Pyrazole derivatives as herbicides

Abstract

Compounds of formula I R 11 is hydrogen, fluorine, chlorine, bromine or methyl; R 12 is hydrogen, halogen, methyl, halomethyl, nitro, amino, hydroxy, OHC—, HOC(O)—, cyano, C 1 -C 4 alkoxycarbonyl or halomethoxy; X 1 is O, S, R 20 N═ or R 25 ON═; R 13 is hydroxy, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 haloalkoxy, C 3 -C 6 -haloalkenyloxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 6 alkenyloxy-C 1 -C 6 alkyl, C 3 -C 6 alkynyloxy-C 1 -C 6 -alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy-C 1 -C 6 alkyl, B 1 -C 1 -C 6 alkoxy, R 21 (R 22 )N, C 1 -C 6 alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, B 1 -C 1 -C 6 alkyl, OHC—, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylcarbonyloxy, C 1 -C 6 haloalkylcarbonyl, C 2 -C 6 alkenylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl-S(O) 2 —, C 1 -C 6 haloalkyl-S(O) 2 —, (C 1 -C 6 -alkyl) 2 N—N═CH—, B 1 -CH═N—, (CH 3 ) 2 N—CH═N—, (C 1 -C 5 -hydroxyalkyl)-CH 2 —, (B 1 -C 1 -C 5 hydroxyalkyl)-CH 2 —, (B 1 -C 1 -C 5 haloalkyl)-CH 2 —, (hydroxy-C 1 -C 5 -alkyl)-O— or (B 1 -C 1 -C 5 hydroxyalkyl)-O—; or X 1 and R 13 together are a group ═N—Y— wherein Y is bonded to the ring nitrogen atom; and R 20 , R 21 , R 22 , R 25 , B 1 and y are as defined in claim 1, and the pyrazole N-oxides, agrochemically acceptable salts and stereoisomers of those compounds of formula I, have good selective herbicidal properties pre- and post-emergence. The preparation of those compounds and the use thereof as herbicidal active ingredients are described.

What is claimed is:  
     
         1 . A compound of formula I  
       
         
           
           
               
               
           
         
         R 1  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, cyano-C 1 -C 4 alkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl, C 3 - or C 4 -alkynyl or C 3 -C 6 cycloalkyl;  
         R 2  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 1 -C 4 alkyl-S(O) 2 — or C 1 -C 4 haloalkyl-S(O) 2 —;  
         R  3  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, halogen, cyano, NH 2 C(S)—, nitro or amino;  
         n 1  is 0, 1 or 2;  
         R 4  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl or C 3 -C 6 cycloalkyl;  
         R 5  is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, cyano, nitro, amino, NH 2 C(O)—, NH 2 C(S)—, C 1 -C 4 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 4 haloalkylcarbonyl, C 2  -C 4 alkenylcarbonyl, C 1 -C 3 alkyl-CH(OH)—, OHC—, HOC(O)—, CIC(O)—, HON═CH—, C 1 -C 4 alkoxy-N═CH—, C 2 -C 4 haloalkenylcarbonyl or C 2 -C 4 alkynylcarbonyl;  
         R 11  is hydrogen, fluorine, chlorine, bromine or methyl;  
         R 12  is hydrogen, halogen, methyl, halomethyl, nitro, amino, hydroxy, OHC—, HOC(O)—, cyano, C 1 -C 4 alkoxycarbonyl or halomethoxy;  
         X 1  is O, S, R 20 N═ or R 25 ON═;  
         R 13  is hydroxy, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 haloalkoxy, C 3 -C 6 -haloalkenyloxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 6 alkenyloxy-C 1 -C 6 alkyl, C 3 -C 6 alkynyloxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy-C 1 -C 6 alkyl, B 1 -C 1 -C 6 alkoxy, R 21 (R 22 )N—, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, B 1 -C 1 -C 6 alkyl, OHC—, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylcarbonyloxy, C 1 -C 6 haloalkylcarbonyl, C 2 -C 6 alkenylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl-S(O) 2 —, C 1 -C 6 haloalkyl-S(O) 2 -, (C 1 -C 6 alkyl) 2 N—N═CH—,  
         
           
             
             
                 
                 
             
           
         
