SEITZ THOMAS (DE)
ZIERKE THOMAS (DE)
MASSA DARIO (DE)
NEWTON TREVOR WILLIAM (DE)
| WO2015052153A1 | 2015-04-16 | |||
| WO2015052152A1 | 2015-04-16 | |||
| WO2012028579A1 | 2012-03-08 | |||
| WO2013072300A1 | 2013-05-23 | |||
| WO2013083859A2 | 2013-06-13 | |||
| WO2013092834A1 | 2013-06-27 | |||
| WO1997046530A1 | 1997-12-11 | |||
| WO1998031676A1 | 1998-07-23 | |||
| WO1998031681A1 | 1998-07-23 | |||
| WO2002018352A1 | 2002-03-07 | |||
| WO2000003988A1 | 2000-01-27 | |||
| WO2001082685A1 | 2001-11-08 | |||
| WO2000026390A2 | 2000-05-11 | |||
| WO1997041218A1 | 1997-11-06 | |||
| WO1998002526A1 | 1998-01-22 | |||
| WO1998002527A1 | 1998-01-22 | |||
| WO2004106529A2 | 2004-12-09 | |||
| WO2005020673A1 | 2005-03-10 | |||
| WO2003014357A1 | 2003-02-20 | |||
| WO2003013225A2 | 2003-02-20 | |||
| WO2003014356A1 | 2003-02-20 | |||
| WO2004016073A2 | 2004-02-26 | |||
| WO1992000377A1 | 1992-01-09 | |||
| WO2002015701A2 | 2002-02-28 | |||
| WO1993007278A1 | 1993-04-15 | |||
| WO1995034656A1 | 1995-12-21 | |||
| WO2003018810A2 | 2003-03-06 | |||
| WO2003052073A2 | 2003-06-26 | |||
| WO1996026202A1 | 1996-08-29 | |||
| WO1997041116A1 | 1997-11-06 | |||
| WO1997041117A1 | 1997-11-06 | |||
| WO1997041118A1 | 1997-11-06 | |||
| WO2001083459A2 | 2001-11-08 | |||
| WO2008074991A1 | 2008-06-26 |
| EP0173657B1 | 1989-12-20 | |||
| US20070191335A1 | 2007-08-16 | |||
| US6277847B1 | 2001-08-21 | |||
| EP0257993A2 | 1988-03-02 | |||
| US5013659A | 1991-05-07 | |||
| US6222100B1 | 2001-04-24 | |||
| EP0242236A1 | 1987-10-21 | |||
| EP0242246A1 | 1987-10-21 | |||
| US5559024A | 1996-09-24 | |||
| EP0374753A2 | 1990-06-27 | |||
| EP0427529A1 | 1991-05-15 | |||
| EP0451878A1 | 1991-10-16 | |||
| EP0392225A2 | 1990-10-17 |
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 76, 1954, pages 88 - 89
ZEITSCHRIFT FUR CHEMIE, vol. 30, no. 12, 1990, pages 436 - 437
CHEMISCHE BERICHTE, vol. 97, no. 2, 1964, pages 396 - 404
RUSSIAN CHEMICAL BULLETIN, INT. ED., vol. 54, no. 4, 2005, pages 1032 - 1037
HETEROATOM CHEMISTRY, vol. 15, no. 3, 2004, pages 199 - 207
"Journal of Chemical Research", SYNOPSES, 1985, pages 190
"Izvestiya Akademii Nauk SSSR", SERIYA KHIMICHESKAYA, 1986, pages 2086 - 8
RUSSIAN CHEMICAL BULLETIN, vol. 53, no. 3, 2004, pages 596 - 614
B. HOCK; C. FEDTKE; R. R. SCHMIDT: "Herbizide [Herbicides]", 1995, GEORG THIEME VERLAG
W. KRAMER ET AL.: "Modern Crop Protection Compounds", vol. 1, 2007, WILEY VCH
| Claims 1. A compound of formula I, an N-oxide or an agriculturally suitable salt thereof, wherein is selected from the group consisting of halogen, C1-C8-alkyl, C1-C8-haloalkyl, nitro, C1-C4-alkoxy-C1-C4-alkyl, cyano-Z1 , C2-C8-alkenyl, C2-C8-alkynyl, C3- C1 O-cycloalkyl-Z1 , C2-C8-haloalkenyl, C3-C8-haloalkynyl, C1-C8-alkoxy, C1-C4- alkoxy-C1-C4-alkoxy-Z1 , C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-al- kylthio-Z1 , C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1 -C4- haloalkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkoxy-Z1 , R b-S(O)k-Z , phe- noxy-Z1 and heterocyclyloxy-Z1 , where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially un- saturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1 , 2, 3 or 4 groups ^ , which are identical or different; R3 is selected from the group consisting of hydrogen, halogen, hydroxy-Z2, nitro, C1- C4-nitroalkyl, cyano, C1-C4-cyanoalkyl, C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl-Z2, C3-C10-cycloalkoxy-Z2, where the C3-C10-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C8-haloalkyl, C2-C8-haloalkenyl, C3-C8-haloalkynyl, C1 -C8- alkoxy-Z2, C1-C8-haloalkoxy-Z2, C3-C10-cycloalkyl-C1-C2-alkoxy, C1-C4-alkoxy- C1-C4-alkoxy-Z2, C1-C4-alkylthio-C1-C4-alkylthio-Z2, C2-C8-alkenyloxy-Z2, C2- C8-alkynyloxy-Z2, C2-C8-haloalkenyloxy-Z2, C3-C8-haloalkynyloxy-Z2 C1-C4- haloalkoxy-C1-C4-alkoxy-Z2, (tri-C1-C4-alkyl)silyl-Z2, R2b-S(O)k-Z2, R2c-C(=O)- Z2, R2dO-C(=O)-Z2, R2dO-N=CH-Z2, R2eR2fN-C(=O)-Z2, R29R2nN-Z2 phenyl- Z2a, heterocyclyl-Z2a, where heterocyclyl is a 3-, 4-, 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocyde, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenyl- Z2a and heterocy-clyl-Z2a are unsubstituted or substituted by 1 , 2, 3 or 4 groups R21 , which are identical or different, rhodano, C3-C6-cycloalkenyl, C3-C6- halocycloalkenyl, C3-C6-cycloalkenyl-C1-C6-alkyl, C3-C6-halocycloalkenyl-C1 -C6- alkyl, OC(O)R22, OC(O)OR25, OC(O)N(R22)2, OS02R25, S020R22, S02N(R22)2, S02N(R22)C(O)R22, S02N(R22)C(O)OR25, S02N(R22)C(O)N(R22)2, N(R22)C(O)OR25, N(R22)C(O)N(R22)2, N(R22)S(O)20R22, N(R22)S(O)2N(R22)2, C(O)N(R22)OR22, C(O)N(R22)N(R22)2, C(O)N(R22)C(O)R22, C(O)N(R22)C(O)OR25, C(O)N(R22)C(O)N(R22)2, C(O)N(R22)S02R25, C(O)N(R22)S020R22, C(O)N(R22)S02N(R22)2, P(O)(OH)2, P(O)(0-C1-C4-alkyl)2, C1-C6-alkyl- OC(O)R22, C1-C6-alkyl-OC(O)OR25, C1-C6-alkyl-OC(O)N(R22)2, C1-C6-alkyl- OS02R25, C1-C6-alkyl-S020R22, C1-C6-alkyl-S02N(R22)2, C1-C6-alkyl- S02N(R22)C(O)R22, C1-C6-alkyl-S02N(R22)C(O)OR25, C1-C6-alkyl- S02N(R22)C(O)N(R22)2, C1-C6-alkyl-N(R22)C(O)OR25, C1-C6-alkyl- N(R22)C(O)N(R22)2, C1-C6-alkyl-N(R22)S(O)20R22, C1-C6-alkyl- N(R22)S(O)2N(R22)2, C1-C6-alkyl-C(O)N(R22)OR22, C1-C6-alkyl- C(O)N(R22)N(R22)2, C1-C6-alkyl-C(O)N(R22)C(O)R22, C1-C6-alkyl- C(O)N(R22)C(O)OR25, C1 -C6-alkyl-C(O)N(R22)C(O)N(R22)2, C1 -C6-alkyl- C(O)N(R22)S02R25, C1-C6-alkyl-C(O)N(R22)S020R22, C1-C6-alkyl- C(O)N(R22)S02N(R22)2, C1-C6-alkyl-P(O)(OH)2 and C1-C6-alkyl-P(O)(0-C1-C4- alkyl)2; is selected from the group consisting of hydrogen, halogen, C1-C8-alkyl, cyano- Z1 , nitro, C3-C7-cycloalkyl, C3-C7-cydoalkyl-C1 -C4-alkyl, where the C3-C7-cy- cloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C2-C8-alkenyl, C2-C8-alkynyl, C1 -C8-haloalkyl, C1 - C3-alkylamino, C1-C3-dialkylamino, C1-C3-alkylamino-S(O)k, C1-C3-alkylcar- bonyl, C1-C8-alkoxy, C1 -C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-Z1 , C1 -C4-alkylthio-C1 -C4-alkyl, C1 -C4-alkylthio-C1 -C4-alkylthio-Z1 , C2-C6- alkenyloxy, C2-C6-alkynyloxy, C1-C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkoxy-Z1 , Rl b-S(O)k-Z1 , phenoxy-Z1 and heterocy- clyloxy-Z1 , where heterocyclyloxy is an oxygen bound 5- or 6- membered mono- cyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aro- matic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1 , 2, 3 or 4 groups R11 , which are identical or different; R5 is selected from the group consisting of halogen, cyano-Z^ , nitro, C1-C8-alkyl, C3- C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halo- genated, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-haloalkyl, C1-C3-alkylamino, C1- C3-dialkylamino, C1-C3-alkylamino-S(O)k, C1-C3-alkylcarbonyl, C1-C8-alkoxy, C1- C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-Z1 , C1-C4-alkylthio-C1-C4- alkyl, C1-C4-alkylthio-C1-C4-alkylthio-Z1 , C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1- C6-haloalkoxy, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkoxy-Z1 , R1 b-S(O)k-Z1 , phenoxy-Z"! and heterocyclyloxy-Z1 , where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic sat- urated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1 , 2, 3 or 4 groups R^ ^ , which are identical or different; R6 is selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cy- cloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforemen- tioned radicals are unsubstituted or partially or completely halogenated, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, Rb-S(O)n-C1-C3-alkyl, Rc-C(=O)-C1-C3-alkyl, RdO-C(=O)-C1-C3-alkyl, ReRfN-C(=O)-C1-C3-alkyl, R9RnN-C1-C3-alkyl, phenyl-Z and heterocyclyl-Z, where heterocyclyl is a 5- or 6- membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially un- saturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phe- nyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups R', which are identical or different; R', R11 , R21 independently of each other are selected from the group consisting of halogen, N02, CN, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl, C1-C6- haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1 -C4- haloalkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy, C3-C7-cycloalkoxy and C1- C6-haloalkyloxy, or two radicals R', R1 1 or R21 bound to the same carbon atom together may form a group =0; Z, z1 , Z2 independently of each other are selected from the group consisting of a covalent bond and C1-C4-alkanediyl; z2a js selected from the group consisting of a covalent bond, C1-C4-alkanediyl, O-C1- C4-alkanediyl, C1-C4-alkanediyl-0 and C1-C4-alkanediyl-0-C1-C4-alkanediyl; Rb, R1 b_ R2b independently of each other are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; Rc, R2c independently of each other are selected from the group consisting of hydro- gen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7- cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C1-C6-alkoxy, C2-C6-alkenyl, C1-C4-al- kyl-C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4- alkoxy-C1-C4-alkyl, C1-C4 -S(O)n-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, C1- C4-dialkylamino-C1-C4-alkyl, C1-C6-cyanoalkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; Rd, R2d independently of each other are selected from the group consisting of hydro- gen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3- C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, C1-C6-haloalkyl, C1-C6-alkoxy, C2-C6-alkenyl, C1-C4-alkyl-C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloal- kynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4 -S(O)n-C1-C4-alkyl, C1-C4-alkylamino- C1-C4-alkyl, C1-C4-dialkylamino-C1-C4-alkyl, C1-C6-cyanoalkyl, phenyl and ben- zyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1 -C4-alkyl, C1 -C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; R2c R2d together with the nitrogen atom, to which they are bound may form a 4,-5-, 6- or 7-membered, saturated or unsaturated cyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; Re, Rf independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenylene, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or Re, Rf together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1 -C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxy and C1-C4-haloalkoxy; R2e, R2f independently of each other have the meanings given for Re, Rf; is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3 C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforemen- tioned radicals are unsubstituted or partially or completely halogenated, C1-C6- haloalkyl, C2-C6-alkenylene, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylsulfonyl, C1-C4-alkylcarbonyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of hal¬ ogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; Rh is selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloal- kynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylsulfonyl, C1-C4-alkylcarbonyl, a radi- cal C(=O)-Rki phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, or R9, Rh together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of =0, halogen, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; R2g , R2h independently of each other have the meanings given for R9, Rh; Rk has the meanings given for Rc; R22 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cyclo- alkyl, C3-C6-cycloalkenyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1- C6-alkoxy-C1-C6-alkyl, C3-C6-cycloalkyl-C1-C6-alkoxy-C1-C6-alkyl, phenyl, phe- nyl-C1-C6-alkyl, heteroaryl, heteroaryl-C1-C6-alkyl, heterocyclyl, heterocyclyl-C1- C6-alkyl, phenyl-0-C1-C6-alkyl, heteroaryl-0-C1-C6-alkyl, heterocyclyl-0-C1-C6- alkyl, phenyl-N(R23)-Ci-C6-alkyl, heteroaryl-N(R23)-Ci-C6-alkyl, heterocyclyl- N(R23)-Ci-C6-alkyl, phenyl-S(O)n-C1-C6-alkyl, heteroaryl-S(O)n-C1-C6-alkyl, het- erocyclyl-S(O)n-C1-C6-alkyl, where the 15 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen, cyano, rhodano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C(O)OR23, C(O)N(R23)2, OR23, N(R23)2, S(O)nR24, S(O)20R23, S(O)2N(R23)2 and R23o-C1-C6-alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups; R23 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl and phenyl; R24 is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl and phe- nyl; R25 is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenylene, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1- C6-alkoxy-C1-C6-alkyl, C3-C6-cycloalkyl-C1-C6-alkoxy-C1-C6-alkyl, phenyl, phe- nyl-C1-C6-alkyl, heteroaryl, heteroaryl-C1-C6-alkyl, heterocyclyl, heterocyclyl-C1- C6-alkyl, phenyl-0-C1-C6-alkyl, heteroaryl-0-C1-C6-alkyl, heterocyclyl-0-C1-C6- alkyl, phenyl-N(R23)-C1-C6-alkyl, heteroaryl-N(R23)-C1-C6-alkyl, heterocyclyl- N(R23)-C1-C6-alkyl, phenyl-S(O)n-C1-C6-alkyl, heteroaryl-S(O)n-C1-C6-alkyl, het- erocyclyl-S(O)n-C1-C6-alkyl, where the 15 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen, cyano, rhodano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C(O)OR23, C(O)N(R23)2, OR23, N(R23)2, S(O)nR24, S(O)20R23, S(O)2N(R23)2 and R230-C1-C6-alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups; R26 is C1-C6-alkyl or C1-C4-alkoxy-C1-C4-alkyl; R27 is selected from the group consisting of hydrogen, cyano and C1- C4-haloalkylcarbonyl; R23, R29 independently of each other are C1-C6-alkyl, or R23, R29 together with the sulfur atom, to which they are bound may form a 5- or 6- membered saturated ring, which may carry as a ring member 1 oxygen atom; k is O, 1 or 2; n is 0, 1 or 2. The compound as claimed in claim 1 , an N-oxide or an agriculturally suitable salt thereof, where Q is . The compound as claimed in claim 1 , an N-oxide or an agriculturally suitable salt thereof, where Q is Q2. The compound as claimed in claim 1 , an N-oxide or an agriculturally suitable salt thereof, where Q is Q3. The compound as claimed in claim 1 , an N-oxide or an agriculturally suitable salt thereof, where Q is Q4. The compound as claimed in any one of claims 1 to 5, an N-oxide or an agriculturally suitable salt thereof, where is selected from the group consisting of halogen, CN, ni- tro, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4- haloalkoxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1- C4-alkyl, C1-C4-, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy-C1-C4-alkoxy, C1-C4-alkyl-S(O)k and C1-C4-haloalkyl-S(O)k, where k is 0 or 2. The compound as claimed in any one of claims 1 to 6, an N-oxide or an agriculturally suita- ble salt thereof, where R2 is R2cR2dNC(O)NH-Z2-. The compound as claimed in any one of claims 1 to 7, an N-oxide or an agriculturally suita- ble salt thereof, where Z2 in R2 is a covalent bond and R2c and R2d independently of each other are selected from the group consisting of hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C4-alkyl, where the C3-C7-cycloalkyl groups in the two aforemen- tioned radicals are unsubstituted or partially or completely halogenated, C1-C6-haloalkyl, C1-C6-alkoxy ,C2-C6-alkenyl, C1-C4-alkyl-C2-C6-alkenyl, C1-C4-alkoxy-C1-C4-alkyl, C1- C4 -S(O)n-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, C1-C4-dialkylamino-C1-C4-alkyl, C1-C6-cyanoalkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-mem- bered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; The compound as claimed in any one of claims 1 to 8, an N-oxide or an agriculturally suita- ble salt thereof, where R3 is selected from the group consisting of hydrogen, halogen, cy- ano, nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C4-alkenyloxy, C3-C4-alkynyloxy or R2b-S(O)k, where k is 0, 1 or 2 and where R^b is selected from C1-C4-alkyl and C1-C4-haloalkyl. The compound as claimed in any one of claims 1 to 9, an N-oxide or an agriculturally suita¬ ble salt thereof, where R^ is hydrogen. The compound as claimed in any one of claims 1 to 10, an N-oxide or an agriculturally suit¬ able salt thereof, where R^ is fluorine. The compound as claimed in any one of claims 1 to 11 , an N-oxide or an agriculturally suitable salt thereof, where R^ is selected from the group consisting of C1-C4-alkyl, C3- C7-cycloalkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl and C1-C4-alkoxy-C1-C4- alkyl. 3. A composition comprising at least one compound as claimed in any one of claims 1 to 12, an N-oxide or an agriculturally suitable salt thereof, and at least one auxiliary, which is customary for formulating crop protection compounds. 4. The use of a compound as claimed in any one of claims 1 to 12, an N-oxide or an agri- culturally suitable salt thereof, or a composition of claim 13 for controlling unwanted vegetation. 5. A method for controlling unwanted vegetation which comprises allowing a herbicidally ef- fective amount of at least one compound as claimed in any one of claims 1 to 12, an N- oxide or an agriculturally suitable salt thereof, or a composition of claim 13 to act on plants, their seed and/or their habitat. |
Description
The present invention relates to benzamide compounds and compositions comprising the same. The invention also relates to the use of the benzamide compounds or the corresponding compositions for controlling unwanted vegetation. Furthermore, the invention relates to methods of applying the benzamide compounds or the corresponding compositions.
