4,7-Dimethyl-3a,4,7,7a-tetrahydro-4,7-epoxy-2-benzofuran-1,3-dione → 3,6-Dimethylphthalic anhydride

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Reaction Conditions

Reaction Steps

1,7-Dimethyl-4,10-dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione 1 (30.0 g, 0.150 mol) is added slowly in portions to stirred 98% sulfuric acid (300 mL) in a 1 L flange flask cooled to −5° C. using a salt-ice bath—note that the temperature is kept below 0° C. during the addition. The mixture is stirred for 30 mins at −5° C. and then allowed to warm up to 22° C. The mixture is carefully poured onto crushed ice (1.5 L). The cream precipitate that formed is filtered off and washed with ice water. The precipitate is dissolved in a 5% aq. sodium hydroxide solution (225 mL) with stirring. Glacial acetic acid (20 mL) is added slowly to the stirred solution. A cream precipitate forms and this is filtered off and discarded. 37% Hydrochloric acid (50 mL) is added to the stirred filtrate and the mixture is stirred for 2 h during which time a precipitate is formed. The precipitate is filtered off and dried in the vacuum oven overnight to yield the product as a cream solid (11.13 g, 41%). The filtrate is allowed to stand overnight during which time further product precipitated out. The second crop of precipitate is filtered off and dried under vacuum to yield the product 2 as a cream solid (5.79 g, 21%): 1H-NMR (300 MHz, CDCl3) δ 7.18 (s, 2H), 2.40 (s, 6H).

Provenance & Evidence