Acridine Synthesis by the Reaction of 2-(Perfluoroalkyl)aniline with ortho-Alkyl-Substituted Aromatic Grignard Reagent: Mechanistic Studies
Lucjan Strekowski A E , Jianguo Zhang B , Jarosław Sączewski C and Ewa Wolińska DA Department of Chemistry, Georgia State University, Georgia 30302-4098, USA.
B Department of Biochemistry and Molecular Biology, The University of Texas Medical Branch, 301 University Blvd., Galveston, Texas 77555-0635, USA.
C Department of Chemical Technology of Drugs, Medical University of Gdańsk, Al. Gen. J. Hallera 107, 80-416 Gdańsk, Poland.
D Department of Chemistry, Siedlce University, 08-110 Siedlce, Poland.
E Corresponding author. Email: Lucjan@gsu.edu
Australian Journal of Chemistry 68(2) 196-202 https://doi.org/10.1071/CH14401
Submitted: 20 June 2014 Accepted: 9 July 2014 Published: 22 September 2014
Abstract
The reaction of 2-(perfluoroethyl)aniline and its higher perfluoroalkyl analogues with an arylmagnesium bromide substituted with a methyl or ethyl group at the ortho position furnishes an acridine containing a shorter perfluoroalkyl group at the 9-position and devoid of the methyl or ethyl group of the Grignard reagent. Yields are in the range of 46–93 %. The intermediary of a substituted aza-ortho-xylylene has been postulated for related transformations in the literature previously, but this intermediate product has never been isolated. As part of this work, the labile product E-27 (half-life of 6 h at 23°C) was isolated for the first time and characterized by infrared spectroscopy, electron impact mass spectrometry, fast atom bombardment mass spectrometry, and 1H NMR. Experimental evidence was also obtained regarding the elimination of the ortho-alkyl group of the Grignard reagent during the course of the reaction as an alcohol.
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