For the purpose of controlling unwanted vegetation, especially in crops, there is an ongo- ing need for new herbicides that have high activities and selectivities together with a substantial lack of toxicity for humans and animals.
WO 2013/072300 and patent EP 0,173,657 B1 describe oxadiazole compounds and their use as hervbicides.
WO 2013/083859 describes substituted N-(tetrazol-5-yl)- and N-(triazol-5-yl)arylcarbox- amide compounds and their use as herbicides.
WO 2013/092834 describes substituted tetrazol compounds and their use as herbicides wherein R 5 is H.
The compounds of the prior art often suffer form insufficient herbicidal activity, in particular at low application rates, and/or unsatisfactory selectivity resulting in a low compatibility with crop plants.
Accordingly, it is an object of the present invention to provide further benzamide com- pounds having a strong herbicidal activity, in particular even at low application rates, a suffi- ciently low toxicity for humans and animals and/or a high compatibility with crop plants. The benzamide compounds should also show a broad activity spectrum against a large number of different unwanted plants.
These and further objectives are achieved by the compounds of formula I, as defined be- low, their N-oxides and their agriculturally suitable salts.
It has been found that the above objectives can be achieved by compounds of the present invention, as defined below, including their N-oxides and their salts, in particular their agricultur- ally suitable salts.
Therefore, the present invention relates to a compound of formula I,
an N-oxide or an agriculturally suitable salt thereof, wherein
Q is Q 1 or Q2 or Q 3 or Q 4 , is selected from the group consisting of halogen, C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, nitro, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, cyano-Z 1 , C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 - C 1 O-cycloalkyl-Z 1 , C 2 -C 8 -haloalkenyl, C 3 -C 8 -haloalkynyl, C 1 -C 8 -alkoxy, C1-C 4 - alkoxy-C 1 -C 4 -alkoxy-Z 1 , C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -al- kylthio-Z 1 , C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, C 1 -C 6 -haloalkoxy, C1 -C 4 - haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkoxy-Z 1 , R 1 b -S(O)k-Z 1 , phe- noxy-Z 1 and heterocyclyloxy-Z 1 , where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially un- saturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by
1 , 2, 3 or 4 groups 1 , which are identical or different; is R 2c R 2d NC(O)NR2c-Z 2 -; is selected from the group consisting of hydrogen, halogen, hydroxy-Z 2 , nitro, C1- C 4 -nitroalkyl, cyano, C 1 -C 4 -cyanoalkyl, C 1 -C 6 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 1 0-cycloalkyl-Z 2 , C 3 -C 1 0-cycloalkoxy-Z 2 , where the C 3 -C 1 0-cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 8 -haloalkyl, C 2 -C 8 -haloalkenyl, C 3 -C 8 -haloalkynyl, C1 -C 8 - alkoxy-Z 2 , C 1 -C 8 -haloalkoxy-Z 2 , C 3 -C 1 0-cycloalkyl-C 1 -C 2 -alkoxy, C 1 -C 4 -alkoxy- C 1 -C 4 -alkoxy-Z 2 , C 1 -C 4 -alkylthio-C 1 -C 4 -alkylthio-Z 2 , C 2 -C 8 -alkenyloxy-Z 2 , C 2 - C 8 -alkynyloxy-Z 2 , C 2 -C 8 -haloalkenyloxy-Z 2 , C 3 -C 8 -haloalkynyloxy-Z 2 , C1-C 4 - haloalkoxy-C 1 -C 4 -alkoxy-Z 2 , (tri-C 1 -C 4 -alkyl)silyl-Z 2 , R 2b -S(O)k-Z 2 , R 2C -C(=O)-
Z 2 , R 2d O-C(=O)-Z 2 , R 2d O-N=CH-Z 2 , R 2e R 2f N-C(=O)-Z 2 , R 2 9R 2n N-Z 2 , phenyl-
Z 2a , heterocyclyl-Z 2a , where heterocyclyl is a 3-, 4-, 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenyl-
Z 2a and heterocy-clyl-Z 2a are unsubstituted or substituted by 1 , 2, 3 or 4 groups R 21 , which are identical or different, rhodano, C 3 -C 6 -cydoalkenyl, C 3 -C 6 - halocycloalkenyl, C 3 -C 6 -cydoalkenyl-C 1 -C 6 -alkyl, C 3 -C 6 -halocycloalkenyl-C 1 -C 6 - alkyl, OC(O)R 22 , OC(O)OR 25 , OC(O)N(R 22 )2, OS02R 25 , S020R 22 , S02N(R 22 )2, S02N(R 22 )C(O)R 22 , S02N(R 22 )C(O)OR 25 ,
S02N(R 22 )C(O)N(R 22 )2, N(R 22 )C(O)OR 25 , N(R 22 )C(O)N(R 22 )2,
N(R 22 )S(O)20R 22 N(R 22 )S(O)2N(R 22 )2, C(O)N(R 22 )OR 22 ,
C(O)N(R 22 )N(R 22 )2, C(O)N(R 22 )C(O)R 22 , C(O)N(R 22 )C(O)OR 25 ,
C(O)N(R 22 )C(O)N(R 22 )2, C(O)N(R 22 )S02R 25 , C(O)N(R 22 )S020R 22 ,
C(O)N(R 22 )S02N(R 22 )2, P(O)(OH)2, P(O)(0-C 1 -C 4 -alkyl)2, C 1 -C 6 -alkyl-
OC(O)R 22 , C 1 -C 6 -alkyl-OC(O)OR 25 , C 1 -C 6 -alkyl-OC(O)N(R 22 )2, C 1 -C 6 -alkyl-
OS02R 25 , C 1 -C 6 -alkyl-S020R 22 , C 1 -C 6 -alkyl-S02N(R 22 )2, C 1 -C 6 -alkyl-
S02N(R 22 )C(O)R 22 , C 1 -C 6 -alkyl-S02N(R 22 )C(O)OR 25 , C 1 -C 6 -alkyl-
S02N(R 22 )C(O)N(R 22 )2, C 1 -C 6 -alkyl-N(R 22 )C(O)OR 25 , C 1 -C 6 -alkyl-
N(R 22 )C(O)N(R 22 )2, C 1 -C 6 -alkyl-N(R 22 )S(O)20R 22 , C 1 -C 6 -alkyl-
N(R 22 )S(O)2N(R 22 )2, C 1 -C 6 -alkyl-C(O)N(R 22 )OR 22 , C 1 -C 6 -alkyl-
C(O)N(R 22 )N(R 22 )2, C 1 -C 6 -alkyl-C(O)N(R 22 )C(O)R 22 , C 1 -C 6 -alkyl-
C(O)N(R 22 )C(O)OR 25 , C 1 -C 6 -alkyl-C(O)N(R 22 )C(O)N(R 22 )2, C 1 -C 6 -alkyl-
C(O)N(R 22 )S02R 25 , C 1 -C 6 -alkyl-C(O)N(R 22 )S020R 22 , C 1 -C 6 -alkyl-
C(O)N(R 22 )S02N(R 22 )2, C 1 -C 6 -alkyl-P(O)(OH)2 and C 1 -C 6 -alkyl-P(O)(0-C 1 -C 4 - alkyl)2;
R^ is selected from the group consisting of hydrogen, halogen, C 1 -C 8 -alkyl, cyano-
Z 1 , nitro, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cy- cloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 1 -C 8 -haloalkyl, C1- C 3 -alkylamino, C 1 -C 3 -dialkylamino, C 1 -C 3 -alkylamino-S(O)k, C 1 -C 3 -alkylcar- bonyl, C 1 -C 8 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-Z 1 , C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkylthio-Z 1 , C 2 -C 6 - alkenyloxy, C 2 -C 6 -alkynyloxy, C 1 -C 6 -haloalkoxy, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkoxy-Z 1 , R 1 b -S(O)k-Z 1 , phenoxy-Z 1 and heterocy- clyloxy-Z 1 , where heterocyclyloxy is an oxygen bound 5- or 6- membered mono- cyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aro- matic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1 , 2, 3 or 4 groups 1 , which are identical or different;
R5 is selected from the group consisting of halogen, cyano-Z 1 , nitro, C 1 -C 8 -alkyl, C 3 - C 7 -cycloalkyl, C 3 -C 7 -cydoalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halo- genated, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 1 -C 8 -haloalkyl, C 1 -C 3 -alkylamino, C1 - C 3 -dialkylamino, C 1 -C 3 -alkylamino-S(O)k, C 1 -C 3 -alkylcarbonyl, C 1 -C 8 -alkoxy, C1 - C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-Z 1 , C 1 -C 4 -alkylthio-C 1 -C 4 - alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkylthio-Z 1 , C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, C1 - C 6 -haloalkoxy, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkoxy-Z 1 , phenoxy-Z 1 and heterocyclyloxy-Z 1 , where heterocyclyloxy is an oxygen bound 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic sat- urated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where the cyclic groups in phenoxy and heterocyclyloxy are unsubstituted or substituted by 1 , 2, 3 or 4 groups R 11 , which are identical or different;
R6 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloal- kynyl, C 1 -C 4 -alkoxy- C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, R b -S(O) n -C 1 - C 3 -alkyl, R c -C(=O)-C 1 -C 3 -alkyl, R d O-C(=O)-C 1 -C 3 -alkyl, R e R f N-C(=O)-C 1 -C 3 - alkyl, R9R n N -C 1 -C 3 -alkyl, phenyl-Z and heterocyclyl-Z, where heterocyclyl is a 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups R', which are identical or different;
R', R1 1 , R21 independently of each other are selected from the group consisting of halogen, N02, CN, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -halocycloalkyl, C1 -C 6 - haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 6 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C1 -C 4 - haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy, C 3 -C 7 -cycloalkoxy and C1 - C 6 -haloalkyloxy, or two radicals R', R 1 1 or R 21 bound to the same carbon atom together may form a group =0;
Z, Z1 , Z2 independently of each other are selected from the group consisting of
a covalent bond and C 1 -C 4 -alkanediyl; is selected from the group consisting of a covalent bond, C 1 -C 4 -alkanediyl, 0-C1- C 4 -alkanediyl, C 1 -C 4 -alkanediyl-0 and C 1 -C 4 -alkanediyl-0-C 1 -C 4 -alkanediyl; Rb, R1 b_ R2b independently of each other are selected from the group consisting of C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloal- kenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, phenyl and heterocydyl, where heterocydyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heter- ocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocydyl are unsub- stituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and se- lected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C1-C 4 - alkoxy and C 1 -C 4 -haloalkoxy;
R C , R 2c independently of each other are selected from the group consisting of hydro- gen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 - cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy ,C 2 -C 6 -alkenyl, C 1 -C 4 -al- kyl-C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C1-C 4 - alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O)n-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -alkyl, C1- C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phenyl, benzyl and heterocydyl, where heterocydyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocydyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy; R d , R 2d independently of each other are selected from the group consisting of hydro- gen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 - C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloal- kynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O)n-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino- C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phenyl and ben- zyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R 2C R 2d together with the nitrogen atom, to which they are bound may form a 4,-5-, 6- or 7-membered, saturated or unsaturated cyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy; independently of each other are selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenylene, C 2 -C 6 - haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or
R e , Rf together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C1-C 4 - alkoxy and C 1 -C 4 -haloalkoxy;
R 2e , R 2f independently of each other have the meanings given for R e , R f ; R9 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 - C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforemen- tioned radicals are unsubstituted or partially or completely halogenated, C1-C 6 - haloalkyl, C 2 -C 6 -alkenylene, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkylcarbonyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of hal- ogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R n is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloal- kynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkylcarbonyl, a radi- cal C(=O)-Rk, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or
R9, R n together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of =0, halogen, C 1 -C 4 -alkyl, C1-C 4 - haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R 2 g, R2h independently of each other have the meanings given for R9, R n ;
R k has the meanings given for R c ;
R 22 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl, C 3 -C 6 -cyclo- alkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -halocycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C1- C 6 -alkoxy-C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, phenyl, phe- nyl-C 1 -C 6 -alkyl, heteroaryl, heteroaryl-C 1 -C 6 -alkyl, heterocyclyl, heterocyclyl-C 1 - C 6 -alkyl, phenyl-0-C 1 -C 6 -alkyl, heteroaryl-0-C 1 -C 6 -alkyl, heterocyclyl-0-C 1 -C 6 - alkyl, phenyl-N(R 23 )-C 1 -C 6 -alkyl, heteroaryl-N(R 23 )-C 1 -C 6 -alkyl, heterocyclyl-
N(R 23 )-C 1 -C 6 -alkyl, phenyl-S(O)n-C 1 -C 6 -alkyl, heteroaryl-S(O)n-C 1 -C 6 -alkyl, het- erocyclyl-S(O)n-C 1 -C 6 -alkyl, where the 15 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen, cyano, rhodano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C(O)OR 23 , C(O)N(R 23 )2, OR 23 ,
N(R 23 )2, S(O)nR 24 , S(O)20R 23 , S(O)2N(R 23 )2 and R 23 0-C 1 -C 6 -alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups;
R 23 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl and phenyl;
R 24 is selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl and phe- nyl;
R 25 is selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenylene, C 3 -C 6 -halocycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C1- C 6 -alkoxy-C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, phenyl, phe- nyl-C 1 -C 6 -alkyl, heteroaryl, heteroaryl-C 1 -C 6 -alkyl, heterocyclyl, heterocyclyl-C 1 - C 6 -alkyl, phenyl-0-C 1 -C 6 -alkyl, heteroaryl-0-C 1 -C 6 -alkyl, heterocyclyl-0-C 1 -C 6 - alkyl, phenyl-N(R 23 )-C 1 -C 6 -alkyl, heteroaryl-N(R 23 )-C 1 -C 6 -alkyl, heterocyclyl-
N(R 23 )-C 1 -C 6 -alkyl, phenyl-S(O)n-C 1 -C 6 -alkyl, heteroaryl-S(O)n-C 1 -C 6 -alkyl, het- erocyclyl-S(O)n-C 1 -C 6 -alkyl, where the 15 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen, cyano, rhodano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C(O)OR 23 , C(O)N(R 23 )2, OR 23 ,
N(R 23 )2, S(O) n R 24 , S(O)20R 23 , S(O)2N(R 23 )2 and R 23 0-C 1 -C 6 -alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups;
R 26 is C 1 -C 6 -alkyl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl;
R 2 ^ is selected from the group consisting of hydrogen, cyano and C1- C 4 -haloalkylcarbonyl;
R 23 , R 2 9 independently of each other are C 1 -C 6 -alkyl, or
R 23 , R 2 9 together with the sulfur atom, to which they are bound may form a 5- or 6- membered saturated ring, which may carry as a ring member 1 oxygen atom; k is 0, 1 or 2;
n is 0, 1 or 2;
The compounds of the present invention, i.e. the compounds of formula I, their N-oxides or their salts, are particularly useful for controlling unwanted vegetation. Therefore, the present invention also relates to the use of a compound of formula I, an N-oxide or a salt thereof or a composition comprising at least one compound of formula I, an N-oxide or an agriculturally suit- able salt thereof for combating or controlling unwanted vegetation.
The invention also relates to a composition comprising at least one compound of the pre- sent invention, including an N-oxide or a salt thereof, and at least one auxiliary. In particular, the invention relates to an agricultural composition comprising at least one compound of the present invention, including an N-oxide or an agriculturally suitable salt thereof, and at least one auxil- iary customary for crop protection formulations.
