoxycarbonyl, C C6dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, Cj alkylthio, CjC4alkylsulfonyl or CONRgR^ or R and R3 independently of one another are C2C6alkenyl, C2C6alkenyl which is substituted by halogen, cyano, nitro, C C4alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triC*C alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or CjC6alkylamino, C2C5 alkoxycarbonyl, C2C6dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, CjC4alkylthio, CjC4alkylsulfonyl or CONR8R9, or R and R3 independently of one another are C3C6alkynyl, C3C6alkynyl which is substituted by halogen, cyano, nitro, CjC8alkoxy, C3C6trialkylsilyl, hydroxyl, amino, ammonium, triCjC4alkylammonium, COOH, COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or CjC6alkylamino, C2C5alkoxycarbonyl, C2C6dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, OR5, NRJQRJJ, CjC4alkyl, formyl, CjC4alkylcarbonyl, COOR7, CjC4alkylthio, CjC4alkylsulfonyl or CONR8R9, or R2 and R3 independently of one another are formyl, CjC8alkylcarbonyl, C2C8alkenylcarbonyl, Cgcycloalkylcarbonyl, C6C9cycloalkenylcarbonyl or C3CgcycloalkylCjC6alkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, hydroxyl, amino, CjC6alkylamino, C2C7dialkylamino, COOH, COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C2C8alkoxycarbonyl, C C10cycloalkoxycarbonyl, CjC8alkylaminocarbonyl or C2C8dialkylaminocarbonyl, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CjC5alkyl, C C5alkoxy, CrC5alkylcarbonyl, CjCsalkylcarbonyloxy, CjC6alkoxycarbonyl, aminocarbonyl, CjC6alkylaminocarbonyl or C2C8dialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CjC alkyl, CrC alkoxy, CjC4alkylcarbonyl, CjC4alkoxycarbonyl, aminocarbonyl, CjC6alkylamino or CjCsalkylcarbonyloxy, or R2 and R3 independendy of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCjC6alkylcarbonyl, biphenylCjCgalkylcarbonyl, naphthylCjC6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylC2C6alkenylcarbonyl or naphthylC2C6alkenylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by C C4alkyl, CjC4alkoxy, CjC alkylthio, CjC4haloalkyl, C C alkylcarbonyl, halogen, cyano, amino, nitro, COOR7, CjC5alkoxycarbonyl, hydroxyl, C C4alkylsulfonyl, CjCsalkylaminocarbonyl or C2C6dialkylaminocarbonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, CjC4alkyl, CrC4alkoxy, Cj alkylthio, COOH, CONH2, CjC5alkylaminocarbonyl, C2C7dialkylaminocarbonyl, CjC alkylcarbonyl or CjCsalkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CjC alkyl, CjC alkoxy, halogen, cyano or nitro, or R and R3 independently of one another are amino, CjC alkylamino, C C6dialkylamino, phenylamino, CjC5alkylcarbonylamino, CjC5alkoxycarbonylamino, hydroxyl, CjC4alkoxy, CjCsalkylcarbonyloxy or phenoxy, R5 is hydrogen, CrC6alkyl, CjC6haloalkyl, C2C6alkoxyalkyl, CjC6cyanoalkyl, phenyl, halophenyl, CjC4alkoxyphenyl, phenylCjC alkyl, CjC alkylcarbonyl, benzoyl, halobenzoyl, CjC4alkylamino, C2C6dialkylamino, C3C6trialkylsilyl, C3C6cycloalkyl, C2C4alkenyl or C3C4alkynyl, R7 is hydrogen, CjC4alkyl, CjC4halogenalkyl, CjC4cyanoalkyl, phenyl, halophenyl, C2C alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R independently of one another are hydrogen, phenyl, halophenyl, CjC alkyl, CjC haloalkyl, CrC4cyanoalkyl, C3C alkenyl, C3C4alkynyl or C2C4alkoxyalkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated, RJO and Ru independently of one another are hydrogen, phenyl, halophenyl, CjC alkyl, CjC haloalkyl, CjC cyanoalkyl, C3C4alkenyl, C3C4alkynyl, C2C4alkoxyalkyl, formyl, CjC4alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substituted by CjC4alkyl, halogen, CjC4alkoxy, hydroxyl, cyano, nitro or C C4alkoxycarbonyl, or RJO and Rjj together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated. |
| 6. | A compound according to claim 5, in which R2 and R3 independently of one another are hydrogen, CjC6alkyl, CjC6alkyl which is substituted by halogen, hydroxyl, amino, ammonium, triCjC4alkylammonium, COOH, COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, or CrC5alkylcarbonyloxy, phenylcarbonyloxy, C C6alkylamino, CjCsalkoxycarbonyl or C2C6dialkylamino, or R2 and R3 independently of one another are formyl, CjC8alkylcarbonyl, C2C8alkenylcarbonyl, Cgcycloalkylcarbonyl, Cgcycloalkenylcarbonyl or C3C8cycloalkylCjC6alkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, hydroxyl, amino, COOH or COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, or R2 and R3 independendy of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CjCsalkyl, C Csalkoxy or C]C6alkoxycarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CjC4alkyl, CjC4alkoxy or CjC4alkoxycarbonyl, or R2 and R3 independendy of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenylCjC6alkylcarbonyl, biphenylCjC6alkylcarbonyl, naphthylCjC6alkylcarbonyl, phenylC2C6alkenylcarbonyl, biphenylC C6alkenylcarbonyl or naphthylC2C6alkenylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by CjC alkyl, CjC4alkoxy, CjC alkylthio, CrC4haloalkyl, C C4alkylcarbonyl, halogen, cyano, amino, nitro, COOH, CjC5alkoxycarbonyl, hydroxyl or CjC4alkylsulfonyl, or R2 and R3 independendy of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, CjC alkyl, CjC4alkoxy, CjC4alkylthio, COOH or CjC5alkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by CjC alkyl, CjC4alkoxy, halogen or cyano. |
| 7. | A compound according to claim 6, in which R2 and R3 are hydrogen, or R2 and R3 independendy of one another are formyl, CjC8alkylcarbonyl, C2C8alkenylcarbonyl, C^cycloalkylcarbonyl, CgCgcycloalkenylcarbonyl or C3C8cycloalkylCjC6alkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, hydroxyl or amino, or R2 and R3 are phenylcarbonyl, it being possible for the phenyl ring to be unsubstituted or substituted by CjC4alkyl, CjC alkoxy, C C4alkylthio, CjC4haloalkyl, halogen, cyano, nitro, COOH, CjC5alkoxycarbonyl, hydroxyl or CjC4alkylsulfonyl. |
| 8. | A compound according to claim 1, in which X is O or S(O)x, where x is 0, 1 or 2, and R4 is methyl which is substituted by halogen, cyano, nitro or OR5, or R4 is C2C8alkyl, C2C8alkenyl, C3C8alkynyl, C3C8cycloalkyl, C5C8cycloalkenyl, C3C8cycloalkylCjC4alkyl or CjC4alkylC3C8cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O or OR5, or R4 is phenyl which is substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, CrC alkyl, CjC4alkyloxy, CjC alkylthio, CjC4haloalkyl, CjC haloalkoxy, CjC4haloalkylthio, C2C6alkoxycarbonylalkoxy, CjC4alkylsulfinyl, CjC alkylsulfonyl, CjC6alkyloxycarbonyl, CjC6alkylcarbonyl, CONH , formyl, CjC5alkylaminocarbonyl, C2C7dialkylaminocarbonyl, CjC4alkylamino, Cgdialkylamino, C3C6trialkylsilyl, C Cgalkylcarbonylamino, CjC6alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, or R is biphenyl, naphthyl, heterocyclyl, CjC4alkylphenyl, CjC4alkylnaphthyl, phenylCjC4alkyl or naphthylCjC alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, COOH, hydroxyl, CjC4alkyl, CjC4alkyloxy, CjC4alkylthio, CjC4haloalkyl, CrC4haloalkoxy, CjC4haloalkylthio, C2C6alkoxycarbonylalkoxy, CjC4alkylsulfmyl, CjC alkylsulfonyl, CjC6alkyloxycarbonyl, C C6alkylcarbonyl, CONH2, formyl, CjC5alkylaminocarbonyl, C C7dialkylaminocarbonyl, C3C6trialkylsilyl, CjC6alkylcarbonylamino, CjC6alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and R5 is hydrogen, CjC6alkyl, C C6haloalkyl, C2C6alkoxyalkyl, CjC6cyanoalkyl, phenyl, halophenyl, CjC alkoxyphenyl, phenylC C4alkyl, CjC4alkylcarbonyl, benzoyl, halobenzoyl, C C alkylamino, C2C6dialkylamino, C3C6trialkylsilyl, C3C6cycloalkyl, C2C4alkenyl or C3C alkynyl. |
| 9. | A compound according to claim 8, in which X is O or S, and R is methyl which is substituted by halogen or cyano, or R4 is C2C8alkyl, C2C8alkenyl, C3C8alkynyl, C3C8cycloalkyl, C5C8cycloalkenyl, C3C8cycloalkylCjC4alkyl or CjC4alkylC3C8cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen or cyano, or R4 is phenyl which is substituted by halogen, cyano, nitro, amino, C C alkyl, C C4alkyloxy, CrC alkylthio, CjC4haloalkyl, CjC4haloalkoxy, C2C6alkoxycarbonylalkoxy, CjC4alkylsulfonyl, CjC6alkyloxycarbonyl, CjC6alkylcarbonyl, formyl, CrC4alkylamino, C^ dialkylamino, C3C6trialkylsilyl or C2C6alkylcarbonyloxy, or R4 is biphenyl, naphthyl, heterocyclyl, CjC4alkylphenyl, Cj alkylnaphthyl, phenylCjC alkyl or naphthylCjC4alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, CrC4alkyl, C C4alkyloxy, CjC alkylthio, CjC4haloalkyl, CjC4haloalkoxy, C2C6alkoxycarbonylalkoxy, CjC4alkylsulfonyl, CjC6alkyloxycarbonyl, CjC6alkylcarbonyl, or CjC6alkylcarbonyloxy. |
| 10. | A compound according to claim 9, in which X is O and R4 is phenyl which is substituted by halogen, cyano, nitro, amino, CjC4alkyl, CjC4alkyloxy, CjC4alkylthio, CjC4haloalkyl, halomethoxy, CjC alkylsulfonyl, CjC4alkylamino or C2C6dialkylamino. |
| 11. | A process for the preparation of the compounds according to claim 1, which comprises (1) reacting a compound of the formula II in which Hal substituents independently of one another are fluorine, chlorine or bromine, with an organometal compound of the formula III in which R is as defined in claim 1 and M is a monovalent or polyvalent metal atom, (2a) reacting the resulting compound of the formula IV in which Rj is as defined in claim 1 and Hal radicals independently of one another are fluorine, chlorine or bromine, with the compound of the formula V HXR4 (V), in which X and R4 are as defined above, to give the compound of the formula VI and (3a) then converting these compounds with the compounds of the formula VE MjNR2R3 (VII), in which R and R3 are as defined above and Mj is hydrogen or a metal atom into the end products of the formula I; or (2b) reacting me compounds of the formula IV with the compounds of the formula VII to give the compounds of the formula VIE in which Rj, R2 and R3 are as defined in claim 1 and Hal is fluorine, chlorine or bromine, and (3 b) then converting these compounds with the compounds of the formula V into the end products of the formula I. |
| 12. | A herbicidal and plantgrowthinhibiting composition, which comprises one or more compounds of the formula I according to claim 1. |
| 13. | A composition according to claim 12, which comprises between 0.1 % and 95 % of active ingredient of the formula I. |
| 14. | A method of controlling undesirable plant growth, which comprises applying an effective amount of an active ingredient of the formula I according to claim 1, or a composition comprising this active ingredient, to the plants or their environment. |
| 15. | A method according to claim 14, wherein an amount of active ingredient of between 0.001 and 5 kg, in particular between 0.005 to 2 kg, is applied per hectare. |
| 16. | A method of inhibiting plant growth, which comprises applying an effective amount of an active ingredient of the formula I according to claim 1, or a composition comprising this active ingredient, to the plants or their environment. |
| 17. | A method according to claim 14 for the selective pre or postemergence control of weeds in crops of useful plants. |
| 18. | 1The use of a composition according to claim 12 for the selective pre or postemergence control of weeds in crops of useful plants. |
| 19. | Seed treated with a composition according to claim 12. |
The present invention relates to novel herbicidally active thiatriazine derivatives, to processes for their preparation, to compositions comprising these compounds, and to then- use for controlling weeds, especially in crops of useful plants or for inhibiting plant growth.
Thiatriazine compounds are described, for example, in Chem. Ber. 121, 383-386 (1988), Z. Naturforsch. 43, 763-768 (1988), Chem. Ber. 126, 2601-2607 (1993), J. Am. Chem. Soc. 1989, 111, 1180-1185, DD 113 006 and in the PhD thesis of W. Jϋrgler, Philipps-University Marburg Lahn, 1988 ("lλ 4 - und lλ 6 -2.4.6-Thiatriazine aus Sulfodiimiden" ["lλ 4 - and lλ 6 -2,4,6-thiatriazines from sulfodiimides]). There has now been found a novel and simple synthetic method for preparing novel thiatriazine derivatives which are substituted by a variety of substituents. Advantages of this synthetic method are not only the ready accessibility of thiatriazine derivatives which are substituted by a variety of substituents, but also the low number of synthetic steps (converging). In addition, the herbicidal and growth-inhibiting properties of the thiatriazine derivatives were found for the first time.
