Oxobenzofuranylide-dihydroindolone

Abstract

Oxobenzofuranylidene-dihydroindolones of formulae trans-(Ia) and cis-(Ib) and of formulae trans-(IIa) and cis-(IIb) wherein A 1 and A 2 are each independently of the other unsubstituted or mono- to tetra-substituted ortho-C 6 -C 18 arylene, and R 1 is hydrogen or an organic radical, with the proviso that when R 1 is hydrogen and A 2 is 1,2-phenylene, A 1 is not 9,10-anthraquinon-1,2-ylene, 4-chloro-3,5-dimethyl-1,2-phenylene or 3,5-dimethyl-1,2-phenylene, processes for their preparation and the use thereof.

1 . An oxobenzofuranylidene-dihydroindolone of formula trans-(Ia) or cis-(Ib)  
       
         
           
           
               
               
           
         
       
       or of formula trans-(IIa) or cis-(IIb)  
       
         
           
           
               
               
           
         
       
       wherein 
 A 1  and A 2  are each independently of the other unsubstituted or mono- to tetra-substituted ortho-C 6 -C 18 arylene, and  
 R 1  is hydrogen, C 1 -C 25 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 24 aryl, a heteroaromatic radical, —(CH 2 ) n —COR 2  or —(CH 2 ) m —OR 3 , 
 wherein R 2  is hydroxy, —OX, or, unsubstituted or mono- or poly-substituted by hydroxy, —OX or by amino, C 1 -C 25 alkoxy, C 1 -C 25 alkylamino or C 1 -C 25 dialkyl-amino, di(C 6 -C 24 aryl)amino, C 1 -C 12 alkyl, C 2 -C 24 alkenyl, and X is a cation, and  
 R 3  is hydrogen or —CO—(C 1 -C 25 alkyl), and n and m denote each independently of the other a whole number in the range from 0 to 6, and  
 a single C—C bond also may have been replaced by a corresponding ether unit, C—O—C,  
 with the proviso that, when R 1  is hydrogen and A 2  is 1,2-phenylene, A 1  is not 9,10-anthraquinon-1,2-ylene, 4-chloro-3,5-dimethyl-1,2-phenylene or 3,5-dimethyl-1,2-phenylene.  
 
 
     
     
         2 . An oxobenzofuranylidene-dihydroindolone according to  claim 1 , wherein A 1  and/or A 2  are/is substituted or unsubstituted 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,2-phenanthrylene, 2,3-phenanthrylene, 3,4-phenanthrylene, 9,10-phenanthrylene, 1,2-anthracenyl, 2,3-anthracenyl or 1,2-anthraquinonylene or 2,3-anthraquinonylene.  
     
     
         3 . An oxobenzofuranylidene-dihydroindolone according to either  claim 1  or  claim 2 , wherein 
 A 1  is  
                     
 and A 2 is  
 wherein  
 R 8 , R 9 , R 11 , R 10 , R 12 , R 13 , R 14  and R 15  are each independently of the others hydrogen, halogen cyano, —NO 2 , —R 16 , —NR 17 R 18 , —NR 19 COR 17 , —NR 19 COOR 17 , —N═CR 17 R 18 , —CONR 19 R 20 , —OR 17 , —O—(C 1 -C 12 alkylene)-COOX, —O—(C 1 -C 12 alkylene)-COOH, —O—(C 1 -C 12 alkylene)-O—CO—R 17 , —O—(C 1 -C 12 alkylene)-COOR 17 , —O—(C 1 -C 12 alkylene)-CONR 19 R 20 , —O—(C 1 -C 12 alkylene)-OR 17 , —(C 1 -C 12 alkylene)-O—CO—R 17 , —(C 1 -C 12 alkylene)-OR 17 , —COOR 17 , —(C 1 -C 12 alkylene)-COOR 17 , —(C 1 -C 12 alkylene)-CONR 19 R 20 , —(C 1 -C 12 alkylene)-COOX, —(C 1 -C 12 alkylene)-COOH, —COOX, —COOH, —SR 17 , —SOR 17 , —SO 2 R 17 , —SO 2 NR 19 R 20 , —SO 3 R 17 , SO 3 H or SO 3 X,  
 wherein 
 R 17 , R 18 , R 19 , and R 20  are each independently of the others hydrogen or R 16 , and  
 R 16  is, unsubstituted or mono- or poly-substituted by halogen, hydroxy, amino, oxo, carboxy, cyano, —COOR 18  or by —COOX, C 1 -C 25 alkyl, C 5 -C 12 cycloalkyl or C 2 -C 24 alkenyl, which may be uninterrupted or interrupted one or more times by O, S or N—(C 1 -C 25 alkyl), N—(C 2 -C 24 alkenyl) when the alkyl has more than two and the alkenyl more than three carbon atoms, or is, unsubstituted or mono- or poly-substituted by halogen, nitro, cyano, —OR 18 , —SR 18 , —NR 19 R 20 , —CONR 19 R 20 , —COOR 18 , —COOX, —COOH, —SO 2 R 18 , —SO 2 NR 19 R 20 , —SO 3 R 18 , —SO 3 X, —SO 3 H, —NR 19 COR 18  or by —NR 19 COOR 18 , C 6 -C 18 aryl, C 7 -C 18 aralkyl or heteroaryl,  
 or  
 R 19  and R 20 , together with the nitrogen atom linking them, are unsubstituted or mono- to tetra-C 1 -C 4 alkyl-substituted pyrrolidinyl, piperidyl, piperazinyl or morpholinyl, or are carbazolyl, phenoxazinyl or phenothiazinyl,  
 it being possible, optionally, for R 8  and R 9 , R 9  and R 11 , R 11  and R 10  and for R 12  and R 13 , R 13  and R 14  or R 14  and R 15  additionally to form, in each case, a substituted or unsubstituted 5- or 6-membered ring.  
 