The invention also relates to a method for combating or controlling unwanted vegetation, which method comprises allowing a herbicidally effective amount of at least one compound of the present invention, including an N-oxide or a salt thereof, to act on unwanted plants, their seed and/or their habitat.
Depending on the substitution pattern, the compounds of formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of formula I, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula I or its mixtures. Suitable compounds of formula I also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitro- gen-sulfur double bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
Depending on the substitution pattern, the compounds of formula I may be present in the form of their tautomers. Hence, the invention also relates to the tautomers of the formula I and the stereoisomers, salts and N-oxides of said tautomers.
The term "N-oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides in compounds of for- mula I can in particular be prepared by oxidizing the ring nitrogen atom(s) of a tetrazole or a tria- zole with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides, or the ring nitrogen atom(s) of a heterocyclic substituent R 1 , R 2 , R 3 , R 4 or R 5 .
The present invention further relates to compounds as defined herein, wherein one or more of the atoms depicted in formula I have been replaced by its stable, preferably non- radioactive isotope (e.g. hydrogen by deuterium, 12 C by 13 C, 14 N by 15 N, 16 0 by 18 O) and in particular wherein at least one hydrogen atom has been replaced by a deuterium atom. Of course, these compounds contain more of the respective isotope than the isotope naturally occurs and thus is anyway present in the compounds of formula I .
The compounds of the present invention may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention in- cludes both amorphous and crystalline compounds of formula I, their enantiomers or diastere- omers, mixtures of different crystalline states of the respective compound of formula I, its enan- tiomers or diastereomers, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the present invention are preferably agriculturally suitable salts. They can be formed by customary methods, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
Useful agriculturally suitable salts are especially the salts of those cations or the acid addi- tion salts of those acids whose cations and anions, respectively, do not have any adverse effect on the herbicidal action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4 + ) and substituted am- monium in which one to four of the hydrogen atoms are replaced by C 1 -C 4 -alkyl, C 1 -C 4 -hydroxy- alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or ben- zyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyeth- oxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltri- ethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sul- fonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensul- fate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, car- bonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of the present invention with an acid of the corresponding anion, preferably with hy- drochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term "undesired vegetation" ("weeds") is understood to include any vegetation grow- ing in non-crop-areas or at a crop plant site or locus of seeded and otherwise desired crop, where the vegetation is any plant species, including their germinant seeds, emerging seedlings and established vegetation, other than the seeded or desired crop (if any). Weeds, in the broad- est sense, are plants considered undesirable in a particular location.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix C n - Cm indicates in each case the possible number of carbon atoms in the group.
The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term "partially or completely halogenated" means that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. A partially or completely halogenated radical is termed below also "halo- radical". For example, partially or completely halogenated alkyl is also termed haloalkyi.
The term "alkyl" as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 car- bon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particu- lar from 1 to 3 carbon atoms. Examples of C 1 -C 4 -alkyl are methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. Examples for C 1 -C 6 -alkyl are, apart from those mentioned for C 1 -C 4 -alkyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dime- thylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2, 2-tri methyl propyl, 1-ethyl-1-methylpropyl and 1 -ethyl-2-methylpropyl. Exam- ples for C 1 -C 10 -alkyl are, apart those mentioned for C 1 -C 6 -alkyl, n-heptyl, 1-methylhexyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 -ethylpentyl, 2-ethylpentyl, 3- ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1 -ethylhexyl, 2-ethylhexyl, 1 ,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.
The term "alkylene" (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is re- placed by one further binding site, thus forming a bivalent moiety.
The term "haloalkyi" as used herein (and in the haloalkyi moieties of other groups com- prising a haloalkyi group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 8 carbon atoms ("C 1 -Cs-haloalkyl"), frequently from 1 to 6 carbon atoms ("C1-C 6 - haloalkyl"), more frequently 1 to 4 carbon atoms ("C 1 -C 4 -haloalkyl"), wherein the hydrogen at- oms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyi moie- ties are selected from C 1 -C 4 -haloalkyl, more preferably from C 1 -C 2 -haloalkyl, more preferably from halomethyl, in particular from C 1 -C 2 -fluoroalkyl. Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like. Examples for C 1 -C 2 -fluoroalkyl are fluo- romethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-tri- fluoroethyl, pentafluoroethyl, and the like. Examples for C 1 -C 2 -haloalkyl are, apart those men- tioned for C 1 -C 2 -fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 2-chloroethyl, 2,2, -di- chloroethyl, 2,2,2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 1 -bromoethyl, and the like. Examples for C 1 -C 4 -haloalkyl are, apart from those men- tioned for C 1 -C 2 -haloalkyl, 1 -fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1 ,1 ,1-trifluoroprop-2-yl, 3-chloropropyl, 4-chlorobutyl and the like.
The term "cycloalkyi" as used herein (and in the cycloalkyi moieties of other groups com- prising a cycloalkyi group, e.g. cycloalkoxy and cycloalkylalkyi) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms ("C 3 -C 1 o-cycloalkyl"), preferably 3 to 7 carbon atoms ("C 3 -C 7 -cycloalkyl") or in particular 3 to 6 carbon atoms ("C 3 -C 6 - cycloalkyl"). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 7 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicyclo[2.2.1 ]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1 ]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
The term "halocycloalkyl" as used herein (and in the halocycloalkyl moieties of other groups comprising an halocycloalkyl group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, preferably 3 to 7 carbon atoms or in particular 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine. Examples are 1- and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl and the like.
The term "cycloalkyl-alkyl" used herein denotes a cycloalkyi group, as defined above, which is bound to the remainder of the molecule via an alkyl group. The term "C 3 -C 7 -cycloalkyl- C 1 -C 4 -alkyl" refers to a C 3 -C 7 -cycloalkyl group as defined above which is bound to the remainder of the molecule via a C 1 -C 4 -alkyl group, as defined above. Examples are cyclopropylmethyl, cy- clopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopen- tylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpro- pyl, and the like.
The term "alkenyl" as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 8 ("C 2 -C 8 -alkenyl"), preferably 2 to 6 carbon atoms ("C 2 -C 6 -alkenyl"), in particular 2 to 4 carbon atoms ("C 2 -C 4 -alkenyl"), and a double bond in any position, for example C 2 -C 4 -alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -meth- ylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1-methyl-2- propenyl or 2-methyl-2-propenyl; C 2 -C 6 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1- methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 2-methyl-1-propenyl, 1-me- thyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl- 1-butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2- propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1-propenyl, 1 -ethyl-2-pro- penyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1-pentenyl, 2-methyl-1- pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl- 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pen- tenyl, 4-methyl-4-pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1-bu- tenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2-bu- tenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-bu- tenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1-ethyl-2-methyl-1 -propenyl, 1-ethyl-2- methyl-2-propenyl and the like, or C 2 -Cs-alkenyl, such as the radicals mentioned for C 2 -C 6 - alkenyl and additionally 1-heptenyl, 2-heptenyl, 3-heptenyl, 1 -octenyl, 2-octenyl, 3-octenyl, 4- octenyl and the positional isomers thereof.
The term "haloalkenyl" as used herein, which may also be expressed as "alkenyl which is substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy and the like refers to un- saturated straight-chain or branched hydrocarbon radicals having 2 to 8 ("C 2 -C 8 -haloalkenyl") or 2 to 6 ("C 2 -C 6 -haloalkenyl") or 2 to 4 ("C 2 -C 4 -haloalkenyl") carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
The term "alkynyl" as used herein denotes unsaturated straight-chain or branched hydro- carbon radicals having usually 2 to 8 ("C 2 -C 8 -alkynyl"), frequently 2 to 6 ("C 2 -C 6 -alkynyl"), prefer- ably 2 to 4 carbon atoms ("C 2 -C 4 -alkynyl") and a triple bond in any position, for example C 2 -C 4 - alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl and the like, C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1 -butynyl, 2-bu- tynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2- butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1 ,1-dimethyl-2-propynyl, 1 - ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1- methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1 - pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl-2-butynyl, 1 ,1-dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1- ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 -ethyl-1 -methyl-2-propynyl and the like.
The term "haloalkynyl" as used herein, which is also expressed as "alkynyl which is sub- stituted by halogen", refers to unsaturated straight-chain or branched hydrocarbon radicals hav- ing usually 2 to 8 carbon atoms ("C 2 -C 8 -haloalkynyl"), frequently 2 to 6 ("C 2 -C 6 -haloalkynyl"), preferabyl 2 to 4 carbon atoms ("C 2 -C 4 -haloalkynyl"), and a triple bond in any position (as men- tioned above), where some or all of the hydrogen atoms in these groups are replaced by halo- gen atoms as mentioned above, in particular fluorine, chlorine and bromine. The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 8 carbon atoms ("d-Ce-alkoxy"), frequently from 1 to 6 carbon atoms ("C 1 -C 6 -alkoxy"), preferably 1 to 4 carbon atoms ("C 1 -C 4 -alkoxy"), which is bound to the remainder of the molecule via an oxygen atom. C 1 -C 2 -alkoxy is methoxy or ethoxy. C 1 -C 4 -alkoxy is additionally, for example, n-propoxy, 1 -methylethoxy (isopropoxy), butoxy, 1 -methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1-dimethylethoxy (tert-butoxy). C 1 -C 6 -alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1-dime- thylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpent- oxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbut- oxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethyl- butoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1-methylpropoxy or 1 -ethyl-2-methylpropoxy. d-Cs-alkoxy is additionally, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof.
The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 8 carbon atoms ("d-Cs-haloalkoxy"), fre- quently from 1 to 6 carbon atoms ("C 1 -C 6 -haloalkoxy"), preferably 1 to 4 carbon atoms ("C1-C 4 - haloalkoxy"), more preferably 1 to 3 carbon atoms ("C 1 -C 3 -haloalkoxy"), wherein the hydrogen atoms of this group are partially or completely replaced by halogen atoms, in particular fluorine atoms. C 1 -C 2 -haloalkoxy is, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCb, OCCI 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroeth- oxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoro- ethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC 2 F5. C 1 -C 4 -haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoro- propoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromo- propoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C 2 F5, OCF 2 - C 2 F5, 1 -(CH 2 F)-2-fluoroethoxy, 1-(CH 2 CI)-2-chloroethoxy, 1-(CH 2 Br)-2-bromoethoxy, 4-fluorobu- toxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. C 1 -C 6 -haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoro- pentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluoro- hexoxy.
The term "alkoxyalkyl" as used herein denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radi- cal usually comprising 1 to 8, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. "C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl" is a C 1 -C 6 -alkyl group, as defined above, in which one hydro- gen atom is replaced by a C 1 -C 6 -alkoxy group, as defined above. Examples are CH2OCH3, CH2- OC 2 H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (l-methylpropoxy)-methyl, (2- methylpropoxy)methyl, CH2-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2- (l-methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1 -methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl,
2- (1 ,1-dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1- methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1-methylpropoxy)-propyl, 2-(2-methylpropoxy)-pro- pyl, 2-(1 ,1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)-propyl,
3- (1-methylethoxy)-propyl, 3-(n-butoxy)-propyl, 3-(1 -methylpropoxy)-propyl, 3-(2- methylpropoxy)-propyl, 3-(1 ,1-dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n- propoxy)-butyl, 2-(1 -methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1-methylpropoxy)-butyl, 2-(2-me- thyl-propoxy)-butyl, 2-(1 ,1 -dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n- propoxy)-butyl, 3-(1 -methylethoxy)-butyl, 3-(n-butoxy)-butyl, 3-(1-methylpropoxy)-butyl, 3-(2- methylpropoxy)-butyl, 3-(1 ,1 -dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n- propoxy)-butyl, 4-(1 -methylethoxy)-butyl, 4-(n-butoxy)-butyl, 4-(1-methylpropoxy)-butyl, 4-(2- methylpropoxy)-butyl, 4-(1 ,1 -dimethylethoxy)-butyl and the like.
The term "haloalkoxy-alkyl" as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an haloalkoxy radical as defined above, usually comprising 1 to 8, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are fluoromethoxymethyl, difluoro- methoxymethyl, trifluoromethoxymethyl, 1 -fluoroethoxymethyl, 2-fluoroethoxymethyl, 1 ,1-difluo- roethoxymethyl, 1 ,2-difluoroethoxymethyl, 2,2-difluoroethoxymethyl, 1 ,1 ,2-trifluoroethoxymethyl, 1 ,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl, pentafluoroethoxymethyl, 1-fluoroeth- oxy-1 -ethyl, 2-fluoroethoxy-1 -ethyl, 1 ,1-difluoroethoxy-1-ethyl, 1 ,2-difluoroethoxy-1 -ethyl, 2,2- difluoroethoxy-1 -ethyl, 1 ,1 ,2-trifluoroethoxy-1 -ethyl, 1 ,2,2-trifluoroethoxy-1 -ethyl, 2,2,2-trifluoro- ethoxy-1 -ethyl, pentafluoroethoxy-1 -ethyl, 1 -fluoroethoxy-2-ethyl, 2-fluoroethoxy-2-ethyl, 1 ,1 - difluoroethoxy-2-ethyl, 1 ,2-difluoroethoxy-2-ethyl, 2,2-difluoroethoxy-2-ethyl, 1 ,1 ,2-trifluoroeth- oxy-2-ethyl, 1 ,2,2-trifluoroethoxy-2-ethyl, 2,2,2-trifluoroethoxy-2-ethyl, pentafluoroethoxy-2-ethyl, and the like.
The term "alkylthio" (also alkylsulfanyl, "alkyl-S" or "alkyl-S(O) k " (wherein k is 0)) as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 8 carbon atoms ("C 1 -Cs-alkylthio"), frequently comprising 1 to 6 carbon atoms ("C 1 -C 6 -alkylthio"), preferably 1 to 4 carbon atoms ("C 1 -C 4 -alkylthio"), which is at- tached via a sulfur atom at any position in the alkyl group. C 1 -C 2 -alkylthio is methylthio or ethyl- thio. C 1 -C 4 -alkylthio is additionally, for example, n-propylthio, 1 -methylethylthio (isopropylthio), butylthio, 1-methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1-dimethyle- thylthio (tert-butylthio). C 1 -C 6 -alkylthio is additionally, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1 ,1 -dimethylpropylthio, 1 ,2-dimethylpropylthio, 2,2-dime- thylpropylthio, 1-ethylpropylthio, hexylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpen- tylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethyl- butylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1 - ethyl-2-methylpropylthio. C 1 -Cs-alkylthio is additionally, for example, heptylthio, octylthio, 2- ethylhexylthio and positional isomers thereof.
The term "haloalkylthio" as used herein refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or completely substituted by fluorine, chlorine, bro- mine and/or iodine. C 1 -C 2 -haloalkylthio is, for example, SCH 2 F, SCHF 2 , SCF 3 , SCH 2 CI, SCHCI 2 , SCCb, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethyl- thio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoro- ethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio or SC 2 F 5 . C 1 -C 4 -haloalkylthio is additionally, for example, 2-fluoro- propylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3- chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoro- propylthio, 3,3,3-trichloropropylthio, SCH2-C 2 F5, SCF2-C 2 F5, 1 -(CH 2 F)-2-fluoroethylthio, 1- (CH 2 CI)-2-chloroethylthio, 1-(CH 2 Br)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4- bromobutylthio or nonafluorobutylthio. C 1 -C 6 -haloalkylthio is additionally, for example, 5-fluoro- pentylthio, 5-chloropentylthio, 5-brompentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluo- rohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio.
The terms "alkylsulfinyl" and "alkyl-S(O)k" (wherein k is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For exam- ple, the term "C 1 -C 2 -alkylsulfinyl" refers to a C 1 -C 2 -alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "C 1 -C 4 -alkylsulfinyl" refers to a C 1 -C 4 -alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "C 1 -C 6 -alkylsulfinyl" refers to a C 1 -C 6 -alkyl group, as defined above, attached via a sulfinyl [S(O)] group. C 1 -C 2 -alkylsulfinyl is methylsulfinyl or ethylsulfinyl. C 1 -C 4 -alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethyl- sulfinyl (isopropylsulfinyl), butylsulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropyl- sulfinyl (isobutylsulfinyl) or 1 ,1-dimethylethylsulfinyl (tert-butylsulfinyl). C 1 -C 6 -alkylsulfinyl is addi- tionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutyl- sulfinyl, 1 ,1-dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 1 -methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpen- tylsulfinyl, 4-methylpentylsulfinyl, 1 ,1-dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 ,3-dime- thylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1 - ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2-trimethylpropylsulfinyl, 1 -ethyl-1 -methylpropylsulfinyl or 1 -ethyl-2-methylpropylsulfinyl.
