Microwave-Assisted Improved Regioselective Synthesis of 12H-Benzopyrano[3,2-c][1]benzopyran-5-ones by Radical Cyclisation

Abstract

Two new effective methodologies have been adopted for the preparation of 4-(2′-bromobenzyloxy)benzopyran-7-ones 3(a–h). In the first methodology, 4-hydroxy[1]benzopyran-2-ones 1(a–d) was alkylated with 2-bromobenzyl bromide 2a or 2-bromo-5-methoxy benzyl bromide 2b under phase transfer catalysis condition using lithium hydroxide/tetrabutyl ammonium bromide in N,N-dimethylformamide at 40–50°C and in the second method the microwave irradiation protocol has been exploited by simply mixing of 4-hydroxy[1]benzopyran-2-ones 1(a–d) with 25% excess of 2-bromobenzyl bromide 2a or 2-bromo-5-methoxy benzyl bromide 2b. A catalytic amount of TBAB and potassium carbonate were added and irradiated in an open Erlenmeyer flask in a microwave oven for 4–10 min. The tributyltin-hydride-mediated radical cyclisation of 3(a–h) was carried out under microwave irradiation to generate 12H-benzopyrano[3,2-c][1]benzopyran-5-ones 4(a–h) in 78–88% yield and in this technique yields were significantly improved and reaction time was shortened compared to the previously reported conventional radical cyclisation method.