CN117603291A - 一种基于Smith降解的环黄芪醇制备方法 - Google Patents
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Abstract
本发明公开了一种基于Smith降解的环黄芪醇制备方法,利用改进的Smith降解法来对黄芪甲苷进行水解,使用硅胶负载的高碘酸钠取代传统的高碘酸钠水溶液,大大减少了溶剂使用量,简化了操作步骤;使用固体酸取代传统的硫酸水溶液,使条件变得温和,避免了黄芪醇等副产物的生成,环黄芪醇收率可以达到85%以上。该方法反应条件温和,操作简便,产生有机废液少,可用于工业化生产。
Description
技术领域
本发明属于医药化工领域,具体为一种基于Smith降解的由黄芪甲苷降解制备环黄芪醇的方法
背景技术
黄芪甲苷是在传统中药黄芪中提取得到的一种皂苷类化合物,是黄芪主要活性成分之一,具有增强免疫力、抗炎、抗病毒、清除自由基等多种生理活性。环黄芪醇为黄芪甲苷的苷元,属于四环三萜类化合物,是目前发现唯一已知的端粒酶激活剂,还可以延缓细胞衰老,具有抗炎、抗氧化等作用。与黄芪甲苷相比,环黄芪醇具有较高的脂溶性,透膜能力增强,具有较好的应用前景。
环黄芪醇是由黄芪甲苷水解得到,目前主流的水解方法主要有:(1)酸水解:该种方法利用酸性较强的酸如盐酸,硫酸等对黄芪甲苷进行水解,操作简单,成本较低,但黄芪甲苷中含有的环丙基不耐酸,极易开环得到副产物黄芪醇,导致该方法收率变低,不易纯化(中国发明公开专利:CN109942663B;CN113968894A;CN104817610A);(2)酶解法:该方法利用酶催化来水解黄芪甲苷,反应条件温和,选择性高,但对反应条件要求苛刻,不利于大量制备(中国发明公开专利:CN105734109A;CN114369636A;CN107058445B;CN111893158A;CN113999887A;CN105566434B;);(3)Smith降解:该方法是皂苷降解的经典方法,条件温和,可以避免副产物的生成,但该方法路线较长,涉及到较多的萃取操作,溶剂消耗量较大(中国发明公开专利:CN103880910A;CN106083979A)。
发明内容
本发明提供一种基于Smith降解的黄芪甲苷水解制备环黄芪醇的方法。本发明通过将传统Smith降解过程中使用的高碘酸钠水溶液,硫酸水溶液用固载或固体试剂进行替换,简化了Smith降解操作流程,且该方法条件温和,避免了副产物的发生,具有较高的收率以及产物纯度。本发明选取廉价、低毒易获得的醇类为反应溶剂,Smith降解所涉及到的氧化、还原、酸解均在同一溶剂中进行,全程无需萃取操作,简化了操作步骤,降低了溶剂成本。
反应式如下:
具体经过如下步骤进行:
(1)将黄芪甲苷溶解于一种醇类溶剂中,将硅胶负载的高碘酸钠加入,室温搅拌12小时后过滤,收集滤液;
(2)在步骤1所得滤液中直接加入硼氢化钠后继续搅拌4小时;
(3)在步骤2所得反应液中加入一种固体酸,继续室温搅拌12小时后过滤,将所得滤液浓缩得到环黄芪醇粗品;
(4)步骤3所得粗品经硅胶柱纯化得到高纯度的环黄芪醇。
步骤1所述的醇类溶剂包括甲醇、乙醇、异丙醇、叔丁醇、乙二醇等,优选甲醇或异丙醇;
步骤2所述的固体酸包括硫酸/二氧化锆、硫酸/活性氧化铝、硫酸氢钠、硫酸氢钾等,优选硫酸/二氧化锆或硫酸氢钾;
步骤4中使用的硅胶为300-400目硅胶,流动相为二氯甲烷和甲醇,二者比例为二氯甲烷/甲醇=20/1;
与现有技术路线比,本发明的优势:
本发明利用Smith降解条件温和,试剂易得的优点,针对Smith降解存在的操作繁琐,所需溶剂量大等缺点,利用改进的Smith降解法来对黄芪甲苷进行降解,使用硅胶负载的高碘酸钠取代传统的高碘酸钠水溶液,避免了传统Smith降解所需的大量萃取操作,大大减少了溶剂使用量,简化了操作步骤。使用固体酸取代传统的硫酸水溶液,使条件变得温和,避免了黄芪醇等副产物的生成。本发明操作简单,成本低,适于工业化生产。
环黄芪醇核磁氢谱数据:
1H NMR (400 MHz, DMSO-d6) δ 4.88 (s, 1H), 4.68 (d, J = 3.1 Hz, 1H),4.55-4.45 (m, 1H), 4.23(d, J = 5.4 Hz, 1H), 4.01 (d, J = 5.7 Hz, 1H), 3.62(t, J = 7.0 Hz, 1H), 3.03 (p, J = 5.2 Hz, 1H), 2.19 (d, J = 7.7 Hz, 1H),1.96-1.76 (m, 4H), 1.71 (dd, J = 11.7, 4.6 Hz, 1H), 1.63-1.47 (m, 4H), 1.45(d, J = 8.1 Hz, 2H), 1.40-1.33 (m, 1H), 1.29-1.22 (m, 3H), 1.21 (d, J = 3.7Hz, 1H),1.18 (s, 3H), 1.14 (s, 6H), 1.11 (s, 3H), 1.03 (s, 3H), 0.89 (s, 3H),0.82 (s, 3H), 0.45 (d, J = 4.0Hz, 1H), 0.24 (d, J = 4.1 Hz, 1H).