The terms "alkylsulfonyl" and "alkyl-S(O)k" (wherein k is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. The term "C 1 -C 2 -alkylsulfonyl" refers to a C 1 -C 2 -alkyl group, as defined above, attached via a sulfonyl
[S(O)2] group. The term "C 1 -C 4 -alkylsulfonyl" refers to a C 1 -C 4 -alkyl group, as defined above, at- tached via a sulfonyl [S(O)2] group. The term "C 1 -C 6 -alkylsulfonyl" refers to a C 1 -C 6 -alkyl group, as defined above, attached via a sulfonyl [S(O)2] group. C 1 -C 2 -alkylsulfonyl is methylsulfonyl or ethylsulfonyl. C 1 -C 4 -alkylsulfonyl is additionally, for example, n-propylsulfonyl, 1-methylethyl- sulfonyl (isopropylsulfonyl), butylsulfonyl, 1 -methylpropylsulfonyl (sec-butylsulfonyl), 2- methylpropylsulfonyl (isobutylsulfonyl) or 1 ,1 -dimethylethylsulfonyl (tert-butylsulfonyl). C 1 -C 6 -al- kylsulfonyl is additionally, for example, pentylsulfonyl, 1 -methylbutylsulfonyl, 2-methylbutyl- sulfonyl, 3-methylbutylsulfonyl, 1 ,1 -dimethylpropylsulfonyl, 1 ,2-dimethylpropylsulfonyl, 2,2-dime- thylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpen- tylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1 , 1-dimethylbutylsulfonyl, 1 ,2-dime- thylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2-trimethylpropylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl.
The term "alkylamino" as used herein denotes in each case a group R * HN-, wherein R * is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms ("C 1 -C 6 -alkyla- mino"), preferably 1 to 4 carbon atoms ("C 1 -C 4 -alkylamino"). Examples of C 1 -C 6 -alkylamino are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso-butyl- amino, tert-butylamino, and the like. The term "dialkylamino" as used herein denotes in each case a group R * R°N-, wherein R * and R°, independently of each other, are a straight-chain or branched alkyl group each usually having from 1 to 6 carbon atoms ("di-(C 1 -C 6 -alkyl)-amino"), preferably 1 to 4 carbon atoms ("di- (C 1 -C 4 -alkyl)-amino"). Examples of a di-(C 1 -C 6 -alkyl)-amino group are dimethylamino, diethyla- mino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl-propyl-amino, methyl-isopropyla- mino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl-amino, ethyl-isopropylamino, ethyl-butyl-amino, ethyl-isobutyl-amino, and the like.
The suffix "-carbonyl" in a group denotes in each case that the group is bound to the re- mainder of the molecule via a carbonyl C=0 group. This is the case e.g. in alkylcarbonyl, haloal- kylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloal- koxycarbonyl.
The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon rad- ical such as phenyl or naphthyl, in particular phenyl.
The term "het(ero)aryl" as used herein refers to a mono-, bi- or tricyclic heteroaromatic hy- drocarbon radical, preferably to a monocyclic heteroaromatic radical, such as pyridyl, pyrimidyl and the like.
The term "3-, 4-, 5- or 6-membered monocyclic or 8-, 9- or 10-membered bicyclic satu- rated, unsaturated or aromatic heterocycle containing 1 , 2, 3 or 4 heteroatoms as ring members selected from the groups consisting of N, O and S" as used herein denotes monocyclic or bicy- die radicals, the monocyclic or bicyclic radicals being saturated, unsaturated or aromatic where N can optionally be oxidized, i.e. in the form of an N-oxide, and S can also optionally be oxi- dized to various oxidation states, i.e. as SO or SO2. An unsaturated heterocycle contains at least one C-C and/or C-N and/or N-N double bond(s). A fully unsaturated heterocycle contains as many conjugated C-C and/or C-N and/or N-N double bonds as allowed by the size(s) of the ring(s). An aromatic monocyclic heterocycle is a fully unsaturated 5- or 6-membered monocyclic heterocycle. An aromatic bicyclic heterocycle is an 8-, 9- or 10-membered bicyclic heterocycle consisting of a 5- or 6-membered heteroaromatic ring which is fused to a phenyl ring or to an- other 5- or 6-membered heteroaromatic ring. The heterocycle may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. As a matter of course, the heterocyclic ring contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.
Examples of a 3-, 4-, 5- or 6-membered monocyclic saturated heterocycle include:
oxirane-2-yl, aziridine-1-yl, aziridine-2-yl, oxetan-2-yl, azetidine-1 -yl, azetidine-2-yl, azetidine-3- yl, thietane-1 -yl, thietan-2-yl, thietane-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahy- drothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-1 -yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazolidin-1 -yl, imidazolidin-2-yl, imidazoli- din-4-yl, oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-2-yl, isoxa- zolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1 ,2,4- oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-1 -yl, 1 ,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, piperidin-1 -yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-3-yl, hexahydro- pyridazin-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, pi- perazin-1 -yl, piperazin-2-yl, 1 ,3,5-hexahydrotriazin-1-yl, 1 ,3,5-hexahydrotriazin-2-yl and
1 ,2,4-hexahydrotriazin-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1 -oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1 -ox- othiomorpholin-4-yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1-dioxothiomorpholin-3-yl, 1 ,1-dioxothiomor- pholin-4-yl and the like.
Examples of a 5- or 6-membered monocyclic partially unsaturated heterocycle include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien- 2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin- 3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxa- zolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5- yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4- yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyra- zol-1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropy- razol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydro- pyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihy- dropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-,
5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2- di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl and 1 ,2,4-di- or tetrahydrotriazin-3-yl.
Examples of a 5- or 6-membered monocyclic fully unsaturated (including aromatic) hetero- cyclic ring include: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyra- zolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thia- zolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,3,4-triazol-1-yl, 1 ,3,4-triazol-2-yl, 2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-oxopyridin-2-yl, 1-oxopyridin-3-yl, 1 -oxopyridin-4-yl,3-pyri- dazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or
6- membered heteroaromatic radical include: benzofuranyl, benzothienyl, indolyl, indazolyl, ben- zimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, iso- chinolinyl, purinyl, 1 ,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like.
If two radicals bound to the same nitrogen atom (for example R e and R f or R 2e and R 2f or
R9 and R h or R2g and R 2h ) together with the nitrogen atom, to which they are bound, form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N, this is for example pyrrolidine-1 -yl, pyrazolidin-1 -yl, imidazolidin-1-yl, oxazolidin-3-yl, thiazolidin-3-yl, isoxazolidin-2-yl, isothiazolin- 2-yl, [1 ,2,3]-triazolidin-1 -yl, [1 ,2,3]-triazolidin-2-yl, [1 ,2,4]-triazolidin-1 -yl, [1 ,2,4]-triazolidin-4-yl, [1 ,2,3]-oxadiazolidin-2-yl, [1 ,2,3]-oxadiazolidin-3-yl, [1 ,2,5]-oxadiazolidin-2-yl, [1 ,2,4]-oxadiazoli- din-2-yl, [1 ,2,4]-oxadiazolidin-4-yl, [1 ,3,4]-oxadiazolidin-3-yl, [1 ,2,3]-thiadiazolidin-2-yl, [1 ,2,3]- thiadiazolidin-3-yl, [1 ,2,5]-thiadiazolidin-2-yl, [1 ,2,4]-thiadiazolidin-2-yl, [1 ,2,4]-thiadiazolidin-4-yl, [1 ,3,4]-thiadiazolidin-3-yl, piperdin-1 -yl, piperazine-1-yl, morpholin-1-yl, thiomorpholin-1-yl, 1 -ox- othiomorpholin-1-yl, 1 ,1 -dioxothiomorpholin-1-yl, azepan-1-yl, 1 ,4-diazepan-1 -yl, pyrrolin-1 -yl, pyrazolin-1 -yl, imidazolin-1-yl, oxazolin-3-yl, isoxazolin-2-yl, thiazolin-3-yl, isothiazolin-1 -yl, 1 ,2- dihydropyridin-1-yl, 1 ,2,3,4-tetrahydropyridin-1-yl, 1 ,2,5,6-tetrahydropyridin-1-yl, 1 ,2-dihydro- pyridazin, 1 ,6-dihydropyridazin, 1 ,2,3,4-tetrahydropyridazin-1-yl, 1 ,2,5,6-tetrahydropyridazin-l- yl, 1 ,2-dihydropyrimidin, 1 ,6-dihydropyrimidin, 1 ,2,3,4-tetrahydropyrimidin-1 -yl, 1 ,2,5,6-tetrahy- dropyrimidin-1 -yl, 1 ,2-dihydropyrazin-1 -yl, 1 ,2,3,4-tetrahydropyrazin-1 -yl, 1 ,2,5,6-tetrahydropyra- zin-1 -yl, pyrrol-1 -yl, pyrazol-1 -yl, imidazol-1 -yl, [1 ,2,3]-1 H-triazol-1 -yl, [1 ,2,3]-2H-triazol-2-yl, [1 ,2,4]-1 H-triazol-1-yl and [1 ,2,4]-4H-triazol-4-yl.
The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formula I are valid on their own as well as preferably in combination with each other, as well as in combination with the stereoisomers, salts, tautomers or N-oxides thereof.
The remarks made below concerning preferred embodiments of the variables further are valid on their own as well as preferably in combination with each other concerning the com- pounds of formula I, where applicable, as well as concerning the uses and methods according to the invention and the composition according to the invention.
Preferred compounds according to the invention are compounds of formula I or a stereoi- somer, salt or N-oxide thereof, wherein the salt is an agriculturally suitable salt. Further pre- ferred compounds according to the invention are compounds of formula I or an N-oxide or salt thereof, especially an agriculturally suitable salt. Particularly preferred compounds according to the invention are compounds of formula I or a salt thereof, especially an agriculturally suitable salt thereof. According to one embodiment of the invention the variable Q in the compounds of formula
I is Q 1 :
(Q 1 )
Herein, the arrow represents the binding site of the variable Q 1 conjugated to the remain- ing part of the compound of formula I. Compounds of formula I wherein Q is Q 1 have the follow- ing formula I.A, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined herein:
According to another embodiment of the invention the variable Q in the compounds of for- mula I is Q 2 :
Herein, the arrow represents the binding site of the variable Q 2 conjugated to the remain- ing part of the compound of formula I. Compounds of formula I wherein Q is Q 2 have the follow- ing formula I.B, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined herein:
According to yet further embodiment of the invention the variable Q in the compounds of formula I is Q 3 :
(Q 3 )
Herein, the arrow represents the binding site of the variable Q 3 conjugated to the remain- ing part of the compound of formula I. Compounds of formula I wherein Q is Q 3 have the follow- ing formula I.C, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined herein:
According to one embodiment of the invention the variable Q in the compounds of formula I is Q 4 :
(Q 4 )
Herein, the arrow represents the binding site of the variable Q 4 conjugated to the remain- ing part of the compound of formula I. Compounds of formula I wherein Q is Q 4 have the follow- ing formula I.D, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined herein:
Preferred compounds according to the invention are compounds of formula I, wherein R 1 is selected from the group consisting of cyano, halogen, nitro, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 - C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloal- koxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-Z 1 , C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 - C 4 -alkylthio-Z 1 , C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, C 1 -C 6 -haloalkoxy, C 1 -C 4 -haloalkoxy-C 1 -C 4 - alkoxy and R1 b -S(O)k, where Z 1 is as defined in claim 1 , where k is 0, 1 or 2 and where R 1b is selected from C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl.
Also preferred compounds according to the invention are compounds of formula I, wherein R 1 is selected from the group consisting of halogen, CN, nitro, C 1 -C 4 -alkyl, C 3 -C 6 -cyclo- alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 - C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 3 -C 4 -alkenyloxy, C 3 -C 4 -alkynyloxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl-S(O)k and C 1 -C 4 -haloalkyl-S(O)k, where k is 0 or 2.
In a preferred embodiment, R 1 is selected from the group consisting of halogen, nitro, C 1 - C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy- C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio and C 1 -C 4 -alkyl- sulfonyl.
In a further preferred embodiment, R 1 is selected from the group consisting of halogen, C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy.
In particular, R 1 is chlorine, fluorine, CF 3 , CH 3 , SO2CH3, N0 2 , CH2OCH2CH2OCH3, CH(CH 2 ) 2 or CH 2 OCH 3 .
Also particular, R 1 is chlorine, CH 3 , or OCH 3 . According to one group of embodiments of the present invention, R 2 is
In a preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2c is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy ,C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 - C 6 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O)n-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -al- kyl, C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heter- ocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or sub- stituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group con- sisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
In another preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2c is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6- membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1- C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
In a preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2d is selected from from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 - C 6 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O)n-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -al- kyl, C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
In another preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2d is selected from from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 - alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, phenyl and benzyl, where phenyl and benzyl are unsub- stituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloal- koxy;
In yet another preferred embodiment, R 2c R 2d together with the nitrogen atom, to which they are bound may form a 4,-5-, 6- or 7-membered, saturated or unsaturated cyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloal- koxy; In a preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2d is selected from from the group consisting of hydrogen, C r C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C r C 4 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, C 2 - C 6 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O) n -C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl and benzyl.
In a more preferred embodiment, R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - and R 2d is selected from from the group consisting of hydrogen, C r C 6 -alkyl, C 3 -C 7 -cycloalkyl-C r C 4 -alkyl, C r C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, and C r C 4 - alkoxy-C r C 4 -alkyl, C1-C 4 -S(O) n -C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -alkyl, C 1 -C 4 -di- alkylamino-C 1 -C 4 -alkyl.
Herein, particularly preferably, R 2d is methyl, ethyl, (C 3 H 5 )-CH2- (CH 2 cPr; cyclopropylme- thyl) or iso-propyl. Herein, very particularly preferably, R 2d is methyl, ethyl, cyclopropyl or phe- nyl, where phenyl is unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C1 - C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
Preferred compounds according to the invention are compounds of formula I, where R3 IS selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl, CI-C 4 - haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 4 -alkenyloxy, C 3 -C 4 -alkynyloxy or R 2b -S(O)k, where k is 0, 1 or 2 and where R 2b is selected from C 1 -C 4 -al- kyl and C 1 -C 4 -haloalkyl.
More preferably, R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C1 -C 4 -alkyl, C1 -C 4 -haloalkyl, C1 -C 4 -alkoxy, C1 -C 4 -haloalkoxy, C1 -C 4 -alkylthio, C1-C 4 - haloalkylthio, C1 -C 4 -alkyl-S(O)2 and C1-C 4 -haloalkyl-S(O)2.
In a particular preferred embodiment, R 3 is selected from the group consisting of hydro- gen, halogen, C1-C 4 -haloalkyl and phenyl, where phenyl is unsubstituted or substituted by 1 , 2,
3 or 4 groups R21 , which are identical or different.
In particular, R 3 is chlorine, fluorine, CF3, SO2CH3, CN, H, Br or CH3.
More particular, R 3 is hydrogen, chlorine, bromine, CF3, or methoxyphenyl.
Preferred compounds according to the invention are compounds of formula I, where R 4 is selected from the group consisting of hydrogen, CHF2, CF3, CN, NO2, CH3 and halogen.
More preferably, R 4 is hydrogen, chlorine, fluorine, CN or CH 3 .
According to a particular embodiment of the invention R 4 is hydrogen, chlorine or fluorine, in particular hydrogen. Preferred compounds according to the invention are compounds of formula I, wherein R 5 is selected from the group consisting of CHF 2 , CF 3 and halogen.
More preferably, R 5 is halogen, in particular chlorine or fluorine, preferably fluorine.
Preferred compounds according to the invention are compounds of formula I, wherein R 6 is selected from the group consisting of C 1 -C 4 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 4 -haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl and C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl.
Preferably, R 6 may be selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 4 -haloalkyl, R c -C(=O)-C r C 2 -alkyl, R d O-C(=O)-C r C 2 -alkyl, R e R f N-C(=O)-C 1 -C 2 -alkyl, R k -C(=O)NH-C r C 2 -alkyl and benzyl, where
R c is C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl,
R d is C 1 -C 4 -alkyl,
R e is hydrogen or C 1 -C 4 -alkyl,
R f is hydrogen or C 1 -C 4 -alkyl, or
R e , R f together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a fur- ther heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 methyl groups,
R k is C 1 -C 4 -alkyl.
More preferred compounds according to the invention are compounds of formula I, wherein R 6 is selected from the group consisting of C 1 -C 4 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 4 -haloal- kyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl and C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl.
Even more preferred compounds according to the invention are compounds of formula I, wherein R 6 is selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl, particularly from methyl, ethyl, n-propyl, methoxymethyl, ethoxymethyl and methoxyethyl.
Particularly preferred compounds according to the invention are compounds of formula I, wherein R 6 is selected from the group consisting of methyl, ethyl, n-propyl and methoxyethyl.
In this context, the variables R', R 11 , R 21 , Z, Z 1 , Z 2 , Z 2a , R b , R 1 b , R 2b , R c , R 2c , R d , R 2d , R e , R 2e , R f , R 2f , R9, R2g, Rh, R2h_ Rk_ n _ ki R22i R23i R24i R25i R26i R27i R28i R29i s and ti independently of each other, preferably have one of the following meanings:
R', R 11 , R 21 independently of each other are selected from halogen, C 1 -C 4 -alkyl, C 3 -C 6 -cy- cloalkyl, C 3 -C 6 -halocycloalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 - alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy and C 1 -C 6 -haloalkyloxy; and more preferably from halogen, C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -alkoxy.
Also more preferably R', R 11 , R 21 independently of each other are selected from halogen, C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -al- ky Ith 10-C1 -C 4 -al ky I and C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy; in particular from halogen, C 1 -C 4 -alkyl, C1-C 4 - alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy; and specifi- cally from CI, F, Br, methyl, ethyl, methoxy and trifluoromethyl.
