coumarins were found to be generally between 3 and
4.5 h at room temperature. Longer reaction times resulted
in a decrease in the yields of desired 3-aminocoumarins
and the formation of the corresponding
3-trifluoroacetamidocoumarin (8) (Scheme 2). For the
parent system, 3-trifluoroacetamidocoumarin (8a)17
was isolated in 14% yield after a reaction time of 31 h.
Yields as high as 35–45% were obtained for substrates
6d and 6e when the reaction was run for 27 h. Evidently,
the 3-aminocoumarin, once formed, is acylated by the
solvent. Indeed, stirring pure 3-aminocoumarin (7a) in
15%. TFA/CHCl3 at room temperature resulted in the
slow formation of compound 8a (tlc analysis). After
stirring for 7 days, roughly equivalent amounts of
compounds 7a and 8a were present in solution (tlc
analysis) and, after a further day’s reaction at reflux, trifluoroacetamidocoumarin
(8a) was isolated in 68%
yield.
coumarins were found to be generally between 3 and
4.5 h at room temperature. Longer reaction times resulted
in a decrease in the yields of desired 3-aminocoumarins
and the formation of the corresponding
3-trifluoroacetamidocoumarin (8) (Scheme 2). For the
parent system, 3-trifluoroacetamidocoumarin (8a)17
was isolated in 14% yield after a reaction time of 31 h.
Yields as high as 35–45% were obtained for substrates
6d and 6e when the reaction was run for 27 h. Evidently,
the 3-aminocoumarin, once formed, is acylated by the
solvent. Indeed, stirring pure 3-aminocoumarin (7a) in
15%. TFA/CHCl3 at room temperature resulted in the
slow formation of compound 8a (tlc analysis). After
stirring for 7 days, roughly equivalent amounts of
compounds 7a and 8a were present in solution (tlc
analysis) and, after a further day’s reaction at reflux, trifluoroacetamidocoumarin
(8a) was isolated in 68%
yield.
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