         B 1 -CH═N—, (CH 3 ) 2 N—CH═N—, (C 1 -C 5 hydroxyalkyl)-CH 2 —, (B 1 -C 1 -C 5 hydroxyalkyl)-CH 2 —, (B 1 -C 1 -C 5 haloalkyl)-CH 2 —, (hydroxy-C 1 -C 5 alkyl)-O— or (B 1 -C 1 -C 5 hydroxyalkyl)-O—;  
         B 1  is cyano, OHC—, HOC(O)—, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl, benzylthiocarbonyl, benzylthiocarbonyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 -alkyl or by C 1 -C 4 haloalkyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylthio-C(O)—, R 26 (R 27 )NC(O)—, phenyl, phenyl mono- to tri-substituted by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl, C 1 -C 6 -alkyl-S(O) 2 —, C 1 -C 6 alkyl-S(O)—, C 1 -C 6 alkylthio, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenylthio or C 3 -C 6 alkynylthio;  
         R 20  is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, cyano, R 23 (R 24 )N—, C 1 -C 6 alkoxycarbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, C 2 -C 6 haloalkoxycarbonyl, OHC—, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkyl-S(O) 2 —, C 1 -C 6 haloalkyl-S(O) 2 —, phenyl, phenyl mono- to tri-substituted by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl, phenyl-C 1 -C 6 alkyl, or phenyl-C 1 -C 6 alkyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl;  
         R 21  and R 22  are each independently hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 -haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, OHC—, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkyl-S(O) 2 — or C 1 -C 6 haloalkyl-S(O) 2 —;  
         R 23  and R 24  are each independently as defined for R 21 ;  
         R 25  is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, benzyl, C 1 -C 6 alkyl-S(O) 2 — or C 1 -C 6 haloalkyl-S(O) 2 —;  
         R 26  and R 27  are each independently hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl, benzyl, or benzyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl; or  
         X 1  and R 13  together form a group ═N—Y— wherein Y is bonded to the ring nitrogen atom;  
         Y is —C(R 31 )(R 32 )—CH 2 —, —C(R 31 )(R 32 )—O—, —C(R 31 )(R 32 )—CH 2 —CH 2 —, —C(R 31 )(R 32 )—CH 2 —O—, —O—CH 2 —, —O—CH 2 —CH 2 —, —O—CH═CH—, —N(R 33 )—CH 2 —, —N(R 33 )—CH 2 —CH 2 —, —N(R 33 )—CH═CH—, —N(R 33 )—C(X 3 )—CH 2 —, —C(X 3 )—CH 2 —, —C(X 3 )—CH 2 —CH 2 —, —C(X 3 )—CH 2 —O—, —C(X 3 )—O—, —C(R 34 )═CH—, —C(R 31 )(R 32 )—CH═CH—, —C(R 34 )═N—, —C(R 31 )(R 32 )—CH═N—, —C(R 31 )(R 32 )—N═CH—, —C(X 3 )—CH═CH—, —N═N—, —C(R 31 )(R 32 )—C(O)—, —C(R 31 )(R 32 )—C(S)—, —C(R 31 )(R 32 )—CH 2 —C(O)—, —C(R 31 )(R 32 )—CH 2 —C(S)—, —N(R 33 )—C(O)—, —N(R 33 )—C(S)—, —N(R 33 )—CH 2 —C(O)—, —N(R 33 )—CH 2 —C(S)—, —O—C(O)—, —O—C(S)—, —C(R 34 )═CH—C(O)— or —C(R 34 )═CH—C(S)—, the right-hand end of the bridge members in the above definitions of Y being bonded to the ring nitrogen atom;  
         R 31  is hydrogen, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;  
         R 32  is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, cyano-C 1 -C 6 alkyl, hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 6 alkenyloxy-C 1 -C 6 alkyl, C 3 -C 6 alkynyloxy-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyloxy-C 1 -C 6 alkyl, C 1 -C 6 haloalkylcarbonyloxy-C 1 -C 6 alkyl, carboxyl, C 1 -C 6 alkoxycarbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 3 -C 6 cycloalkoxycarbonyl, C 1 -C 4 alkoxy-C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl-NHC(O)—, (C 1 -C 6 alkyl) 2 NC(O)—, C 3 -C 6 alkenyl-NHC(O)—, C 1 -C 6 alkyl-(C 3 -C 6 -alkenyl)NC(O)—, C 3 -C 6 alkynyl-NHC(O)—, aminocarbonyl, C 1 -C 6 alkylthio-C(O)—, C 3 -C 6 -alkenylthio-C(O)—, C 3 -C 6 alkynylthio-C(O)—, benzyloxycarbonyl, benzyloxycarbonyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl, phenoxycarbonyl, C 1 -C 6 alkyl-S(O) 2 NHC(O)—, C 1 -C 6 alkyl-S(O) 2 (C 3 -C 6 alkenyl)N—C(O)—, C 1 -C 6 haloalkyl-S(O) 2 NHC(O)—, HON═CH—, C 1 -C 6 alkoxy-N═CH—, C 3 -C 6 alkenyloxy-N═CH—, C 3 -C 6 alkynyloxy-N═CH—, HOC(O)—C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl-C 1 -C 6 alkyl, C 3 -C 6 alkenyloxycarbonyl-C 1 -C 6 alkyl, C 3 -C 6 alkynyloxycarbonyl-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, CIC(O)—, H 2 NC(S)—, OHC—, cyano, phenyl, phenyl mono- to tri-substituted by halogen, C 1 -C 4 alkyl or by C 1 -C 4 -haloalkyl, phenyl-C 1 -C 6 alkyl, or phenyl-C 1 -C 6 alkyl mono- to tri-substituted at the phenyl ring by halogen, C 1 -C 4 alkyl or by C 1 -C 4 haloalkyl;  
         X 3  is O, S, R 20 N═ or R 25 ON═;  
         R 33  is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkyl-S(O) 2 — or B 2 -C 1 -C 6 -alkyl;  
         B 2  is cyano, HOC(O)—, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 alkoxy; and  
         R 34  is as defined for R 32  or is halogen, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkyl-S(O)— or C 1 -C 6 alkyl-S(O) 2 —,  
         or a pyrazole N-oxide, an agrochemically acceptable salt or a stereoisomer of that compound of formula I.  
       