Z, Z 1 , Z 2 independently of each other are selected from a covalent bond, methanediyl and ethanediyl, and in particular are a covalent bond.
Z 2a is selected from a covalent bond, C 1 -C 2 -alkanediyl, 0-C 1 -C 2 -alkanediyl, C 1 -C 2 -al- kanediyl-0 and C 1 -C 2 -alkanediyl-0-C 1 -C 2 -alkanediyl; more preferably from a covalent bond, me- thanediyl, ethanediyl, O-methanediyl, O-ethanediyl, methanediyl-O, and ethanediyl-O; and in particular from a covalent bond, methanediyl and ethanediyl.
R b , R 1b , R 2b independently of each other are selected from C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl and heterocyclyl are unsubstituted or substituted by 1 , 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl and C 1 -C 2 -alkoxy.
More preferably R b , R 1b , R 2b independently of each other are selected from C 1 -C 4 -alkyl, C 2 - C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -haloalkynyl, C 3 -C 6 -cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S.
In particular, R b , R 1b , R 2b independently of each other are selected from C 1 -C 4 -alkyl, C1-C 4 - haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl, phenyl and hetero- cyclyl, where heterocyclyl is a 5- or 6-membered aromatic heterocyclic radical having 1 or 2 ni- trogen atoms as ring members.
R c , R 2c , R k independently of each other are selected from hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 - cycloalkyl, which is unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C1-C 6 - alkoxy ,C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 - haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -S(O) n -C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -alkyl, C r C 4 -dialkylamino-C 1 -C 4 -alkyCl, 1 -C 6 -cyanoalkyl, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -alkoxy.
More preferably R c , R 2c , R k independently of each other are selected from hydrogen, C1-C 4 - alkyl, C 1 -C 4 -haloalkyl, C 2 -C-alkenyl, C 2 -C-haloalkenyl, C 2 -C-alkynyl, C 3 -C 6 -cycloalkyl, phenyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic saturated, partially unsatu- rated or aromatic heterocycle, which contains 1 , 2 or 3 heteroatoms as ring members, which are selected from the group consisting of O, N and S.
In particular, R c , R 2c , R k independently of each other are selected from hydrogen, C1-C 4 - alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 3 -C 6 -cycloalkyl, phenyl and heterocy- clyl, where heterocyclyl is a 5- or 6-membered aromatic heterocyclic radical having 1 or 2 nitro- gen atoms as ring members. R d , R 2d independently of each other are selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or partially or completely halogenated, C 1 -C 6 - haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 - alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O) n -C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino- C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
More preferably R d , R 2d independently of each other are selected from C 1 -C 6 -alkyl, C1-C 6 - haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 - alkyl and C 3 -C 7 -cycloalkyl, which is unsubstituted or partially or completely halogenated; and in particular from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl and C 3 -C 6 -cycloalkyl.
R 2c , R 2d together with the nitrogen atom, to which they are bound may form a 4,-5-, 6- or 7- membered, saturated or unsaturated cyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C r C 4 - alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R e , R f , R 2e , R 2f independently of each other are selected from hydrogen, C 1 -C 6 -alkyl, C 3 - C 7 -cycloalkyl, which is unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 - C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl and benzyl, where phenyl and benzyl are unsubstituted or substituted by 1 , 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -alkoxy, or R e and R f or R 2e and R 2f together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -alkoxy.
More preferably R e , R f , R 2e , R 2f independently of each other are selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl and benzyl, or R e and R f or R 2e and R 2f together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated or unsaturated N- bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2 or 3 groups, which are identical or different and selected from the group consisting of halogen, C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl.
In particular, R e , R f , R 2e , R 2f independently of each other are selected from hydrogen and C 1 -C 4 -alkyl, or R e and R f or R 2e and R 2f together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2 or 3 methyl groups.
R9, R2g independently of each other are selected from hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 - cycloalkyl, which is unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 - alkylsulfonyl, C 1 -C 4 -alkylcarbonyl, phenyl and benzyl.
More preferably Rg, R2g independently of each other are selected from hydrogen, C1-C 6 - alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, benzyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and C 3 -C 7 -cycloalkyl, which is unsubstituted or partially or completely halogenated; and in particular from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, benzyl and C 3 -C 6 - cycloalkyl.
R h , R 2h independently of each other are selected from hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 - cycloalkyl, which is unsubstituted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 - alkylsulfonyl, C 1 -C 4 -alkylcarbonyl, phenyl, benzyl and a radical C(=O)-R k , where R k is H , C1-C 4 - alkyl, C 1 -C 4 -haloalkyl or phenyl.
More preferably R h , R 2h independently of each other are selected from hydrogen, C1-C 6 - alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, benzyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and C 3 -C 7 -cycloalkyl, which is unsubstituted or partially or completely halogenated; and in particular from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, benzyl and C 3 -C 6 - cycloalkyl; or
R9 and R h or R2g and R 2h together with the nitrogen atom, to which they are bound may form a 5-, 6- or 7-membered, saturated or unsaturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is
unsubstituted or may carry 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of =0, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -alkoxy;
more preferably Rg and R h or R2g and R 2h together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated or unsaturated N-bound heterocyclic radi- cal, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubstituted or may carry 1 , 2 or 3 groups, which are identical or different and se- lected from the group consisting of halogen, C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl;
and in particular, Rg and R h or R2g and R 2h together with the nitrogen atom, to which they are bound may form a 5- or 6-membered, saturated N-bound heterocyclic radical, which may carry as a ring member a further heteroatom selected from O, S and N and which is unsubsti- tuted or may carry 1 , 2 or 3 methyl groups.
n and k independently of each other are 0 or 2, and in particular 2.
R 22 is selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halocycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 - alkoxy-C 1 -C 6 -alkyl, phenyl, phenyl-C 1 -C 6 -alkyl, heteroaryl, heteroaryl-C 1 -C 6 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 6 -alkyl, phenyl-0-C 1 -C 6 -alkyl, heteroaryl-0-C 1 -C 6 -alkyl, heterocyclyl-0-C 1 -C 6 - alkyl, where the 9 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C(O)OR 23 , C(O)N(R 23 ) 2 , OR 23 , N(R 23 ) 2 , S(O) n R 24 and R 23 0-C 1 -C 6 -alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups.
More preferably R 22 is selected from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy- C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl, phenyl and phenyl-C 1 -C 2 -alkyl. In particular, R 22 is hydrogen or C 1 -C 4 -alkyl.
R 23 is selected from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 3 -C 6 -cycloalkyl. In partic- ular, R 23 is hydrogen or C 1 -C 4 -alkyl. R 24 is selected from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 3 -C 6 -cycloalkyl. In particular, R 24 is C 1 -C 4 -alkyl.
R 25 is selected from C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkoxy-C 1 -C 6 -al- kyl, phenyl, phenyl-C 1 -C 6 -alkyl, heteroaryl, heteroaryl-C 1 -C 6 -alkyl
, heterocyclyl, heterocyclyl-C 1 -C 6 -alkyl, phenyl-0-C 1 -C 6 -alkyl, heteroaryl-0-C 1 -C 6 -alkyl, hetero- cyclyl-0-C 1 -C 6 -alkyl, where the 9 aforementioned radicals are substituted by s residues selected from the group consisting of nitro, halogen,C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C(O)OR 23 , C(O)N(R 23 ) 2 , OR 23 , N(R 23 ) 2 , S(O) n R 24 and R 23 0-C r C 6 -alkyl, and where heterocyclyl bears 0, 1 or 2 oxo groups.
More preferably R 25 is selected from C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -al- kyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl, phenyl and phenyl-C 1 -C 2 -alkyl. In particular, R 25 is C 1 -C 4 -alkyl.
R 26 is selected from the group consisting of methyl, ethyl and methoxyethyl.
R 27 is selected from the group consisting of hydrogen, cyano and trifluoroacetyl.
R 28 is ethyl and R 29 is ethyl, or R 28 and R 29 together are -(CH 2 ) 5 - or -(CH 2 )2-0-(CH 2 )2-. s is 0, 1 , 2 or 3. In one particular embodiment of the invention, s is 0. In another particular embodiment of the invention, s is 1 , 2 or 3.
t is 0 or 1. In one particular embodiment of the invention, t is 0. In another particular em- bodiment of the invention, t is 1.
Particularly preferred are compounds of formula I, wherein the variables R 1 and R 3 have the following meanings:
R 1 is selected from the group consisting of halogen, nitro, C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 - C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 - alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio and C 1 -C 4 -alkylsulfonyl; and R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 -
C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio and C 1 -
C 4 -alkylsulfonyl.
Especially preferred are compounds of formula I, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of halogen, nitro, cyclopropyl, C 1 -C 4 -alkyl, C 1 - C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and C 1 - C 4 -alkyl-S(O) 2 ;
R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - with R 2c and R 2d independently of each other selected from the group consisting of
hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkyl, C 1 - C 6 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -S(O) n -C 1 -C 4 -alkyl, C 1 -C 4 -alkamino-C 1 -C 4 -alkyl, C 1 -C 4 -dialkamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl and benzyl
R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 - C 4 -haloalkyl and C 1 -C 4 -alkyl-S(O) 2 ;
R 4 is selected from the group consisting of hydrogen, cyano, methyl and halogen; R 5 is selected from the group consisting of halogen, CHF2 and CF3;
R 6 is selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl.
Also especially preferred are compounds of formula I, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of halogen, nitro, cyclopropyl, C 1 -C 4 -alkyl, C 1 - C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 - alkyl and C 1 -C 4 -alkyl-S(O) 2 ;
R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - with R 2c and R 2d independently of each other selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -al- kyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubsti- tuted or partially or completely halogenated, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy ,C 2 -C 6 - alkenyl, C 1 -C 4 -alkyl-C 2 -C 6 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C1-C 4 -S(O)n-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino-C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino-C 1 -C 4 -alkyl, C 1 -C 6 -cyanoalkyl, phe- nyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6-membered monocyclic satu- rated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroa- toms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, CI-C 4 - alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 -
C 4 -haloalkyl and C 1 -C 4 -alkyl-S(O) 2 ;
R 4 is selected from the group consisting of hydrogen, cyano, methyl and halogen;
R 5 is selected from the group consisting of halogen, CHF2 and CF3;
R 6 is selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl.
Also especially preferred are compounds of formula I, where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy;
R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - with R 2c and R 2d independently of each other selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6- membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1- C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R 3 is selected from the group consisting of hydrogen, halogen, C 1 -C 4 -haloalkyl;
R 4 is selected from the group consisting of hydrogen;
R 5 is selected from the group consisting of halogen;
R 6 is selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl. Specifically preferred are compounds of formula I , where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of chlorine, methyl, methoxy;
R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - with R 2c and R 2d independently of each other selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, where the C 3 -C 7 -cycloalkyl groups in the two aforementioned radicals are unsubstituted or par- tially or completely halogenated, phenyl, benzyl and heterocyclyl, where heterocyclyl is a 5- or 6- membered monocyclic saturated, partially unsaturated or aromatic heterocycle, which contains 1 , 2, 3 or 4 heteroatoms as ring members, which are selected from the group consisting of O, N and S, where phenyl, benzyl and heterocyclyl are unsubstituted or substituted by 1 , 2, 3 or 4 groups, which are identical or different and selected from the group consisting of halogen, C1- C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R 3 is selected from the group consisting of hydrogen, chlorine, bromine, trifluoromethyl and methoxyphenyl;
R 4 is selected from the group consisting of hydrogen;
R 5 is selected from the group consisting of fluorine;
R 6 is selected from the group consisting of methyl, ethyl, methoxyethyl and ethoxymethyl.
Specifically preferred are compounds of formula I , where the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of chlorine, nitro, methyl, cyclopropyl, trifluorome ¬ thyl, methoxymethyl, CH2OCH2CH2OCH3 and methylsulfonyl;
R 2 is R 2c R 2d NC(O)NR 2c -Z 2 - with R 2c and R 2d independently of each other selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkyl, C 1 C 6 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl
R 3 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, ni- tro, methyl, trifluoromethyl and methylsulfonyl;
R 4 is selected from the group consisting of hydrogen, cyano, methyl, chlorine and fluorine;
R 5 is selected from the group consisting of chlorine and fluorine;
R 6 is selected from the group consisting of methyl, ethyl, propyl, methoxymethyl, methoxy- ethyl and ethoxymethyl.
Especially preferred are compounds of formula I , where the variables R 1 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of halogen, nitro, cyclopropyl, C 1 -C 4 -alkyl, C 1 -C 4 - haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and C 1 -C 4 - alkyl-S(O) 2 ;
R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 -
C 4 -haloalkyl and C r C 4 -alkyl-S(O) 2 ;
R 4 is selected from the group consisting of hydrogen, cyano, methyl and halogen;
R 5 is selected from the group consisting of halogen, CHF2 and CF3;
R 6 is selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl. Especially preferred are compounds of formula I, where the variables R 1 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of chlorine, nitro, methyl, cyclopropyl, trifluorome- thyl, methoxymethyl, CH2OCH2CH2OCH3 and methylsulfonyl;
R 3 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl and methylsulfonyl;
R 4 is selected from the group consisting of hydrogen, cyano, methyl, chlorine and fluorine; R 5 is selected from the group consisting of chlorine and fluorine;
R 6 is selected from the group consisting of methyl, ethyl, propyl, methoxymethyl, methoxy- ethyl and ethoxymethyl.
Specifically preferred are compounds of formula I, where the variables R 1 , R 3 , R 4 , R 5 and R 6 have the following meanings:
R 1 is selected from the group consisting of chlorine, nitro, methyl, cyclopropyl, trifluoro- methyl, methoxymethyl, CH2OCH2CH2OCH3 and methylsulfonyl;
R 3 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl and methylsulfonyl;
R 4 is selected from the group consisting of hydrogen, cyano, methyl, chlorine and fluo- rine;
R 5 is selected from the group consisting of chlorine and fluorine;
R 6 is selected from the group consisting of methyl, ethyl, propyl, methoxymethyl, meth- oxyethyl and ethoxymethyl.
Examples of preferred compounds I.A, wherein Q is Q 1 and R 4 is H, are the individual com- pounds compiled in Tables 1 to 20 below. Moreover, the meanings mentioned below for the in- dividual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly in question.
