Fluorescent diketopyrrolopyrroles

Abstract

Fluorescent diketopyrrolopyrroles (“DPPs”) of the formula I wherein R 1 and R 2 , independently from each other, stand for C 1 -C 25 -alkyl, allyl which can be substituted one to three times with C 1 -C 3 alkyl or Ar 3 , —CR 3 R 4 —(CH 2 ) m —Ar 3 , wherein R 3 and R 4 independently from each other stand for hydrogen or C 1 -C 4 alkyl, or phenyl which can be substituted on to three times with C 1 -C 3 alkyl, Ar 3 stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen or phenyl, which can be substituted with C 1 -C 8 alkyl or C 1 -C 8 alkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, and wherein C 1 -C 25 -alkyl or —CR 3 R 4 —(CH 2 ) m —Ar 3 , preferably C 1 -C 25 -alkyl, can be substituted with a functional group capable of increasing the solubility in water such as a tertiary amino group, —SO 3 − , or PO 4 2− , Ar 1 , and Ar 2 , independently from each other, stand for  wherein R 5 stands for C 1 -C 6 alkyl, —NR 8 R 9 , —OR 10 , —S(O) n R 8 , —Se(O) n R 8 , or phenyl, which can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, wherein R 8 and R 9 , independently from each other, stand for hydrogen, C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, —CR 3 R 4 —(CH 2 ) m —Ph, R 10 , wherein R 10 stands for C 6 -C 24 -aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein Ph, the aryl and heterocyclic radical can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, or halogen, or R 8 and R 9 stand for —C(O)R 10 , wherein R 11 can be C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, R 10 , —OR 12 or —NR 13 R 14 , wherein R 12 , R 13 , and R 14 stand for C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, C 6 -C 24 -aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the aryl and heterocyclic radical can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, or —NR 8 R 9 stands for a five- or sixmembered heterocyclic radical in which R 8 and R 9 together stand for tetramethylene, pentamethylene, —CH 2 —CH 2 —O—CH 2 —CH 2 —, or —CH 2 —CH 2 —NR 5 —CH 2 —CH 2 —, preferably —CH 2 —CH 2 —O—CH 2 —CH 2 —, and n stands for 0, 1, 2 or 3, and wherein R 6 and R 7 , independently from each other, stand for hydrogen or R 5 , but do not stand simultaneously for hydrogen, processes for its preparation, its uses and compositions comprising the compounds I.

1 . Fluorescent diketopyrrolopyrroles (“DPPs”) of the formula I  
       
         
           
           
               
               
           
         
         wherein R 1  and R 2 , independently from each other, stand for C 1 -C 25 -alkyl, allyl which can be substituted one to three times with C 1 -C 3 alkyl or Ar 3 , —CR 3 R 4 —(CH 2 ) m —Ar 3 , wherein R 3  and R 4  independently from each other stand for hydrogen or C 1 -C 4 alkyl, or phenyl which can be substituted on to three times with C 1 -C 3  alkyl,  
         Ar 3  stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen or phenyl, which can be substituted with C 1 -C 8 alkyl or C 1 -C 8 alkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, and wherein C 1 -C 25 -alkyl or —CR 3 R 4 —(CH 2 ) m —Ar 3 , preferably C 1 -C 25 -alkyl, can be substituted with a functional group capable of increasing the solubility in water such as a tertiary amino group, —SO 3   − , or PO 4   2− ,  
         Ar 1  and Ar 2 , independently from each other, stand for  
         
           
             
             
                 
                 
             
           
         
          wherein 
 R 5  stands for C 1 -C 6 alkyl, —NR 8 R 9 , —OR 10 , —S(O) n R 8 , —Se(O) n R 8 , or phenyl, which can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, 
 wherein R 8  and R 9 , independently from each other, stand for hydrogen, C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, —CR 3 R 4 —(CH 2 ) m —Ph, R 10 , wherein R 10  stands for C 6 -C 24 -aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein Ph, the aryl and heterocyclic radical can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, or halogen, or R 8  and R 9  stand for —C(O)R 10 , wherein R 11  can be C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, R 10 , —OR 12  or —NR 13 R 14 , wherein R 12 , R 13 , and R 14  stand for C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, C 6 -C 24 -aryl, or  
 a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the aryl and heterocyclic radical can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, or —NR 8 R 9  stands for a five- or sixmembered heterocyclic radical in which R 8  and R 9  together stand for tetramethylene, pentamethylene, —CH 2 —CH 2 —O—CH 2 —CH 2 —, or —CH 2 —CH 2 —NR 5 —CH 2 —CH 2 —, preferably —CH 2 —CH 2 —O—CH 2 —CH 2 —, and n stands for 0, 1, 2 or 3,  
 
