Tricyclic benzoylpyrazole derivatives

Abstract

Tricyclic benzoylpyrazole derivatives of the formula I where: X is oxygen, sulfur, S═O, S(═O) 2 , CR 6 R 7 , NR 8 or a bond; Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle; R 1 , R 2 , R 6 , R 7 are hydrogen, alkyl, haloalkyl, alkoxy or haloalkoxy; R 3 is halogen, alkyl, haloalkyl, alkoxy or haloalkoxy; R 4 is hydrogen, nitro, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, unsubstituted or substituted aminosulfonyl or unsubstituted or substituted sulfonylamino; R 5 is hydrogen, alkyl or halogen; l is 0, 1 or 2; R 8 is hydrogen, alkyl, haloalkyl, alkylcarbonyl, formyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylsulfonyl or haloalkylsulfonyl; R 9 is substituted pyrazol-4-ylcarbonyl or substituted 5-oxopyrazolin-4-ylmethylidene; and their agriculturally useful salts; processes and intermediates for preparing the tricyclic benzoylpyrazole derivatives; compositions comprising them and the use of these derivatives or of the compositions comprising them for controlling undesirable plants are described.

1 .- 20 . (canceled)  
   
   
       21 . A tricyclic benzoylpyrazole compound of formula I  
     
       
         
         
             
             
         
       
       where:  
       X is oxygen, sulfur, S═O, S(═O) 2 , CR 6 R 7 , or NR 8 ;  
       Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen;  
       R 1 , R 2 , R 6 , R 7  are hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy;  
       R 3  is halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy;  
       R 4  is hydrogen, nitro, halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, aminosulfonyl, N—(C 1 -C 6 -alkyl)aminosulfonyl, N,N-di(C 1 -C 6 -alkyl)aminosulfonyl, N—(C 1 -C 6 -alkylsulfonyl)amino, N—(C 1 -C 6 -haloalkylsulfonyl)amino, N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -alkylsulfonyl)amino or N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -haloalkylsulfonyl)amino;  
       R 5  is hydrogen, C 1 -C 6 -alkyl or halogen;  
       R 8  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkylcarbonyl, formyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -haloalkoxycarbonyl, C 1 -C 6 -alkylsulfonyl or C 1 -C 6 -haloalkylsulfonyl;  
       l is 0, 1 or 2;  
       R 9  is a radical IIa or IIb  
       
         
           
           
               
               
           
         
         where  
       
       R 10  is hydroxyl, mercapto, halogen, OR 13 , SR 13 , SO 2 R 14 , NR 15 R 16  or N-bonded heterocyclyl, where the heterocyclyl radical may be partially or fully halogenated and/or may carry one to three of the following radicals: 
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;  
 
       R 11  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, hydroxyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy;  
       R 12  is hydrogen, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio or C 1 -C 6 -haloalkylthio;  
       R 13  is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 20 -alkylcarbonyl, C 2 -C 20 -alkenylcarbonyl, C 2 -C 6 -alkynylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 3 -C 6 -alkenyloxycarbonyl, C 3 -C 6 -alkynyloxycarbonyl, C 1 -C 6 -alkylthiocarbonyl, C 1 -C 6 -alkylaminocarbonyl, C 3 -C 6 -alkenylaminocarbonyl, C 3 -C 6 -alkynylaminocarbonyl, N,N-di(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkenyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 1 -C 6 -alkoxy)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkenyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl, N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl, di(C 1 -C 6 -alkyl)aminothiocarbonyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl, N—(C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl or N,N-di(C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups: 
 cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxycarbonyl, di(C 1 -C 4 -alkyl)amino-C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl, C 1 -C 4 -alkylaminocarbonyl, di(C 1 -C 4 -alkyl)aminocarbonyl, aminocarbonyl, C 1 -C 4 -alkylcarbonyloxy or C 3 -C 6 -cycloalkyl;  
 is phenyl, heterocyclyl, phenyl-C 1 -C 6 -alkyl, heterocyclyl-C 1 -C 6 -alkyl, phenylcarbonyl-C 1 -C 6 -alkyl, heterocyclylcarbonyl-C 1 -C 6 -alkyl, phenylcarbonyl, heterocyclylcarbonyl, phenoxycarbonyl, phenyloxythiocarbonyl, heterocyclyloxycarbonyl, heterocyclyloxythiocarbonyl, phenylaminocarbonyl, N—(C 1 -C 6 -alkyl)-N-(phenyl)aminocarbonyl, heterocyclylaminocarbonyl, N—(C 1 -C 6 -alkyl)-N-(heterocyclyl)aminocarbonyl, phenyl-C 2 -C 6 -alkenylcarbonyl or heterocyclyl-C 2 -C 6 -alkenylcarbonyl, where the phenyl and the heterocyclyl radical of the 18 lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:  
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, heterocyclyl or N-bonded heterocyclyl, where the two lastmentioned substitutents for their part may be partially or fully halogenated and/or may carry one to three of the following radicals:  
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;  
 