     
     
         2 . A compound of formula I according to  claim 1  having the formula Ia  
       
         
           
           
               
               
           
         
       
       R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , X 1  and n 1  are as defined in  claim 1 .  
     
     
         3 . A process for the preparation of a compound of formula I  
       
         
           
           
               
               
           
         
       
       wherein R 11 , R 12  and W are as defined in claim  1 ; X 1  is O or S; R 13  is C 1 -C 6 alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 -haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, B 1 -C 1 -C 6 alkyl,  
       
         
           
           
               
               
           
         
       
       (C 1 -C 5 hydroxyalkyl)-CH 2 —, (B 1 -C 1 -C 5 hydroxyalkyl)-CH 2 — or (B 1 -C 1 -C 5 haloalkyl)-CH 2 —; and B 1 is as defined in  claim 1 , which comprises oxidising a compound of formula III  
       
         
           
           
               
               
           
         
       
       in a suitable solvent to form a compound of formula V  
       
         
           
           
               
               
           
         
       
       and subsequently rearranging that compound in an inert solvent in the presence of an anhydride or in the presence of antimony pentachloride to yield, after aqueous working up, a compound of formula II  
       
         
           
           
               
               
           
         
       
       the radicals R 11 , R 12  and W in the compounds of formulae II, III and V being as defined above, and then alkylating that compound in the presence of an inert solvent and a base with a compound of formula VI  
       R 13 —L  (VI),  
       wherein R 13  is as defined above and L is a leaving group, to form the compounds of formulae I and IV  
       
         
           
           
               
               
           
         
       
       wherein R 11 , R 12 , R 13  and W are as defined above and X 1  is O, and subsequently, where appropriate after separating off the compound of formula I, functionalising the pyridone group thereof according to the definition of X 1  and R 13 .  
     
     
         4 . A process for the preparation of a compound of formula I  
       
         
           
           
               
               
           
         
       
       wherein R 11 , R 12  and W are as defined in claim  1 ; X 1  is S; R 13  is hydroxy, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, B 1 -C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylcarbonyloxy, C 1 -C 6 haloalkylcarbonyl, C 2 -C 6 alkenylcarbonyl or C 1 -C 6 alkoxycarbonyl; and B 1  is as defined in  claim 1 , which comprises first of all oxidising a compound of formula III  
       
         
           
           
               
               
           
         
       
       to yield a compound of formula V  
       
         
           
           
               
               
           
         
       
       chlorinating or brominating that compound to form a compound of formula VIII  
       
         
           
           
               
               
           
         
       
       the radicals R 11 , R 12  and W in the compounds of formulae III, V and VIII being as defined above and Hal in the compound of formula VIII being chlorine or bromine, subsequently converting the compound of formula VII with a suitable sulfur reagent into a compound of formula Ic  
       
         
           
           
               
               
           
         
       
       and reacting that compound in the presence of a solvent and a base with a compound of formula XI  
       R 14 —L  (XI),  
       wherein R 14  is C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, B 1 -C 1 -C 6 alkyl or C 1 -C 6 alkylcarbonyl; B 1  is as defined above; and L is a leaving group.  
     
     
         5 . A compound of formula VIII  
       
         
           
           
               
               
           
         
       
       wherein R 11 , R 12  and W are as defined in  claim 1  and Hal is chlorine or bromine.  
     
     
         6 . A herbicidal and plant-growth-inhibiting composition having a herbicidally effective content of a compound of formula I according to  claim 1  and comprising an inert carrier.  
     
     
         7 . A composition according to  claim 6  comprising from 0.1% to 95% of a compound of formula I.  
     
     
         8 . A method of controlling undesired plant growth, which comprises applying a compound of formula I, or a composition comprising that compound, in a herbicidally effective amount to the crops of useful plants or to the locus thereof.  
     
     
         9 . The use of a composition according to  claim 6  in the control of undesired plant growth.