高锰酸钾用量对制备香紫苏内酯和降龙涎二醇的影响
|
摘要
以香紫苏醇为原料,经高锰酸钾氧化制备香紫苏内酯;另外,以香紫苏醇为原料,经高锰酸钾氧化和四氢铝锂还原制备降龙涎二醇。2种产物均经红外光谱、核磁共振氢谱和碳谱等进行了表征。主要探讨了氧化剂高锰酸钾用量对制备香紫苏内酯和降龙涎二醇的影响。结果表明,当n(香紫苏醇)∶n(KMnO4)=1∶5.6,反应温度为25~30℃,反应时间为5 h时,香紫苏内酯和降龙涎二醇的收率最高,分别为38.0%和22.5%。
Sclareolide was synthesized via potassium permanganate oxidation with sclareol as starting material.Besides,ambradiol was synthesized via potassium permanganate oxidation with sclareol as starting material and followed by lithium aluminum hydride reduction. Both the two products were characterized by IR,1HNMR and 13 CNMR. Effect of KMnO4 dosage on the preparation of sclareolide and ambradiol was examined. Results showed that,based on 25 ~ 30 ℃ of reaction temperature for 5 h,when potassium permanganate dosage is n( sclareol) ∶ n( KMn O4) = 1∶ 5. 6,yield of sclaeolide achieves 38. 0% and that of ambradiol achieves 22. 5%.
Sclareolide was synthesized via potassium permanganate oxidation with sclareol as starting material.Besides,ambradiol was synthesized via potassium permanganate oxidation with sclareol as starting material and followed by lithium aluminum hydride reduction. Both the two products were characterized by IR,1HNMR and 13 CNMR. Effect of KMnO4 dosage on the preparation of sclareolide and ambradiol was examined. Results showed that,based on 25 ~ 30 ℃ of reaction temperature for 5 h,when potassium permanganate dosage is n( sclareol) ∶ n( KMn O4) = 1∶ 5. 6,yield of sclaeolide achieves 38. 0% and that of ambradiol achieves 22. 5%.
引文
[1]王文军,陈莎,戴乾圜.龙涎香的组成及降龙涎醚的合成研究进展[J].有机化学,2001,21(3):167-172.
[2]翟周平.香紫苏内酯合成新工艺的研究[J].香料香精化妆品,2002,75(6):1-2.
[3]陈恩治.烟用香料大柱三烯酮的合成[J].北京工商大学学报:自然科学版,2011,29(3):16-19.
[4]FRATER G,BAJGROWICZ J A,KRAFT P.Fragrance chemistry[J].Tetrahedron,1998,54(52):7633-7703.
[5]SIBIERTSEVA V E,KUSTOVA S D,TOKAREVA V YA.Industrial method for producing ambroxide[J].Maslozhirovaya Promyshlennost,1979,12:25-26.
[6]DEREK H R,SHYAMAl I P,DENNIS K T,et al.An efficient synthesis of(-)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]uran from(-)-sclareol[J].Tetrahedron Letters,1994,35(32):5801-5804.
[7]MARTRES P,PERFETTI P,ZAHRA J P,et al.A short and efficient synthesis of(-)-ambrox from(-)-sclareol using a ruthenium oxide catalyzed key step[J].Tetrahedron Letters,1993,34(2):629-632.
[8]BARTON D H,TAYLOR D K,TSE C I.An improved synthesis of(-)-dodeca hydro-3a,6,6,9a-tetramethylnaphthol[2,1-b]furan via ozonolysis of(-)-sclareol[J].Tetrahedron Letters,1994,35(51):9505-9508.
[9]HENLEY W M,JOSEPY N S,TEAGUE J C.Two stage oxidation of sclareol:US,3050532[P].1962-08-21.
[10]BARRERO A F,ALVAREZ-MANZANEDA E J,CHAHBOUN R,et al.Degradation of the side chain of(-)-sclareol:A very short synthesis of nor-ambreinolide and ambrox[J].Synthetic Communications,2004,34(19):3631-3643.
[11]MOULINES J,BATS J P,LAMIDEY A M,et al.About a practical synthesis of ambrox from sclareol:A new preparation of a ketone key intermediate and a close look at its baeyer-villiger oxidation[J].Helvetica Chimica Acta,2004,87(10):2695-2705.
[12]魏俊发,吴亚,石先莹,等.香紫苏内酯的合成方法:CN,1683352A[P].2005-02-04.
[13]翟周平,胡新予,赵新春,等.四丁基溴化铵催化过氧化氢氧化香紫苏醇合成香紫苏内酯的研究[J].香料香精化妆品,2009(4):1-3.
[2]翟周平.香紫苏内酯合成新工艺的研究[J].香料香精化妆品,2002,75(6):1-2.
[3]陈恩治.烟用香料大柱三烯酮的合成[J].北京工商大学学报:自然科学版,2011,29(3):16-19.
[4]FRATER G,BAJGROWICZ J A,KRAFT P.Fragrance chemistry[J].Tetrahedron,1998,54(52):7633-7703.
[5]SIBIERTSEVA V E,KUSTOVA S D,TOKAREVA V YA.Industrial method for producing ambroxide[J].Maslozhirovaya Promyshlennost,1979,12:25-26.
[6]DEREK H R,SHYAMAl I P,DENNIS K T,et al.An efficient synthesis of(-)-dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]uran from(-)-sclareol[J].Tetrahedron Letters,1994,35(32):5801-5804.
[7]MARTRES P,PERFETTI P,ZAHRA J P,et al.A short and efficient synthesis of(-)-ambrox from(-)-sclareol using a ruthenium oxide catalyzed key step[J].Tetrahedron Letters,1993,34(2):629-632.
[8]BARTON D H,TAYLOR D K,TSE C I.An improved synthesis of(-)-dodeca hydro-3a,6,6,9a-tetramethylnaphthol[2,1-b]furan via ozonolysis of(-)-sclareol[J].Tetrahedron Letters,1994,35(51):9505-9508.
[9]HENLEY W M,JOSEPY N S,TEAGUE J C.Two stage oxidation of sclareol:US,3050532[P].1962-08-21.
[10]BARRERO A F,ALVAREZ-MANZANEDA E J,CHAHBOUN R,et al.Degradation of the side chain of(-)-sclareol:A very short synthesis of nor-ambreinolide and ambrox[J].Synthetic Communications,2004,34(19):3631-3643.
[11]MOULINES J,BATS J P,LAMIDEY A M,et al.About a practical synthesis of ambrox from sclareol:A new preparation of a ketone key intermediate and a close look at its baeyer-villiger oxidation[J].Helvetica Chimica Acta,2004,87(10):2695-2705.
[12]魏俊发,吴亚,石先莹,等.香紫苏内酯的合成方法:CN,1683352A[P].2005-02-04.
[13]翟周平,胡新予,赵新春,等.四丁基溴化铵催化过氧化氢氧化香紫苏醇合成香紫苏内酯的研究[J].香料香精化妆品,2009(4):1-3.