       R 14  is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, di(C 1 -C 6 -alkyl)amino or di(C 1 -C 6 -haloalkyl)amino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups: 
 cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxycarbonyl, di(C 1 -C 4 -alkyl)amino-C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl, C 1 -C 4 -alkylaminocarbonyl, di(C 1 -C 4 -alkyl)aminocarbonyl, aminocarbonyl, C 1 -C 4 -alkylcarbonyloxy or C 3 -C 6 -cycloalkyl;  
 is phenyl, heterocyclyl, phenyl-C 1 -C 6 -alkyl, heterocyclyl-C 1 -C 6 -alkyl, phenoxy, heterocyclyloxy, where the phenyl and the heterocyclyl radical of the lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:  
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;  
 
       R 15  is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, di(C 1 -C 6 -alkyl)amino or C 1 -C 6 -alkylcarbonylamino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three radicals of the following group: 
 cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxycarbonyl, di(C 1 -C 4 -alkyl)amino-C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl, C 1 -C 4 -alkylaminocarbonyl, di(C 1 -C 4 -alkyl)aminocarbonyl, aminocarbonyl, C 1 -C 4 -alkylcarbonyloxy or C 3 -C 6 -cycloalkyl;  
 is phenyl, heterocyclyl, phenyl-C 1 -C 6 -alkyl or heterocyclyl-C 1 -C 6 -alkyl, where the phenyl or heterocyclyl radical of the four lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:  
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;  
 
       R 16  is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl or C 1 -C 6 -alkylcarbonyl;  
       or an agriculturally useful salt thereof.  
     
   
   
       22 . The tricyclic benzoylpyrazole compound of formula I defined in  claim 21  where R 9  is IIa.  
   
   
       23 . The tricyclic benzoylpyrazole compound of formula I defined in  claim 21  where X is oxygen, sulfur or CR 6 R 7 .  
   
   
       24 . The tricyclic benzoylpyrazole compound of formula I defined in  claim 21  where 
 Y together with the two carbons to which it is attached forms a heterocycle selected from the following group: dihydroisoxazolediyl, isoxazolediyl or tetrahydroisoxazolediyl.    
   
   
       25 . The tricyclic benzoylpyrazole compound of formula I defined in  claim 21  where 
 R 1 , R 2  are hydrogen;    R 3  is C 1 -C 6 -alkyl;    R 4  is nitro, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio or C 1 -C 6 -alkylsulfonyl;    R 5  is hydrogen;    l is 0 oder 1.    
   
   
       26 . The tricyclic benzoylpyrazole compound of formula I defined in  claim 21  where 
 R 10  is hydroxyl;    R 11  is C 1 -C 6 -alkyl or C 3 -C 6 -cycloalkyl;    R 12  is hydrogen or C 1 -C 6 -alkyl.    
   