The present invention therefore provides compounds of the formula I
in which
R_ is C r C 2 oalkyl . C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C 1 -C 17 alkyl, C r C 17 alkyl-C 3 -Cgcycloalkyl, C 2 -C 17 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkenyl, C 2 -C 17 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkynyl, C 2 -C 17 alkynyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C r C 17 alkyl, C 1 -C 17 alkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 17 alkenyl, C 2 -C 17 alk- enyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 17 alkynyl, C 2 -C 17 alkynyl-C5-C 8 cyclo- alkenyl, C 3 -C 8 cycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 3 -C 8 cycloalkyl,
C 2 -C 17 alkynyl-C 2 -C 17 alkenyl or C 2 -C 17 alkenyl-C 2 -C 1 alkynyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 ,
-CONR 8 R 9 , -NR 10 R π , =NR 12 , =N-NR 13 R 14 , phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R n or -CONRgRg, or
R j is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, -OR 5 , S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 R n , =NR 12 , =N-NR 13 R 14 ,
C r C 17 alkyl, C 2 -C 17 alkenyl, C 2 -C 17 alkynyl, C 3 -Cgcycloalkyl, C 5 -Cgcycloalkenyl, phenyl, biphenyl, naphthyl, C 1 -C 17 alkyl which is substituted by halogen, cyano, nitro, -OR 5 ,
-CONR 8 R 9 or -NRι 0 R n , C 2 -C 17 alkenyl which is substituted by halogen, cyano, nitro,
-OR 5 , -CONR 8 R 9 or -NR 10 R π , C 2 -C 17 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R n , phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR^R-^, biphenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π or naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RH, or
R j is phenyl, biphenyl, naphthyl, Cj-Cioalkylphenyl, C r C 10 alkylbiphenyl,
C r C 10 alkylnaphthyl, C 2 -Cjoalkenylphenyl, C 2 -Cιoalkenylbiphenyl,
C 2 -C 1 (*alkenylnaphthyl, C 2 -C 10 alkynylphenyl, C 2 -C 10 alkynylbiphenyl or
C 2 -C 10 alkynylnaphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 or -NR 10 R π , in which
R 5 is hydrogen, C r C 6 alkyl, C C 6 haloalkyl, C 2 -C5alkoxyalkyl, C j -Cgcyanoalkyl, phenyl, halophenyl, C r C alkoxyphenyl, phenyl-C r C 4 alkyl, C-^-Cγalkylcarbonyl, benzoyl, halobenzoyl, C r C 6 alkylamino, C 2 -C 8 dialkylamino, -N=CH , -N=CH-C r C 4 alkyl,
-N=C(C r C 4 alkyl) 2 , C 3 -C 6 trialkylsilyl, C 3 -C 7 cycloalkyl, C 2 -C 7 alkenyl or C 3 -C 7 alkynyl, n is 0, 1 or 2,
R 6 is hydrogen or cyano if n is 0, or
R 6 is C r C 5 alkyl, C j -Cshaloalkyl, C 1 -C 5 hydroxyalkyl, phenyl, naphthyl,
C r C 4 alkylphenyl, C r C alkylnaphthyl, halophenyl, halonaphthyl, heterocyclyl, haloheterocyclyl or C 3 -C 7 cycloalkyl,
R 7 is hydrogen, C--C 12 alkyl, C r C 12 haloalkyl, C r C 6 nitroalkyl, C r C 6 cyanoalkyl, phenyl, naphthyl, halophenyl, halonaphthyl, C 2 -C 10 alkoxy alkyl, C 2 -C 10 alkylcarbonyl, heterocyclyl, haloheterocyclyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl, -N=CH 2 ,
-N=CH-C r C 4 -alkyl, -N=C(C r C 4 alkyl) 2 or C 2 -C 6 dialkylamino,
R 8 and R 9 independently of one another are hydrogen, phenyl, naphthyl, halophenyl,
halonaphthyl, C r C 8 alkyl, C r C 8 haloalkyl, C r C 8 alkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, C -C 7 cyanoalkyl, C 3 -C 7 alkenyl, C 3 -C 7 alkynyl,
C 2 -C 8 alkoxyalkyl, -N=CH 2 , -N=CH-C r C 4 alkyl, -N=C(C r C 4 alkyl) 2 , C r C 6 alkylamino or
C 2 -C 6 dialkylamino, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R 10 and R π independently of one another are hydrogen, phenyl, naphthyl, halophenyl, halonaphthyl, C C 8 alkyl, Cj-Cghaloalkyl, C j -Cgalkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, C 2 -C 7 cyanoalkyl, C 3 -C 7 alkenyl, C 3 -C 7 alkynyl,
C 2 -C 8 alkoxyalkyl, -N=CH 2 , -N=CH-C r C 4 alkyl, -N=C(C r C 4 alkyl) 2 , C r C 6 alkylamino,
C 2 -C 6 dialkylamino, formyl, C 2 -C 8 alkylcarbonyl, phenylcarbonyl or naphthylcarbonyl, it being possible therein for the phenyl or naphthyl moiety to be substituted by C r C 4 alkyl, halogen, C r C alkoxy, hydroxyl, cyano, nitro or C 2 -C 6 alkoxycarbonyl, or
R 10 and R together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R 12 is hydrogen, C r C 8 alkyl, C r C 8 haloalkyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, C C 4 alkylphenyl, Cj- alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, C r C 4 alkylnaphthyl, C r C alkoxynaphthyl, phenyl-C j -C β alkyl or naphthyl- - alkyl, and
R 13 and R 1 independently of one another are hydrogen, C r C 6 alkyl, C 2 -C 6 alkylcarbonyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, C r C alkylphenyl, C r C 4 alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, C r C alkylnaphthyl or
C j - C 4 alkoxynaphthy 1,
R 2 and R 3 independently of one another are hydrogen, C r C 6 alkyl, C r C 6 alkyl which is substituted by halogen, cyano, nitro, C r C 8 alkoxy, phenyl, naphthyl, phenoxy, naphthoxy, phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rπ or -CONR 8 R 9 , naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rπ or -CONRgRς,, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , naphthoxy with is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 Rc),
C r C 8 -alkylthio, phenthio, naphthio, phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NRJQRΠ or -CONRsR^, naphthio which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Ci- alkylammonium, C 2 -C 8 alkoxycarbonyl, -COOH, -COOM, in which M is ammonium or alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl,
C 2 -C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, C r C 6 alkylamino,
C 2 -C 5 alkoxycarbonyl or C 2 -C 12 dialkylamino, or
R 2 and R 3 independently of one another are C 2 -C 6 alkenyl, C 2 -C 6 alkenyl which is
substituted by halogen, cyano, nitro, Cj-Cgalkoxy, phenoxy, naphthoxy, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ or -CONR 8 R 9 , naphthoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , C r C 8 alkylthio, phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , naphthio which is substituted by halogen, cyano, nitro, -OR 5 , -NRJORJJ or -CONR 8 R 9 , C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C alkylammonium, C 2 -C 8 alkoxycarbonyl, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, C 2 -C 5 alkylcarbonyloxy, phenylcarbonyloxy or naphthylcarbonyloxy, C r C 6 alkylamino, C2-C 5 alkoxycarbonyl or C 2 -C 12 dialkylamine, or
R 2 and R 3 independently of one another are C^Cgalkynyl, C 2 -C 6 alkynyl which is substituted by halogen, cyano, nitro, C C 8 alkoxy, phenoxy, naphthoxy, C C 8 alkylthio, phenthio, naphthio, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , naphthoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONRsR^ phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rπ or -CONR 8 R 9 , naphthio which is substituted by halogen, cyano, nitro, -OR5, -NR 10 R π or -CONR 8 R 9 , C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C r C 4 alkylammonium, C 2 -C 8 alkoxycarbonyl, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, or R and R 3 independently of one another are formyl, C 2 -C 15 alkylcarbonyl, C 2 -C 15 alkenylcarbonyl, C -C cycloalkylcarbonyl, C 6 -C 9 cycloalkenylcarbonyl or C 3 -C 8 cycloalkyl-C 2 -C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, C 1 -C 6 alkylamino, C 2 -C 12 dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 2 -C 8 alkoxycarbonyl, C -C 10 cycloalkoxycarbonyl, C 2 -C 8 alkylaminocarbonyl or C 3 -C 1 dialkylaminocarbonyl, or R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C r C 5 alkyl, C j -Csalkoxy, C 2 -C 5 alkylcarbonyl, C 2 -C 5 alkylcarbonyloxy, C -C 6 alkoxycarbonyl, aminocarbonyl, C -C 6 alkylamino or C 3 -C 11 dialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, C r C 5 alkyl, C r C 5 alkoxy, C 2 -C 5 alkylcarbonyl, C 2 -C 6 alkoxylcarbonyl, aminocarbonyl, C 2 -C 6 alkylamino or C 2 -C 5 alkylcarbonyloxy, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-C 2 -C 6 alkylcarbonyl, biphenyl-C 2 -C 6 alkylcarbonyl, naphthyl- C -C 6 alkylcarbonyl, phenyl-C 3 -C 6 alkenylcarbonyl, biphenyl-C 3 -C 6 alkenylcarbonyl, naphthyl-C 3 -C 6 alkenylcarbonyl, phenyl-C 3 -C 6 alkynylcarbonyl, biphenyl-C 3 -C 6 - alkynylcarbonyl or naphthyl-C 3 -C 6 alkynylcarbonyl, it being possible for these substituents
to be substituted by C j -Csalkyl, C r C 5 alkoxy, C j -C 5 alkylthio, C ] -C 5 haloalkyl, C 2 -C 5 alkylcarbonyl, halogen, cyano, amino, nitro, -COOH, C 2 -C 8 alkoxycarbonyl, hydroxyl, C 2 -C 5 alkylaminocarbonyl or C 2 -C 12 dialkylaminocarbonyl, or R and R 3 independently of one another are phenyl-C r C 6 alkyl, biphenyl-C r C 6 alkyl, naphthyl-C j -Cgalkyl, phenyl-C 2 -C 6 alkenyl, biphenyl-C 2 -C 6 alkenyl, naphthyl-C 2 -C 6 alkenyl, phenyl-C -C 6 alkynyl, biphenyl-C 2 -C 6 alkynl or naphthyl-C 2 -C 6 alkynyl, it being possible for these substituents to be substituted by C r C 5 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkinyl, hydroxyl, C r C 5 alkoxy, formyl, C -C 6 alkylcarbonyl, C 2 -C 5 alkoxycarbonyl, C^Cgalkylaminocarbonyl, C 3 -C 9 dialkylaminocarbonyl, nitro or Cj-Csalkylthio, or
R and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, Cj-Csalkyl, C r C 5 alkoxy, C r C 5 alkylthio, -COOH, -CONH 2 , C 2 -C 6 alkylaminocarbonyl, C 3 -C 10 di- alkylaminocarbonyl, C 2 -C 5 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl, or R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by C r C 5 alkyl, C r C 5 alkoxy, halogen, cyano or nitro, or R 2 and R 3 independently of one another are amino, C r C 6 alkylamino, C 2 -C 8 dialkylamino, phenylamino, naphthylamino, C-j-Cgalkylcarbonylamino, C 2 -C 1 oalkoxycarbonylamino, hydroxyl, C r C 6 alkoxy, C 2 -C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, X is O or S(O) x , in which x is 0, 1 or 2, and
R 4 is C r C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 1 -C 4 alkyl or -Qalkyl-Cs-Cgcycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or -OR5, or R 4 is phenyl, naphthyl, heterocyclyl, C r C 4 alkylphenyl, C 1 -C 4 alkylnaphthyl, phenyl-C r C alkyl or naphthyl- - alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, C r C 10 alkyl, C r C 10 alkyloxy, Ci-Cjoalkylthio, C r C 10 haloalkyl, C r C 10 haloalkylthio, C 3 -C 10 alkoxycarbonylalkoxy, C r C 6 alkylsulfιnyl, C r C 6 alkylsulfonyl, C 2 -C 6 alkyloxycarbonyl, C 2 -C 6 alkylcarbonyl, -CONH 2 , formyl, C 2 -C 7 alkylaminocarbonyl, C 3 -C 1 jdialkylaminocarbonyl, C 3 -C 6 trialkylsilyl, C 2 -C 10 alkylcarbonylamino, C 2 -C 10 alkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, C r C 4 alkyl, C r C 4 alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R 4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, =O, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C r C 10 alkylthio, Cj-Cjøhaloalkyl, hydroxyl, C 3 -C 10 alkoxycarbonylalkoxy, C r C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, C 2 -C 6 alkyloxycarbonyl, C 2 -C 6 alkylcarbonyl, -CONH 2 , formyl, C 2 -C 7 alkylaminocarbonyl,
0 3 -C j j dialkylaminocarbonyl, C 3 -C 6 trialkylsilyl, C -C 1 oalkylcarbonylamino,
C 2 -C 10 alkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cj-C 4 alkyl, C C alkoxy, cyano, nitro or amino, and salts of the compounds of the formula I, the compounds of the formulae la, Ia l5 Ia 2 , Ia 3 and Ia 4 being excluded:
The present invention also relates to compounds of the formula I
in which
R j is C r C 2 oalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 17 alkyl, C r Ci 7 alkyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkenyl, C 2 -C 17 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkynyl, C 2 -C 17 alkynyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C r C 17 alkyl,
-C^alkyl-Cs- cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 17 alkenyl, C^Cπalkenyl-Cs- cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 17 alkynyl, C 2 -C 17 alkynyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl-C 5 -Cgcycloalkenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloa__kenyl-C 3 -C 8 cycloalkyl, C -C 17 alkynyl-C 2 -C 17 alkenyl or C -C 17 alkenyl-C 2 -Cj 7 alkynyl, it being possible for the substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 R π , =NR 1 , =N-NRι 3 R 14 , phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R π or -CONR 8 R 9 , or R j is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 R π , =NR 12 , =N-NR 13 R 14 , C j -C^alkyl, C 2 -C 17 alkenyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, phenyl, biphenyl, naphthyl, C r C 17 alkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 Rπ, C 2 -C 17 alkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 2 -C| 7 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONRsRg or -NR 10 R π , C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R n , biphenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , or naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , or R is phenyl, biphenyl, naphthyl, C C 10 alkylphenyl, C r C 10 alkylbiphenyl, C r C 10 alkylnaphthyl, C 2 -C 10 alkenylphenyl, C -C 10 alkenylbiphenyl, C 2 -C 10 alkenylnaphthyl, C-j-Cjoalkynylphenyl, C 2 -C 10 alkynylbiphenyl or C 2 -C 10 alkynylnaphthyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 or -NR 10 R π , in which
R 5 is hydrogen, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkoxy alkyl, C r C 6 cyanoalkyl, phenyl, halophenyl, C r C 4 alkoxyphenyl, phenyl-C r C 4 alkyl, C r C 7 alkylcarbonyl, benzoyl, halobenzoyl, C r C 6 alkylamino, C 2 -C 8 dialkylamino, -N=CH 2 , -N=CH-C r C 4 alkyl, -N=C(C r C 4 alkyl) 2 , C 3 -C 6 trialkylsilyl, C 3 -C 7 cycloalkyl, C 2 -C 7 alkenyl or C 3 -C 7 alkynyl, n is 0, 1 or 2,
R 6 is hydrogen or cyano if n is 0 or
R 6 is C r C 5 alkyl, C r C 5 haloalkyl, C r C 5 hydroxyalkyl, phenyl, naphthyl, C r C 4 alkylphenyl, C r C 4 alkylnaphthyl, halophenyl, halonaphthyl, heterocyclyl,
haloheterocyclyl or C 3 -C 7 cycloalkyl,
R 7 is hydrogen, C C 12 alkyl, C r C 12 haloalkyl, C 1 -C 6 nitroalkyl, C j -C 6 cyanoalkyl, phenyl, naphthyl, halophenyl, halonaphthyl, C 2 -C 10 alkoxyalkyl, C r C 10 alkylcarbonyl, heterocyclyl, haloheterocyclyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl, -N=CH 2 ,
-N=CH-C r C 4 alkyl, -N=C(C r C 4 alkyl) 2 or C 2 -C 6 dialkylamino,
R 8 and R 9 independently of one another are hydrogen, phenyl, naphthyl, halophenyl, halonaphthyl, C C 8 alkyl, C r C 8 haloalkyl, Cj-C 8 alkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, C r C 7 cyanoalkyl, C 3 -C 7 alkenyl, C 3 -C 7 alkynyl or
C 2 -C 8 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
RJO and R π independently of one another are hydrogen, phenyl, naphthyl, halophenyl, halonaphthyl, Cj-C 8 alkyl, C j -C 8 haloalkyl, C j -C 8 alkoxy, phenoxy, naphthoxy, halophenoxy, halonaphthoxy, Cj-C 7 cyanoalkyl, C 3 -C alkenyl, C 3 -C 7 alkynyl,
C -C 8 alkoxyalkyl, Cj-C 6 alkylamino, C -C 6 dialkylamino, formyl, C -C 8 alkylcarbonyl, phenylcarbonyl or naphthylcarbonyl, it being possible therein for the phenyl or naphthyl moiety to be substituted by Cj-C alkyl, halogen, C j -C 4 alkoxy, hydroxy, cyano, nitro or
C j -C 6 alkoxycarbonyl, or
RJO and RJJ together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R 12 is hydrogen, Cj-C 8 alkyl, Cj-C 8 haloalkyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, C -C 4 alkylphenyl, Cj-C 4 alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, Cj-C 4 alkylnaphthyl, C j -C alkoxynaphthyl, phenyl-C j -C 6 alkyl or naphthyl-Cj-C 6 alkyl, and
R 13 and R 14 independently of one another are hydrogen, C j -C 6 alkyl, C j -Cgalkylcarbonyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, C j -C alkylphenyl, C j -C 4 alkoxyphenyl, naphthyl, cyanonaphthyl, nitronaphthyl, halonaphthyl, C j -C 4 alkylnaphthyl or
C j -C alkoxynaphthyl,
R 2 and R 3 independently of one another are hydrogen, C -C 6 alkyl, C j -C 6 alkyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cj-C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl,
C j -Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cj-Cgalkylamino,
C j -Csalkoxycarbonyl, C 2 -C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for these aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NR j0 R H , Cj-C 4 alkyl, formyl, C r C 4 alkylcarbonyl, COOR 7 , C r C 4 alkylthio, Cj-C 4 alkylsulfonyl or CONR 8 R 9
R 2 and R 3 independently of one another are C 2 -C 6 alkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Cj-C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, C 2 -C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cj-C 6 alkylamino, C -C 5 alkoxycarbonyl, C 2 -C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for these aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NR 10 RJJ, C j -C 4 alkyl, formyl, C r C 4 alkylcarbonyl, COOR 7 , Cj-C 4 alkylthio, C j -C 4 alkylsulfonyl or CONR 8 R 9 , or
R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C r C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, C j -C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, C j -C 6 alkylamino, Cj-C 5 alkoxycarbonyl, C 2 -C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for these aromatic rings to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NR 10 RJJ, C j -C alkyl, formyl, C r C 4 alkylcarbonyl, COOR 7 , Cj-C 4 alkylthio, C j -C 4 alkylsulfonyl or CONR 8 R 9 , or
R 2 and R 3 independently of one another are formyl, C j -C 15 alkylcarbonyl, C 2 -C 15 alkenylcarbonyl, C -C 9 cycloalkylcarbonyl, Ce-Cgcycloalkenylcarbonyl or C 3 -C 8 cycloalkyl-Cj-C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, C j -C 6 alkylamino, C 2 -C 12 dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or Cj-C 8 alkoxycarbonyl, C -C j ocycloalkoxycarbonyl, C j -C 8 alkylaminocarbonyl or C 2 -C 12 dialkylaminocarbonyl, or R and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C -Csalkyl, C -Csalkoxy, C j -C 5 alkylcarbonyl, Cj-Csalkylcarbonyloxy, C r C 6 alkoxycarbonyl, aminocarbonyl, C -C 6 alkylaminocarbonyl or C 2 -Cjjdialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, C r C 5 alkyl, C j -C 5 alkoxy, C -C 5 alkylcarbonyl, C j -C 6 alkoxycarbonyl, aminocarbonyl, Cj-C 6 alkylamino or C j -C 5 alkylcarbonyloxy, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-C j -C 6 alkylcarbonyl, biphenyl-C j -C 6 alkylcarbonyl, naphthyl-C -C 6 alkylcarbonyl, phenyl-C 2 -C 6 alkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl, naphthyl-C 2 -C 6 alkenylcarbonyl,
phenyl-C 3 -C 6 alkynylcarbonyl, biphenyl-C 3 -C 6 alkynylcarbonyl or naphthyl-C 3 -C 6 alkynylcarbonyl, it being possible for these substituents to be substituted by C j -C 5 alkyl, Cj-C 5 alkoxy, Cj-C 5 alkylthio, C r C 5 haloalkyl, C j -C 5 alkylcarbonyl, halogen, cyano, amino, nitro, -COOR 7 , Cj-C 8 alkoxycarbonyl, hydroxyl, C j -Csalkylsulfinyl, C j -C 5 alkylsulfonyl, C -C 6 alkylaminocarbonyl or C 2 -C 12 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, C j -Csalkyl, C j -C 5 alkoxy, Cj-C 5 alkylthio, -COOH, -CONH 2 , Cj-C 6 alkylaminocarbonyl, C 2 -C odialkylaminocarbonyl, C -C 5 alkylcarbonyl or C j -Cs-dkoxycarbonyl, or R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by C -C 5 alkyl, C j -Csalkoxy, halogen, cyano or nitro, or R 2 and R 3 independently of one another are amino, C j -C 6 alkylamino, C 2 -C 8 dialkylamino, phenylamino, naphthylamino, Cj-C 6 alkylcarbonylamino, C j -C j0 alkoxycarbonylamino, hydroxyl, C r C 6 alkoxy, Cj-C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, X is O or S(O) x , in which x is 0, 1 or 2, and
R 4 is Cj-C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-Cj-C alkyl or Cj-C 4 alkyl-C 3 -C 8 cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O or -OR 5 , or R 4 is phenyl, biphenyl, naphthyl, heterocyclyl, C j -C 4 alkylphenyl, C j -C alkylnaphthyl, phenyl-Cj-C alkyl or naphthyl-Cj-C 4 alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, Cj-C 10 alkyl, C r C 10 alkyloxy, C r C 6 alkylamino, di-C 2 -C 8 alkylamino, C j -C 10 alkylthio, C j -C j øhaloalkyl, Cj-Cjohaloalkoxy, Cj-Cjohaloalkylthio, C 2 -C 10 alkoxycarbonylalkoxy, C j -C 6 alkylsulfinyl, Cj-C 6 alkylsulfonyl, Cj-C 6 alkyloxycarbonyl, C j -C 6 alkylcarbonyl, -CONH 2 , formyl, Cj-C 7 alkylaminocarbonyl, C 2 -Cjjdialkylaminocarbonyl, C 3 -C 6 trialkylsilyl, Cj-Cjoalkylcarbonylamino, Cj-C 10 alkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, C j -C alkyl, Cj-C alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, =O, Cj-C 10 alkyl, C r C 10 alkoxy, Cj-C 10 alkylthio, C -C 10 haloalkyl, hydroxyl, C 3 -Cjoalkoxycarbonylalkoxy, C r C 6 alkylsulfinyl, C j -C 6 alkylsulfonyl, C 2 -C 6 alkyloxycarbonyl, C 2 -C 6 alkylcarbonyl, -CONH 2 , formyl, C 2 -C 7 alkylaminocarbonyl, C 3 -Cj jdialkylaminocarbonyl, C 3 -C 6 trialkylsilyl, C 2 -C 10 alkylcarbonylamino, C 2 -Cjoalkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cj-C alkyl, C C 4 alkoxy, cyano, nitro or amino, and salts of the compounds of the formula I,
the compounds of the formulae la, Iaj, Ia 2 , Ia 3 and Ia 4 being excluded:
nn CC 4 HH 9 - S χ CI(CH 2 ) 4 - S (i a ) an d
0 - phen y'
The alkyl groups in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl or eicosyl, and the branched isomers of these. Alkoxy, alkenyl and alkynyl radicals are derived from the abovementioned alkyl radicals. The alkenyl and alkynyl radicals can be mono- or polyunsaturated.
