Acetic Acid → 2-Butene-1,4-diol diacetate

Participants

Reaction Steps

Another control run was carried out, employing the same reaction vessel as that utilized in Examples I and II above. In this run, the reactor was charged with 3.9 grams (50 mmoles) of lithium nitrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.0 grams (204 mmoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath and pressured to 30 psig with oxygen, and heated to 140° C for 3 hours. Oxygen was added to the reactor intermittently in the same manner as in Example I. At the end of the reaction period, the reactor was vented and the contents fractionally distilled through an 18 inch Vigreaux column, fraction 1 boiling at 46° - 51° C at 55 mm Hg, weighed 88.4 grams while fraction 2 boiling at 74° - 78° C at 6 mm Hg, weighed 2.1 grams and the distillation residue fraction 3 weighed 17.7 grams and was a thick black tar. Fractions 1 and 2 were analyzed by gas-liquid phase chromatography, which indicated that there was obtained 1.16 grams (6.7 mmoles) of 1,2-diacetoxy-3-butene and 0.43 grams (2.5 mmoles) of 1,4-diacetoxy-2-butene for a total yield of 9.2 mmoles of the diacetoxy butenes. This represents a yield of 4.5% based on the butadiene charged. This result shows that a much lower yield of diacetoxy butenes was obtained when the bismuth catalyst component is omitted from the reaction mixture.

Provenance & Evidence