 
     
     
         4 . An oxobenzofuranylidene-dihydroindolone according to  claim 3 , wherein at least one of the radicals R 8 , R 9 , R 11 , R 10 , R 12 , R 13 , R 14  and R 15  is a radical selected from the group consisting of the radicals Z 1 , Z 2 , Z 3  and Z 4    
       
         
           
           
               
               
           
         
       
       wherein 
 R 22 , R 23 , R 24 , R 25 , R 26 , R 27  and R 28  are each independently of the others hydrogen, halogen, cyano, —NO 2 , —R 16 , —NR 17 R 18 , —NR 19 COR 17 , —NR 19 COOR 17 , —N═CR 17 R 18 , —CONR 19 R 20 , —OR 17 , —O—(C 1 -C 12 alkylene)-COOX, —O—(C 1 -C 12 alkylene)-COOH, —O—(C 1 -C 12 alkylene)-O—CO—R 17 , —O—(C 1 -C 12 alkylene)-COOR 17 , —O—(C 1 -C 12 alkylene)-CONR 19 R 20 , —O—(C 1 -C 12 alkylene)-OR 17 , —(C 1 -C 12 alkylene)-O—CO—R 17 , —(C 1 -C 12 alkylene)-OR 17 , —COOR 17 , —(C 1 -C 12 alkylene)-COOR 17 , —(C 1 -C 12 alkylene)-CONR 19 R 20 , —(C 1 -C 12 alkylene)-COOX, —COOX, —COOH, —SR 17 , —SOR 17 , —SO 2 R 17 , —SO 2 NR 19 R 20 , —SO 3 R 17  or SO 3 X, SO 3 H, the radicals R 17 , R 18 , R 19 , R 20  being as above, and  
 R 21 , independently of R 1 , has the same definition as R 1 , and  
 A 3  is a single bond or is, unsubstituted or mono- or poly-substituted by C 1 -C 25 alkyl, C 6 -C 24 aryl, halogen, hydroxy, —OX, oxo, cyano, —COOR 6 , —COOX, —COOH, —SO 3 R 6 , —SO 3 X or by —SO 3 H, C 1 -C 24 alkylene or C 5 -C 12 cycloalkylene or —OOC—(C 1 -C 24 alkylene)-COO—, —COO—(C 1 -C 24 alkylene)-OOC—, —NR 19 CO—(C 1 -C 24 alkylene)-CONR 19 —, —CONR 19 —(C 1 -C 24 alkylene)—NR 19 CO—; C 6 -C 24 arylene or heteroarylene.  
 
     
     
         5 . An oxobenzofuranylidene-dihydroindolone according to either  claim 1  or  claim 2 , wherein 
 A 1  is  
                     
 wherein R 8 , R 9 , R 11 , and R 10  are as defined in  claim 3 ,  
 and A 2  is a bivalent radical Z 5  or Z 6    
                     
 wherein R 13 , R 14 , R 21 , R 22 , R 23 , R 24  and R 27  are as defined in  claim 4 .  
 