Suitable cycloalkyl substituents have 3 to 8 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The corresponding cycloalkenyl substituents can be mono- or else polyunsaturated, for example cyclopentadienyl or cyclooctatetraenyl.
If alkyl, alkenyl or alkynyl are substituents on a cycloalkyl, cycloalkenyl, phenyl, biphenyl, naphthyl or heterocyclyl, these ring systems can also be polysubstituted by alkyl, alkenyl or alkynyl.
Halogen is, as a rule, fluorine, chlorine, bromine or iodine. The same also applies to halogen in connection with other meanings, such as haloalkyl or halophenyl.
Heterocyclyl is to be understood as meaning ring systems which, in addition to carbon atoms, have at least one hetero atom, such as nitrogen, oxygen and/or sulfur. They can be saturated or unsaturated. Such ring systems preferably have 3 to 8 ring atoms. This also applies to those heterocycles which are formed by 2 substituents bonded to a nitrogen atom, as is the case in groups such as -NR 10 RJJ.
Preferred heterocycles Rj which are suitable are, for example, oxiranyl, dioxolanyl, dioxanyl, 2,3-dihydro[l,4]dioxinyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, pyridinyl, pyrimidinyl, pyrrolyl, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, dihydrofuranyl, thiophenyl, 2,3-dihydrothiophenyl, tetrahydrothiophenyl and dihydropyranyl.
Heterocyclyl as a substituent of a group R can be, for example, oxiranyl, dioxolanyl, pyrrolidinyl, piperidinyl, morpholinyl, pyridinyl, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, dihydrofuranyl, dihydropyranyl or phthalimidyl.
Heterocycles R 6 are preferably, inter alia, pyridinyl, pyrimidinyl and triazinyl.
Preferred heterocycles R 7 are, for example, oxetanyl, pyridyl, thiophenyl and furanyl.
R 8 and R 9 preferably form rings such as piperidinyl, morpholinyl and pyrrolidine.
Preferred examples of heterocycles formed by R 10 and R j j , or R 2 and R 3 , together with the nitrogen atom to which these radicals are bonded, are piperidinyl, morpholinyl, pyrrolidinyl and imidazolyl.
Heterocycles R 9 are preferably thiophenyl, furanyl, pyridinyl and oxetanyl.
Phenyl and naphthyl rings R can be substituted by carbo- or heterocyclic radicals which are formed by 2 adjacent substituents from these phenyl or naphthyl rings. The carbocycles have preferably 4 to 6 carbon atoms, such as cyclobutyl, cyclopentyl and cyclohexyl. Suitable heterocyclic groups are, in particular, dioxolanyl and tetrahydrofuranyl .
Heterocycles R such as succinimidyl, pyridinyl, thiophenyl or furanyl can have fused to them carbocycles, such as phenyl or cyclohexenyl.
Heterocycles R 2 and R 3 are preferably pyridinyl, pyrrolidinyl and pyrimidinyl.
Heterocycles formed by -NR 2 R 3 encompass, for example, succinimidyl, imidazolyl and triazolyl, it being possible for such groups to have fused to them carbocycles, such as phenyl or cyclohexene.
Heterocyclylcarbonyl R 2 or R 3 is, for example, pyridinyl, pyrrolidinyl, triazolyl, thiophenyl, furanyl or isoxazolyl.
In substituents such as -N=C(C 1 -C 4 -alkyl) 2 , the alkyl radicals can be identical or different. They are preferably identical. The same also applies to the alkyl radicals in dialkylamino, dialkylaminocarbonyl, trialkylammonium and trialkylsilyl substituents.
In the definitions cyanoalkyl, alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonyl, alkylcarbonylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonylalkoxy and alkenylcarbonyl, the cyano or carbonyl carbon atom is not included in the upper and lower limits of the number of carbon atoms in each case specified.
Suitable alkali metals and alkaline earth metals are, for example, lithium, sodium, potassium, magnesium, calcium or barium.
The invention also encompasses the salts which the compounds of the formula I can form, in particular with amines, alkali metal bases and alkaline earth metal bases or quaternary ammonium bases.
Salt formers amongst the alkali metal hydroxides and alkaline earth metal hydroxides are, in particular, the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.
Examples of amines which are suitable for the formation of ammonium salts are ammonia as well as primary, secondary and tertiary Cj-C 18 alkylamines, Cj- hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine,
dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o, m, p-toluidines, phenylenediamines, benzidines, naphthylamines and o, m, p-chloroanilines; but in particular triethylamine, isopropylamine and di-isopropylamine.
The compounds of the formula I have an asymmetric centre in the sulfur atom of the thiatriazine ring. This is why the preparation of these compounds gives racemates, which can be separated into the corresponding enantiomers by customary separation methods. If the substituents of the thiatriazine ring have further asymmetric centres, it is also possible to separate the corresponding diastereoisomers in the customary manner. The present invention also encompasses such diastereoisomers and enantiomers.
In preferred compounds of the formula I, Rj is C r C 20 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C 1 -Cj 7 alkyl, Cj-C 17 alkyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkenyl, C 2 -C 17 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkynyl, C 2 -Cj 7 alkynyl-C 3 -C 8 cycloalkyl, C -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-Cj-C 17 alkyl, Cι-Cj 7 alkyl-C 5 -C 8 cycloalkenyl, C 5 -Cgcycloalkenyl-C 2 -C 17 alkenyl, C 2 -C j7 alkenyl-C 5 -Cgcycloalkenyl, C 5 -Cgcycloalkenyl-C 2 -Cj 7 alkynyl, C 2 -C 17 alkynyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 3 -C 8 cycloalkyl, C 2 -Cj 7 alkynyl-C 2 -Cj 7 alkenyl or C 2 -Cj 7 alkenyl-C 2 -C 17 alkynyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) π R 6 , -COOR 7 , -CONR 8 R 9 , -NRJ Q RJJ, =NR 12 , =N-NRJ 3 R 14 , phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Ru or -CONR 8 R 9 , or
Rj is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONRgR,,, -NRJ 0 RJ J , =NRj 2 , =N-NR 13 Rj 4 ,
C j -C 17 alkyl, C 2 -Cj 7 alkenyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, phenyl, biphenyl, naphthyl, Cj-Cj 7 alkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R J, C -C 17 alkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJQRJJ, C 2 -C 17 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONRsRg or -NR 10 RJJ, C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 RJJ, C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 RJJ, phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 RJJ, biphenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR j0 Rnor naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RJJ, and R 5 , R 6 , R 7 , R 8 , Re,, R 10 , Rn, R 12 , R 13 , R 14 and n are as defined above.
In a group of preferred compounds of the formula I, Rj is C r C 20 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 17 alkyl, C r C 17 alkyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkenyl, C 2 -C 17 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 17 alkynyl or C 2 -C 17 alkynyl-C 3 -C 8 cycloalkyl, it being possible for these substituents to be substituted by halogen or -OR 5 , and R 5 is as defined above.
In a further preferred group of the compounds of the formula I, R j is a non-aromatic heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, -OR5, -S(O) n R 6 , -COOR 7 , -CONR 8 R9, -NR 10 R n , =NR 12 , =N-NR 13 R 14 , C r C 17 alkyl, C 2 -C 17 alkenyl, C 2 -C 17 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, phenyl, biphenyl, naphthyl, C r C 17 alkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 Rπ, C 2 -C 17 alkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 2 -C 17 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 Rn, C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 Rc, or -NR 10 Rπ, phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 Rπ, biphenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R n or naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 Rn.
Particularly preferred amongst this group of compounds of the formula I are those in which R j can be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NRJORJJ, =NR 12 , =N-NRJ 3 RJ 4 , C j -C j7 alkyl, C 2 -C 17 alkenyl, C 2 -C j7 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C j -C 17 alkyl which is substituted by halogen, cyano,
nitro, -OR 5 , -CONRgR 9 or -NR 10 Rjj, C 2 -Cj 7 alkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R n , C 2 -C 17 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RJJ, C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJQRJJ, C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONRsRg or -NRJ Q R .
In another group of particularly suitable compounds of the formula I, R 2 and R 3 independently of one another are hydrogen, Cj-C 6 alkyl, C j -C 6 alkyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, phenyl, phenoxy, phenyl which is substituted by halogen, cyano, nitro, -OR 5 , -NRJQR or -CONRsRς,, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 RJ J or -CONR 8 R 9 , C r C 8 alkylthio, phenthio, phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ or -CONR 8 Rc>, or
R 2 and R 3 independently of one another are C 2 -C 6 alkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, phenoxy, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ or -CONR 8 R 9 , C r C 8 alkylthio, phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 RJJ or -CONR 8 R 9 , or
R 2 and R 3 independently of one another are C 2 -C 6 alkynyl, C 2 -C 6 alkynyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, phenoxy, naphthoxy, C -C 8 alkylthio, phenthio, phenoxy which is substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ or
-CONR 8 R 9 , phenthio which is substituted by halogen, cyano, nitro, -OR 5 , -NR 10 RJJ or
-CONR 8 R 9 , or
R 2 and R 3 independently of one another are formyl, C 2 -C 15 alkylcarbonyl,
C 2 -C 15 alkenylcarbonyl, C 4 -C 9 cycloalkylcarbonyl, Cg-Cgcycloalkenylcarbonyl or
C 3 -Cgcycloalkyl-C 2 -C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, C j -C 6 alkylamino,
C -C 12 dialkylamino, -COOH, C 2 -Cgalkoxycarbonyl, C -C jQ cycloalkoxycarbonyl,
C 2 -Cgalkylaminocarbonyl or C 3 -C 12 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are heterocyclylcarbonyl, or
R and R 3 independently of one another are phenylcarbonyl, phenyl-C 2 -C 6 alkylcarbonyl, phenyl-C 3 -C 6 alkenylcarbonyl or phenyl-C 3 -C 6 alkynylcarbonyl, it being possible for these substituents to be substituted by Cj-C 5 alkyl, C -C 5 alkoxy, C j -C 5 alkylthio,
C j -Cshaloalkyl, C 2 -C 5 alkylcarbonyl, halogen, cyano, amino, nitro, -COOH,
C 2 -C 8 alkoxycarbonyl, hydroxyl, C 2 -C 5 alkylaminocarbonyl or
C 2 -C 12 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl-C j -C 6 alkyl, phenyl-C 2 -C 6 alkenyl or phenyl-C 2 -C 6 alkynyl, it being possible for these substituents to be substituted by
C j -C 5 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, hydroxyl, C j -C 5 alkoxy, formyl,
C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl,
C 3 -C 9 dialkylaminocarbonyl, nitro or Cj-C 5 alkylthio, or
R 2 and R 3 independently of one another are phenyl or phenyl which is substituted by halogen, cyano, nitro, Cj-C 5 alkyl, Cj-C 5 alkoxy, C r C 5 alkylthio, -COOH, -CONH 2 ,
C 2 -C 6 alkylaminocarbonyl, C 3 -Cjodialkylaminocarbonyl, C 2 -C 5 alkylcarbonyl or
C 2 -C 5 alkoxycarbonyl, or
R and R 3 independently of one another are amino, C j -C 6 alkylamino, C 2 -C dialkylamino, phenylamino, C 2 -C 6 alkylcarbonylamino, C 2 -CjQalkoxycarbonylamino, hydroxyl,
Cj-C 6 alkoxy, C 2 -C 6 alkylcarbonyloxy or phenoxy.
Amongst these, particularly suitable compounds of the formula I are those in which
R 2 and R 3 independently of one another are hydrogen, C j -C 6 alkyl, C 2 -C 6 alkenyl,
C -C 6 alkynyl, C -C 15 alkylcarbonyl, C -C 15 alkenylcarbonyl, -Cgcycloalkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro or hydroxyl, or
R 2 and R 3 independently of one another are amino, C j -C 6 alkylamino, C 2 -C 8 dialkylamino, phenylamino, C 2 -C 6 alkylcarbonylamino or C 2 -C 10 alkoxycarbonylamino.
In other groups of preferred compounds of the formula I, X is O or R 4 is phenyl or phenyl which is substituted by halogen.
Preferred compounds of the formula I are those in which Rj is Cj-C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C j -C 6 alkyl, Cj-C 8 alkyl-C 3 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 10 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkynyl, C 2 -C 8 alkynyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C j -C 6 alkyl, Cj-C 8 alkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkynyl, C 2 -C 8 alkynyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 3 -C 8 cycloalkyl, C 2 -C 8 alkynyl-C 2 -C 6 alkenyl or C 2 -C 8 alkenyl-C 2 -C 6 alkynyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NRJ Q RJ J, =NR 2 , phenyl, biphenyl, naphthyl or heterocyclyl, it being possible for these phenyl, naphthyl and heterocyclyl substituents to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJ J or -CONR 8 R 9 , or R j is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its
carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, nitro, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NR 10 Rn. =NR 12 , =N-NRj 3 R 14 ,
C j -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, phenyl, biphenyl, naphthyl, Cj-C 8 alkyl which is substituted by halogen, cyano, nitro, -OR 5 ,
-CONR 8 R 9 or -NRJ Q RJ J, C 2 -C 8 alkenyl which is substituted by halogen, cyano, nitro,
-OR 5 , -CONR 8 R 9 or -NRJQRJ J, C 2 -C 8 alkynyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R or -NRJQRJ J, C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RJ J, C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NR 10 R π , phenyl which is substituted by halogen, cyano, nitro, Cj-C 6 alkyl, C j -C 6 haloalkyl, -OR 5 , -CONR 8 R 9 or -NR 10 RJJ, biphenyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RJJ, or naphthyl which is substituted by halogen, cyano, nitro, -OR 5 , -CONR 8 R 9 or -NRJ Q RJ , or
R j is phenyl, biphenyl, naphthyl, Cj-C alkylphenyl, C j -C 4 alkylbiphenyl,
C j -C 4 alkylnaphthyl, C 2 -C 4 alkenylphenyl, C 2 -C 4 alkenylbiphenyl, C 2 -C 4 alkenylnaphthyl,
C 2 -C 4 alkynylphenyl, C 2 -C 4 alkynylbiphenyl or C 2 -C alkynylnaphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, -OR 5 , -S(O) n R 6 , -COOR 7 ,
-CONR 8 R 9 or -NRJ Q RJJ , in which
R 5 is hydrogen, Cj-C 6 alkyl, Cj-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, C j -C 6 cyanoalkyl, phenyl, halophenyl, Cj-C 4 alkoxyphenyl, phenyl-C j -C alkyl, C j -C alkylcarbonyl, benzoyl, halobenzoyl, Cj-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl, C 3 -C 6 cycloalkyl,
C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, n is 0, 1 or 2,
R 6 is hydrogen or cyano if n is 0, or
R 6 is Cj-C 4 alkyl, C r C 4 haloalkyl, phenyl, C j -C 4 alkylphenyl, halophenyl, heterocyclyl, haloheterocyclyl or C 3 -C 6 cycloalkyl,
R 7 is hydrogen, Cj-C alkyl, Cj-C haloalkyl, C j -C cyanoalkyl, phenyl, halophenyl,
C 2 -C 4 alkoxyalkyl, heterocyclyl or haloheterocyclyl,
R 8 and R 9 independently of one another are hydrogen, phenyl, halophenyl, C j -C alkyl,
C j -C 4 haloalkyl, Cj-C 4 cyanoalkyl, C 3 -C alkenyl, C 3 -C alkynyl or C 2 -C 4 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R O and R j independently of one another are hydrogen, phenyl, halophenyl, C j -C alkyl,
C j -C 4 haloalkyl, Cj-C 4 cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 2 -C 4 alkoxyalkyl, formyl,
C j -C 4 alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substituted by Cj-C 4 alkyl, halogen, C r C 4 alkoxy, hydroxyl, cyano, nitro or
C -C 4 alkoxycarbonyl, or
RJO and RJJ together with the nitrogen atom to which they are bonded to form a
heterocycle which can be halogenated, and
R 12 is hydrogen, C j -C alkyl, C -C 4 haloalkyl, phenyl, halophenyl, cyanophenyl, nitrophenyl, Cj-C 4 alkylphenyl, C j -C 4 alkoxyphenyl or phenyl-C r C 4 alkyl.