   
       27 . A process for preparing the compound of formula I where R 10 =halogen as claimed in  claim 21 , which comprises reacting a tricyclic benzoylpyrazole compound of formula Iα (=I where R 10 =hydroxyl),  
     
       
         
         
             
             
         
       
     
     where the variables R 1  to R 5 , R 11  and R 12 , X, Y and l are as defined in  claim 21 , with a halogenating agent.  
   
   
       28 . A process for preparing the compound of formula I where R 10 =OR 13  as claimed in  claim 21 , which comprises reacting a tricyclic benzoylpyrazole compound of formula Iα (=I where R 10 =hydroxyl),  
     
       
         
         
             
             
         
       
     
     where the variables R 1  to R 5 , R 11  and R 12 , X, Y and l are as defined in  claim 21 , with a compound of formula III  
       L 1 R 13   III  
     where the variable R 13  is as defined in  claim 21  and L 1  is a nucleophilically replaceable leaving group.  
   
   
       29 . A process for preparing the compound of formula I where R 10 =OR 13 , SR 13 , NR 15 R 16  or N-bonded heterocyclyl as claimed in claim  21 , which comprises reacting a compound of formula Iβ (≡I where R 10 =halogen),  
     
       
         
         
             
             
         
       
     
     where the variables R 1  to R 5 , R 11  and R 12 , X, Y and l are as defined in  claim 21 , with a compound of formula IVα, IVβ, IVγ or IVδ 
                       
HOR 13 HSR 13 NHR 15 R 16 H(N-bonded heterocyclyl) Ivo. IVp ivy IV8  
     where the variables R 13  to R 16  are as defined in  claim 21 , optionally in the presence of a base.  
   
   
       30 . A process for preparing the compound of formula I where R 10 =SO 2 R 14  as claimed in  claim 21 , which comprises reacting a compound of formula Iγ (≡I where R 10 =SR 14 ),  
     
       
         
         
             
             
         
       
     
     where the variables R 1  to R 5 , R 11  and R 12 , X, Y and l are as defined in  claim 21 , with an oxidizing agent.  
   
   
       31 . A process for preparing the compound of formula I where R 9 =IIa as claimed in  claim 21 , which comprises reacting a metalated pyrazole compound of formula V where M is a metal and R 10  to R 12  are as defined in  claim 21 , except for R 10 =hydroxyl and mercapto, with a tricyclic benzoic acid compound of formula VIα where R 1  to R 5 , X, Y and l are as defined in  claim 21  and L 2  is a nucleophilically replaceable leaving group.  
     
       
         
         
             
             
         
       
     
   
   
       32 . A process for preparing the compound of formula Iα (=I where R 10 =hydroxyl) as claimed in  claim 21 , which comprises acylating a pyrazole of formula VII in which the variables R 11  and R 12  are as defined in  claim 21   
     
       
         
         
             
             
         
       
     
     with an activated tricyclic benzoic acid of formula VIβ or with a tricyclic benzoic acid of formula VIγ,  
     
       
         
         
             
             
         
       
     
     where the variables R 1  to R 5 , X, Y and l are as defined in  claim 21  and L 3  is a nucleophilically replaceable leaving group, and rearranging the acylation product, optionally in the presence of a catalyst.  
   
   
       33 . A process for preparing the compound of formula Iα (≡I where R 10 =hydroxyl) as claimed in  claim 21 , which comprises reacting a pyrazole of formula VII in which the variables R 11  and R 12  are as defined in  claim 21 , or an alkali metal salt thereof,  
     
       
         
         
             
             
         
       
     
     with a tricyclic benzene compound of formula IX where L 4  is a leaving group and the variables X, Y, R 1  to R 5  and l are as defined in  claim 21   
     
       
         
         
             
             
         
       
     
     in the presence of carbon monoxide, a catalyst and a base.  
   
   
       34 . A composition, comprising a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof as claimed in  claim 21  and auxiliaries which are customary for formulating crop protection agents.  
   
