Cyanated benzoxanthene and benzothioxanthene compounds

Abstract

The present invention relates to cyanated compounds of the formula (I) wherein at least one of the radicals R 2 , R 3 , R 4 and R 5 is CN, and the remaining radicals are selected from hydrogen, chlorine and bromine; X is O, S, SO or SO 2 ; m is 0, 1, 2, 3 or 4; R 1 is selected from bromine, chlorine, cyano, —NR a R b , C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy, C 3 -C 24 -cycloalkyl, heterocycloalkyl, heteroaryl, C 6 -C 24 -aryl, C 6 -C 24 -aryloxy, C 6 -C 24 -aryl-C 1 -C 10 -alkylene, etc.; A is a diradical selected from diradicals of the general formulae (A.1), (A.2), (A.3), and (A.4) wherein R 6 , (R 7 ) n , (R 8 ) o and (R 9 ) p are as defined in the claims and in the description. The invention further relates to color converters comprising at least one polymer as a matrix material and at least one cyanated compound of formula (I) or mixtures thereof as a fluorescent dye, to the use of the color converters and to lighting devices comprising at least one LED and at least one color converter.

1 . A compound of the formula (II): 
       
         
           
           
               
               
           
         
         wherein: 
         at least one of the radicals R 2 , R 3 , R 4  and R 5  is bromine or chlorine and remaining radicals R 2 , R 3 , R 4  and R 5  are hydrogen; 
         X is S, SO or SO 2 ; 
         A is a radical of formulae (A.1), (A.2), (A.3), or (A.4): 
       
       
         
           
           
               
               
           
         
         * in each case denotes the point of attachments to the remainder of the molecule; 
         n is 0, 1, 2, 3 or 4; 
         o is 0, 1, 2 or 3; 
         p is 0, 1, 2 or 3; 
         R 6  is hydrogen, a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 3 -C 24 -cycloalkyl, a C 6 -C 24 -aryl or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, aryl, and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 6a , and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by one or more heteroatoms or heteroatomic groups of O, S and NR c ; 
         each R 7  independently from each other is bromine, chlorine, cyano, —NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 7a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S and NR c ; 
         each R 8  independently from each other is bromine, chlorine, cyano, NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 8a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S and NR c ; 
         each R 9  independently from each other is bromine, chlorine, cyano, NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 9a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally e interrupted by at least one of O, S and NR c ; 
         R 1a , R 6a , R 7a , R 8a , R 9a  are independently of one another a C 1 -C 24 -alkyl, a C 1 -C 24 -fluoroalkyl, a C 1 -C 24 -alkoxy, fluorine, chlorine or bromine; 
         R a , R b , R c  are independently of one another hydrogen, a C 1 -C 20 -alkyl, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a hetaryl or a C 6 -C 24 -aryl; 
         R 1  is bromine, chlorine, cyano, —NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl, aryloxy and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 1a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S and NR c ; and 
         m is 0, 1, 2, 3 or 4. 
       
     
     
         2 . A process for preparing a benzo[k,l]xanthene compound of formula (III.1): 
       
         
           
           
               
               
           
         
         wherein: 
         A is a radical of formulae (A.1), (A.2), (A.3) or (A.4): 
       
       
         
           
           
               
               
           
         
