精细化工
精細化工
정세화공
FINE CHEMICALS
2001年
6期
354-355,368
,共3页
徐小明%唐洪%陈兵%徐寿颐
徐小明%唐洪%陳兵%徐壽頤
서소명%당홍%진병%서수이
4,4′-双环己二酮%单保护%单乙二醇缩4,4′-双环己二酮
4,4′-雙環己二酮%單保護%單乙二醇縮4,4′-雙環己二酮
4,4′-쌍배기이동%단보호%단을이순축4,4′-쌍배기이동
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3 h,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(NH\-3)=100 g/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%。
對4,4′-雙環己二酮的閤成以及單保護反應進行瞭研究，在30 ℃下，用重鉻痠作為氧化劑,反應3 h,將4,4′-雙環己二醇氧化為4,4′-雙環己二酮，產率為75.4％。在硫痠氫鉀催化下，用n(乙二醇)∶n(4,4′-雙環己二酮)=1.2∶1.0進行脫水縮閤反應，在甲苯溶液中除去部分未保護的原料，在乙痠乙酯溶液中用亞硫痠氫鈉提取單保護產物，用ρ(NH\-3)=100 g/L的氨水脫去亞硫痠氫鈉，單乙二醇縮4,4′-雙環己二酮的產率31％,氣相色譜測定其質量分數為99.7%。
대4,4′-쌍배기이동적합성이급단보호반응진행료연구，재30 ℃하，용중락산작위양화제,반응3 h,장4,4′-쌍배기이순양화위4,4′-쌍배기이동，산솔위75.4％。재류산경갑최화하，용n(을이순)∶n(4,4′-쌍배기이동)=1.2∶1.0진행탈수축합반응，재갑분용액중제거부분미보호적원료，재을산을지용액중용아류산경납제취단보호산물，용ρ(NH\-3)=100 g/L적안수탈거아류산경납，단을이순축4,4′-쌍배기이동적산솔31％,기상색보측정기질량분수위99.7%。
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.