 and wherein R 6  and R 7 , independently from each other, stand for hydrogen or R 5 , but do not stand simultaneously for hydrogen, preferably R 6  stands for R 5  and R 7  for hydrogen.  
 
       
     
     
         2 . Process for the preparation of a compounds I according to  claim 1  in treating in a first step the DPP derivative of formula V  
       
         
           
           
               
               
           
         
       
       wherein Ar 1  and Ar 2  are defined as in  claim 1 , with a base, then, in a second step, treating the reaction mixture obtained in the first step with an usual alkylating agent, wherein in the first step the base is a hydride, an alkali metal alkoxide or a carbonate, and the alkylating agent is a sulfonate, tosylate, mesylate, carbonate, sulfate, or halogen compound of the formula (R 1 ) 1 or 2 X, wherein X stands for SO 3 —, (p-Me-phenyl)SO 2 —, (2,4,6-trimethyl-phenyl)SO 2 —, —CO 3 —, —SO 4 —, or halogen, or a mixture of (R 1 ) 1 or 2 X and (R 2 ) 1 or 2 X.  
     
     
         3 . Process for the preparation of the compounds I according to  claim 1   (a) in treating in a first step the DPP derivative of formula VI                           wherein R 1  and R 2  are defined as in  claim 1 , Hal stands for halogen, with a nucleophilic agent such as a secondary amine, HNR 8 R 9 , a thiol, HSR 8 , or HS(O) n R 8 , an alcohol, HOR 10 , a diselenide, R 8 (O) n Se—Se(O) n R 8 , preferably in a molar ratio of DPP VI:nucleophilic agent in the range of 1.2:1 to 0.8:1, or, if R 2  has the same meaning as R 1  in the range of from 1:2.5 to 1:1, in the presence of an anhydrous dipolar aprotic solvent, and of an anhydrous base in an amount in the range of from usually 0.1 to 15 moles per mole of the nucleophilic agent, at a temperature in the range of from usually 100 to 220° C. and under a pressure generally in the range of from 100 to 300 kPa, and optionally isolating the obtained compound V,    (b) then treating the obtained compound V (as defined in  claim 2) , with a base, thereafter in a second step, treating the reaction mixture obtained in the first step of (b) with an usual alkylating agent, wherein in the first step of (b) the base is a hydride, an alkali metal alkoxide or a carbonate, and the alkylating agent is a sulfonate, tosylate, mesylate, carbonate, sulfate, or halogen compound of the formula (R 1 ) 1 or 2 X, wherein X stands for SO 3 —, (p-Me-phenyl)-SO 2 —, (2,4,6-trimethyl-phenyl)SO 2 —, —CO 3 —, —SO 4 —, or halogen, or a mixture of (R 1 ) 1 or 2 X and (R 2 ) 1 or 2 X.    
     
     
         4 . Method of coloring high molecular weight organic materials by incorporating the DPP compounds I according to  claim 1  by known methods in the art.  
     
     
         5 . Composition comprising 
 (a) 0.01 to 50% by weight, based on the total weight of the colored high molecular weight organic material, of a fluorescent DPP I according to  claim 1 , and    (b) 99.99 to 50% by weight, based on the total weight of the colored high molecular weight organic material, of a high molecular organic material, and    (c) if desired, customary additives in effective amounts.    
     
     
         6 . Composition according to  claim 6 , wherein the high molecular weight organic material is a polyamide, a polystyrene, preferably high impact polystyrene, polymethylmethacrylate or an ABS copolymer.  
     
     
         7 . Method of using a DPP I according to  claim 1  for the preparation of inks, colorants. pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, or for the preparation of polymeric ink particles, toners, dye lasers and electroluminescent devices, wherein the DPP I is applied in a manner known in the art.