3,4-Diacetoxy-1-butene → 3-Formylbut-2-enyl acetate

Participants

Reaction Conditions

Reaction Steps

An autoclave equipped with a gas inlet, a sampling port and an electromagnetic stirrer and having an internal volume of 300 ml, was charged with 50 ml (52.7 g, 0.306 mol) of 3,4-diacetoxy-1-butene and a solution of 2.58 mg of rhodium dicarbonyl acetylacetonate and 140 mg (0.5 mmol) of tricyclohexylphosphine in 50 ml of toluene under nitrogen while avoiding their contact with air. Then, the atmosphere inside the autoclave was replaced with a gaseous mixture of hydrogen and carbon monoxide at a molar ratio of 1/1. The pressure inside the autoclave was adjusted to 90 atmospheric pressure (gauze pressure) with the same gaseous mixture and the temperature inside the autoclave was raised to 80° C. The hydroformylation was effected for 2 hours at 80° C. while maintaining the pressure inside the autoclave at 90 atmospheric pressure (gauze pressure) with the gaseous mixture of hydrogen and carbon monoxide at a molar ratio of 1/1. Analysis of the reaction solution with gas chromatography under the same conditions of Example 1 showed that the conversion of the 3,4-diacetoxy-1-butene was 44% and the selectivity to the hydroformylated product was 99%. The anaysis also showed that the reaction solution contained 13.55 g (67 mmol) of 1,2-diacetoxy-3-formylbutane and 8.29 g (41 mmol) of 4,5-diacetoxypentanal and 3.55 g (25 mmol) of 3-methyl-4-oxo-2-butenyl acetate which was formed by the elimination of acetic acid from 1,2-diacetoxy-3-formylbutane. The ratio i/n was 2.2 (=69/31), wherein 3-methyl-oxo-2-butenyl acetate was calculated as 1,2-diacetoxy-3-formylbutane.

Provenance & Evidence