     
     
         6 . An oxobenzofuranylidene-dihydroindolone according to  claim 1 , which is a compound of formula (LI)  
       
         
           
           
               
               
           
         
       
       wherein 
 P 1 , P 2 , P 3  are each independently of the others a radical selected from the group consisting of the radicals Z 1 , Z 2 , Z 3  and Z 4  according to  claim 4 , and  
 A 4  is a trivalent radical.  
 
     
     
         7 . An oxobenzofuranylidene-dihydroindolone (LI) according to  claim 6 , wherein the trivalent radical is  
       
         
           
           
               
               
           
         
       
     
     
         8 . A cis- and trans-bisbenzofuranone derivative of an oxobenzofuranylidene-dihydroindolone according to either  claim 1  or  claim 3 , which is a compound of formula  
       
         
           
           
               
               
           
         
       
       wherein 
 A 5  and A 6  denote each independently of the other two hydrogen atoms, with the proviso that they do not simultaneously denote two hydrogen atoms; they furthermore denote each independently of the other a substituted or unsubstituted isatin radical  
                     
 
     
     
         9 . A composition comprising at least one oxobenzofuranylidene-dihydroindolone according to any one of  claims 1  to  8 .  
     
     
         10 . A process for the preparation of an oxobenzofuranylidene-dihydroindolone of formula trans-(Ia) or cis-(Ib) according to  claim 1  by reaction of a benzofuranone or bisbenzofuranone derivative with an isatin derivative in the presence of an acidic or basic catalyst, which process comprises reacting a compound of formula (XXIX)  
       
         
           
           
               
               
           
         
         wherein A 1  is as defined in  claim 1 , with a compound of formula (XXX) or (XXXa)  
         
           
             
             
                 
                 
             
           
         
         wherein  
         Y is O, S, NH, N—(C 1 -C 24 alkyl), N—(C 5 -C 18 aryl) or N—(C 7 -C 28 aralkyl) and  
         Hal is halogen, and  
         A 2  is as defined in  claim 1 .  
       
     
     
         11 . A process for the preparation of an oxobenzofuranylidene-dihydroindolone of formula trans-(Ia) or cis-(Ib) according to  claim 1  by reaction of a benzofuranone or bisbenzofuranone derivative with an oxindole derivative in the presence of an acidic or basic catalyst, which process comprises reacting a compound of formula (XXXI) or (XXXIa)  
       
         
           
           
               
               
           
         
         wherein A 1  is as defined in  claim 1  and Y and Hal are as defined in  claim 10 , with a compound of formula (XXXII)  
         
           
             
             
                 
                 
             
           
         
         wherein A 2  is as defined in  claim 1 .  
       
     
     
         12 . A process for the preparation of a compound of formula trans-(IIa) or cis-(IIb) according to  claim 1  by reaction of a benzofuranone or bisbenzofuranone derivative with an indoxyl derivative in the presence of an acid or a base, which process comprises reacting a compound of formulae (XXXI) or (XXXIa) with a compound of formula (XXXIV)  
       
         
           
           
               
               
           
         
       
       wherein A 2  is as defined in  claim 1 .  
     
     
         13 . A process for the preparation of a compound of formula trans-(Ia), trans-(IIa) or cis-(Ib), cis-(IIb) according to  claim 1  by reaction of a benzofuranone or bisbenzofuranone derivative with an indoxyl or isatin derivative in the presence of an acid or a base, which process comprises reacting a compound of formula (XXXI) or (XXXIa) according to  claim 11  with 
 (a) an imine of formula (XXXV)  
                     wherein A 2  and Y are as defined in  claim 1  and  claim 10 ,    or    
 (b) a ketal of formulae (XXXVI) or (XXXVII)  
                     
 wherein 
 R 43  is C 1 -C 6 alkyl and R 44  is an unsubstituted or substituted bivalent C 1 -C 6 alkylene radical.  
 
 
     
     
         14 . Use of an oxobenzofuranylidene-dihydroindolone according to any one of  claims 1  to  7  or prepared according to a process of  claims 10  to  13  and of the composition according to  claim 9  in the colouring or pigmenting of organic or inorganic materials, especially in the production of inks or colourrants for surface-coatings, printing inks, mineral oils, lubricating greases or waxes, colourants or pigmented plastics, non-impact-printing material, colour filters, cosmetic articles, toners or colouring of woodstains.