附图说明
图1为环黄芪醇的1H NMR谱图(400 MHz, DMSO-d6)。
具体实施方式
实施例1:
将1g黄芪甲苷溶解于30mL甲醇中,加入3g硅胶负载的高碘酸钠(50%),室温反应12小时后过滤,得到的滤液加入100mg硼氢化钠,室温反应4小时后加入5g硫酸氢钠,继续室温搅拌12小时后过滤,浓缩得环黄芪醇粗品。粗品经硅胶(300-400目)柱纯化(二氯甲烷:甲醇=20:1)得到环黄芪醇。
实施例2:
将1g黄芪甲苷溶解于50mL甲醇中,加入5g硅胶负载的高碘酸钠(35%),室温反应12小时后过滤,得到的滤液加入150mg硼氢化钠,室温反应4小时后加入5g硫酸氢钠,继续室温搅拌12小时后过滤,浓缩得环黄芪醇粗品。粗品经硅胶(300-400目)柱纯化(二氯甲烷:甲醇=20:1)得到环黄芪醇。
实施例3:
将1g黄芪甲苷溶解于30mL乙醇中,加入3g硅胶负载的高碘酸钠(50%),50oC反应12小时后过滤,得到的滤液加入100mg硼氢化钠,室温反应4小时后加入5g硫酸/二氧化锆,继续室温搅拌12小时后过滤,浓缩得环黄芪醇粗品。粗品经硅胶(300-400目)柱纯化(二氯甲烷:甲醇=20:1)得到环黄芪醇。
实施例4:
将1g黄芪甲苷溶解于50mL乙醇中,加入5g硅胶负载的高碘酸钠(35%),50oC反应12小时后过滤,得到的滤液加入150mg硼氢化钠,室温反应4小时后加入5g硫酸/二氧化锆,继续室温搅拌12小时后过滤,浓缩得环黄芪醇粗品。粗品经硅胶(300-400目)柱纯化(二氯甲烷:甲醇=20:1)得到环黄芪醇。
Claims (6)
1.一种基于Smith降解的环黄芪醇制备方法,其特征在于,经过以下步骤:将黄芪甲苷溶解于一种醇类溶剂中,加入硅胶负载的高碘酸钠,室温搅拌12小时后过滤,在滤液中直接加入硼氢化钠后继续搅拌4小时后加入一种固体酸,继续室温搅拌12小时后过滤,将所得滤液浓缩得到环黄芪醇粗品,经硅胶柱纯化得到高纯度的环黄芪醇。
2.如权利要求1所述的一种基于Smith降解的环黄芪醇制备方法,其特征在于,所述的醇类溶剂为甲醇、乙醇、异丙醇、叔丁醇、乙二醇。
3.如权利要求1所述的一种基于Smith降解的环黄芪醇制备方法,其特征在于,所述的固体酸为硫酸/二氧化锆、硫酸氢钾、硫酸氢钠。
4.如权利要求1所述的一种基于Smith降解的环黄芪醇制备方法,其特征在于,所述的硅胶负载的高碘酸钠,其含量为30%-60%。
5.如权利要求1所述的一种基于Smith降解的环黄芪醇制备方法,其特征在于,所述的黄芪甲苷与醇类溶剂的质量体积比为1g:20-80mL。
6.如权利要求1所述的一种基于Smith降解的环黄芪醇制备方法,其特征在于,所述的黄芪甲苷与所需硼氢化钠的质量比为1g:0.1g-0.7g。
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