Particularly preferred amongst these compounds are those in which R j is Cj-CjQalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-Cj-C 6 alkyl, C j -C 8 alkyl-C 3 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C 10 alkynyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkynyl, C 2 -C 8 alkynyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C j -C 6 alkyl, C j -C 8 alkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkynyl, C 2 -C 8 alkynyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloa]_kenyl-C 5 -C 8 cycloa]_kenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 3 -Cgcycloalkyl, C -Cgalkynyl-C 2 -C 6 alkenyl or C 2 -C 8 alkenyl-C 2 -C 6 alkynyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, =O, -OR 5 , -COOR 7 , -CONR 8 R 9 , -NR 10 Ru or phenyl, it being possible for this phenyl ring to be unsubstituted or substituted by halogen, or Rj is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, =O, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONR 8 R 9 , -NRI Q RJJ, C r C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -Cgcycloalkenyl, phenyl, C j -C 8 alkyl which is substituted by halogen, cyano, -OR 5 , -CONR 8 R 9 or -NR 10 Ru, C 2 -C 8 alkenyl which is substituted by halogen, cyano, -OR 5 , -CONR 8 R 9 or -NRJ Q R J, C 2 -C 8 alkynyl which is substituted by halogen, cyano, -OR 5 , -CONRsRς, or -NRJ Q RJJ, C 3 -C 8 cycloalkyl which is substituted by halogen, cyano, -OR 5 , -CONR 8 R 9 or -NR 10 RJJ, C 5 -C 8 cycloalkenyl which is substituted by halogen, cyano, -OR 5 , -CONR 8 R 9 or -NRJ Q RJJ, phenyl which is substituted by halogen, cyano, nitro, Cj-C 4 alkyl, Cj-C 6 haloalkyl, -OR 5 , -CONRsRς, or -NR 10 RJJ, or R is phenyl, biphenyl, naphthyl, Cj-C 4 alkylphenyl, Cj-C 4 alkylbiphenyl, C j -C alkylnaphthyl, C 2 -C 4 alkenylphenyl, C -C 4 alkenylbiphenyl, C 2 -C 4 alkenylnaphthyl, C 2 -C 4 alkynylphenyl, C 2 -C 4 alkynylbiphenyl or C 2 -C alkynylnaphthyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, -OR 5 , -S(O) n R 6 , -COOR 7 , -CONRgRg or -NRI Q RJJ, in which
R 5 is hydrogen, C j -C 6 alkyl, C r C 6 haloalkyl, C -C 6 alkoxyalkyl, C j -Cgcyanoalkyl, phenyl-C j -C 4 alkyl, Cj-C 4 alkylcarbonyl, benzoyl, halobenzoyl, C 3 -C 6 trialkylsilyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, n is 0, 1 or 2, R 6 is hydrogen or cyano if n is 0 or
R 6 is C j -C 4 alkyl, C -C 4 haloalkyl, phenyl or Cj-C 4 alkylphenyl,
R 7 is hydrogen, Cj-C 4 alkyl, C j -C 4 haloalkyl, C j -C 4 cyanoalkyl, phenyl, halophenyl,
C 2 -C 4 alkoxyalkyl, heterocyclyl or haloheterocyclyl,
R 8 and R 9 independently of one another are hydrogen, phenyl, halophenyl, C j -C 4 alkyl,
C j -C 4 haloalkyl, Cj-C cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or C -C 4 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R o and R independently of one another are hydrogen, phenyl, halophenyl, C j -C alkyl,
C j -C haloalkyl, C r C cyanoalkyl, C 3 -C alkenyl, C 3 -C alkynyl, C 2 -C alkoxyalkyl, formyl,
C 1 -C alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substituted by C -C 4 alkyl, halogen, C j -C 4 alkoxy, hydroxyl, cyano, nitro or
C j -C 4 alkoxycarbonyl, or
R 10 and R π together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated.
Very particularly preferred compounds of the formula I are those in which R is C j -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 6 alkyl, C j -C 8 alkyl-C 3 -C 8 cycloalkyl, C-j-C j oalkenyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 3 -C 8 cycloalkyl, C 2 -C j oalkynyl, C 3 -C 8 cycloalkyl-C 2 -C 6 alkynyl, C 2 -C 8 alkynyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C j -C 6 alkyl, C j -C 8 alkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkenyl, C 2 -C 8 alkenyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 2 -C 6 alkynyl, C -C 8 alkynyl-C 5 -C 8 cycloalkenyl, C 3 -Cgcycloalkyl-C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl-C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-C 5 -C 8 cycloalkenyl, C 5 -C 8 cycloalkenyl-C 3 -C 8 cycloalkyl, C 2 -C 8 alkynyl-C 2 -C 6 alkenyl or C 2 -C 8 alkenyl-C 2 -C 6 alkynyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, =O, -OR 5 , -COOR 7 , -CONR 8 R 9 , -NRJQRJJ or phenyl, it being possible for this phenyl ring to be unsubstituted or substituted by halogen, or
R j is heterocyclyl, the heterocycle being bonded to the thiatriazine ring via one of its carbon atoms and it being possible for the heterocycle to be substituted by halogen, cyano, =O, C j -C alkoxy, C j -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, C -C 8 alkyl which is substituted by halogen, C 2 -C 8 alkenyl which is substituted by halogen, C 2 -C 8 alkynyl which is substituted by halogen, phenyl which is substituted by halogen, cyano, nitro, Cj-C 4 alkyl or C j -C alkoxy, or
R j is phenyl, biphenyl, naphthyl, Cj-C 4 alkylphenyl, C j -C 4 alkylbiphenyl, C j -C alkylnaphthyl, C 2 -C alkenylphenyl or C 2 -C 4 alkynylphenyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, -OR 5 , -S(O) n R 6 ,
-COOR 7 , -CONR 8 R 9 or -NR j0 R π , in which
R 5 is hydrogen, Cj-C 6 alkyl, Cj-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, C j -C 6 cyanoalkyl, phenyl-Cj-C alkyl, Cj-C alkylcarbonyl, benzoyl, halobenzoyl, C 3 -C 6 trialkylsilyl,
C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, n is 0, 1 or 2,
R 6 is hydrogen or cyano if n is 0, or
R 6 is C j -C 4 alkyl, C j -C 4 haloalkyl, phenyl or C j -C 4 alkylphenyl,
R 7 is hydrogen, C -C 4 alkyl, Cj-C haloalkyl, Cj-C 4 cyanoalkyl, phenyl, halophenyl,
C -C 4 alkoxyalkyl, heterocyclyl or haloheterocyclyl,
R 8 and R 9 independendy of one another are hydrogen, phenyl, halophenyl, C j -C 4 alkyl,
C j -C 4 haloalkyl, C -C 4 cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or C 2 -C 4 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
R 10 and RJJ independently of one another are hydrogen, phenyl, halophenyl, C j -C 4 alkyl,
Cj-C 4 haloalkyl, C -C 4 cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 2 -C alkoxyalkyl, formyl,
Cj-C alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be unsubstituted or substituted by Cj-C 4 alkyl, halogen, C j -C 4 alkoxy, hydroxyl, cyano, nitro or C j -C alkoxycarbonyl, or
RJO and RJJ together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated.
Other preferred compounds of the formula I are those in which R 2 and R 3 independently of one another are hydrogen, Cj-C 6 alkyl, C -C 6 alkyl which is substituted by halogen, cyano, nitro, Cj-C 4 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C -C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, C j -Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cj-C 6 alkylamino, C j -Csalkoxycarbonyl, C 2 -C 6 dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R j j , C j -C 4 alkyl, formyl, C j -C 4 alkylcarbonyl, COOR 7 , Cj-C 4 alkylthio, C j -C 4 alkylsulfonyl or -CONR 8 Rc ) , or R 2 and R 3 independently of one another are C 2 -C 6 alkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, Cj-C 4 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C j -C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or Cj-C 6 alkylamino, C 2 -C 5 alkoxycarbonyl, C 2 -C 6 dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ, C j -C alkyl, formyl, C j -C 4 alkylcarbonyl, COOR 7 , C r C 4 alkylthio, C r C 4 alkylsulfonyl or -CONRgRc,, or
R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, Cj-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C j -C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C j -C 6 alkylamino, C 2 -C5alkoxycarbonyl, C 2 -C 6 dialkylamino or phenyl, it being possible for the phenyl ring to be unsubstituted or substituted by halogen, cyano, nitro, -OR 5 , -NRJ Q RJJ, Cj-C 4 alkyl, formyl, C j - alkylcarbonyl, COOR 7 , C r C 4 alkylthio, C r C 4 alkylsulfonyl or -CONR 8 R < -, or R 2 and R 3 independently of one another are formyl, C j -C 8 alkylcarbonyl, C 2 -C 8 alkenylcarbonyl, -Cgcycloalkylcarbonyl, Cg-Cgcycloalkenylcarbonyl or C 3 -C 8 cycloalkyl-C 1 -C 6 alkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, hydroxyl, amino, C j -C β alkylamino, C 2 -C 7 dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal atom or alkaline earth metal atom, or C 2 -C 8 alkoxycarbonyl, C 4 -C Qcycloalkoxycarbonyl, C j -C 8 alkylaminocarbonyl or C 2 -C 8 dialkylaminocarbonyl, or R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Cj-Csalkyl, C j -Csalkoxy, C j -C 5 alkylcarbonyl, Cj-Csalkylcarbonyloxy, C r C 6 alkoxycarbonyl, aminocarbonyl, C j -C 6 alkylaminocarbonyl or C 2 -C 8 dialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, C -C 4 alkyl, C j -C alkoxy, C j -C 4 alkylcarbonyl, C j -C alkoxycarbonyl, aminocarbonyl, Cj-Cgalkylamino or C j -Csalkylcarbonyloxy, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-C j -C 6 alkylcarbonyl, biphenyl-C j -C 6 alkylcarbonyl, naphthyl-Cj-C 6 alkylcarbonyl, phenyl-C 2 -C 6 alkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl or naphthyl-C -C 6 alkenylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by C j -C alkyl, C j -C 4 alkoxy, C j -C 4 alkylthio, Cj-C 4 haloalkyl, Cj-C 4 alkylcarbonyl, halogen, cyano, amino, nitro, -COOR 7 , C j -C 5 alkoxycarbonyl, hydroxyl, C j -C alkylsulfonyl, C j -C 5 alkylaminocarbonyl or C 2 -C 6 dialkylaminocarbonyl, or
R 2 and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, C j -C 4 alkyl, C j -C 4 alkoxy, Cj-C 4 alkylthio, -COOH, -CONH 2 , C j -C 5 alkylaminocarbonyl, C 2 -C 7 dialkylaminocarbonyl, C j -C 4 alkylcarbonyl or C j -C 5 alkoxycarbonyl, or R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Cj-C 4 alkyl, C -C alkoxy, halogen, cyano or nitro, or R 2 and R 3 independently of one another are amino, C -C 4 alkylamino, C 2 -C 6 dialkylamino, phenylamino, Cj-C 5 alkylcarbonylamino, Cj-C 5 alkoxycarbonylamino, hydroxyl, C j -C 4 alkoxy, C -C 5 alkylcarbonyloxy or phenoxy,
R 5 is hydrogen, Cj-C 6 alkyl, Cj-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, Cj-C 6 cyanoalkyl, phenyl, halophenyl, Cj-C 4 alkoxyphenyl, phenyl-Cj-C 4 alkyl, C r C 4 alkylcarbonyl, benzoyl, halobenzoyl, Cj-C -alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl, C 3 -C 6 cycloalkyl,
C 2 -C 4 alkenyl or C 3 -C 4 alkynyl,
R 7 is hydrogen, Cj-C 4 alkyl, Cj-C 4 halogenalkyl, Cj-C 4 cyanoalkyl, phenyl, halophenyl,
C 2 -C alkoxyalkyl, heterocyclyl or haloheterocyclyl,
R 8 and R 9 independently of one another are hydrogen, phenyl, halophenyl, C j -C alkyl,
C j -C 4 haloalkyl, Cj-C cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C alkynyl or C 2 -C 4 alkoxyalkyl, or
R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated,
RJO and RJJ independently of one another are hydrogen, phenyl, halophenyl, C j -C 4 alkyl,
C j -C 4 haloalkyl, Cj-C cyanoalkyl, C 3 -C alkenyl, C 3 -C 4 alkynyl, C 2 -C 4 alkoxyalkyl, formyl,
C j -C alkylcarbonyl or phenylcarbonyl, it being possible therein for the phenyl moiety to be substituted by Cj-C 4 alkyl, halogen, Cj-C 4 alkoxy, hydroxyl, cyano, nitro or
C j -C alkoxycarbonyl, or
RJO and RJJ together with the nitrogen atom to which they are bonded form a heterocycle which can be halogenated.
Amongst these, particularly preferred compounds are those in which R 2 and R 3 independently of one another are hydrogen, Cj-C 6 alkyl, C j -Cgalkyl which is substituted by halogen, hydroxyl, amino, ammonium, tri-Cj-C 4 alkylammonium, -COOH, -COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, or Cj-C 5 alkylcarbonyloxy, phenylcarbonyloxy, Cj-C 6 alkylamino, C r C 5 alkoxycarbonyl or C 2 -Cgdialkylamino, or
R 2 and R 3 independently of one another are formyl, C j -C 8 alkylcarbonyl, C 2 -C 8 alkenylcarbonyl, C 4 -C 9 cycloalkylcarbonyl, Cg-Cgcycloalkenylcarbonyl or C 3 -Cgcycloalkyl-C j -Cgalkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, hydroxyl, amino, -COOH or -COOM, where M is ammonium or an alkali metal atom or alkaline earth metal atom, or R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C j -Csalkyl, C j -Csalko y or C j -Cgalkoxycarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, C j -C alkyl, C r C 4 alkoxy or C r C 4 alkoxycarbonyl, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-C j -Cgalkylcarbonyl, biphenyl-C j -C 6 alkylcarbonyl, naphthyl-C -Cgalkylcarbonyl, phenyl-C -C 6 alkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl or naphthyl-C 2 -C 6 alkenylcarbonyl, it being possible for
these substituents to be unsubstituted or substituted by C j -C 4 alkyl, C*-C 4 alkoxy,
C j -C 4 alkylthio, Cj-C 4 haloalkyl, Cj-C 4 alkylcarbonyl, halogen, cyano, amino, nitro,
-COOH, Cj-C 5 alkoxycarbonyl, hydroxyl or Cj-C 4 alkylsulfonyl, or
R and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano,
C j -C 4 alkyl, Cj-C 4 alkoxy, Cj-C 4 alkylthio, -COOH or C j -C 5 alkoxycarbonyl, or
R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by C -C 4 alkyl, C j -C 4 alkoxy, halogen or cyano.
Very particularly preferred compounds of the formula I are those in which R 2 and R 3 are hydrogen, or
R 2 and R 3 independently of one another are formyl, C -C 8 alkylcarbonyl,
C 2 -C 8 alkenylcarbonyl, -Cpcycloalkylcarbonyl, Cg-C^cycloalkenylcarbonyl or
C 3 -C 8 cycloalkyl-Cj-C 6 alkylcarbonyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, hydroxyl or amino, or
R 2 and R 3 are phenylcarbonyl, it being possible for the phenyl ring to be unsubstituted or substituted by Cj-C 4 -alkyl, C r C 4 -alkoxy, Cj-C 4 -alkylthio, C j -C 4 haloalkyl, halogen, cyano, nitro, -COOH, C r C 5 alkoxycarbonyl, hydroxyl or C j -C 4 alkylsulfonyl.
Other preferred compounds of the formula I are those in which X is O or S(O) x , where x is
0, 1 or 2, and
R is methyl which is substituted by halogen, cyano, nitro or OR 5 , or
R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl,
C 3 -C 8 cycloalkyl-Cj-C alkyl or Cj-C alkyl-C 3 -C 8 cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, =O or -OR 5 , or
R is phenyl which is substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl,
Cj-C 4 alkyl, C r C 4 alkyloxy, Cj-C 4 alkylthio, C r C 4 haloalkyl, C j -C haloalkoxy,
C -C 4 haloalkylthio, C 2 -C 6 alkoxycarbonylalkoxy, Cj-C 4 alkylsulfinyl, C j -C 4 alkylsulfonyl,
Cj-Cgalkyloxycarbonyl, Cj-C 6 alkylcarbonyl, -CONH 2 , formyl, C j -Csalkylaminocarbonyl,
C 2 -C 7 dialkylaminocarbonyl, C -C 4 alkylamino, C 2 -C 6 dialkylamino,
C 3 -Cgtrialkylsilyl, Cj-Cgalkylcarbonylamino, Cj-C 6 alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, or
R 4 is biphenyl, naphthyl, heterocyclyl, C -C 4 alkylphenyl, C j -C alkylnaphthyl, phenyl-C j -C 4 alkyl or naphthyl-C -C 4 alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl,
C -C alkyl, Cj-C 4 alkyloxy, Cj-C 4 alkylthio, C r C 4 haloalkyl, C j -C 4 haloalkoxy,
C j -C haloalkylthio, C 2 -C 6 -alkoxycarbonylalkoxy, Cj-C 4 alkylsulfιnyl, C -C 4 alkylsulfonyl,
C j -C 6 alkyloxycarbonyl, Cj-C 6 alkylcarbonyl, -CONH 2 , formyl, C j -C 5 alkylaminocarbonyl,
C 2 -C 7 dialkylaminocarbonyl,
C 3 -C 6 trialkylsilyl, Cj-C 6 alkylcarbonylamino, Cj-C 6 alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and
R 5 is hydrogen, C j -C 6 alkyl, Cj-C 6 haloalkyl, C 2 -C 6 alkoxy alkyl, C j -C 6 cyanoalkyl, phenyl, halophenyl, Cj-C 4 alkoxyphenyl, phenyl-Cj-C 4 alkyl, Cj-C 4 alkylcarbonyl, benzoyl, halobenzoyl, Cj-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl, C 3 -C 6 cycloalkyl,
C -C 4 alkenyl or C 3 -C 4 alkynyl.
