Oxygen → 2-Butene-1,4-diol diacetate

Participants

Reaction Conditions

Reaction Steps

Another run was conducted employing the same apparatus as that used in Example I but in this run there was no source of halide in the catalyst system. The reactor was charged with 3.4 grams (20 millimoles) of ceric oxide, 7.6 grams (75 millimoles) of lithium acetate dihydrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 10.0 grams (185.2 millimoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath, pressured to 30 psig with oxygen and heated to 140° C. About one hour was required for the oil bath temperature to reach the reaction temperature desired, after which a reaction period of 5.3 hours was employed. During the reaction the reactor was pressured to 120 psig with oxygen intermittently. At the end of the reaction period (5.3 hours) the reactor was vented and 1.8 grams of unreacted butadiene was recovered in a cold trap. The reaction mixture was diluted with ether and 2.67 grams of a solid precipitate was collected by filtration and dried. The ether solution filtrate was washed with water, neutralized with sodium carbonate solution, dried over magnesium sulfate, filtered, and the ether then removed by distillation. The distillation residue (21.3 g) was a pale brown oil. It was analyzed by gas-liquid chromatography which showed that the residue was 86 percent ether with the remainder being the diacetoxy butenes. Specifically, there was produced 11 millimoles of 1,2-diacetoxy-3-butene and 3 millimoles of 1,4-diacetoxy-2-butene for a total yield of 14 millimoles of diacetoxy butenes which represents a yield of 7 percent bases on the butadiene charged.

Provenance & Evidence