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THE ROLE OF MEROSTABILIZED, LINNETT, AND BENZYLIC STRUCTURES OF BIRADICALOID INTERMEDIATES IN DETERMINING THE REGIOCHEMISTRY OF 1,3 DIPOLAR ADDITION REACTIONS
Abstract
The precursor of open chain Reissert analogues was prepared by reaction of mandelonitrile with aniline to form 2-anilino-2-phenylacetonitrile. A range of open chain Reissert compounds was made by reacting the acetonitrile with p-nitrobenzoyl chloride, p-methylbenzoyl chloride, and p-methoxybenzoyl chloride. Each of the Reissert compounds was treated with fluoroboric acid to form the munchnone iminium salt. Each was reacted with ethyl propiolate and ethyl phenylpropiolate to yeild highly substituted pyrroles. The ratio of the regioisomeric products of each of the reactions was established by HPLC. Identification of the regioisomers was accomplished by alternate syntheses, and by 300 MHz ('1)H-NMR analyses. Based on the regiochemical data gathered, 1,3 dipolar cycloaddition reactions of munchnone iminium salts with substituted acetylenes are highly regioselective. Regioisomeric product ratios indicate that merostabilization has a greater effect on the regiochemistry of the reaction than Linnett stabilization, which in turn is stronger than benzylic stabilization for the reactions of munchnone iminium salts with substituted acetylenes.
Subject Area
Analytical chemistry
Recommended Citation
LANGRIDGE, DENTON CUMMINGS HALL, "THE ROLE OF MEROSTABILIZED, LINNETT, AND BENZYLIC STRUCTURES OF BIRADICALOID INTERMEDIATES IN DETERMINING THE REGIOCHEMISTRY OF 1,3 DIPOLAR ADDITION REACTIONS" (1984). Doctoral Dissertations Available from Proquest. AAI8500092.
https://scholarworks.umass.edu/dissertations/AAI8500092