Amongst these, particularly preferred compounds are those in which X is O or S, and R 4 is methyl which is substituted by halogen or cyano, or
R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 3 -C 8 cycloalkyl-Cj-C 4 alkyl or Cj-C 4 alkyl-C 3 -C 8 cycloalkyl, it being possible for these substituents to be unsubstituted or substituted by halogen or cyano, or R is phenyl which is substituted by halogen, cyano, nitro, amino, C j -C 4 alkyl, C j -C alkyloxy, Cj-C alkylthio, Cj-C haloalkyl, C j -C 4 haloalkoxy, C 2 -C 6 alkoxycarbonylalkoxy, C j -C alkylsulfonyl, C j -C 6 alkyloxycarbonyl, C j -C 6 alkylcarbonyl, formyl, Cj-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 -C 6 trialkylsilyl or C 2 -C 6 alkylcarbonyloxy, or
R 4 is biphenyl, naphthyl, heterocyclyl, C j -C 4 alkylphenyl, C j -C 4 alkylnaphthyl, phenyl-C j -C alkyl or naphthyl-Cj-C 4 alkyl, it being possible for these substituents to be unsubstituted or substituted by halogen, cyano, nitro, amino, C j -C 4 alkyl, C j -C alkyloxy, Cj-C 4 alkylthio, Cj-C 4 haloalkyl, Cj-C 4 haloalkoxy, C 2 -C 6 alkoxycarbonylalkoxy, C j -C 4 alkylsulfonyl, C j -C 6 alkyloxycarbonyl, C j -C 6 alkylcarbonyl, C 3 -C 6 trialkylsilyl or C j - C 6 alky lcarbony loxy .
Very particularly preferred compounds of the formula I are those in which X is O, and R 4 is phenyl which is substituted by halogen, cyano, nitro, amino, Cj-C alkyl, C j -C 4 alkyloxy, C j -C 4 alkylthio, C C 4 haloalkyl, halomethoxy, C j -C 4 alkylsulfonyl, Cj-C 4 alkylamino or C 2 -C 6 dialkylamino.
The compounds of the formula I can be prepared, on the one hand, via process steps which are known per se using known starting materials, and, on the other hand, via a process which was not known per se. The latter process, which was not known per se, comprises starting from the trihalogenated thiatriazine of the formula II
in which Hal substituents independently of one another are fluorine, bromine or, in particular, chlorine, this thiatriazine together with its preparation being described in Chem. Ber. (1991) 124, 1347-1352 and Z. Chem. 16 (1976) 358-359, and reacting it, to introduce the substituent Rj, with the corresponding organometal compound of the formula III
in which Rj is as defined above and M is a monovalent or polyvalent metal atom which, depending on the valency, can carry a corresponding number of R j groups. Examples of suitable metals are, in particular, lithium, magnesium, zinc, aluminium, silicon and tin, and furthermore also manganese and titanium. The polyvalent metal atoms can also carry, besides one or more Rj groups, further substituents such as halogen, cyano, C 1 -C alkyl or tetrafluoroborate. The organometal compound of the formula HI can furthermore be used in combination with salts, such as aluminium chloride, tin chloride, zinc chloride or cerium chloride, or aluminium bromide, zinc bromide and/or copper bromide, amongst which aluminum chloride, aluminium bromide, zinc chloride and zinc bromide are preferred.
The compounds of the formula IH can be prepared by customary methods, for example by reacting the corresponding halide Rj -halogen with the metal M, if appropriate with an addition of a metal halide, or by halogen/metal exchange of R r Br or R -I with a reactive organometal compound, for example butyllithium, and reaction with a compound of the metal M which carries at least one leaving group, such as halogen, or by abstraction of a proton of the molecule Rj-H with a strong base, for example a metal alkoxide, for example potassium tert-butoxide, or metal hydride, for example sodium hydride or lithium aluminium hydride, or a metal amide, for example lithium diisopropylamide, or, in particular, an organometal compound, for example butyllithium, and treatment with a compound of the metal M which carries at least one leaving group, for example cyano, alkoxy or, in particular, halogen, and, if appropriate, one or more Cj-C 4 alkyl groups.
Introduction of the R group can be effected in an aprotic solvent, such as a hydrocarbon, for example hexane, heptane or toluene, or an ether, such as dioxane, diethyl ether or, in
particular, tetrahydrofuran, at temperatures from -100°C to 150°C, in particular -80°C to 50°C (depending on the solvent).
To prepare the compounds of the formula IV in which the sulfur atom of the thiatriazine is bonded to an aromatic or heteroaromatic part of R j , the reaction of the corresponding compound R j -H with a compound of the formula II can be carried out under the conditions of a Friedel-Crafts reaction, i.e. in the presence of a Lewis acid, for example aluminium trichloride, zinc chloride or tin tetrachloride, in an aprotic solvent, for example benzene, nitrobenzene or dichloromethane.
In the case of compounds of the formula I in which R j additionally to the abovementioned definitions is also a group of the formula IX or X
in which A is hydrogen, fluorine, chlorine, bromine, iodine, C -C 7 alkyl, C -C / alkyl which is substituted by halogen or Cj-C 3 alkoxy, or C j -C 4 alkoxy; B is hydrogen, fluorine, chlorine, bromine, iodine, Cj-C 7 alkyl, C r C 7 alkyl which is substituted by halogen or C -C 3 alkoxy, or Cj-C 4 alkoxy; G is hydrogen, Cj-C 7 alkyl, C j -C 7 alkyl which is substituted by halogen or Cj-C 3 alkoxy, Cj-C 4 alkoxy or trimethylsilyl; D is fluorine, chlorine, bromine, iodine, Cj-C 6 alkoxy, Cj-Cgalkylthio, thiocyanato, cyano or C -C 5 alkylcarbonyloxy; and E is C j -C 8 alkyl, C j -C 8 alkyl which is substituted by Cj-C 4 alkoxy, acetoxy, benzyloxy or halogen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl which is substituted by C -C 4 alkoxy, acetoxy, benzyloxy or halogen, Cj-C 5 alkylcarbonyl, C 6 -C 8 aryl or (C j -C alkyl) 3 silyl, the compounds of the formula IV can be prepared advantageously from compounds of the formula XI
in which the substituents A and E, A and B, A and G, and G and E in each case together can form a ring, for example
; in which RQ is C r C 3 alkyl, C j -C 3 alkoxy, acetoxy, benzyloxy or
halogen; and n 0 is 0, 1, 2 or 3, by reacting the compound of the formula XI with a compound of the formula II in the presence or absence of a Lewis acid, for example aluminium trichloride, zinc chloride or tin tetrachloride, in an aprotic solvent, for example hexane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, ether or tetrahydrofuran, at temperatures from -78°C to the boiling point of the solvent, but in particular at -40°C to +40°C, and, if desired, the crude product obtained is subsequently treated with an acid-binding agent, such as tertiary amine, for example triethylamine or pyridine, or a mineral base, for example sodium hydrogen carbonate, sodium carbonate or potassium carbonate, if appropriate in aqueous solution, to neutralize the acid H-halogen.
If the reactivity of the substituent R in the compound of the formula I makes difficult the preparation of the organometal compound of the formula HI, then this labile functional
group R j can advantageously be protected and subsequently re-eliminated at the level of the compounds of the formulae IV, VI, VIII or I, analogously to the procedure described in, for example, 'Protective Groups in Organic Synthesis', Editors Th. W. Greene and P. G. M. Wuts, Wiley Interscience, 1991. For example, a) an alcohol can be protected in the form of a tert-butyl dimethylsilyl ether, and this protective group can be re-eliminated with tetrabutylammonium fluoride; or b) a carbonyl group can be protected in the form of 1,3-dioxane and then again hydrolyzed under acidic conditions to give the carbonyl group; or c) a carboxylic acid can be protected in the form of the ortho-ester and then be recovered under aqueous-acidic and subsequently basic conditions.
The reactive substituents in Rj in the compounds of the formula I can also be introduced by known methods from less reactive precursors at the level of the compounds of the formulae IV, VI, VIII or I, for example by the method described in 'Advanced Organic Chemistry: Reactions, Mechanisms and Structure', Editor J. March, McGraw-Hill, 1983, or in 'Comprehensive Organic Transformations', Editor R. C. Larock, VCH, 1989. Such less reactive precursors can be, for example, halogens, such as bromine, chlorine or iodine, carbon-carbon double or triple bonds, or ethers or thioethers.
A large number of suitable conversion reactions for the preparation of functional groups is described in the specialist literature. For example,
a) a halide can be converted by reduction to give the corresponding alkane or by nucleophilic substitution to give the corresponding nitrile, ether, thioether, ester, azide or thiocyanate; or b) a carbon-carbon double bond can be hydrogenated, halogenated on the allyl position, oxidized to give the corresponding epoxide or cis-diol, or subjected to ozonolysis to give the carbonyl derivative or to oxidative hydroborination to give the alkanol; or c) a nitrile group can be hydrolyzed to give the carboxamide or the carboxylic acid; or d) a thioether can be oxidized to give the sulfoxide or the sulfone, it being possible for these latter compounds to be deprotonated in the α-position and further reacted with electrophilic reagents; or e) an azide can be reduced to give the corresponding amine and, if desired, subsequently acylated.
The resulting compounds of the formula IV
are novel and thus also provided by the present invention.
The substituents -NR 2 R 3 - and -XR 4 can then be introduced into the compound of the formula IV in any desired sequence.
The reaction of the compounds of the formula IV with the compounds of the formula V
H-XR 4 (V),
in which X and R are as defined above, to give the compounds of the formula VI
is advantageously carried out in such a way that, prior to the reaction with the compounds of the formula IV, the compounds of the formula V are pretreated with a base, such as a metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide, such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts. Alternatively, it is also possible to treat the reaction mixture of the compounds of the formulae IV and V with the abovementioned bases. Solvents which are suitable for this step are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene, ethers such as tetrahydrofuran, dioxane or diethyl ether, and tertiary amides, such as dimethylformamide. It is also possible to employ a mixture of these solvents with water, in which case it is advantagoeus to use a phase transfer catalyst. As a rule, the reaction temperatures are between -50°C and 100°C, preferably between 0°C and 40°C.
The compounds of the formula V are known and can be prepared in a manner known to
the expert.
The compounds of the formula VI are novel and are also provided by the present invention.
They can be converted into the end products of the formula I by means of a reaction with a compound of the formula VII
M j -NR 2 R 3 (VII),
in which R 2 and R 3 are as defined above and Mj is hydrogen or a metal atom such as lithium, sodium, potassium or calcium, the process advantageously being carried out in the presence of a base. If R 2 and/or R 3 are hydrogen, then Mj is preferably hydrogen. If R 2 or R 3 is an acyl group, Mj is preferably lithium, sodium or potassium.
Solvents which are suitable for this reaction are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene or dichloromethane, ethers such as diethyl ether, dioxane or tetrahydrofuran, alcohols such as ethanol or isopropanol, esters such as ethyl acetate, nitriles such as acetonitrile, or water. The reaction temperatures are in the range of -70°C to 100°C, in particular 0°C to 40°C.
If Mj is hydrogen, an acid binder is preferably used for trapping the HHal acid. This can be, for example, a second equivalent of the compound of the formula VII or a tertiary amine such as triethylamine, pyridine or an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogencarbonate. In the event that R 2 , R 3 and M j are hydrogen, an excess of base can be used. The process may be carried out under pressure.
The compounds of the formula VII and their preparation are described in the literature.
The reaction conditions to be adhered to for the reaction of compound VI with compound VII must also be observed when the compound of the formula IV is first to react with the base of the formula VII. The resulting compounds of the formula VIE
are also novel and provided by the present invention.
The further reaction of the compounds of the formula VIE with the compounds of the formula V is effected analogously to the procedure in the reaction of the compounds of the formulae IV and V. However, an amine such as triethylamine is additionally added to the reaction mixture in amounts which range from catalytic to an excess.
The end products of the formula I can be isolated in the customary manner by concentrating and/or evaporating the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatographic methods.
Conventional derivatization of compounds of the formula I allows other compounds of the formula I to be prepared.
A variety of methods and techniques are suitable for the use according to the invention for the compounds of the formula I, IV, VI or VIII or for compositions comprising these compounds, for example the following:
i) Seed dressing a) The seeds are dressed by shaking them, in a vessel, together with an active ingredient formulated as a wettable powder until the active ingredient is distributed uniformly on the seed surface (dry seed dressing). Up to 4 g of active ingredient of the formula I, IV, VI, VIII (in the case of a 50% formulation: up to 8.0 g of wettable powder) per kg seed is used.
b) Seed dressing with an emulsion concentrate of the active ingredient or with an aqueous solution of the active ingredient of the formula I, IV, VI or VIE formulated as a wettable powder by method a) (wet seed dressing).
c) Dressing by immersing the seed into a mixture comprising up to 1000 ppm of active
ingredient of the formula I, IV, VI or VIII for 1 to 72 hours, if desired followed by drying of the seeds (seed soaking).
Naturally, dressing the seed or treating the seedling which has just begun to germinate are the preferred methods of application because the treatment with the active ingredient is directed entirely towards the target crop. As a rule, 0.001 g to 4.0 g of active ingredient are used per kg of seed, it being possible to deviate from these limit concentrations up or down, depending on the method, which also makes possible the addition of other active ingredients or micronutrients (repeated dressing).
ii) Controlled release of active ingredient
The active ingredient is applied in solution to mineral granule carriers or polymerized granules (urea/formaldehyde) and allowed to dry. If desired, a coating can be applied additionally (coated granules) which allows controlled release of the active ingredient over a certain period.
The compounds of the formula I, IV, VI or VIE can be used as pure active ingredients, i.e. as they are obtained in synthesis, but they are preferably processed in the customary manner together with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The methods of application, such as spraying, atomizing, dusting, wetting, scattering or pouring, as well as the nature of the compositions, are chosen to suit the intended aims and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I, IV, VI or VIII or at least one active ingredient of the formula I, IV, VI or VIE and, if desired, one or more solid or liquid additives, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredients with the additives, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) can additionally be used for the preparation of the formulations.
The following are suitable as solvents: aromatic hydrocarbons, in particular the fractions C 8 to C 12 , such as mixtures of alkylbenzenes, for example xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols such as ethanol, propanol or butanol; glycols as well as
their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils as well as their esters, such as rapeseed oil, castor oil or soya oil; if appropriate, also silicone oils.
Solid carriers which are used, for example, for dust and dispersible powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silica or highly-disperse absorptive polymers. Possible paniculate, adsorptive carriers for granules are either porous types, for example pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are, for example, calcite or sand. Moreover, a large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues, can be used.
Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated. Surfactants are also to be understood as meaning surfactant mixtures.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble, synthetic surface-active compounds.
Soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C 22 ) for example the sodium or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tallow oil. Mention must also be made of the fatty acid methyltaurinates.
However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alky lary lsulf onates .
As a rule, the fatty alcohol sulfonates or fatty alcohol sulfates are in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have, as a rule, an alkyl radical having 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium salt or calcium salt of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural
fatty acids. This group also includes the salts of the sulfuric esters and the sulfonic acids of fatty alcohol/ethylene oxide addition products. The sulfonated benzimidazole derivatives preferably have 2 sulfonyl groups and a fatty acid radical having approximately 8-22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product.
Suitable phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14) ethylene oxide adduct, or phospholipids, are also possible.
Possible non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Other suitable non-ionic surfactants are the water-soluble polyethylene oxide addition products with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and have 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds conventionally have 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide addition products, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Other substances which are suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts which have, as N substituent, at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants conventionally used in the art of formulation which can also be used in the compositions according to the invention are described, inter alia, in the following publications:
- "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.
- M. and J. Ash, "Encyclopedia of Surfactants", Vol. HE, Chemical Publishing Co., New York, 1980-1981.
- Dr. Helmut Stache "Tensid-Taschenbuch" [Surfactants Guide], Carl Hanser Verlag, Munich/Vienna 1981.
As a rule, the herbicidal preparations comprise as a rule 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient of the formula I, 1 to 99 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.
While concentrated compositions are more preferred as commercially available goods, the end consumer uses, as a rule, dilute compositions.
The compositions can also comprise further additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilizers or other active ingredients for achieving specific effects.
In particular, preferred formulations are composed as follows: (% = percent by weight)
Emulsifiable concentrates:
Active ingredient: 1 to 90 %, preferably 5 to 50 %
Surface-active agent: 5 to 30 %, preferably 10 to 20 %
Solvent: 15 to 94 %, preferably 70 to 85 %
Dusts:
Active ingredient: 0.1 to 50 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
Active ingredient: 5 to 75 %, preferably 10 to 50 %
Water: 94 to 24 %, preferably 88 to 30 %
Surface active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: Active ingredient: 0.5 to 90 %, preferably 1 to 80 % Surface-active agent: 0.5 to 20 %, preferably 1 to 15 % Solid carrier: 5 to 95 %, preferably 15 to 90%
Granules: Active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % Solid carrier: 99.5 to 70 %, preferably 97 to 85 %
As a rule, the active ingredients of the formula I are successfully employed at rates of application of 0.001 to 5 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired effect can be determined by experiments. It depends on the nature of the effect, the development stage of the crop plant and of the weed as well as on the application (location, timing, method) and can vary within wide limits due to these parameters.
The compounds of the formula I are distinguished by growth-inhibiting and herbicidal properties which make them outstandingly suitable for use in crops of useful plants, in particular in cereals, cotton, soya beans, oilseed rape, maize and rice.
The examples which follow illustrate the invention in greater detail without imposing any limitation.
The nomenclature used hereinbelow is based on the numbering showed below:
6 5
1 £ \ 4
2 3
Preparation Examples:
Example HI: Preparation of 3,5-dichloro-l-pentylthiatriazine
A solution of 13.4 g of A1C1 3 (0.1 mol) in 400 ml of THF is cooled to -70°C. A solution of pentylmagnesium bromide in ether is then added dropwise, and the mixture is allowed to come to 20°C and, after 15 minutes, is again cooled to -70°C. 20.5 g of trichlorothiatriazine in 50 ml of THF are subsequently added with stirring. The reaction mixture is kept for 2 hours at this temperature. It is then allowed to warm to room temperature and poured into 400 ml of ice- water. The organic phase is treated with dilute aqueous hydrochloric acid and then washed with water until neutral and dried using sodium sulfate. After filtration and concentration of the phase, an oily residue is obtained, and this is taken up in 200 ml of hexane. Insoluble components are removed and the solution which remains is cooled. White crystals of the compound given above form which have a melting point of 34°C after recrystallization.
