New Synthetic Routes to Alkyl‐Substituted and Functionalized Perylenes

Abstract 3,9(10)‐Dialkynyl‐ and 3‐monoalkynyl‐substituted perylenes ( 16 and 20 ) and their ω‐functionalized derivatives 27 , 30 , 33 , 35 can be synthesized easily and in high yields as well as the 3‐alkyl‐9(10)‐alkynyl‐substituted perylenes 39 and 42 . This is achieved by a palladium‐catalyzed coupling reaction of monobromoperylenes 19 and 38 and dibromoperylene 15 with 1‐alkynes and ω‐functionalized 1‐alkynes, respectively. The quantitative conversion of the alkynes into the corresponding alkyl‐substituted perylene derivatives 17 , 21 , 28 , 31 , 34 , 36 , 40 and 43 can be accomplished by catalytic hydrogenation. Further conversions of 28 , 31 , 34 , 36 , 40 and 43 provide the functionalized perylenes 29 , 32 , 37 , 41 and 44 .