   
       35 . A process for preparing the composition defined in  claim 34 , which comprises mixing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof and auxiliaries which are customary for formulating crop protection agents.  
   
   
       36 . A method for controlling undesirable vegetation, which comprises allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof as claimed in  claim 21  to act on plants, their habitat or on seed.  
   
   
       37 . A tricyclic benzoic acid compound of formula VI  
     
       
         
         
             
             
         
       
     
     in which the variables X, Y, R 1  to R 3  and R 5  and l are as defined in  claim 21  and 
 R 4  is nitro, halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, aminosulfonyl, N—(C 1 -C 6 -alkyl)aminosulfonyl, N,N-di(C 1 -C 6 -alkyl)aminosulfonyl, N—(C 1 -C 6 -alkylsulfonyl)amino, N—(C 1 -C 6 -haloalkylsulfonyl)amino, N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -alkylsulfonyl)amino or N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -haloalkylsulfonyl)amino;  
 R 17  is hydroxyl or a radical which can be removed by hydrolysis.  
 
   
   
       38 . A tricyclic benzene compound of formula IX  
     
       
         
         
             
             
         
       
     
     in which the variables X, Y, R 1  to R 3  and R 5  and l are as defined in  claim 21  and 
 R 4  is nitro, halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, aminosulfonyl, N—(C 1 -C 6 -alkyl)aminosulfonyl, N,N-di(C 1 -C 6 -alkyl)aminosulfonyl, N—(C 1 -C 6 -alkylsulfonyl)amino, N—(C 1 -C 6 -haloalkylsulfonyl)amino, N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -alkylsulfonyl)amino or N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -haloalkylsulfonyl)amino;  
 R 5  is hydrogen or C 1 -C 6 -alkyl;  
 L 4  is halogen, C 1 -C 6 -alkylsulfonyloxy, C 1 -C 6 -haloalkylsulfonyloxy or phenylsulfonyloxy, where the phenyl ring of the lastmentioned radical may be unsubstituted or partially or fully halogenated and/or may carry one to three of the following radicals: 
 nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy.  
 
 
   
   
       39 . An aniline compound of formula XV  
     
       
         
         
             
             
         
       
     
     in which the variables X, Y, R 1  to R 3  and R 5  and 1 are in each case as defined in  claim 21  and 
 R 4  is nitro, halogen, cyano, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, aminosulfonyl, N—(C 1 -C 6 -alkyl)aminosulfonyl, N,N-di(C 1 -C 6 -alkyl)aminosulfonyl, N—(C 1 -C 6 -alkylsulfonyl)amino, N—(C 1 -C 6 -haloalkylsulfonyl)amino, N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -alkylsulfonyl)amino or N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -haloalkylsulfonyl)amino.  
 
   
   
       40 . A nitrile compound of formula XVI  
     
       
         
         
             
             
         
       
     
     in which the variables X, Y, R 1  to R 3  and l are in each case as defined in  claim 21  and 
 R 4  is nitro, halogen, cyano, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkinylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, aminosulfonyl, N—(C 1 -C 6 -alkyl)aminosulfonyl, N,N-di-(C 1 -C 6 -alkyl)aminosulfonyl, N—(C 1 -C 6 -alkylsulfonyl)amino, N—(C 1 -C 6 -haloalkylsulfonyl)amino, N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -alkylsulfonyl)amino or N—(C 1 -C 6 -alkyl)-N—(C 1 -C 6 -haloalkylsulfonyl)amino;  
 R 5  is hydrogen or C 1 -C 6 -alkyl.  
 
   
   
       41 . The compound of formula I defined in  claim 21 , wherein 
 X is O or S;    Y together with the two carbons to which it is attached forms an isoxazole ring which is saturated, partially saturated or unsaturated; and    R 9  is a radical IIa.    
   
   
       42 . The compound of formula I defined in  claim 41 , wherein R 10  is hydroxyl, mercapto, halogen, OR 13 , SR 13 , SO 2 R 14  or NR 15 R 16 .