         m is 0, 1, 2, 3 or 4; 
         each R 1  independently from each other is bromine, chlorine, cyano, a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl, aryloxy and-aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 1a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S or NR c ; 
         * in each case denotes the point of attachments to the remainder of the molecule; 
         n is 0, 1, 2, 3 or 4; 
         o is 0, 1, 2 or 3; 
         p is 0, 1, 2 or 3; 
         R 6  is hydrogen, a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 3 -C 24 -cycloalkyl, a C 6 -C 24 -aryl or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, aryl, and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 6a , and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by one or more heteroatoms or heteroatomic groups of O, S and NR c ; 
         each R 7  independently from each other is bromine, chlorine, cyano, —NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 7a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S and NR c ; 
         each R 8  independently from each other is bromine, chlorine, cyano, NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 8a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy, and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally interrupted by at least one of O, S and NR c ; 
         each R 9  independently from each other is bromine, chlorine, cyano, NR a R b , a C 1 -C 24 -alkyl, a C 1 -C 24 -haloalkyl, a C 1 -C 24 -alkoxy, a C 1 -C 24 -haloalkoxy, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a heteroaryl, a C 6 -C 24 -aryl, a C 6 -C 24 -aryloxy, or a C 6 -C 24 -aryl-C 1 -C 10 -alkylene, where rings of cycloalkyl, heterocycloalkyl, heteroaryl, aryl and aryl-alkylene are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R 9a  and where C 1 -C 24 -alkyl, C 1 -C 24 -haloalkyl, C 1 -C 24 -alkoxy, C 1 -C 24 -haloalkoxy and the alkylene moiety of the C 6 -C 24 -aryl-C 1 -C 10 -alkylene are optionally e interrupted by at least one of O, S and NR c ; 
         R 1a , R 6a , R 7a , R 8a , R 9a  are independently of one another a C 1 -C 24 -alkyl, a C 1 -C 24 -fluoroalkyl, a C 1 -C 24 -alkoxy, fluorine, chlorine or bromine; and 
         R a , R b , R c  are independently of one another hydrogen, a C 1 -C 20 -alkyl, a C 3 -C 24 -cycloalkyl, a heterocycloalkyl, a hetaryl or a C 6 -C 24 -aryl, 
         the process comprising reacting a 4,5-dihalogen-naphthalenedicarboxylic acid derivate of formula (VII) with a boronic acid derivative of formula (VIII) in the presence of a base and a transition metal catalyst: 
       
       
         
           
           
               
               
           
         
         wherein: 
         Hal in each case is chlorine or bromine; and 
         R l  and R m  are each independently hydrogen or a C 1 -C 4 -alkyl, or R l  and R m  together form an 1,2-ethylene or 1,2-propylene moiety the carbon atoms of which are optionally unsubstituted or all or in part substituted by methyl groups. 
       
     
     
         3 . The process of  claim 2 , wherein R 2  and R 4  are each cyano, and R 3  and R 5  are each hydrogen. 
     
     
         4 . The process of  claim 2 , wherein A is a radical of the formula (A.2). 
     
     
         5 . The process of  claim 4 , wherein:
 R 6  is selected from the group consisting of a linear C 1 -C 24 -alkyl, a radical of the formula (B.1) and a radical of the formula (B.2):   
       
         
           
           
               
               
           
         
         # represents the bonding site to the nitrogen atom; 
         R d  and R e , in the formula (BA), independently from each other are a C 1 -C 23 -alkyl, where the sum of the carbon atoms of the R d  and R e  radicals is an integer from 2 to 23; and 
         R f , R g  and R h , in the formula (B.2) are independently a C 1 - to C 20 -aralkyl, where the sum of the carbon atoms of the R f , R g  and R h  radicals is an integer from 3 to 23. 
       
     
     
         6 . The process of  claim 4 , wherein R 6  is selected from the group consisting of a radical of the formula (C.1), a radical of the formula (C.2) and a radical of the formula (C.3): 
       
         
           
           
               
               
           
         
         # represents the bonding side to the nitrogen atom; 
         B where present, is a C 1 -C 10 -alkylene group optionally interrupted by one or more nonadjacent groups selected from —O— and —S—; 
         y is 0 or 1; 
         R i  is independently of one another a C 1 -C 24 -alkyl, a C 1 -C 24 -fluoroalkyl, fluorine, chlorine or bromine; 
         R k  is independently a C 1 -C 24 -alkyl; 
         x in formulae C.2 and C.3 is 1, 2, 3, 4 or 5. 
       
     
     
         7 . The process of  claim 2 , wherein m is zero or one.