Squaraine chemistry. Synthesis of bis(4-dimethylaminophenyl)squaraine from dialkyl squarates. Mechanism and scope of the synthesis

Abstract

The mechanism and the scope of the synthesis of bis(4-dialkylaminoaryl)squaraines from di-n-butyl squarate and N,N-dialkylanilines have been studied. Results show that water and acid are key factors of the synthesis, and these two factors have been optimized. Yields of squaraine are also found to be sensitive to the steric effect provided by the alkyl chain in dialkyl squarates as well as to the concentration of the aniline reagent used in the synthesis. Mechanistic results suggest that alkyl squarate is the precursor of the synthesis, and that squaraine is formed by diarylation of alkyl squarate with an N,N-dialkylaniline derivative. Under optimized conditions, a number of squaraines have been synthesized. Yields, which are comparable to those synthesized from squaric acid, are obtained. Product analysis with good material balance has been achieved, and results show that arylation and diarylation of the starting di-n-butyl squarate are major side reactions in the squaraine synthesis.