Table 1 Compounds of formula I.A (I.A-1.1 - I.A-1 .288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 2 Compounds of formula I.A (I.A-2.1 - I.A-2.288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 3 Compounds of formula I.A (I.A-3.1 - I.A-3.288) in which R 2 is MeEtNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 4 Compounds of formula I .A (I.A-4.1 - I.A-4.288) in which R 2 is MeEtNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 5 Compounds of formula I .A (I.A-5.1 - I.A-5.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 6 Compounds of formula I .A (I.A-6.1 - I.A-6.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 7 Compounds of formula I .A (I.A-7.1 - I.A-7.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 8 Compounds of formula I .A (I.A-8.1 - I.A-8.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 9 Compounds of formula I .A (I.A-9.1 - I.A-9.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 10 Compounds of formula I .A (I.A-10.1 - I.A-10.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 1 1 Compounds of formula I .A (I.A-1 1 .1 - I.A-1 1.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 12 Compounds of formula I .A (I.A-12.1 - I.A-12.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 13 Compounds of formula I .A (I.A-13.1 - I.A-13.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 14 Compounds of formula I .A (I.A-14.1 - I.A-14.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 15 Compounds of formula I .A (I.A-15.1 - I.A-15.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 16 Compounds of formula I .A (I.A-16.1 - I.A-16.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 17 Compounds of formula I .A (I.A-17.1 - I.A-17.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 18 Compounds of formula I .A (I.A-18.1 - I.A-18.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 19 Compounds of formula I .A (I.A-19.1 - I.A-19.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 20 Compounds of formula I .A (I.A-20.1 - I.A-20.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table A
Examples of preferred compounds I.B, wherein Q is Q 2 and R 4 is H, are the individual com- pounds compiled in Tables 21 to 40 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 21 Compounds of formula I.B (I.B-1.1 - I.B-1 .288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 22 Compounds of formula I.B (I.B-2.1 - I.B-2.288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 23 Compounds of formula I.B (I.B-3.1 - I.B-3.288) in which R 2 is MeEtNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 24 Compounds of formula I.B (I.B-4.1 - I.B-4.288) in which R 2 is MeEtNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 25 Compounds of formula I.B (I.B-5.1 - I.B-5.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 26 Compounds of formula I.B (I.B-6.1 - I.B-6.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 27 Compounds of formula I.B (I.B-7.1 - I.B-7.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 28 Compounds of formula I.B (I.B-8.1 - I.B-8.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 29 Compounds of formula I.B (I.B-9.1 - I.B-9.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 30 Compounds of formula I.B (I.B-10.1 - I.B-10.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 31 Compounds of formula I.B (I.B-1 1 .1 - I.B-1 1.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 32 Compounds of formula I.B (I.B-12.1 - I.B-12.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 33 Compounds of formula I.B (I.B-13.1 - I.B-13.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 34 Compounds of formula I.B (I.B-14.1 - I.B-14.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 35 Compounds of formula I.B (I.B-15.1 - I.B-15.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 36 Compounds of formula I.B (I.B-16.1 - I.B-16.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 37 Compounds of formula I.B (I.B-17.1 - I.B-17.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 38 Compounds of formula I.B (I.B-18.1 - I.B-18.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 39 Compounds of formula I.B (I.B-19.1 - I.B-19.288) in which R 2 is (Et)cPrNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 40 Compounds of formula I.B (I.B-20.1 - I.B-20.288) in which R 2 is (Et)cPrNC(O)NH - and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Examples of preferred compounds I.C, wherein Q is Q 3 and R 4 is H, are the individual compounds compiled in Tables 41 to 60 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 41 Compounds of formula I.C (I.C-1.1 - I.C-1.288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 42 Compounds of formula I.C (I.C-2.1 - I.C-2.288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 43 Compounds of formula I.C (I.C-3.1 - I.C-3.288) in which R 2 is MeEtNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 44 Compounds of formula I.C (I.C-4.1 - I.C-4.288) in which R 2 is MeEtNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 45 Compounds of formula I.C (I.C-5.1 - I.C-5.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 46 Compounds of formula I.C (I.C-6.1 - I.C-6.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 47 Compounds of formula I.C (I.C-7.1 - I.C-7.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 48 Compounds of formula I.C (I.C-8.1 - I.C-8.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 49 Compounds of formula I.C (I.C-9.1 - I.C-9.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 50 Compounds of formula I.C (I.C-10.1 - I.C-10.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 51 Compounds of formula I.C (I.C-1 1 .1 - I.C-1 1.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 52 Compounds of formula I.C (I.C-12.1 - I.C-12.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 53 Compounds of formula I.C (I.C-13.1 - I.C-13.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 54 Compounds of formula I.C (I.C-14.1 - I.C-14.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 55 Compounds of formula I.C (I.C-15.1 - I.C-15.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 56 Compounds of formula I.C (I.C-16.1 - I.C-16.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 57 Compounds of formula I.C (I.C-17.1 - I.C-17.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 58 Compounds of formula I.C (I.C-18.1 - I.C-18.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 59 Compounds of formula I.C (I.C-19.1 - I.C-19.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 60 Compounds of formula I.C (I.C-20.1 - I.C-20.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Examples of preferred compounds I.D, wherein Q is Q 4 and R 4 is H, are the individual com- pounds compiled in Tables 61 to 80 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 61 Compounds of formula I.D (I.A-1 .1 - I.D-1 .288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 62 Compounds of formula I.D (I.A-2.1 - I.D-2.288) in which R 2 is (Me) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 63 Compounds of formula I.D (I.A-3.1 - I.D-3.288) in which R 2 is MeEtNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 64 Compounds of formula I.D (I.D-4.1 - I.D-4.288) in which R 2 is MeEtNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 65 Compounds of formula I.D (I.D-5.1 - I.D-5.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 66 Compounds of formula I.D (I.D-6.1 - I.D-6.288) in which R 2 is (Me)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 67 Compounds of formula I.D (I.D-7.1 - I.D-7.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 68 Compounds of formula I.D (I.D-8.1 - I.D-8.288) in which R 2 is (Me)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 69 Compounds of formula I.D (I.D-9.1 - I.D-9.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 70 Compounds of formula I.D (I.D-10.1 - I.D-10.288) in which R 2 is (Me)(CH 3 OCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 71 Compounds of formula I.D (I.D-1 1 .1 - I.D-1 1.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 72 Compounds of formula I.D (I.D-12.1 - I.D-12.288) in which R 2 is (Me)(CH 3 SCH 2 CH 2 - )NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 73 Compounds of formula I.D (I.D-13.1 - I.D-13.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 74 Compounds of formula I.D (I.D-14.1 - I.D-14.288) in which R 2 is (N-morpho- lino)NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 75 Compounds of formula I.D (I.D-15.1 - I.D-15.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 76 Compounds of formula I.D (I.D-16.1 - I.D-16.288) in which R 2 is (Et) 2 NC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 77 Compounds of formula I.D (I.D-17.1 - I.D-17.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 78 Compounds of formula I.D (I.D-18.1 - I.D-18.288) in which R 2 is (Et)iPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 79 Compounds of formula I.D (I.D-19.1 - I.D-19.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 80 Compounds of formula I.D (I.D-20.1 - I.D-20.288) in which R 2 is (Et)cPrNC(O)NH- and R 5 is CI and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Further examples of preferred compounds I.A, wherein Q is Q 1 and R 4 is H, are the individual compounds compiled in Tables 81 to 87 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 81 Compounds of formula I.A (I.A-81 .1 - I.A-81.288) in which R 2 is (iPr)cPrNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 82 Compounds of formula I.A (I.A-82.1 - I.A-82.288) in which R 2 is (cPr) 2 NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 83 Compounds of formula I.A (I.A-83.1 - I.A-83.288) in which R 2 is (Me)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 84 Compounds of formula I.A (I.A-84.1 - I.A-84.288) in which R 2 is (Et)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 85 Compounds of formula I.A (I.A-85.1 - I.A-85.288) in which R 2 is (iPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 86 Compounds of formula I.A (I.A-86.1 - I.A-86.288) in which R 2 is (nPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 87 Compounds of formula I.A (I.A-87.1 - I.A-87.288) in which R 2 is (Me)(4-CI- Ph)NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Further examples of preferred compounds I.B, wherein Q is Q 2 and R 4 is H, are the individual compounds compiled in Tables 88 to 94 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 88 Compounds of formula I.B (I.B-88.1 - I.B-88.288) in which R 2 is (iPr)cPrNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 89 Compounds of formula I.B (I.B-89.1 - I.B-89.288) in which R 2 is (cPr) 2 NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 90 Compounds of formula I.B (I.B-90.1 - I.B-90.288) in which R 2 is (Me)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 91 Compounds of formula I.B (I.B-91 .1 - I.B-91.288) in which R 2 is (Et)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 92 Compounds of formula I.B (I.B-92.1 - I.B-92.288) in which R 2 is (iPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 93 Compounds of formula I.B (I.B-93.1 - I.B-93.288) in which R 2 is (nPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 94 Compounds of formula I.B (I.B-94.1 - I.B-94.288) in which R 2 is (Me)(4-CI- Ph)NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Further examples of preferred compounds I.C, wherein Q is Q 3 and R 4 is H, are the individual compounds compiled in Tables 95 to 101 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 95 Compounds of formula I.C (I.C-95.1 - I.C-95.288) in which R 2 is (iPr)cPrNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 96 Compounds of formula I.C (I.C-96.1 - I.C-96.288) in which R 2 is (cPr) 2 NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 97 Compounds of formula I.C (I.C-97.1 - I.C-97.288) in which R 2 is (Me)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 98 Compounds of formula I.C (I.C-98.1 - I.C-98.288) in which R 2 is (Et)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 99 Compounds of formula I.C (I.C-99.1 - I.C-99.288) in which R 2 is (iPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 100 Compounds of formula I.C (I.C-100.1 - I.C-100.288) in which R 2 is (nPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 101 Compounds of formula I.C (I.C-101.1 - I.C-101 .288) in which R 2 is (Me)(4-CI- Ph)NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Further examples of preferred compounds I.D, wherein Q is Q 4 and R 4 is H, are the individual compounds compiled in Tables 102 to 108 below. Moreover, the meanings mentioned below for the individual variables in the Tables are, per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 102 Compounds of formula I.D (I.D-102.1 - I.D-102.288) in which R 2 is (iPr)cPrNC(O)NH
- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 103 Compounds of formula I.D (I.D-103.1 - I.D-103.288) in which R 2 is (cPr) 2 NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 104 Compounds of formula I.D (I.D-104.1 - I.D-104.288) in which R 2 is (Me)PhNC(O)NH
- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 105 Compounds of formula I.D (I.D-105.1 - I.D-105.288) in which R 2 is (Et)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 106 Compounds of formula I.D (I.D-106.1 - I.D-106.288) in which R 2 is (iPr)PhNC(O)NH
- and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A; Table 107 Compounds of formula I.D (I.D-107.1 - I.D-107.288) in which R 2 is (nPr)PhNC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
Table 108 Compounds of formula I.D (I.D-108.1 - I.D-108.288) in which R 2 is (Me)(4-CI- Ph)NC(O)NH - and R 5 is F and the combination of R 1 , R 3 and R 6 for a compound corresponds in each case to one row of Table A;
The compounds of formula I can be prepared by standard methods of organic chemistry, e.g. by the methods described in schemes 1 to 15. The substituents, variables and indices used in schemes 1 to 15 are as defined above for the compounds of formula I, if not specified other- wise.
The compounds of formula l.A can be prepared analogous to Scheme 1 below.
Scheme 1 :
Likewise, the compounds of formula I.B can be prepared analogous to Scheme 2 below: Scheme 2:
Likewise, the compounds of formula I.C can be prepared analogous to Scheme 3 below: Scheme 3:
5-Amino-1-R-tetrazole compounds of formula III can be reacted with benzoyl derivatives of formula II to afford compounds of formula l.A. Likewise, 5-amino-1-R-1 ,2,4-triazole of formula IV can be reacted with benzoyl derivatives of formula II to afford compounds of formula I.B. Likewise, 4-amino-1 ,2,5-oxadiazole compounds of formula V can be reacted with benzoyl deriv- atives of formula II to afford compounds of the formula I.C. Herein, X is a leaving group, such as halogen, in particular CI, an anhydride residue or an active ester residue. Especially in case of X being halogen the reaction is suitably carried out in the presence of a base. Suitable bases are for example carbonates, such as lithium, sodium or potassium carbonates, amines, such as tri- methylamine or triethylamine, and basic N-heterocycles, such as pyridine, 2,6-dimethylpyridine or 2,4,6-trimethylpyridine. Suitable solvents are in particular aprotic solvents such as pentane, hexane, heptane, octane, cyclohexane, dichloromethane, chloroform, 1 ,2-dichlorethane, ben- zene, chlorobenzene, toluene, the xylenes, dichlorobenzene, trimethylbenzene, pyridine, 2,6- dimethylpyridine, 2,4,6-trimethylpyridine, acetonitrile, diethyl ether, tetrahydrofuran, 2-methyl tet- rahydrofuran, methyl tert-butylether, 1 ,4-dioxane, Ν,Ν-dimethyl formamide, N-methyl pyrroli- dinone or mixtures thereof. The starting materials are generally reacted with one another in equimolar or nearly equimolar amounts at a reaction temperature usually in the range of -20°C to 100°C and preferably in the range of -5°C to 50°C.
Alternatively, compounds of formula I can also be prepared as shown in Schemes 4, 5 and 6. Reaction of 5-amino-1-R-tetrazole of formula III with a benzoic acid derivative of formula VI yields compound I. A. Likewise, reaction of 5-amino-1 -R-1 ,2,4-triazole of formula IV with a benzoic acid derivative of formula VI yields compound I.B. Likeweise, reaction of a 4-amino- 1 ,2,5-oxadiazole compound V with a benzoic acid derivative of formula VI yields compound I.C. The reaction is preferably carried out in the presence of a suitable activating agent, which con- verts the acid group of compound VI into an activated ester or amide. For this purpose activat- ing agents known in the art, such as 1 ,1 ',carbonyldiimidazole (CDI), dicyclohexyl carbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 2,4,6-tripropyl-1 , 3,5,2,4, 6-triox- atriphosphorinane-2,4,6-trioxide (T3P) can be employed. The activated ester or amide can be formed, depending in particular on the specific activating agent used, either in situ by contacting compound V with the activating agent in the presence of compound III or IV, or in a separate step prior to the reaction with compound III or IV. It may be advantageous, especially in cases where DCC or EDC are used as activating agent, to include further additives in the activating reaction, such as hydroxybenzotriazole (HOBt), nitrophenol, pentafluorophenol, 2,4,5-trichloro- phenol or N-hydroxysuccinimide. It may further be advantageous to prepare the activated ester or amide in the presence of a base, for example a tertiary amine. The activated ester or amide is either in situ or subsequently reacted with the amine of formula III or IV to afford the amide of formula I. The reaction normally takes place in anhydrous inert solvents, such as chlorinated hy- drocarbons, e.g. dichloromethane or dichloroethane, ethers, e.g. tetrahydrofuran or 1 ,4-dioxane or carboxamides, e.g. N,N-dimethylformamide, Ν,Ν-dimethylacetamide or N-methylpyrrolidone. The reaction is ordinarily carried out at temperatures in the range from -20°C to +25°C.
Scheme 4:
Furthermore, compounds of formula I . A, can be obtained by treating N-(1 H-tetrazol-5- yl)benzamides of formula VII and compounds of formula I .B, can be obtained by treating N-(1 H- 1 ,2,4-triazol-5-yl)benzamides of formula VI I I with, for example, alkylating agents such as alkyl halides according to Schemes 7 and 8.
Scheme 7:
The 5-amino-1 -R-tetrazoles of formula I I I, where R 6 is, for example, hydrogen or an alkyl, are either commercially available or are obtainable according to methods known from the literature. For example, 5-amino-1 -R-tetrazole can be prepared from 5-aminotetrazole according to the method described in the Journal of the American Chemical Society, 1954, 76, 923-924 (Scheme 9).
Scheme 9:
Alternatively, 5-amino-1-R-tetrazole compounds of formula III can be prepared according to the method described in the Journal of the American Chemical Society, 1954, 76, 88-89 (Scheme 10).
Scheme 10:
(III)
As shown in Scheme 1 1 , 5-amino-1 -R-triazoles of formula IV are either commercially available or are obtainable according to methods described in the literature. For example, 5- amino-1-R-triazole can be prepared from 5-aminotriazole according to the method described Zeitschrift fiir Chemie, 1990, 30, 12, 436-437.
Scheme 1 1 :
Alternatively, 5-amino-1-R-triazole compounds of formula IV, can also be prepared analo- gous to the synthesis described in Chemische Berichte, 1964, 97, 2, 396-404, as shown in Scheme 12.
Scheme 12:
The compounds of formulae III, IV and V and the benzoic acid precursors of formulae II and V can be obtained by purchase or can be prepared by processes known in the art or dis- closed in the literature, e.g. in WO 9746530, WO 9831676, WO 9831681 , WO 2002/018352, WO 2000/003988, US 2007/0191335, US 6277847.
The 4-amino-1 ,2,5-oxadiazole compounds of the formula V are either commercially availa- ble or are obtainable according to methods known from the literature. For example, 3-alkyl-4- amino-1 ,2,5-oxadiazoles can be prepared from β-ketoesters pursuant to a procedure described in Russian Chemical Bulletin, Int. Ed., 54(4), 1032-1037 (2005), as depicted in Scheme 13. Scheme 13:
(V)
As shown in Scheme 14, the compounds of the formula V, where R 6 is halogen, can be prepared from commercially available 3,4-diamino-1 ,2,5-oxadiazole according to procedures described in the literature, e.g. by the Sandmeyer-type reaction disclosed in Heteroatom Chem- istry, 15(3), 199-207 (2004). Scheme 14:
As shown in Scheme 15, the compounds of the formula V, where R 6 is a nucleophilic resi- due, can be prepared by introducing the nucleophilic residue via the substitution of a leaving group L, e.g. halogene, in the 4-position of the 1 ,2,5-oxadiazoles compounds of formula IX in accordance to precedures disclosed, for example in Journal of Chemical Research, Synopses (6), 190 (1985), in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (9), 2086-8 (1986) or in Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya), 53(3), 596-614 (2004).
Scheme 15:
As a rule, the compounds of formula I including their stereoisomers, salts, tautomers and N-oxides, and their precursors in the synthesis process, can be prepared by the methods de- scribed above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of for- mula I by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, ole- fination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatog- raphy, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystalliza- tion or trituration.
The present invention also relates to a composition comprising at least one compound of formula I, an N-oxide or an agriculturally suitable salt thereof and at least one auxiliary, which is customary for formulating crop protection compounds.
The invention also relates to the use of a compound of formula I, an N-oxide or an agriculturally suitable salt thereof or a composition of the present invention for controlling unwanted vegetation.
The invention also relates to a method for controlling unwanted vegetation, which comprises allowing a herbicidally effective amount of at least one compound of formula I, an N- oxide or an agriculturally suitable salt thereof or a composition of the present invention to act on plants, their seed and/or their habitat.
The compounds of formula I and their agriculturally suitable salts are useful as herbicides. They are useful as such or as an appropriately formulated composition. The herbicidal composi- tions comprising the compound I, in particular the preferred aspects thereof, control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and weed grasses in crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
Depending on the application method in question, the compounds of formula I, in particu- lar the preferred aspects thereof, or compositions comprising them can additionally be em- ployed in a further number of crop plants for eliminating unwanted plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec, altissima, Beta vulgaris spec, rapa, Brassica napus var. napus, Brassica na- pus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossy- pium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vul- gare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Ni- cotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vul- garis, Picea abies, Pinus spec, Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Sola- num tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
The term "crop plants" also includes plants which have been modified by breeding, muta- genesis or genetic engineering. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mu- tations or natural recombination (i.e. reassembly of the genetic information). Here, in general, one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.