Example H2: Preparation of 3,5-dichloro-l-methylthiatriazine
A solution of 18.5 g of trichlorothiatriazine (0.09 mol) in 200 ml of methylene chloride is cooled to -75°C. A solution of dimethylaluminium chloride in hexane is then added dropwise under protective gas. The temperature should not exceed -65 °C. The reaction mixture is then held for 40 minutes at -70°C. It is then allowed to come to -45°C, and 9 ml of water are added dropwise. After the mixture has warmed to room temperature, it is filtered, and the filtrate is dried using sodium sulfate. After concentration, a residue is obtained, and this is taken up in 50 ml of hexane and 20 ml of ether. After the crude product has been filtered off, it is washed with hexane and dried in vacuo. This gives colourless crystals of the compound given above having a melting point of 101°C (decomposition).
Example H3: Preparation of 3-(2-ethoxycarbonylphenyloxy)-5-chloro-l-phenylthiatriazine 3.4 g of ethyl salicylate are dissolved in 15 ml of DMF and the solution is treated with 0.88 g of sodium hydride (55 % in oil) at 0-10°C. This solution is then added dropwise to a solution of 5.0 g of 3,5-dichloro-l-phenylthiatriazine (prepared analogously to Example HI) in 10 ml of DMF. After the mixture has been stirred for 12 hours at room temperature, it is filtered and concentrated. The residue is taken up in methylene chloride, washed with water, dried using sodium sulfate and evaporated. After pre-purification by chromatography on silica gel using a mixture of hexane and ethyl acetate (7:1) and recrystallization from the abovementioned mixture, crystals of the abovementioned compound having a melting point of 88-90°C are obtained.
Example H4: Preparation of 3-amino-5-chloro-l-methylthiatriazine Ammonia is passed at a temperature of 10-20°C into a solution of 11.04 g of
3,5-dichloro-l-methylthiatriazine (obtained as described in Example H2) in 1.5 1 of acetonitrile. After the mixture has been stirced for 1.5 hours at 20°C, 120 ml of water are added. The mixture is cooled to 5°C, solid is filtered off, and the residue is washed with water and cold acetonitrile and ether and dried. This gives the abovementioned product having a melting point of 156°C (decomposition).
Example H5: Preparation of 3-chloro-5-isopropylamino-l-methylthiatriazine 14.8 g of isopropylamine are added dropwise at room temperature to a solution of 23.0 g of dichloromethylthiatriazine (obtained as described in Example H2) in 175 ml of THF. The reaction mixture is then treated with ethyl acetate and water. The product is extracted with ethyl acetate, this phase is washed with water and dried using sodium sulfate. After the mixture has been filtered and the filtrate concentrated, the crude product is taken up in methylene chloride and refiltered. The filtrate is treated with hexane, stirred for 2 hours, filtered, and the residue is washed with pentane and dried. This gives the abovementioned compound in crystalline form having a melting point of 120-122°C.
Example H6: Preparation of 3-amino-5-(2,6-dichlorophenoxy)-n-pentylthiatriazine 2.2 g of aminochloropentylthiatriazine (obtained by the methods described in Examples HI and H4), 1.6 g of dichlorophenyl, 0.4 g of sodium hydroxide (dissolved in 1 ml of water) and 1.48 g of a 40% aqueous solution of trimethylamine are introduced into 100 ml of THF. The mixture is stirred for 12 hours and concentrated, and the residue is stirred with water and diethyl ether. After filtration, the solid is washed with water and dried. Recrystallization from a THF/hexane mixture gives the abovementioned compound having a melting point of 200°C (decomposition).
Example H7: Preparation of 3-methoxy-l-methyl-5-methylaminothiatriazine 123 mmol of sodium methylate are added to a suspension of 10.0 g of 3-chloro-l-methyl-5-methylaminothiatriazine (obtained analogously to the method described in Example H4) in 250 ml of methanol, which has been cooled to 15°C, and 2.6 g of trimethylamine are then passed in. After the mixture has been stirred for 14 hours it is evaporated, the residue is stirred with methylene chloride, the mixture is filtered, and the solid is washed with pentane and dried. This gives the abovementioned compound having a melting point of 153-154°C.
Example H8: Preparation of 3,5-dichloro-l-phenylthiatriazine
0.15 g of aluminium trichloride is added at -20°C to a solution of 10.2 g of trichlorothiatriazine (0.05 mol) and 7.5 g of phenyltrimethylsilane (0.05 mol) in 40 ml of
dichloromethane. This reaction mixture is heated slowly at 20°C and stirred for 2 hours at this temperature. After this, 300 g of ice- water are added and the mixture is extracted using dichloromethane. The combined organic phases are washed with water until neutral and dried over sodium sulfate. After the desiccant has been filtered off and the filtrate concentrated, the desired product is obtained as crystals of m.p. 91-94°C.
Example H9: Preparation of l-(tert-butylethynyl)-3,5-dichlorotriazine A solution of lithium tetrakis(tert-butylethynyl)alanate, prepared from 3.24 g of lithium aluminium hydride (0.0855 mol), 0.2 g of diethylamine and 33.7 g of tert-butylacetylene (0.41 mol) in 250 ml of tetrahydrofuran in analogy to Bull. Acad. Sci. of USSR (engl. transl.) 1965, pages 165-167, editor L.I. Zakharkin et al., is added dropwise at -75°C to a solution of 52.4 g of trichlorothiatriazine (0.256 mol) in 400 ml of dichloromethane. The reaction mixmre is kept for 1 hour at this temperature. A cold solution of 48 g of Rochelle salt and 9 g of potassium carbonate in 450 ml of water is added. After a further addition of
1 litre of water and 1 litre of ether, the phases are separated. The aqueous phase is extracted with ether and the organic phase washed with saturated sodium hydrogencarbonate solution until neutral and dried over sodium sulfate. Removal of the desiccant by filtration and evaporation of the filtrate gives the desired product as crystals. After recrystallization from hexane, a melting point of 73-74.5°C is determined.
Example H 10: Preparation of 3,5-dichloro-l-phenylthiatriazine A solution of 5.12 g of trichlorothiatriazine (0.025 mol) in 20 ml of benzene is slowly added dropwise at 0°C to a vigorously stirred suspension of 6.0 g of aluminium trichloride (0.045 mol) in 80 ml of benzene and 10 ml of pentane. The reaction mixture is stirred for
2 hours at 0°C and subsequently for a further hour at 20°C. The reaction mixture is again cooled to 0°C and treated with ice and ether. The aqueous phase is extracted with ether and the combined organic phases are washed with aqueous saturated sodium hydrogen- carbonate solution until neutral and dried over sodium sulfate. After removal of the desiccant by filtration and concentration of the filtrate, the crude product obtained is the desired compound which after purification by chromatography is identical with the compound obtained in Example H8.
Example HI 1: Preparation of 3-amino-l-cyclohexyl-5-methanesulfinylthiatriazine A solution of 6.45 g of 3-chloroperbenzoic acid (0.02057 mol) in 110 ml of chloroform is added dropwise in the course of 1.5 hours at 20°C to a vigorously stirred suspension of 4.57 g of 3-amino-l-cyclohexyl-5-methylthiothiatriazine (0.0187 mol) in 70 ml of chloroform and 1.9 g of sodium hydrogencarbonate. After stirring of the reaction mixture
has continued for 4 hours, it is treated with 180 ml of aqueous semisaturated sodium hydrogencarbonate solution. The phases are separated and the water phase is extracted using dichloromethane. The combined organic phases are dried over sodium sulfate. After the desiccant has been removed by filtration and the filtrate concentrated, the residue is subjected to flash chromatography over silica gel using ethyl acetate/ethanol 4/1. Recrystallization from ethyl acetate/methylene chloride gives the desired product as crystals having an m.p. of 134-138°C (decomposition).
Example HI 2: Preparation of l-cyclohexyl-3-isopropylthio-5-propylaminothiatriazine 0.77 g of propylamine (0.013 mol) in 5 ml of tetrahydrofuran is added dropwise at 20°C to a solution of 1.75 g of 3-chloro-l-cyclohexyl-5-isopropylthiothiatriazine (0.006 mol) in 25 ml of tetrahydrofuran. After 1 hour, the reaction mixture is filtered off with suction over silica gel and the residue is washed with tetrahydrofuran. The filtrate is evaporated and the residue recrystallized from ethyl acetate/hexane. The desired compound is obtained as crystals having an m.p. of 73-74°C.
Example H13: Preparation of 3-amino-l-(3-bromo-2-methoxytetrahydropyran-3-yl)- 5-chlorothiatriazine
A suspension of 1.16 g of 3-amino-5-chloro-l-(5,6-dihydro-4H-pyran-3-yl)thiatriazine (0.005 mol) in 40 ml of methanol is treated at 5°C with a solution of 0.80 g of bromine (0.005 mol) in 10 ml of methanol and stirring is subsequently continued for 1 hour at 20°C. After this, the reaction mixture is evaporated in vacuo, the residue is taken up in dichloromethane, and the mixture is extracted by shaking with a saturated sodium hydrogencarbonate solution. The organic phase is separated off and dried over sodium sulfate. After the desiccant has been removed by filtration and the filtrated concentrated, the residue obtained is triturated with ether. The desired compound is obtained as crystals having an m.p. of 188°C (decomposition).
Example H 14: Preparation of 3-amino-5-chloro-l-(2-methoxytetrahydropyran-3-yl)- thiatriazine
A suspension of 0.61 g of 3-amino-l-(3-bromo-2-methoxytetrahydropyran-3-yl)-5-chloro- thiatriazine (0.00177 mol), 0.06 g of bisazobutyronitrile and 0.62 g of tri-n-butyltin hydride in 50 ml of benzene is stirred at reflux temperature. After 1 hour, the mixture is evaporated in vacuo and the residue obtained is stirred with hexane. After filtration and washing the crystals with hexane, the product is recrystallized from diisopropyl ether. The desired product has an m.p. of 167-168°C (decomposition).
Example H15: Preparation of 3,5-dichloro-l-(2,3-dimethylpropyl)thiatriazine A Grignard solution prepared from 29.9 g of l-bromo-2,2-dimethylpropane (0.198 mol) and 5.0 g of magnesium (0.208 mol) in 120 ml of tetrahydrofuran is added slowly to a mixture of 26.9 g of zinc chloride (0.198 mol) and 400 ml of tetrahydrofuran at -20°C. After the mixture has been heated to 0°C, it is again cooled to -30°C, and a solution of 40.5 g of 1,3,5-trichlorothiatriazine in 200 ml of tetrahydrofuran is added dropwise at this temperature. The temperature is slowly raised to 0°C and kept for 2 hours at 0°C. The reaction mixmre is subsequently poured into 600 g of ice- water and extracted with pentane. The organic phase is washed with aqueous sodium hydrogencarbonate solution until neutral and dried over sodium sulfate. After the desiccant has been removed by filtration and the filtrate concentrated, the residue is recrystallized from pentane. The crystals of the desired product show an m.p. of 48-51 °C.
Example HI 6: Preparation of 2-(l-cyclohexyl-5-phenoxythiatriazin-3-yl)- isoindole- 1 ,3-dione
A mixture of 1.0 g of 3-amino-l-cyclohexyl-5-phenoxythiatriazine (0.00344 mol), 0.69 ml of pyridine (0.0086 mol), 0.55 ml of phthalic acid dichloride (0.00378 mol) in 30 ml of 1,2-dimethoxyethane is stirred for 6 hours at reflux temperature. After the mixture has cooled, it is poured into 70 ml of saturated aqueous sodium hydrogencarbonate solution and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate. After filtration and concentration of the organic phase, the residue is subjected to flash chromatography over silica gel using ethyl acetate/hexane 35/65. Recrystallization from ether/hexane gives the desired compound as crystals having an m.p. of 145-146°C.
Example H 17: Preparation of 3-methoxy-l-methyl-5-methylaminothiatriazine 2.6 g of trimethylamine (0.045 mol) are passed at 15°C into a suspension of 10.0 g of 3-chloro-l-methyl-5-methylaminothiatriazine (0.056 mol) in 250 ml of methanol. The reaction mixmre is stirred for 14 hours and subsequently evaporated in vacuo. The residue is stirred with dichloromethane and filtered off over kieselguhr. The filtrate obtained is evaporated and the product is stirred with pentane and filtered with suction. Washing of the solid obtained by filtration with suction with pentane and drying gives the desired compound as crystals having an m.p. of 153-154°C.
Example HI 8: Preparation of 3-(3-cyanopropylamino)-l-cyclohexyl-5- phenoxythiatriazine
0.35 g of sodium hydroxide (0.00875 mol) is added to a solution of 2.98 g
3-(N-3-cyanopropylacetamido)-l-cyclohexyl-5-phenoxythiatr iazine (0.00746 mol) in
50 ml of ethanol. After the reaction mixture has been stirred for 0.5 hour at 22°C, it is treated with 40 ml of water and the suspension obtained is filtered with suction. The solid obtained by filtration with suction is washed with water and dried. This gives the desired compound as crystals having an m.p. of 170-172°C.
Example HI 9: Preparation of 3-(N-3-cyanopropylacetamido)-l-cyclohexyl-5- phenoxythiatriazine
A solution of 2.5 g of 3-acetamido-l-cyclohexyl-5-phenoxy thiatriazine (0.00752 mol) in 50 ml of N,N-dimethylformamide is treated at 40°C with 0.22 g of sodium hydride (0.00902 mol). After the evolution of gas has ceased, 1.14 mg of 4-bromopropionitrile (0.001128 mol) are added at 22°C and the mixture is stirred for 1 hour. After water has been added carefully, the reaction mixture is poured into 80 ml of water and the product extracted using ethyl acetate. The organic phase is washed with brine and dried over sodium sulfate. After the desiccant has been removed by filtration and the filtrate concentrated, the crude product is subjected to flash chromatography over silica gel using ethyl acetate/hexane 1/1. Evaporation of the fractions obtained allows the desired compound to be isolated as an oil.
Example H20: Preparation of l-cyclohexyl-3-valeroylamino-5-phenoxythiatriazine 0.92 g of 2-valeroyl-3-oxo-4,5-benzo-l,2-thiazoline-l,l-dioxide (0.00344 mol), prepared analogously to Synthetic communications 14(4), 353-362 (1984), 0.72 ml of triethylamine (0.00516 mol) and a catalytic amount of 4-dimethylaminopyridine are added to a suspension of 1.0 g of 3-amino-l-cyclohexyl-5-phenoxythiatriazine (0.00344 mol) in 40 ml of 1,2-dichloroethane. The reaction mixture is stirred for 12 hours at reflux temperature and subsequently evaporated in vacuo. The residue is purified by chromatography over silica gel using toluene/ethyl acetate 4/1. Recrystallization from ether/hexane gives the desired product as crystals having an m.p. of 116°C.
Example H21: Preparation of 3-acetamido-l-pentyl-5-phenylthiothiatriazine 0.75 g of pyridine (0.0095 mol) and 0.97 g of acetic anhydride (0.0095 mol) are added to a solution of 1.4 g of 3-amino-l-pentyl-5-phenylthiothiatriazine (0.00475 mol) in 50 ml of 1,2-dimethoxyethane and the reaction mixture is stirred for 12 hours at reflux temperature. The reaction mixture is then evaporated in vacuo and the residue treated with ethyl acetate and water. The organic phase is separated off, washed with water and dried over sodium sulfate. After the desiccant has been removed by filtration, the filtrate is concentrated and the residue obtained is subjected to flash chromatography over silica gel using ethyl acetate/hexane. Concentration of the fractions gives the desired compound as crystals
having an m.p. of 89-90°C.
Example H22: Preparation of (E)-3,5-dichloro-l-(2-methylhex-l-enyl)thiatriazine A solution of (E)-dimethyl-l-(2-methylhex-l-enyl)alane is prepared analogously to Tetrahedron 1994, 5189-5202 from 16.43 g 1-hexyne (0.2 mol), 310 ml of a 2.0 molar trimethylalumimum solution in hexane (0.62 mol) and 8.0 g of ZrCl 2 (Cp) 2 (0.0274 mol) in 600 ml of dichlormethane. This solution is added dropwise in the course of 1.25 hours to a solution of 39.07 g of trichlorothiatriazine (0.191 mol) in 400 ml of tetrahydrofuran cooled to -40°C. Stirring of the reaction mixture obtained is continued for 1 hour under cold conditions, 40 ml of water are then carefully added at -30°C, and the mixture is allowed to defrost slowly (evolution of gas). The mixture is then subjected to filtration with suction over kieselguhr, the filtrate is extracted with water and washed with sodium hydrogencarbonate solution until neutral and the organic phase is dried over sodium sulfate. Filtration and concentration of the filtrate give a residue which is recrystallized from hexane. The crystals obtained having an m.p. of 59-62°C are those of the desired compound.
Example H23: Preparation of 3,5-dichloro-l-(5,6-dihydro-4H-pyran-3-yl)thiatriazine A solution of 61.3 g of trichlorothiatriazine (0.3 mol) in 600 ml of dichloromethane is cooled in an ice bath and treated with 0.41 g of zinc chloride. 27.7 g of 3,4-dihydro-2H-pyran is slowly added dropwise to this mixture with vigorous stirring. After this, stirring is continued for 1 hour, and 60 ml of triethylamine are subsequently added dropwise. Stirring of this suspension is continued for 0.5 hour at 22°C, and the mixture is then filtered with suction. The residue obtained is washed with ether, and the filtrate is concentrated and treated with water. After the mixture has been filtered, the residue obtained is washed with water and dried. The crude product is subjected to flash chromatography over silica gel using dichloromethane/ether 1:1. After the fractions obtained have been evaporated, crystals of the desired compound having an m.p. of 127°C (decomposition) form.
