Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them

Abstract

Novel herbicidal and defoliant substituted aniline derived compounds represented by general structure (I) are described. W, X, Y, Z, and Q are as defined in the disclosure. Also described are the processes for the manufacture of these compounds and agriculturally suitable compositions containing these as active ingredients which are useful as herbicides for general or selective pre-emergent or post-emergent control of undesired plant species and defoliants at very low concentrations of these biologically active compounds.

1. A compound represented by the formula I or its salts 
                 
 
       wherein X is hydrogen, halogen, nitro, amino, NHR, N(R) 2 , amide, thioatnide thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamnde, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, benzyloxy, amyloxy, or heteroaryloxy;
 Y is hydrogen, halogen, or nitro;  
 W is hydrogen, OR, SR, NHR, N(R) 2 , CH 2 R, CH(R) 2 , C(R) 3 , halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R; R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxybarbonyl alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;  
 Q is heterocycle: 
                 
 
  wherein R 1  is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;  
 R 2  is alkyl or haloalkyl;  
 R 1  and R 2  could combine to form a five- or six-membered heterocyclic ring;  
 R 3  is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;  
 R 8  and R 9  are independently oxygen, or sulfur;  
 Q6, Q7, and Q10 may optionally be unsaturated containing one or two double bonds in the 6-membered ring;  
 Z is amino, hydroxyl, thiol, formyl, carboxyl, cyano, alkylcarbonyl, arylcarbonyl, azido, or one of the following: 
                 
 
 
       wherein R 4  is alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl,  aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkyklcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocycloalkyl; and R 5  is hydrogen or any one of the groups represented by R 4 ; or R 4  and R 5  could combine to form a 4-8 membered heterocyclic ring; 
                 
  wherein R 6  represents alkyl, haloalkyl, dialkylamino, unsubstituted or substituted aryl and heteroaryl; and R 7  represents hydrogen, halogen or any of the groups represented by R 6 ;  
  —OR 4 ,  
  —SR 4 ,  
  —CH 2 R 10 ,  
  —CH(R 10 ) 2 ,  
  —C(R 10 ) 3 , or  
  —CH═CHR 10    
 
       wherein R 10  is carboxyl, alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkyithiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl;
 provided that ( 1)  Z is not alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkythio, alkenyl, haloalkenyl, amino, monoalkylamino, dialkylamino, alkoxyalkoxy alkoxyalkoxy, hydroxyl, alkynyloxy or cyano, when Q is Q1 and R 2  is haloalkyl.  
 
     
     
       2. The compound according to  claim 1  wherein Z is represented by the following: 
                 
 wherein R 4  and R 5  are the same as defined in  claim 1 ; or —CH 2 R 10 ,  
 wherein R 10  is the same as defined in  claim 1 .  
 
     
     
       3. The compound according to claims  1  or  2  wherein X is halogen or cyano;
 Y is halogen;  
 W is OR;  
 R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, or carboxyl.  
 
     
     
       4. The compound according to  claim 1  wherein Q is 
                 
 
       wherein R 1  is alkyl, amino, or haloalkyl;
 R 2  is haloalkyl;  
 R 3  is hydrogen;  
 R 8  and R 9  are independently oxygen, or sulfur.  
 
     
     
       5. The compound according to  claim 1  wherein X is a halogen;
 Y is fluorine;  
 W is OR; R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with halogen or cyano;  
 Q is 
                 
 
  wherein R 1  is alkyl, amino, or haloalkyl;  
 R 2  is haloalkyl;  
 R 3  is hydrogen;  
 R 8  R 9  are independently oxygen, or sulfur;  
 Z is represented by the following: 
                 
 
 
        wherein R 4  is alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl,  aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl, or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocyclcoalkyl  heterocycloalkyl; and R 5  is hydrogen;
  or —CH 2 R 10 ,  
 wherein R 10  is carboxyl, alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein teh  the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl.  
 
     
     
       6. A compound selected from the group consisting of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione ;  and 3-( 2 -amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-amino-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione   3 -(   2   - amino -   4   - chloro -   3   - methoxyphenyl )-   1   - amino -   6   - trifluoromethyl -   2 , 4   (   1 H, 3 H )- pyrimidinedione;  
     3   -(   2   - amino -   4   - chloro -   6   - fluro -   3   - methylphenyl )-   1   - methyl -   6   - trifluoromethyl -   2 , 4   (   1 H, 3 H )- pyrimidinedione; and  3   -(   2   - amino -   4   - chloro -   3   - difluoromethoxy -   6   - fluorophenyl )-   1 methyl -   6   - trifluoromethyl -   2 , 4   (   1 H, 3 H )- pyrimidinedione.    
 