Accordingly, the term "crop plants" also includes plants which, by breeding and genetic engineering, have acquired tolerance to certain classes of herbicides, such as hydroxy- phenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as, for example, sulfonylureas (EP-A-0257993, US 5,013,659) or imidazolinones (see, for example, US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, such as, for example, glypho- sate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors, such as, for exam- ple, glufosinate (see, for example, EP-A-0242236, EP-A-242246), or oxynil herbicides (see, for example, US 5,559,024). Numerous crop plants, for example Clearfield® oilseed rape, tolerant to imidazolinones, for example imazamox, have been generated with the aid of classic breeding methods (muta- genesis). Crop plants such as soybeans, cotton, corn, beet and oilseed rape, resistant to glyphosate or glufosinate, which are available under the tradenames RoundupReady ® (glypho- sate) and Liberty Link ® (glufosinate) have been generated with the aid of genetic engineering methods.
Accordingly, the term "crop plants" also includes plants which, with the aid of genetic engi- neering, produce one or more toxins, for example those of the bacterial strain Bacillus ssp. Tox- ins which are produced by such genetically modified plants include, for example, insecticidal proteins of Bacillus spp., in particular B. thuringiensis, such as the endotoxins CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetative insec- ticidal proteins (VIPs), for example VIP1 , VIP2, VIP3, or VIP3A; insecticidal proteins of nema- tode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins of animal organisms, for example wasp, spider or scorpion toxins; fungal toxins, for example from Strepto- mycetes; plant lectins, for example from peas or barley; agglutinins; proteinase inhibitors, for ex- ample trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors, ribo- some-inactivating proteins (RIPs), for example ricin, corn-RIP, abrin, luffin, saporin or bryodin; steroid-metabolizing enzymes, for example 3-hydroxysteroid oxidase, ecdysteroid-IDP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blockers, for example inhibitors of sodium channels or calcium channels; juvenile hormone es- terase; receptors of the diuretic hormone (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the plants, these toxins may also be produced as pre- toxins, hybrid proteins or truncated or otherwise modified proteins. Hybrid proteins are charac- terized by a novel combination of different protein domains (see, for example, WO
2002/015701 ). Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP- A 451 878, WO 03/018810 and WO 03/052073. The methods for producing these genetically modified plants are known to the person skilled in the art and disclosed, for example, in the pub- lications mentioned above. Numerous of the toxins mentioned above bestow, upon the plants by which they are produced, tolerance to pests from all taxonomic classes of arthropods, in par- ticular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera) and to nema- todes (Nematoda).
Genetically modified plants which produce one or more genes coding for insecticidal tox- ins are described, for example, in the publications mentioned above, and some of them are commercially available, such as, for example, YieldGard ® (corn varieties producing the toxin CrylAb), YieldGard ® Plus (corn varieties which produce the toxins CrylAb and Cry3Bb1 ), Star- link ® (corn varieties which produce the toxin Cry9c), Herculex ® RW (corn varieties which pro- duce the toxins Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN ® 33B (cotton varieties which produce the toxin CrylAc), Bollgard ® I (cotton va- rieties which produce the toxin CrylAc), Bollgard ® II (cotton varieties which produce the toxins CrylAc and Cry2Ab2); VIPCOT ® (cotton varieties which produce a VIP toxin); NewLeaf ® (potato varieties which produce the toxin Cry3A); Bt-Xtra ® , NatureGard ® , KnockOut ® , BiteGard ® , Pro- tecta ® , Bt1 1 (for example Agrisure ® CB) and Bt176 from Syngenta Seeds SAS, France (corn va- rieties which produce the toxin CrylAb and the PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn varieties which produce a modified version of the toxin Cry3A, see
WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn varieties which produce the toxin Cry3Bb1 ), IPC 531 from Monsanto Europe S.A., Belgium (cotton varieties which pro- duce a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Bel- gium (corn varieties which produce the toxin Cryl F and the PAT enzyme).
Accordingly, the term "crop plants" also includes plants which, with the aid of genetic engi- neering, produce one or more proteins which are more robust or have increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis-related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties producing two resistance genes against Phytophthora /nfestans from the wild Mexican potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).
Accordingly, the term "crop plants" also includes plants whose productivity has been im- proved with the aid of genetic engineering methods, for example by enhancing the potential yield (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral path- ogens.
The term "crop plants" also includes plants whose ingredients have been modified with the aid of genetic engineering methods in particular for improving human or animal diet, for ex- ample by oil plants producing health-promoting long-chain omega 3 fatty acids or monounsatu- rated omega 9 fatty acids (for example Nexera ® oilseed rape).
The term "crop plants" also includes plants which have been modified with the aid of ge- netic engineering methods for improving the production of raw materials, for example by in- creasing the amylopectin content of potatoes (Amflora ® potato).
Furthermore, it has been found that the compounds of formula I are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable. In this regard, there have been found compositions for the desiccation and/or defoliation of plants, processes for preparing these compositions and methods for desiccating and/or defoliating plants using the compounds of formula I.
As desiccants, the compounds of formula I are particularly suitable for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.
Also of economic interest is to facilitate harvesting, which is made possible by
concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pomaceous fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the readily controllable defoliation of useful plants, in particular cotton.
Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.
The compounds of formula I, or the herbicidal compositions comprising the compounds of formula I, can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed. The use forms depend on the intended purpose; in each case, they should ensure the finest possible distribution of the active ingredients according to the invention.
The herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I, and auxiliaries which are customary for the formulation of crop protection agents.
Examples of auxiliaries customary for the formulation of crop protection agents are inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, if appropriate colorants and, for seed formulations, adhesives.
Examples of thickeners (i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion) are
polysaccharides, such as xanthan gum (KelzanO from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), and also organic and inorganic sheet minerals, such as Attaclay® (from Engelhardt).
Examples of antifoams are silicone emulsions (such as, for example, Silikon ® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
Bactericides can be added for stabilizing the aqueous herbicidal formulation. Examples of bactericides are bactericides based on diclorophen and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas), and also isothiazolinone derivates, such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).
Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol. Examples of colorants are both sparingly water-soluble pigments and water-soluble dyes.
Examples which may be mentioned are the dyes known under the names Rhodamin B, C.I.
Pigment Red 1 12 and C.I. Solvent Red 1 , and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
Suitable inert auxiliaries are, for example, the following:
mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone, and water.
Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants and also
emulsifiers) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g. Borrespers-types, Borregaard),
phenolsulfonic acids, naphthalenesulfonic acids (Morwet types, Akzo Nobel) and
dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, Lupamine types), polyethyleneimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.
Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the compounds of formula I or la, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
The concentrations of the compounds of formula I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The formulations or ready-to-use preparations may also comprise acids, bases or buffer systems, suitable examples being phosphoric acid or sulfuric acid, or urea or ammonia.
The compounds of formula I of the invention can for example be formulated as follows: 1 . Products for dilution with water
A. Water-soluble concentrates
10 parts by weight of active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active com- pound dissolves upon dilution with water. This gives a formulation with an active compound content of 10% by weight.
B. Dispersible concentrates
20 parts by weight of active compound are dissolved in 70 parts by weight of cyclohexa- none with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilu- tion with water gives a dispersion. The active compound content is 20% by weight.
C. Emulsifiable concentrates
15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formula- tion has an active compound content of 15% by weight.
D. Emulsions
25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier (e.g. Ultraturrax) and made into a homogeneous emulsion. Di- lution with water gives an emulsion. The formulation has an active compound content of 25% by weight.
E. Suspensions
In an agitated ball mill, 20 parts by weight of active compound are comminuted with addi- tion of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an or- ganic solvent to give a fine active compound suspension. Dilution with water gives a stable sus- pension of the active compound. The active compound content in the formulation is 20% by weight.
F. Water-dispersible granules and water-soluble granules
50 parts by weight of active compound are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an ac- tive compound content of 50% by weight.
G. Water-dispersible powders and water-soluble powders
75 parts by weight of active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable disper- sion or solution of the active compound. The active compound content of the formulation is 75% by weight.
H. Gel formulations In a ball mill, 20 parts by weight of active compound, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are ground to give a fine suspension. Dilution with water gives a stable suspension with active com- pound content of 20% by weight.
2. Products to be applied undiluted
I. Dusts
5 parts by weight of active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dusting powder with an active compound content of 5% by weight.
J. Granules (GR, FG, GG, MG)
0.5 parts by weight of active compound are ground finely and associated with 99.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight. K. ULV solutions (UL)
10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active com- pound content of 10% by weight.
The compounds of formula I or the herbicidal compositions comprising them can be applied pre- or post-emergence, or together with the seed of a crop plant. It is also possible to apply the herbicidal compositions or active compounds by applying seed, pretreated with the herbicidal compositions or active compounds, of a crop plant. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
In a further embodiment, the compounds of formula I or the herbicidal compositions can be applied by treating seed.
The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multi- layer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of formula I according to the invention or the compositions prepared therefrom. Here, the herbicidal compositions can be applied diluted or undiluted.
The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tu- bers, cuttings and similar forms. Here, preferably, the term seed describes corns and seeds.
The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
The rates of application of active compound are from 0.001 to 3.0, preferably 0.01 to 1 .0, kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage. To treat the seed, the compounds of formula I are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
It may also be advantageous to use the compounds of formula I in combination with saf- eners. Safeners are chemical compounds which prevent or reduce damage to useful plants without substantially affecting the herbicidal action of the compounds of formula I on unwanted plants. They can be used both before sowing (for example in the treatment of seed, or on cut- tings or seedlings) and before or after the emergence of the useful plant. The safeners and the compounds of formula I can be used simultaneously or in succession.
Suitable safeners are, for example, (quinolin-8-oxy)acetic acids, 1 -phenyl-5-haloalkyl-1 H-
1 ,2,4-triazole-3-carboxylic acids, 1 -phenyl-4,5-dihydro-5-alkyl-1 A -pyrazole-3,5-dicarboxylic ac- ids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophe- nylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocar- bonyl)phenyl]sulfonyl]-2-benzamides, 1 ,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazole- carboxylic acids, phosphorothiolates and O-phenyl N-alkylcarbamates and their agriculturally useful salts and, provided that they have an acid function, their agriculturally useful derivatives, such as amides, esters and thioesters.
To broaden the activity spectrum and to obtain synergistic effects, the compounds of the formula I can be mixed and jointly applied with numerous representatives of other herbicidal or growth-regulating groups of active compounds or with safeners. Suitable mixing partners are, for example, 1 ,2,4-thiadiazoles, 1 ,3,4-thiadiazoles, amides, aminophosphoric acid and its deriv- atives, aminotriazoles, anilides, aryloxy/heteroaryloxyalkanoic acids and their derivatives, ben- zoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1 ,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivates, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofu- ran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahy- drophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyra- zoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and their derivatives.
Moreover, it may be useful to apply the compounds of formula I alone or in combination with other herbicides or else also mixed with further crop protection agents, jointly, for example with compositions for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for alleviating nutritional and trace element deficiencies. Other additives such as nonphytotoxic oils and oil concentrates may also be added.
Examples of herbicides which can be used in combination with the compounds of formula
I according to the present invention are:
b1 ) from the group of the lipid biosynthesis inhibitors:
alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cy- cloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, halox- yfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
b2) from the group of the ALS inhibitors:
amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-so- dium, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam, cloransulam-me- thyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, fla- zasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyr- sulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imaza- methabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfu- ron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfu- ron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-me- thyl, pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-me- thyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-me- thyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-me- thyl and tritosulfuron;
b3) from the group of the photosynthesis inhibitors:
ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromacil, bromo- fenoxim, bromoxynil and its salts and esters, chlorobromuron, chloridazone, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat- dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isoproturon, isouron, karbutilate, lenacil, linuron, metamitron, methabenzthiazuron, metobenzuron, me- toxuron, metribuzin, monolinuron, neburon, paraquat, paraquat-dichloride, paraquat- dimetilsulfate, pentanochlor, phenmedipham, phenmedipham-ethyl, prometon, prometryn, pro- panil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, ter- bumeton, terbuthylazine, terbutryn, thidiazuron and trietazine;
b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:
acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, bu- tafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluorogly- cofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfen- trazone, thidiazimin, 2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethy l)-1 (2A^-pyrim- idinyl]-4-fluoro-N-[(isopropyl)methylsulfamoyl]benzamide (H-1 ; CAS 372137-35-4), ethyl [3-[2- chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phe- noxy]-2-pyridyloxy]acetate (H-2; CAS 353292-31 -6), N-ethyl-3-(2,6-dichloro-4-trifluoro- methylphenoxy)-5-methyl-1 A/-pyrazole-1-carboxamide (H-3; CAS 452098-92-9), N-tetrahydro- furfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl- 1 A -pyrazole-1-carboxamide (H-4; CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-met hyl-1 pyra- zole-1-carboxamide (H-5; CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluo- romethylphenoxy)-5-methyl-1 A -pyrazole-1 -carboxamide (H-6; CAS 45100-03-7), 3-[7-fluoro-3- oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan- 2,4-dione, 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl )-3,4-dihydro-2H- benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione, 2-(2,2,7-Trifluoro-3-oxo-4-prop-2-ynyl-3,4- dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione and 1 -Methyl-6-trifluo- romethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro- 2H-benzo[1 ,4]oxazin-6-yl)-1 H-pyrimi- dine-2,4-dione;
b5) from the group of the bleacher herbicides:
aclonifen, amitrol, beflubutamid, benzobicyclon, benzofenap, clomazone, diflufenican, flu- ridone, flurochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon, picolinafen, pyrasulfu- tole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 4-hydroxy- 3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridy l]carbonyl]bicyclo[3.2.1 ]oct-3-en-2- one (H-7; CAS 352010-68-5) and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyri mi- dine (H-8; CAS 180608-33-7);
b6) from the group of the EPSP synthase inhibitors:
glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate);
b7) from the group of the glutamine synthase inhibitors:
bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium;
b8) from the group of the DHP synthase inhibitors:
asulam;
b9) from the group of the mitose inhibitors:
amiprophos, amiprophos-methyl, benfluralin, butamiphos, butralin, carbetamide, chlor- propham, chlorthal, chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, propham, propyzamide, tebutam, thiazopyr and trifluralin;
b10) from the group of the VLCFA inhibitors:
acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethanamid, dime- thenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, metolachlor-S, naproanilide, napropamide, pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone (KIH-485) and thenylchlor;
Compounds of the formula 2:
in which the variables have the following meanings:
Y is phenyl or 5- or 6-membered heteroaryl as defined at the outset, which radicals may be substituted by one to three groups R aa ; R A , R B , R c , R D are H, halogen or C 1 -C 4 -alkyl; A is O or NH; q is 0 or 1. According to a preferred embodiment, the one to three groups R aa are identical are different and selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 - C 4 -alkoxy and C 1 -C 4 -haloalkoxy.
Compounds of the formula 2 have in particular the following meanings:
R A is H; R B , R c are F; R D is H or F; A is oxygen; q is 0 or 1.
Particularly preferred compounds of the formula 2 are:
3-[5-(2,2-difluoroethoxy)-1 -methyl-3-trifluoromethyl-1 H-pyrazol-4-ylmethane- sulfonyl]-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-1 ); 3-{[5-(2,2-difluoroethoxy)-1 -methyl-3- trifluoromethyl-1 H-pyrazol-4-yl]fluoromethanesulfonyl}-5,5-dimethyl-4,5-dihyd roisoxazole (2-2); 4-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmeth yl)-2-methyl-5-trifluoromethyl-2H- [1 ,2,3]triazole (2-3); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)fluoromethy l]-2-methyl-5- trifluoromethyl-2H-[1 ,2,3]triazole (2-4); 4-(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmethyl)-2- methyl-5-trifluoromethyl-2H-[1 ,2,3]triazole (2-5); 3-{[5-(2,2-difluoroethoxy)-1 -methyl-3- trifluoromethyl-1 H-pyrazol-4-yl]difluoromethanesulfonyl}-5,5-dimethyl-4,5-dih ydroisoxazole (2-6); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)difluoromet hyl]-2-methyl-5-trifluoromethyl-2H- [1 ,2,3]triazole (2-7); 3-{[5-(2,2-difluoroethoxy)-1 -methyl-3-trifluoromethyl-1 H-pyrazol-4- yl]difluoromethanesulfonyl}-4-fluoro-5,5-dimethyl-4,5-dihydr oisoxazole (2-8); 4-[difluoro-(4- fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)methyl]- 2-methyl-5-trifluoromethyl-2H- [1 ,2,3]triazole (2-9);
b1 1 ) from the group of the cellulose biosynthesis inhibitors:
chlorthiamid, dichlobenil, flupoxam and isoxaben;
b12) from the group of the decoupler herbicides:
dinoseb, dinoterb and DNOC and its salts;
b13) from the group of the auxin herbicides:
2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and es- ters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, MCPA and its salts and esters, MCPA- thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidine- carboxylic acid (H-9; CAS 858956-08-8) and its salts and esters;
b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, nap- talam and naptalam-sodium;
b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dime- thipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flur- primidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxazi- clomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro- 3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (H-10; CAS 499223-49-3) and its salts and esters.
Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfa- mide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furi- lazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1 - oxa-4-azaspiro[4.5]decane (H-1 1 ; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloro- acetyl)-1 ,3-oxazolidine (H-12; R-29148, CAS 52836-31 -4).
The active compounds of groups b1 ) to b15) and the safeners C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names
(http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide
[Herbicides], Georg Thieme Verlag, Stuttgart, 1995. Further herbicidally active compounds are known from WO 96/26202, WO 97/41 1 16, WO 97/41 1 17, WO 97/41 1 18, WO 01/83459 and WO 2008/074991 and from W. Kramer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1 , Wiley VCH, 2007 and the literature quoted therein.
