单乙二醇缩4,4′-双环己二酮的合成研究

对 4,4′ 双环己二酮的合成以及单保护反应进行了研究 ,在 30℃下 ,用重铬酸作为氧化剂 ,反应 3h ,将 4,4′ 双环己二醇氧化为 4,4′ 双环己二酮 ,产率为 75 4%。在硫酸氢钾催化下 ,用n(乙二醇 )∶n(4 ,4′ 双环己二酮 ) =1 2∶1 0进行脱水缩合反应 ,在甲苯溶液中除去部分未保护的原料 ,在乙酸乙酯溶液中用亚硫酸氢钠提取单保护产物 ,用 ρ(NH3 ) =10 0g/L的氨水脱去亚硫酸氢钠 ,单乙二醇缩 4,4′ 双环己二酮的产率 31% ,气相色谱测定其质量分数为 99 7%

Synthesis of Bicyclohexane-4,4

Bicyclohexane-4,4′-dione was synthesized and the carbonyl groups were partially protected.Bicyclohexane-4,4′-diol was oxidized to bicyclohexane-4,4′-dione in 75.4% yield by using chromic acid at 30 ℃ for 3 h.Under the catalysis of potassium bisulfate,bicyclohexane-4,4′-dione was subjected to dehydrating condensation with ethylene glycol ［n(bicyclohexane-4,4′-dione)∶n(ethylene glycol)=1.2∶1.0］.The unprotected material was partially removed by aqueous sodium bisulfite solution from the toluene solution.By using high concentration aqueous sodium bisulfite solution,bisulfite addition product of bicyclohexane-4,4′-dione mono-ethyleneketal formed in ethyl acetate.The addition product was treated with 100 g/L aqueous ammonia to obtain bicyclohexane-4,4′-dione mono-ethyleneketal with overall yield of 31％ and purity of 99.7% by GC.