The compounds listed in the tables below can be prepared analogously to Examples HI to H23.
Table 1: Compounds of the formula I
. R
Comp. R j NC , XRA Physical data
No. (m.p. °C)
1.001 CH 3 - -NH 2 -OCH 3 166-167 1.002 CH 3 - -NH 2 -S-C 3 H 7 (i) 185-186
1.003 CH 3 - -NH 7
1.005 CH 3 - -NH— u CH 3 -S-C 3 H 7 (i) 116-117
1.006 CH 3 - -NHCH 3 -OCH 3 153-154 1.007 CH 3 - -NH-iC 3 H 7 -OCH 3 128-130
1.008 CH, -NH-NH-COOt-C 4 H 9 178-179
1.010 n-C 3 H 7 - -NH,
1.011 i-C 3 H 7 - -NH, *o
,R 2
Comp. Rj NC Rs XR, Physical data No. (m.p. °C)
1.022 cY -NH, 181-182
(decomp.)
1.023 -NH—* CH. 134-135
1.025 Br(CH 2 ) 4 - -NH 2 130
-NH, 135
-NH, 169
solid
solid
. R
Comp. Rj N -- R 3 XR 4 Physical data
No. (m.p. °C)
1.031 HO-(CH 2 ) 4 - -NH 2 -° 7 solid
solid
solid
1.034 S ( CH 2 ) 4 - , NH2 ■ °Λ / solid
035 ( SOlid 2 ) 4 -
1.036 ? ° -NH, solid
1.038 O 2 N(CH 2 ) 4 - -NH 2 solid
1.040 NC-(CH 2 ) 4 - -NH 2
.R,
Comp. Rj N ~~R 3 XR 4 Physical data
No. (m.p. °C)
1.041 C1-(CH 2 ) 4 - -NH 2 Λ 138
1.052 iC 4 H 9 -CH 2 - -NH 2 -O
. R 2
Comp. Rj N R, XR, Physical data
No. (m.p. °C)
1.054 t HcrG≡C- -NH 2 168-169 (decomp.)
1.056 cCgHjjCH -NH 2 158
1.057 tC 4 Hc,-G≡C- -NH 2 178-180 (decomp.)
, R 2
Comp. Rj N R, XR„ Physical data No. (m.p. °C)
1.062 CC 6 HJJCH 2 - -NH, 166
1.063 cC 6 HnCH 2 - -NH 2 169-170
1.068 CH, ■ o- -NH,
.R 2
Comp. Rj N Rs XR_. Physical data No. (m.p. °C)
1.075 n-C 5 Hjj- -NH 2 131-132 '
. R 2
Comp. Rj N Rs XR, Physical data No. (m.p. °C)
1.077 n-C 5 H π - -NH 2 140-141
1.078 n-C 5 H π - -NH, 180-181
1.079 n-C 5 H π - -NH, 227 (decomp.)
1.080 n-C 5 H j j- -NH, 159-161
1.081 n-C 5 Hjj- -NH, o 0- 135-136
NO,
1.082 n-C 5 H j j - -NH, 137-139
F 3 C
1.083 n-C 5 Hjj- -NH, 153-154
.R 2
Comp. Rj N Rs XR„ Physical data No. (m.p. °C)
1.084 n-C 5 Hjj- -NH, 124-126
1.085 n-C 5 H π - -NH, 145-147
1.086 n-C 5 H ιr -NH, 168-170
solid
145
135-138
solid
"°" ~CH3 soiid
-OCH 3
-CHQ-CH 3
CH 3
.R 2
Comp. Rj NC Rs XR, Physical data
No. (m.p. °C)
1.095 n-C 5 Hjj- -NH, *o- CN
152-153
148 " 149
1.104 n-C 5 H jj - -NH,
1.105 n-C 5 Hjj- -NH,
1.106 n-C 5 H π - -NH, solid
. R
Comp. Rj NC , XRΛ Physical data No. (m.p. °C)
1.107 n-C 5 Hjj- -NH, solid
1.108 n-C 5 Hjj- -NH, 172-175
1.109 n- Hn- -NH, 108-111
1.110 n-C 5 H π - -NH, -i 155-156
resin
1.112 n-C 5 H j j- -N oil
1.113 n-C 5 H jj - -NHH- CH 3 oil
. R,
Comp. R NC , XR, Physical data No. (m.p. °C)
1.114 n-C 5 Hjj- -N oil
♦ O 89-90
1.120 c-C ή 6H n ιr -NH, 215-216
(decomp.)
1.121 C-C 6 HJJ- -NH, 224-228
(decomp.)
Comp. R j N Rs XR 4 Physical data No. (m.p. °C)
1.122 C-C 6 HJJ- -NH, -S- V- F 185-186
1.123 c-C Λ 6H n ιr -NH, 206-208
1.124 c-C Λ 6H n ιr -NH, 200-203
1.125 c-C fi 6H n ιr -NH, 205-207
, R 2
Comp. R j N _ Rs XR. Physical data No. (m.p. °C)
1.126 C-C 6 HJJ- -NH, 183-185
1.127 c-C 6 Hjj- -NH, 184-185
1.128 c-C 6 H n - -NH, solid
1.129 C-C 6 HJJ- -NH, solid
1.130 c-C fi 6H n ιr -NH, 244 (decomp.)
1.131 c-C 6 Hjj- -NH, -° ^ Y H 3 125-126
COOEt
. R 2
Comp. R N C Rs XR, Physical data No. (m.p. °C)
1.132 c-C 6 H 11 " -NH, 180-182
1.133 c-C 6 H n - -NH, 196-198
1.134 c-C 6 H 11 " -NH, > 240
1.135 c-C 6 H n - -NH, 202-205
1.136 C-C 6.H n ιr -NH, solid
1.137 c-C f i 6H n ιr -NH, 227
1.138 c-C 6 Hjj- -NH, *>Q 197-199
COOEt
1.139 c-C 6 H j - -NH, -0<^ COOEt 165-169
1.140 C-C 6 HJJ- -NH 2 > 240
. R 2
Comp. Rj N C Rs XR_, Physical data No. (m.p. °C)
1.141 c-C 6 H i r -NH, XX, 174-175
1.142 c-C 6 Hjj- -NH, 235 (decomp.)
1.143 C-C 6 HJJ- -NH, 225 (decomp.)
CN
1.144 c-C fi 6H n ιr -NH, -O- 202 (decomp.)
1.145 c-C fi 6H n ιr -NH, 223 (decomp.)
1.146 c-C fi 6H n ιr -NH, N0 2 220 (decomp.)
1.147 c-C 6 H π - -NH, o Q- CH 3 CH 3
1.148 c-C 6 H j j- -NH 2 203-205 (decomp.)
. R 2
Comp. R j N Rs XR, Physical data
No. (m.p. °C)
1.149 c-C 6 H π - -NH, -σ ci
CH,
1.150 c-C 6 H ir -NH,
1.151 c-C Λ 6H n ιr -NH,
1.152 c-CgH jj - -NH,
1.153 c-C 6 H n - -NH,
1.154 c-C 6 H j j - -NH,
1.155 c-C 6 H j j- -NH, 153-154
1.156 c-C 6 Hjj- -NH, 193-194
I
. R 2
Comp. R j NC Rs XR, Physical data No. (m.p. °C)
-O-CH 2 -CF 3 131-133 -O-CH-(CF 3 ) 2 140-142
,R 2
Comp. R j N^ Rs No.
1.167 c-C 6 H jj - -NH 2
1.168 c-C 6 H jj - -NH 2
1.169 c-C 6 H jj - -NH 2
1.170 c-C 6 H jj - -NH 2
1.171 c-C 6 H π - -NH 2
1.172 c-C 6 H jj - -NH 2
1.173 c-C 6 H jj - -NH 2
1.174 c-C 6 H jj - -NH 2
1.175 c-C 6 H jj - -NH,
1.176 c-C 6 H jj - -NH,
-NHCO HC = CH
1.177 c-C 6 H jj - • °^ 156-157
NH-
1.179 c-C 6 H π - « -0 116-117
1.180 c-C 6 H π - -NH CCIs < -® 128-129
.R
,R 2
Comp. Rj N. • Rs XR, Physical data No. (m.p. °C)
-o-Q 161-164
144-145
83-84
■ °-0 84-85
.R,
Comp. R j N R 3 XR 4 Physical data
No. ( m -P- ° C )
O
1.211 C-C 6 HJJ- J"*. _o_® 102-104
N CH 2 — C≡CH
~
1.212 C-C 6 HJJ- -N j>-- ~ " 3 -°~θ 48-50
\
CH 2 — CH— CH 2
1.213 c-C 6 Hjj- 84"85
1.214 c-C 6 H n - 91-93
.R 2
Comp. Rj N C Rs XR, Physical data No. (m.p. °C)
Diast. 1 O
Diast. 2
1.220 c-C 6 Hjj- N - n- C 3 H 7 - 0~ ~ 63-64
CH 2 — CH— CH 2
1.221 c-C 6 H π - ■ °-o 147-148
1.222 C-C 6 HJJ- -NH-(CH 2 ) 3 -CN 170-171
1.223 C-C 6 HJJ- -NH-CH 2 -O-Et -o-Q 140-141
.R,
Comp. R N , XR„ Physical data
No. (m.p. °C)
163-165
215-217
1.235 c-C 6 Hjj- -NH CH, 91-94
1.236 c-C 6 H 11 " -NH •CH, 165-175
1.237 C-C 6 HJJ- -NH - CH, 134-136
1.238 c-C 6 H„- -NH-NH-COOt-C 4 H 9 174-176
108-110
solid
R
1.242 c-C 6 Hjj- -NH' • CH, 143-145
1.243 c-C 6 H n - -NH' • CH, 7-158
1.244 c-C 6ς n Hιιιr- - H. ■ CHCI, 160-162
1.245 c-C 6 H π - COOEt
NH— U -CHCI,
1.246 c-C fi 6H n ιr 128-134 OOEt
1.247 c-C 6 H j j- -NH-(CH 2 ) 6 -NH 2 oil
1.248 C-C 6 HJJ- -NH(CH 2 ) 6 -NH 3 Θ C1 Θ 168 (decomp.)
1.249 c-C 6 H n - -NH(CH 2 ) 6 NHCOOtC 4 H 9 resin
Comp. Rj N - R 3 XR. Physical data No. (m.p. °C)
1.250 c-C 6 Hjj- -NH - JL CHCI, 136-139 (decomp.)
1.251 C-C 6 HJJ- -NH, ~° U 200-202 (decomp.)
1.252 C-C 6 HJJ- -NH, 201 (decomp.)
1.253 165 (decomp.)
(diastereomer 1)
1.254 -NH, -O -o 161 (decomp.)
(diastereomer 2)
(decomp.)
(diastereomer 1)
. R 2
Comp. R N^ R, XR^ Physical data No. (m.p. °C)
1.256 157 (decomp.)
1.257 155 (decomp.) (diastereomer 1)
1.258 177 (decomp.) (diastereomer 2)
Br
1.259 t -NH, < -o 158-159
(decomp.)
1.260 176 (decomp.)
1.261 199 (decomp.) (diastereomer 1)
.R 2
Comp. Rj N _ Rs
No.
1.262
(diastereomer 2)
1.265 c-C 6 H 11 -NH, Cl 201-204
1.266 n-C 5 H 11 -NH, -°^ "°"S^ 160 ' 162
1.268 CH 2 CH(CH 2 ) 3 -NH 2 153-156 Br Br
1.270 c-C 6 Hjj -NH-NH, 109-111
.R,
Comp. Rj N : XR, Physical data
No. (m.p. °C)
1.275 CH 3 (CH 2 ) 127-128
1.276 CH 3 (CH 2 ) 143-144
1.277 CH 3 (CH 2 )
1.278 CH 3 (CH 2 ) 3 CH- -NH, 166-167 CH 3
. R 2
Comp. Rj N Rs XRΛ Physical data No. (m.p. °C)
1.279 CH 3 (CH 2 ) 3 167-169
1.280 CH 3 (CH 2 ) 3 CH- .NH 2 ■ ■
CH 3
1.281 n-C 8 H j7 -NH 2 XJ 105-106
1.282 n-C 8 H 17 -NH, 120-121
1.283 n-C 8 H 17 -NH, X i - 114-115
1.285 n-Cj 2 H 25 -NH, 110-111
1.286 c-C 6 H jj -NH-(n-C 6 Hj 3 ) 105-107
.R 2
Comp. R N. • Rs XR, Physical data No. (m.p. °C)
1.288 c-C 6 Hjj -NH-N=CH-Ph 95
hysical data
Comp. R N^ R, XRΛ P (m.p. °C)
No.
1.295 n-C 5 Hjj -NH 2 -OCH 2 -CN 135-137
200 (decomp.)
(decomp.)
1.298 , 183 (decomp.)
Isomer 1
175 (decomp.)
190 (decomp.)
1.301 n-CgHjg -NH 2
/ R
Comp. Rj cal data
N -R 3 XR, Physi
No. (m.p. °C)
1.302 n-CHjc, -NH, 110
1.303 n-C9Hj 9 -NH, xχ r 115
1.304 n-C 7 H 15 -NH, • O 118
1.306 n-C 7 H 15 -NH, 8 r 121
. R 2
Comp. R j N Rs XR, Physical data No. (m.p. °C)
1.314 (CH 2 ) 2 - -NH. 182-183
1.315 ©- < CH 2>2 -NH, 167-168
1.316 189-190
1.317 c-C fi 6H n ll -NH, -OCH 2 CCl 2 CF 3 188-190
1.318 n-C 8 H 17 -NH(CH 2 ) 6 NH 2 124-125
(CH 3 SO 3 H) 2
/ R 2 XR 4 Physical data
Comp. Ri N - 3 (m.p. °C) No.
1.319 c-C 6 H j j -NH 2 -OCH 2 (CF 2 ) 2 CF 3 159-160 1.320 c-C 6 H π -NH 2 -OCH 2 CF 2 CF 3 145-146
150 (decomp.)
. R 2
Comp. Rj N Rs XR„ Physical data No. (m.p. °C)
1.332 n-C 5 H π 95-103
(CH 3 SO 2 H) 2
1.333 t-C 4 H 9 -CH 2 - -NH 2 170-172
1.334 t-C 4 H9-CH 2 - -NH 2 184-185
1.335 t-C 4 H9-CH 2 - -NH 2 140-141
*&
-R,
Comp. R NC , XRΛ Physical data No. (m.p. °C)
1.337 157-158 diastereo- isomer 1
1.338 n-C 8 H 17 -NH-COCH 3
1.339 n-C 7 H 15 -NH-COCH 3
1.340
ι.34i
1.342 4-Cl-C 6 H 4 -NH
.R,
Comp. Rj N , XR, Physical data
No. (m.p. °C)
220 (decomp.)
(Z)
1.347 nC 4 H 9 OCH=CH- -NH 2 (E)
(E)
.R,
Comp. Rj N , XR Δ Physical data No. (m.p. °C)
1.350 (CH 3 ) 3 Si(CH 2 ) 3 - -NH 2 152-154
1.351 (CH 3 ) 3 Si(CH 2 ) 3 - -NH 2
1.352 (CH 3 ) 3 Si(CH 2 ) 3 - -NH 2
1.354 CH 3 0* -NH, CI 205-207
1.355 Cl
1.357 -NH,
'&
/ R cal data
Comp. Rj N -R 3 XR Δ Physi (m.p. °C)
No.
1.358 H2N -t ~ -NH 2 205 (decomp.)
1.361 i-C 4 H_ 9 -NHCH 3
. R 2
Comp. R NC R, XR, Physical data
No. (m.p. °C)
-NHNH 2 119-120
-N(CH 3 ) 2 oil
-N(CH 3 ) 2 oil
-NH-NH 2 resin
-NH-N=CH-iC 3 H 7 69-70
-NH-OH resin
-NH-nC 3 H 7 73-74 -NH 2 172-173
1.373 c-C 6 H 11 -S-iC 3 H 7 resin
1.374 Br-(CH 2 ) 5 - -NH 2 ~ 116-118
1.375 I-(CH 2 ) 5 - -NH, •o- 118
1.376 C1-(CH 2 )5- "NHi 125
1.377 n-C 5 H n -NH 2 - *O--n-C 3 H 7 75-76
1.378 CH 3 - NH-CO -O-CH,
1.379 N≡CS(CH 2 ) 5 - -NH 2
1.380 CH 3 COO(CH 2 ) 5 - -NH 2
1.381 vQr- S-(CH 2 ) 5 - -NH 2
^ R 2 Comp. R j N R 3 XR 4 Physical data
No. (m-P- ° c >
1.382 cC 6 H π S(CH 2 ) 5 - -NH 2
1.383 N 3 -(CH 2 ) 4 - -NH 2
1.384 c-C 4 H 7 -CH 2 - -NH 2
1.385 CH 2 =CH-(CH 2 ) 2 - -NH 2
1.387 NaO 3 SS(CH 2 ) 4 - -NH 2
1.389 HS-(CH 2 ) 4 - -NH 2
.R 2
Comp. Rj NC R, XR, Physical data No. (m.p. °C)
.R 2
Comp. Rj N Rs XRΛ Physical data
No. (m.p. °C)
1.402 c-C 6 H jj -NHOC 2 H 5 $
1.408 Br-CH 2 - -NHCOCH 3 -O- V-N0 2 Cl
.R 2
Comp. Rj N Rs XR„ Physical data No. (m.p. °C)
(CH 3 ) 2 -C≡CH
-O-N=C(i-C 3 H 7 ) 2
OCH 2 COOCH 3
1.414 c-C 6 H n -NHCO(CH 2 ) 2 -COOCH 3 ' °Λ_)~ F
1.416 c-C 6 H j j -NH — ■
1.418 CH 2 =CH- -NH 2
Comp. Rj N Rs XR Δ Physical data No. (m.p. °C)
1.419 c-C 6 Hjj -NH .*
1.421 c-C 6 H jj -NH-(CH 2 ) 5 -COOH -o-TS
1.422 c-C 6 H jj -NH-(CH 2 ) 5 -COO θ Na Θ -O F
1.423 (CH 3 ) 3 -Si-CH 2 - -NH 2 .o-ø-α
1.424 (CH 3 ) 2 CH(CH 2 . r -NH 2 140°C
Table 2: Compounds of the formula IV
Comp. Rj Physical data
No. (m.p. °C)
2.001 CH 3 - 101 (decomp.)
2.002 C 2 H 5 - 107-108 (decomp.)
2.003 n-C 3 H 7 -
2.004 i-C 3 H 7 -
2.005 n-C 4 H 9 - 43-44
2.006 t- Hx,-
2.008 CH 3 -(^ -
127 (decomp.)