The invention also relates to compositions in the form of a crop protection composition for- mulated as a 1 -component composition comprising an active compound combination compris- ing at least one compound of the formula I and at least one further active compound, preferably selected from the active compounds of groups b1 to b15, and at least one solid or liquid carrier and/or one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.
The invention also relates to compositions in the form of a crop protection composition formu- lated as a 2-component composition comprising a first component comprising at least one com- pound of the formula I, a solid or liquid carrier and/or one or more surfactants and a second component comprising at least one further active compound selected from the active com- pounds of groups b1 to b15, a solid or liquid carrier and/or one or more surfactants, where addi- tionally both components may also comprise further auxiliaries customary for crop protection compositions.
In binary compositions comprising at least one compound of the formula I as component A and at least one herbicide B, the weight ratio of the active compounds A:B is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 . In binary compositions comprising at least one compound of the formula I as component A and at least one safener C, the weight ratio of the active compounds A:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 .
In ternary compositions comprising both at least one compound of the formula I as com- ponent A, at least one herbicide B and at least one safener C, the relative parts by weight of the components A:B are generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 ; the weight ratio of the components A:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 ; and the weight ratio of the components B:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 . Preferably, the weight ratio of the components A + B to the component C is in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 .
Examples of particularly preferred compositions according to the invention comprising in each case one individualized compound of the formula I and one mixing partner or a mixing partner combination are given in Table B below.
A further aspect of the invention relates to the compositions B-1 to B-1236 listed in Table
B below, where in each case one row of Table B corresponds to a herbicidal composition com- prising one of the compounds of formula I individualized in the above description (component 1 ) and the further active compound from groups b1 ) to b15) and/or safener C stated in each case in the row in question (component 2). The active compounds in the compositions described are in each case preferably present in synergistically effective amounts.
The compounds of formula I and the compositions according to the invention may also have a plant-strengthening action. Accordingly, they are suitable for mobilizing the defense sys- tem of the plants against attack by unwanted microorganisms, such as harmful fungi, but also viruses and bacteria. Plant-strengthening (resistance-inducing) substances are to be under- stood as meaning, in the present context, those substances which are capable of stimulating the defense system of treated plants in such a way that, when subsequently inoculated by un- wanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. The compounds of formula I can be employed for protecting plants against attack by un- wanted microorganisms within a certain period of time after the treatment. The period of time within which their protection is effected generally extends from 1 to 28 days, preferably from 1 to 14 days, after the treatment of the plants with the compounds of formula I, or, after treatment of the seed, for up to 9 months after sowing.
The compounds of formula I and the compositions according to the invention are also suit- able for increasing the harvest yield.
Moreover, they have reduced toxicity and are tolerated well by the plants.
The preparation of the compounds of formula I is illustrated by examples; however, the subject matter of the present invention is not limited to the examples given.
I. Synthesis examples
With appropriate modification of the starting materials, the procedures given in the synthesis ex- amples below were used to obtain further compounds I. The compounds obtained in this man- ner are listed in the table that follows, together with physical data.
The products shown below were characterized by determination of the melting point, NMR spectroscopy or the masses ([m/z]) determined by HPLC-MS spectrometry.
HPLC-MS = high performance liquid chromatography coupled with mass spectrometry; HPLC column: 15 RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50 * 4.6 mm; mobile phase: acetonitrile + 0.1 % trifluoroacetic acid (TFA)/water + 0.1 % TFA, using a gradient from 5:95t o 100:0 over 5 minutes at 40'C, flow rate 1.8 ml/min.
MS: quadrupole electrospray ionization, 80 V (positive mode)
AcSK: potassium thioacetate
p-HPLC = preparative HPLC
Example 1 : Preparation of 4-bromo-3-[[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-methyl- N-(1 - methyltetrazol-5-yl)benzamide of the formula I.A-3.85, entry 7.
Step 1 : methyl 3-amino-4-bromo-6-fluoro-2-methyl-benzoate
Commercially available methyl 3-amino-6-fluoro-2-methyl-benzoate (CAS [848678-60-4, 30.0 g, 0.16 mol) was dissolved in anhydrous DMF (220 ml) and treated in portions with NBS (N-bromo- succinimide) at room temperature. The reaction was slightly exothermic and was kept below 29 °C via cooling. The reaction mixture was stirred overnight, concentrated in vacuo and treated with methyl-fe -butyl ether (MTBE, 450 ml) and water (400 ml) and extracted a second time with MTBE (200 ml). The combined organic phases were washed with water (3 x 250 ml) and brine (1 x 250 ml), dried over magnesium sulfate and the solvent evaporated in vacuo to yield the product (41 .1 g, 96% yield). LC-MS (M+H): 263.8 Step 2: methyl 4-bromo-6-fluoro-3-isoc anato-2-meth l-benzoate
Triphosgene (bis(trichloromethyl) carbonate, 53.2 g, 0.18 mol) was dissolved in toluene (350 ml) and treated with a solution of methyl 3-amino-4-bromo-6-fluoro-2-methyl-benzoate (23.5 g, 0.09 mol) in 100 ml of toluene. Temperature was increased stepwise to reflux with evolution of gas observed starting at a temperature of approx. 85 °C. Reflux was kept for 6h and the reaction mixture stirred overnight at room temperature. Afterwards the reaction mixture was evaporated in vacuo to leave the product (15.5 g, 99%) as an orange solid which was used without further purification for the next step.
Step 3: methyl 4-bromo-3-[[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-methyl- benzoate
Methyl 4-bromo-6-fluoro-3-isocyanato-2-methyl-benzoate (15.00 g, 52.07 mmol) was dissolved in THF (180 ml) and ethyl(methyl)amine (3.45 g, 59.88 mmol) was added dropwise at room tem- perature. The temperature increased to a maximum of 29 °C. Stirring was continued overnight at RT and the solvent afterwards evaporated in vacuo. The remainder was triturated with methyl acetate several times. This gave in several portions solids yielding in total to 17.83 g (98%) of the title compound. LC-MS (M+H): 346.7
Step 4: 4-bromo-3-[[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-meth l-benzoic acid
Methyl 4-bromo-3-[[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-methyl- benzoate (13.95 g (40.18 mmol) was suspended in THF (250 ml) and treated with a solution of lithium hydroxide (2.89 g, 120.58 mmol) in water (50 ml) and stirred at 50 °C for 25 h. The amount of THF was reduced by concentration in vacuo and the remaining aqueous phase was washed with ethyl acetate. The pH value was adjusted to ca. pH 1-2 by addition of hydrochloric acid (1 molar). The product pre- cipitated upon this treatment and additional cooling with ice and was filtered off. Drying in vacuo yielded 10.55 of a solid (79%) of the title compound which was used without further purification in the next step.
Step 5: 4-bromo-3-[[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-methyl- N-(1-methyltetrazol-5- yl)benzamide
1-Methyltetrazol-5-amine (2.38 g, 24.0 mmol) was dissolved in anhydrous THF (120 ml) and cooled to -70°C under argon atmosphere. A solution of methyl lithium in THF (3 molar, 24.0 mmol) was added dropwise at this temperature and the reaction mixture warmed up to 0 °C. At this temperature the solution prepared in the following manner was added dropwise: 4-Bromo-3- [[ethyl(methyl)carbamoyl]amino]-6-fluoro-2-methyl-benzoic acid
(4.00 g, 12.0 mmol) was suspended in dichloromethane (DCM, 100 ml) and cooled to -78°C un- der argon atmosphere and DAST (diethlyamino sulfur trifluoride, 2.13 g, 13.2 mmol) was added via syringe. Cooling was continued for 2.5 h and the reaction mixture afterwards allowed to warm up to RT for 15 h. The solvent was evaporated in vacuo and re-dissolved in anhydrous THF (80 ml).
After addition if this solution stirring was continued at RT for 3h and the reaction mixture care- fully quenched by addition of water (60 ml). The major amounts of THF were evaporated in vacuo and the remainder adjusted to a pH value of ca. 1 by addition of aqueous hydrochloric acid (2 molar). Extraction with ethyl acetate (3 x 60 ml), drying of the combined organic phases with magnesium sulfate and evaporation of the solvent yielded crude product which was purified by column chromatography to yield the title compound (1.10 g, 22%).
H NMR (400 MHz, MeOD), δ 7.5 (d, 1 H), 4.05 (s, 3H), 3.45 (m, 2H), 3.05 (s, 3H), 2.35 (s, 3H), 1.2 (t, 3H)
Example 2: Preparation of 4-bromo-3-(diethylcarbamoylamino)-6-fluoro-2-methyl-N-(1-met hylte- trazol-5-yl)benzamide of the formula I.A-15.85, entry 5.
Step 1 : 6-Fluoro-2-methyl-3-nitro-benzoyl chloride
Commercially available 6-fluoro-2-methyl-3-nitro-benzoic acid (38.4 g, 193 mmol) was sus- pended in toluene (300 ml) and treated with thionyl chloride (21 g, 1 .5 equiv.) and 2 drops of DMF and slightly warmed up while adding thionyl chloride (32.1 g, 1 .4 equiv.) keeping the reac- tion temperature in a range of ca. 55-65 °C. Gas evolved and the mixture became clear. The mixture was heated up to reflux for additional 3 hours. Evaporation in vacuo yielded the title compound in quantitative yield (42.3 g). This product was used for the next step without further purification.
Step 2: 6-Fluoro-2-methyl-N-(1 -methyltetrazol-5-yl)-3-nitro-benzamide
1-Methyltetrazol-5-amine (40.2 g, 406 mmol) was dissolved in anhydrous THF (850 ml) and cooled to -75°C under argon atmosphere. A solution of methyl lithium in THF (2,3 molar, ca. 0.4 mol) was added dropwise at this temperature and the reaction mixture warmed up to ca. 0 °C. At this temperature a solution of 6-fluoro-2-methyl-3-nitro-benzoyl chloride in THF (42.3 g, 50 ml) was added keeping the temperature around 0 °C. Afterwards the reaction mixture was warmed up to room temperature and stirred overnight. The reaction mixture was quenched with aqueous hydrochloric acid (200 ml, 2M) and phases separated, the organic phase dried over magnesium sulphate and the solvent evaporated to yield the crude product (42.8 g) as a solid which was used without further purification in the next step.
Step 3: 3-Amino-6-fluoro-2-methyl-N-(1-methyltetrazol-5-yl)benzamide
6-Fluoro-2-methyl-N-(1-methyltetrazol-5-yl)-3-nitro-benzamid e (48.2 g, 172 mmol) was sus- pended in methanol (1 I) at RT. A solution of SnC x 2 H2O (134 g, 593 mmol) in cone, hydro- chloric acid (37% in water) was added in a temperature range of 45-65 °C and heated up to re- flux for 2.5 h. After cooling down, the methanol was evaporated, 1 I water added and sodium hy- droxide solution (50% in water) to adjust the pH to a value of about 5-6. Extraction with several portions of ethyl acetate (total of ca. 3 I), drying and evaporation led to 40.7 g (163 mmol, ca. 95% yield) of the product.
Step 4: 3-Amino-4-bromo-6-fluoro-2-methyl-N-(1 -methyltetrazol-5-yl)benzamide
3-Amino-6-fluoro-2-methyl-N-(1-methyltetrazol-5-yl)benzamide (20.5 g, 81 .9 mmol) was sus- pended at RT in glacial acetic acid (260 I) and heated to 65 °C to dissolve the amine. A solution of bromine (1 equiv.) in glacial acetic acid (40 ml) was added dropwise over a period of ca. 1.5 h and the mixture stirred thereafter for additional 1 .5 h. The glacial acetic acid was evaporated in vacuo and water added at ice cooling (300 ml) and stirred at this temperature for 1 h. The formed precipitate was filtered off and dried in vacuo to yield 24.5 g (91 %) of the product as a lilac solid.
Step 5: 4-bromo-3-(diethylcarbamoylamino)-6-fluoro-2-methyl-N-(1-met hyltetrazol-5-yl)ben- zamide
predominatly
via this imidoylchloride
Remark: The reaction with triphosgene leads in most cases predominantly to the formation of the imidoylchlorides as intermediates instead of the respective carboxamides, but can be con- verted back into a carboxamide after the formation of the urea (i.e. after addition of the respec- tive amine to the isocyanate) by careful reaction with hydroxide solution as described in the fol- lowing procedure:
A solution of 3-amino-4-bromo-6-fluoro-2-methyl-N-(1-methyltetrazol-5-yl)b enzamide (10.0 g, 30.0 mmol) in n-butyl acetate was added dropwise to a solution of triphosgene (13.5 g,
45.5 mmol) in the same solvent (ca. 200 ml) and heated to reflux until the evolution of gas ceased. The solvent was evaporated in vacuo and the remainder dissolved in THF and diethyl amine added (2.34 g, ca. 1 .1 equiv.) and stirred overnight. The pH value was adjusted to ca. 9 by addition of sodium hydroxide solution (2 molar in water) and stirred again overnight. Further hydroxide solution was added to reach a pH of 13 and stirring continued for 1 d. Water was added, the THF evaporate in vacuo, the aqueous phase washed with methyl fe -butyl ether and adjusted with hydrochloric acid solution to pH 5. Extraction with ethyl acetate yielded a crude product which was crystallized from ethyl acetate/methanol to yield the product (1 1.4 g, ca. 89%). 1 H NMR (400 MHz, d6-DMSO), δ 12 (br s, 1 H), 8.0 (s, 1 H), 7.70 (d, 1 H), 4.00 (s, 3 H), 3.3 (m, 4 H), 2.25 (s, 6 H), 1.15 (t, 3 H). Example 3: 3-Amino-4-bromo-6-fluoro-2-methyl-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)benzamide as an example for the preparation of intermediates leading to compounds with Q 2 , Q 3 and Q 4 :
3-Amino-6-fluoro-2-methyl-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)benzamide (3.2 g, 13 mmol), pre- pared from 6-fluoro-2-methyl-3-nitro-benzoic acid similar to Example 2, step 1 -3 (cf. above), was dissolved in anhydrous DMF (40 ml) and treated in portions with NBS (N-bromo succinimide) at room temperature. The reaction was slightly exothermic. The reaction mixture was stirred for 4.5 h, concentrated in vacuo and treated with methyl-fe -butyl ether (MTBE, 100 ml) and water whereupon a solid was formed and separated via filtration.
The remainder was tried in vacuo and the organic phase separately dried over magnesium sul- fate and the solvent evaporated in vacuo. This combined to a total von 3.67 g of the title com- pound.
The compounds according to Tables I to IV below were prepared in accordance with the methods described above:
Table II: compounds of the formula I as shown above wherein Q is Q 2 , R 4 is H and R 5 is F
Table III: compounds of the formula I as shown above wherein Q is Q 3 , R 4 is H and R 5 is F
Table IV: compounds of the formula I as shown above wherein Q is Q 4 , R 4 is H and R 5 is F
II. Use examples
The herbicidal activity of the compounds of formula (I) was demonstrated by the
following greenhouse experiments: The culture containers used were plastic flowerpots containing loamy sand with
approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subse- quently covered with transparent plastic hoods until the plants had rooted.
This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
Depending on the species, the plants were kept at 10 - 25°C or 20 - 25°C,
respectively.
The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated. Evaluation was carried out using a scale from 0 to 100.100 means no emergence of
the plants, or complete destruction of at least the aerial moieties, and 0 means no
damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
At an application rate of 250g/ha the following compounds were tested in pre-emergence tests against AMARE (Amaranthus retroflexus), CHEAL (Chenopodium album) and ECHCG (Echi- nocloa crus-galli) and showed a control of >85 %: Entries no.1, 5, 7, 8, 11, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 26, 28, 31, 32, 33, 34.
At an application rate of 250g/ha the following compounds were tested in post-emergence tests against
ALOMY (Alopecurus myosuroiedes) and showed a control of >85 %:
Entries of Table I no.1,2,5-8, 11, 13-16, 18,21-22,26.28,31,34,35,39,4042-45,47,48, 50, 52-54, 58, 59, 62, 66-70, 73, 76-78, 84-86, 93, 99-100, 103-105, 115;
Entries of Table II no.1, 2;
Entries of Table III no.1; ECHCG (Echinocloa crus-galli) and showed a control of >85 %:
Entries Table I no.1-3, 5-11, 13-24, 26, 28, 30-32, 34-35, 38-40, 42-45, 47-48, 50, 52-54, 58- 59, 62-70, 72-74, 79, 84-87, 89-91, 93, 99, 100, 103-105, 115, 119.
Entries of Table II no.1, 3; AMARE (Amaranthus retroflexus) and showed a control of >85 %:
Entries Table I no.1-11, 13-28, 31-39, 42-45, 47-48, 50, 52-54, 58-59, 62-70, 73, 84-86, 91, 93, 99, 100, 103-105, 115;
Entries of Table II no.1-3;
CHEAL (Chenopodium album) and showed a control of >85 %:
Entries Table I no.1-11, 13-29, 31-40, 42-45, 47-48, 50-54, 56-60, 62-70, 72-74, 79, 84-87, 89- 91, 93, 99, 100, 103-105, 115, 119;
Entries of Table II no.1-3;
Entries of Table III no.1-3, 5;
Entries of Table IV no.1 ;