marți, 8 februarie 2011

PDA for PDIs!

This paper caught my eye because I recalled my one regular commenter (come on dear readers...where are you? :'-( ) working with perylenes in the past. The reactant in the middle is imide-substituted perylene diimide, PDI. DMP PDI, compound 1a, has some interesting solid-state photochemical quirks, so who knows, substituting the perylene core could lead to the next big thing in photonic organics. So the author says.

The first reaction described looks less than impressive: for 1a, 26% came out a mixture of dibrominated isomers (1,6-3a and 1,7-3a), 57% came out monobrominated, and 15% remained unreacted. Restricted rotation of the bulky R groups about the C-N bond meant two isomers for each potentially brominated carbon. The author goes on to describe a reaction using a refluxing solution of bromine that gives exclusively dibrominated product overnight, with a 1,7/1,6 ratio of 3:1. The regioisomers can be separated by recrystallization from a 1:1 solution of dichloromethane and hexane.

Sonogashira coupling of 2a with TMS acetylene works, as does nucleophilic substitution by piperidine.

Bromination causes an interesting "core twist" vibration involving, well, the twisting of the perylene core. Energy barriers associated with the motion were relatively low and thus interconversion between the two "twist states" of the molecule is relatively easy.