     
     
       7. A herbicidal composition, characterized in that it contains at least one compound according to  claim 1  or  6  and an agricultural adjuvant. 
     
     
       8. A process for preparing a compound represented by the formula I-1 or its salts: 
                 
 
       wherein X is hydrogen, halogen, nitro, amino, NHR, N(R) 2 , ainide amide, thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamide, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, benzloxy benzyloxy, aryloxy or heteroaryloxy;
 Y is hydrogen, halogen, or nitro;  
 W is hydrogen, OR, SR, NH, N(R) 2 , CH 2 R, CH(R) 2 , C(R) 3 , halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R; R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;  
 Q is a heterocycle: 
                 
 
  wherein R 1  is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;  
 R 2  is alkyl or haloalkyl;  
 R 1  and R 2  could combine to form a five- or six-membered heterocyclic ring;  
 R 3  is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;  
 R 8  and R 9  are independently oxygen, or sulfur;  
 Q6, Q7, and Q10 may optionally be unsaturated containing one or two double bonds in the 6-membered ring;  
 Z′ is one of the following: 
                 
 
  wherein R 4  is alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl,  aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl, or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkyklcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkyithiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocycloalkyl; and R 5  is hydrogen or any one of the groups represented by R 4 ; or R 4  and R 5  could combine to form a 4-8 membered heterocyclic ring; 
                 
 
  wherein R 6  represents alkyl, haloallcyl  haloalkyl , dialkylamino, unsubstituted or substituted aryl and heteroaryl; and R 7  represents hydrogen, halogen or any of the groups represented by R 6 ;  
  —CH 2 R 10 ,  
  —CH(R 10 ) 2 ,  
  —C(R 10 ) 3 , or  
  —CH═CHR 10    
 wherein R 10  is carboxyl, alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, 25  alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkyithiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl,  aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl; 
 provided that (1)  Z′ is not alkyl, haloalkyl, alkenyl, haloalkenyl, monoalkylamino, or dialkylamino, when Q is Q1 and R 2  is haloalkyl,  
 
 
       which comprises of reacting a compound represented by the formula II: 
                 
 
       with a compound selected from the group consisting of an alkyl halide, alkyl acid halide, aryl acid halide, alkyl acid anhydride, aryl acid anhydride, alkylhaloformate, alkyl isocyanate, aryl isocyanate, alkyl dihalide, aliphatic aldehyde, aliphatic ketone, aromatic aldehyde, and aromatic ketone. 
     
     
       9. A compound represented by the formula III: 
                 
 
       wherein X is hydrogen, halogen, nitro, amino, NHR, N(R) 2 , amide, thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamide, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonylalkoxy, benzyloxy, aryloxy, or heteroaryloxy;
 Y is hydrogen, halogen, or nitro;  
 W is hydrogen, OR, SR, NHR, N(R) 2 , CH 2 R, CH(R) 2 , C(R) 3 , halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R; R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;  
 Q is a heterocycle: 
                 
 
  wherein R 1  is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;  
 R 2  is alkyl or haloalkyl;  
 R 1  and R 2  could combine to form a five- or six-membered heterocyclic ring;  
 R 3  is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;  
 R 8  and R 9  are independently oxygen or sulfur;  
 M is nitro,  
 
       provided that  1 - methyl -   6   - trifluoromethyl -   3   -(   4   - bromo -   2   - fluoro -   5   - hydroxy -   6   - nitrophenyl )-   2 , 4   (   1 H, 3 H )- pyrimidinedione and  1   - methyl -   6   - trifluoromethyl -   3   -(   4   - chloro -   2   - fluoro -   5   - hydroxy -   6   - nitrophenyl )-   2 , 4   (   1 H, 3 H )- pyrimidinedione are excluded.    
     
     
       10. A method for controlling undesired vegetation which comprises applying to a locus to be protected a herbicidally effective amount of a compound of  claim 1  or  6 . 
     
     
       11. The method of  claim 10  wherein the locus to be protected is a cereal crop field. 
     
     
       12. The method of  claim 11  wherein the compound of  claim 1   is applied to soil as a preemergent herbicide. 
     
     
       13. The method of  claim 11  wherein the compound of  claim 1   is applied to plant foliage. 
     
     
       14. A method to defoliate potato and cotton using a compound of  claim 1  or  6 .