Physical data (m.p. °C)
2.020 - S-(CH 2 ) 4 -
42-43
2.028 o- CH 5 137-138 (decomp.)
2.030 s-C 4 H 9 - 2.031 cC 6 H π CH 2 - 97
Comp. RJ Physical data
No. (m.p. °C)
2.032 iC 4 H9-CH 2 -
CH-(CH 2 ) 3 -
2.035
CH 2 31
2.038 cC 5 H 9 -
2.039 130 (decomp.)
2.041 CH 3 " \_/ " 96-97
2.042 H ° ~
CH 3
2.045 HO-^
Physical data (m.p. °C)
34 105-106
2.052 n-C j sH^ 51-52
2.053 C CHH 22 CCH1 (CH 2 ) 3 Br Br
Comp. Rj Physical data
No. (m.p. °C)
2.058 CH 3 (CH 2 ) 4 CH- oil CH a
2.060 n-C 8 H 17 27
125 (decomp.)
2.064 n-C H 19 54-55
2.068 C1-(CH 2 ) 5 - oil
Physical data (m.p. °C)
29 48-51
Oel oil
111-112 (decomp.)
77-78
107-109
2.077 Cl crystals
oil
Comp. Rj Physical data No. (m.p. °C)
Br
2.092 ct crystals
crystals
crystals crystals crystals
73-76
73-76
2.102
Comp. Rj Physical data No. (m.p. °C)
130 (decomp.)
87
109-110 (decomp.) oil
crystals
100 (decomp.)
2.116 F-CH 2 - 2.117 CH 2 =CH-CH 2 - 2.118 CH 3 -CH=CH-
2.119 crystals
2.120 134-135 (decomp.)
2.121
Comp. Rj Physical data No. (m.p. °C)
2.123 Q<™ 3 oil
2.124 (Z)C 2 H 5 O-CH=C(CH 3 )- 115 (decomp.)
2.125 (E)C2H 5 O-CH-=C(CH 3 )- 94-95 (decomp.)
Table 3: Compounds of the formula VI
XR, Physical data (m.p. °C)
-OCH 3 -S-C 3 H 7 (i)
3.009 n-C 4 H 9 -
Comp. Rj XR 4 Physical data
No. (Smp. °C)
3.021 I-(CH 2 ) 4 -
0 - (CH 2 ) 4 -
3.025 C = 0
I
CH, X
3.026 HO-(CH 2 ) 4 -
(CH, 2) X "
3.027
CH,S
XR 4 Physical data
(m.p. °C)
-Ό
X
Comp. R j XR, Physical data No. (Smp. °C)
.
Comp. R j XR, Physical data No. (m.p. °C)
3.053 nC 4 H 9 -C≡C- _>
I C
3.057 cQft j CH;,-
Comp. R j XR, Physical data No. (Smp. °C)
Comp. R j XR, Physical data No. (m.p. °C)
3.075 n-C 5 H jj - resin
Comp. R j XR 4 Physical data
No. (Smp* °C)
3.084 n-C 5 H π - -o CN
3.087 n-C 5 H jj - -O-C 3 H 7 (i)
3.088 n-C 5 H π - -O-CH 2 -CH=CH 2
3.089 n-C 5 H n - -O-c-C 6 H n
3.091 n-C 5 H jj - -O-C 5 H π (n)
Comp. Rj XRΛ Physical data No. (m.p. °C)
3.094 n-C 5 H„- « o- OCH,
3.100 C-C 6 HJJ-
Comp. Rj XR„ Physical data
No. (Smp. °C)
3.101 c-C 6 H n - NH 2 resin
3.104 c-C 6Λ n lιr
Comp. Rj XR 4 Physical data
No. (m.p. °C)
3.110 c-C 6 H j j- 130 (decomp.)
3.111 c-C 6 H jj - resin
Comp. Ri XRΛ Physical data No. (Smp. °C)
3.113 c-C 6 H j j- resin
3.118 c-C ή 6H n ιr
COOEt
3.119 c-C 6 Hj- ■ ° COOEt
3.120 c-C 6 H n - resin
Comp. Rj XR, Physical data No. (m.p. °C)
Comp. R XR, Physical data No. (Smp. °C)
I
Comp. Rj XR, Physical data
No. (m.p. °C)
3.144 c-C 6 H n - -O-CH 2 -CF 3
3.145 c-C 6 Hjj- -O-CH-(CF 3 ) 2
3.147 c-C 6 H n - -OCH 3
XR, Physical data (Smp. °C)
-OC 3 H 7 (i)
-OC 5 H π (n)
-O-C 6 H jj (cycl.)
-O-CH 2 -CH=CH 2
-SCH 3
- o - \=N
-0- ^N
Comp. Rj XR Δ Physical data No. (m.p. °C)
Comp. R, XR, Physical data No. (Smp. °C)
Comp. Rj XRΛ Physical data No. (m.p. °C)
3.186 or Si(CH 3 ),
Comp. R j XR. Physical data No. (Smp. °C)
3.190 n-CgH j g -O
3.193 n-C 7 H 15 XX
3.195 n-C ■ 7 7H n 15 Xχ r
Comp. Rj XR 4 Physical data No. (m.p. °C)
3.204 " (CH 2 ) 2 -
Comp. R XR, Physical data No. (Smp. °C)
3.208 c-C 6 Hjj -OCH 2 (CF 2 ) 2 CF 3
3.209 c-C 6 Hjj -OCH 2 CF 2 CF 3
X
Comp. Rj XR. Physical data
No. (m.p. °C)
3.222 t-C 4 H 9 -CH 2 -
*&
Comp. Rj No.
3.227 4-Cl-C 6 H 4
(Z)
3.229 nC 4 H 9 OCH=CH- (Z)
Comp. R j No.
(E)
3.231 nC 4 H 9 OCH=CH- (E)
3.232 nC 4 H 9 OCH=CH- 121 (E)
3.235 (CH 3 ) 3 Si(CH 2 ) 3 - -°- ~F
3.236
Comp. Rj No.
3.244 c-C 6 H j j -S-iC 3 H 7
3.245 Br-(CH 2 ) 5 - • °^o
3.246 I-(CH2) 5 - •o-
Comp. j XR, Physical data
No. (Smp. °C)
F F
NH.
3.267 n-C 5 H n ^
Comp. R XR A Physical data No. (m.p. °C)
Comp. Rj XRΛ Physical data No. (Smp. °C)
3.279 (CH 3 ) 2 CH(CH 2 ) 2 - ( ~ Λ S-(CH 2 ) 4 -
Comp. R XR, Physical data No. (m.p. °C)
Table 4: Compounds of the formula VIE
4.011 CH, -NH
. R 2
Comp. Rj N^ R, Physical data No. (m.p. °C)
4.015 cY -NH, 181 (decomp.)
. -,
S(CH 2 ) 4 -
4.026 I -NH, (CH 2 ) 2 OH
.R
Comp. R j N- R3 Physical data
No. (m.p. °C)
4.029 O 2 N(CH 2 ) 4 - -NH 2
4.030 C1-(CH 2 ) 4 - -NH 2
4.031 NC-(CH 2 ) 4 - -NH 2
4.032 C1-(CH 2 ) 4 - -NH 2
0(CH 2 ) 2 -
4.033 I -NH 2 (CH 2 ) 2 I 2
4.034 NC-(CH 2 ) 5 - -NH 2
4.035 i- J -NH 2
4.036 n-C 6 H j3 - -NH 2
4.037 n-C 7 H 15 - -NH 2
4.038 Z ~ CH 2- -NH 2
4.040 s-C 4 H 9 - -NH 2
4.041 cC 6 H jj CH -NH 2 173 (decomp.)
0(CH 2 ) 2 -
4042 I -NH 2 (CH 2 ) 2 CI 2
4.043 -NH 2
,R 2
Comp. Rj NC Ft, Physical data No. (m.p. °C)
4.045 tC 4 H 9 -C=C- -NH 2 155-158 (decomp.) CH-(CH 2 ) 3 -
4.046 -NH 2 119-120
CH,
4.047 nC 4 H 9 -C≡C- -NH 2 resin
C
III 4.048 -NH, resin
4.049 cC 5 H 9 - -NH,
4.052 CH. Or -NH 2 180 (decomp.)
.R 2
Comp. Rj NC F Physical data No. (m.p. °C)
OH
4.057 -NH, t-C 4 H 9
4.059 n-C 5 H jj - -NH, 139
OEt CH 3 COOEt
4.062 n-C 5 H π - -NH-CH 2 -COOEt
4.063 c-C 6 H jj - -NH 2
4.065 C-C 6 HJJ- -NH-(CH 2 ) 3 -CN
4.066 c-C 6 H j j- -NH-CH 2 -O-Et
4.067 C-C 6 HJJ- -NHCH 3
4.081 n-C j2 H 25 -NH 2 112-113
4.082 CH 2 CH(CH 2 ) 3 -NH 2
Br Br
4.083 c-C 6 H j j -NH-NH 2 136 (decomp.)
4.084 -NH, crystals
. R 2
Comp. Rj N _ R, Physical data No. (m.p. °C)
4.086 -NH, crystals
4.087 -NH, 130 (decomp.)
93-95
118-120 (decomp.)
113-114 58-60
4.095 c-C 6 H π -NH- - NH— ( , 135 (decomp.)
■•
4.096 -NH, 195 (decomp.)
Comp. R j N ' -
■ Ra Physical data No. (m.p. °C)
CH 2 =CH
124-126
171 (decomp.) 165-168 (decomp.)
4.116 nC 4 H 9 OCH=CH- -NH 2 135 (decomp.)
(Z)
4.117 nC 4 H 9 OCH=CH- -NH 2 170 (decomp.)
(E)
4.118 (CH 3 ) 3 Si(CH 2 ) 3 - -NH 2
177 (decomp.)
crystals
• R 2
Comp. Rj N R, Physical data No. (m.p. °C)
4.123 i-C 4 H 9 -N(CH 3 ) 2 4.124 i-C 4 H -NHNH 2 4.125 c-C 6 H jj -N(CH 3 ) 2 4.126 c-C 6 H j j -NH-NH 2 4.127 c-C 6 H j j -NH-N=CH-iC 3 H 7 4.128 c-C 6 H π -NH-OH 4.129 c-C 6 H j j -NH-nC 3 H 7
4.135 CH 3 COO(CH 2 ) 5 - -NH 2
4.137 cC 6 H π S(CH 2 ) 5 - -NH 2 4.138 N 3 -(CH 2 ) 4 - -NH 2 4.139 c-C 4 H 7 -CH 2 - -NH 2 4.140 CH 2 =CH-(CH 2 ) 2 - -NH 2
4.142 NaO 3 SS(CH 2 ) 4 - -NH 2
4.144 HS-(CH 2 ) 4 - -NH 2 4.145 H 2 NC HHCCHH 22 S(CH 2 ) 4 - _NH 2 OOOH
4.146 CH 3 ϊCH-iC 3 H 7 -NH,
. Re
Comp. R j NC , Physical data
No. (m.p. °C)
4.147 iC 3 H 7 NH(CH 2 ) 4 - -NH 2
4.149 -NH, 108 (decomp.)
4.152 -NH, 165 (decomp.)
4.153 c-C 6 H j j -NHOC 2 H 5
4.154 c-C 6 H j j -NHOH
4.156 Br-CH 2 - -NH 2
4.157 c-C 6 H jj -NH-C(CH 3 ) 2 -G≡CH
4.158 C1-CH 2 - -NH 2
4.159 I-CH 2 - -NH 2
crystals
. R 2
N _ R, Physical data (m.p. °C)
-NH 2
COOH -NH ■■•}- (CH 2 ) 4 -NHCOO(t-C 4 H β ) H
H
-NH-(CH 2 ) 4 i COOH NHCOO(t-C 4 H 9 )
4.164 c-C 6 H n -NH-(CH 2 ) 5 -COOH resin
4.165 c-C 6 H n -NH-(CH 2 ) 5 -COO θ Na® 150 (decomp.)
4.166 (CH 2 ) 3 CH(CH 2 ) 2 - -NH 2
4.167 (E)-i-C 4 H 9 θ-CH=CH- -NH 2
4.168 (Z)-i-C 4 H9O-CH=CH- -NH 2
crystals
crystals
.R,
N
4.189 -NH, 166 (decomp.)
Formulation Examples of active ingredients of the formula I (% = percent by weight)
FI. Emulsion concentrates a) b) c) d)
Active ingredient according 5 % 10 % 25 % 50 % to the table
Calcium dodecylbenzene- 6 % 8 % sulfonate
Castor oil polyglycol ether 4 % (36 mol of EO) Octylphenol polyglycol ether 2 % (7-8 mol of EO) Cyclohexanone 10 % 20 % Mixture of aromatic hydro¬ 85 % 78 % 55 % 16 % carbons C 9 -C 12
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
F2. Solutions a) b) c) d)
Active ingredient according 5 % 10 % 50 % 90 % to the table
Dipropylene glycol methyl ether 20 % 20 % Polyethylene glycol MW 400 20 % 10 % N-Methyl-2-pyrrolidone 30 % 10 % Mixture of aromatic hydro¬ 75 % 60 % carbons C 9 -C 12
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
Active ingredient according 5 % 25 % 50 % 80 %
to the table
Sodium lignosulfonate 4 %
Sodium lauryl sulfate 2 % 3 4 %
Sodium diisobutylnaphthalene- 6 6 % sulfonate
Octylphenol polyglycol ether
(7-8 mol of EO)
Highly disperse silica 1 % 3 % 5 % 10
Kaolin 88 % 62 % 35 %
The active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powder which can be diluted with water to give suspensions of any concentration.
F4. Coated granules a) b ) c)
Active ingredient according 0 . 1 15 % to the table
Highly disperse silica 0 . 9 % 2 % 2 %
Inorganic carrier 99 . 0 % 93 % 83 %
(0 0.1 - 1 mm) for example CaCO 3 or SiO 2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
F5. Coated granules c)
Active ingredient according 0 . 1 15 to the table
Polyethylene glycol MW 200 1 . 0 % 2 % 3 %
Highly disperse silica 0 . 9 % 1 % 2 %
Inorganic carrier 98 . 0 % 92 % 80 %
(00.1 - 1 mm) for example CaCO 3 or SiO 2
In a mixer, the finely ground active ingredient is applied uniformly to the carrier material which has been moistened with polyethylene glycol. This gives dust-free coated granules.
F6. Extruder granules a) b) c) d)
Active ingredient according 0.1 3 % 15 to the table
Sodium lignosulfonate 1.5 % 2 % 3 % 4 %
Carboxymethylcellulose 1.4 % 2 % 2 % 2 %
Kaolin 97.0 % 93 % 90 %
The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
F7. Dusts a) b) c)
Active ingredient according 0.1 to the table
Talc 39.9 % 49 % 35 %
Kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingedient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
Active ingredient according 3 % 10 % 25 % 50 % to the table
Ethylene glycol 5 % 5 % 5 % 5 %
Nonylphenol polyglycol ether 1 % 2 %
(15 mol of EO)
Sodium lignosulfonate - * 6 *6 4 *5 D "6
Carboxymethylcellulose 1 % 1 % 1 % 1 %
37% aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution
Silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 %
Water 87 7 9 62 38 %
The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Biological examples
Example B 1 : Herbicidal action before emergence of the plants
Monocotyledon and dicotyledon test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on (5001 of water/ha) in the form of an aqueous suspension (prepared with the formulation of Example FI) to give a dose of 2 kg of a.s./ha. The test plants are subsequently grown in a greenhouse under optimal conditions. After a test period of 3 weeks, the experiment is evaluated on the basis of a nine-step key (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.
Table Bl: pre-emergence action:
Test plant: A vena Setaria Sinapis Stellaria Active ingredient No.
1.015 2 1 1.016 1 1 1.018 2 1 1.019 1 1 1.021 4 1 1.039 2 9 1.060 3 3 3 1.075 2 1 1 1.076 2 2 4 1.078 3 1 1 1.079 3 1 4 1.081 2 2 3
1.108 1.112 1.113 1.121 1.128 1.134 1.136 1.137 1.140 1.141 1.150 1.161 1.191 1.235 1.237 1.240 1.241 1.259 1.278 1.282 1.293
The same results are obtained when the compounds of the formula I are formulated in accordance with suitable examples F2 to F8.
Example B2: Post-emergence herbicidal action
Monocotyledon and dicotyledon test plants are grown in standard soil in the greenhouse in plastic pots and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension of the test substances of the formula I, prepared with a 25% wettable powder (Example F3, b)), which corresponds to a dose of 2000 g of a.s./ha (5001 of water/ha). The test plants are subsequently grown on in the greenhouse under optimal conditions. After a test period of approximately 18 days, the experiment is evaluated using a nine-step key (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action. In this experiment, the compounds of the formula I have a powerful herbicidal action. The same results are obtained when the compounds of the formula I are formulated in accordance with Examples FI to F2 and F4 to F8.
Table B2: post-emergence action:
Test plant: Avena Setaria Sinapis Stellaria active ingredient No.
1.237 5 1 1.141 2 1 1.075 2 1 1.137 5 2 1.021 3 1
The same results are obtained when the compounds of the formula I are formulated in accordance with suitable examples F2 to F8.