Physicochemical Study on Leuco Triarylmethane Dyes ; Unusual Carbon-Carbon Bond Cleavage Involving an Elimination of Dimethylaniline

概要

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Upon heating of the leuco triarylmethane dyes (2a) and (2b) with excess phosphoryl chloride under reflux, these compounds underwent a normal chlorination followed by a de-anilination process to give (3a) and (3b), respectively. Replacement of the p-dimethylamino substituent with a p-methoxy substituent on the 4,4-diaryl groups had a marked effect on the reaction ; only the 1-chlorinated products, (4a) and (4b), were formed even upon heating under reflux for 10 hours. On heating of (2b) in TFA, only 1-trifluoroacetoxylation occurred. Thus, the driving force of this type of de-anilination could be ascribed to a combination of greater orbital interaction between phosphoryl chloride and the HOMO of dimethylaniline, and the aromaticity of the resulting phthalazine molecule, resulting in a special type of carbon-carbon bond cleavage.
公益社団法人日本薬学会の論文
1981-10-25