CN1269835C - 一种催化热解制备低极性人参皂苷及其苷元的方法 - Google Patents
一种催化热解制备低极性人参皂苷及其苷元的方法 Download PDFInfo
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- CN1269835C CN1269835C CNB021447802A CN02144780A CN1269835C CN 1269835 C CN1269835 C CN 1269835C CN B021447802 A CNB021447802 A CN B021447802A CN 02144780 A CN02144780 A CN 02144780A CN 1269835 C CN1269835 C CN 1269835C
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- Prior art keywords
- acid
- ginsenoside
- aglycon
- low polarity
- ginsenosides
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Abstract
一种催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:原料人参皂苷以酸为催化剂,经110~180℃高温蒸制0.5~10小时。本发明明确了人参皂苷高温热解所需的催化剂,解决了红参炮制工艺中天然人参皂苷高温热解的机制或本质问题,为制备低极性人参皂苷提供了一个简便高效的方法。使用本发明提供的方法制备低极性人参皂苷,工艺简便、质量可控、原料苷元转化率高,主要产物苷元总收率高,成本低;联用分离纯化技术,可大批量地制备单体低极性人参皂苷。所制备的低极性人参皂苷单体或其混合物既可与各种法定的药用或食品的赋型剂和配合剂配伍制备成各种剂型用于医药、化妆品和功能食品用途,也可作为合成其它生物活性化合物的原料。
Description
技术领域:
本发明涉及由人参皂苷或含有人参皂苷的植物(可来源于人参、三七、西洋参和绞股蓝等的根茎叶及其制品如白参、红参或其提取物等)制备低极性人参皂苷的方法,特别是涉及到以酸为催化剂、高温热解制备人参皂苷衍生物的方法。
背景技术:
人参具有多种生理和药理作用,如抗肿瘤、增强免疫、改善微循环、平稳血压、调节血糖、降血脂、安神、抗衰老、抗紧张、调节消化机能、预防消化道溃疡、提高生命质量、增强记忆及学习能力等。在抗肿瘤方面,人参具有:1、调控肿瘤细胞的基因表达和促分化;2、抑制肿瘤的浸润和转移;3、抑制肿瘤诱导的新生血管生成;4、降低化疗药物的毒副作用;5、逆转肿瘤耐药性、提高化疗药灵敏度、增强化疗疗效等。
人参的药用形式有鲜参、白参和红参,三者的关系是鲜参经常温干燥获白参,而经蒸制后干燥为红参。使用经验和药学研究表明红参的药效高于白参和鲜参。现代研究进一步证明红参的独特药效得益于其中含特有的Rg2、Rg3、Rh类、Rk类和多炔类化合物如人参炔醇等天然微量或稀有成分。传统上,人参的炮制仅以红参的外观与质地而非有效成分的含量为标准。近来,日本专利公开(62-158490)报道了人参组织培养物经110~160℃高温处理后,其中人参皂苷Rh类含量大幅度提高;美国专利(5776460)报道了经120~180℃处理0.5~20小时后,人参中低极性皂苷增高了20~40倍。但是,两个专利均未涉及高温热解的转化机理,其结果是仅仅控制温度,人参热解产物的质和量均无法恒定,也即不同批次的产品中天然人参皂苷的转化率不同,产品中低极性皂苷的含量和比例各异。美国专利(5776460)显示,三醇型人参皂苷经高温热解后,多数转化为挥发性物质,无法大量获得所需皂苷如Rg2、F4、Rg6、Rh1、Rh4和Rk3等。
本发明的研究表明,人参中的丙二酸、天冬氮酸和谷氨酸等是人参热解的天然催化剂,通过定量使用本发明中的催化剂,反应可控,可目标化和最大化地制备低极性微量人参皂苷及其衍生物,开发和应用价值极大。
发明的技术内容:
本发明提供了一种以人参皂苷或含有人参皂苷的植物为原料的人参皂苷衍生物的制备方法,本法简单、方便、成本低,可大规模、批量地制备低极性人参皂苷及其衍生物,其特征为催化剂和高温热解(或蒸制)是本发明的必须或必要条件。
本发明所提供的方法中,所用原料为任何含有人参皂苷的植物(如人参、三七、西洋参和绞股蓝等的根茎叶及其制品)及其组织培养物,所述植物可以任何部位(如须、根、茎叶等)和任何形式(组织块、粉末或其提取物)存在,或下述任何纯度的单体人参皂苷或二至多种单体人参皂苷混合物:
天然人参皂苷:Rb1、Rb2、Rb3、Rc、Rd、Rg1、Re和Rf等;
3位羟基游离的二醇型人参皂苷:20-O-β-D-葡萄糖-20(S)-原人参二醇[20-O-β-D-glucopyranosyl -20(S)-protopanaxadiol,简称C-K]、20-O-α-L-阿拉伯糖(1→6)-βD-葡萄糖-20(S)-原人参二醇[20-O-α-L-arabinopyranosyl(1→6)-β-D-glucopyranosyl 20(S)-protopanaxadiol,简称C-Y]、20-O-α-L-阿拉伯糖(1→6)-βD-葡萄糖-20(S)-原人参二醇[20-O-α-L-arabinofuranosyl(1→6)-β-D-glucopyranosyl 20(S)-protopanaxadiol,简称Mc]和20-O-β-D-木糖-β-D-葡萄糖-20(S)-原人参二醇[20-O-β-D-xylopyranosyl(1→6)-β-D-glucopyranosyl-20(S)-protopanaxadiol,简称Mx];
6位羟基游离的三醇型人参皂苷:20-O-β-D-葡萄糖-20(S)-原人参二醇[20-O-β-D-glucopyranosyl-20(S)-protopanaxatriol,简称F1]。
本发明所提供的方法中,所用催化剂为下述酸中的一种酸或二至多种混合酸。(1)多元有机酸如草酸、丙二酸、丁二酸、丁烯二酸、酒石酸、苹果酸、柠檬酸、己二酸、苯二甲酸、天冬氨酸、谷氨酸等;(2)一元有机酸如氨基酸、糖醛酸、甲酸、冰醋酸、乳酸、丙酸、丁酸、戊酸、苯甲酸、水杨酸、磺基水杨酸、苯磺酸、一氟乙酸、二氟乙酸、三氟乙酸、一氯乙酸、二氯乙酸、三氯乙酸等;(3)无机酸如硼酸、盐酸、硫酸、磷酸等。人参皂苷与催化剂的摩尔比为1∶0.01~1∶1;催化剂的使用方式为将催化剂制备成水溶液与原料浸润混合后蒸制。
本发明所提供的方法中,热解温度为110~180℃,时间为0.5~10小时。
本发明所提供的方法中,催化剂为酸,可选用范围较宽。硝酸等无机强酸对皂苷破坏大,且因最终产品多为食品或药品而不宜使用。综合水解时间、收率、工艺过程、成本和质量等多方面的因素,丙二酸和丁二酸为最佳选择。催化剂的种类(酸性强弱)和用量(添加量)直接与热解温度和作用时间密切相关:1、催化剂的种类和用量与最适温度的关系为超过最适温度时,皂苷破坏增多,反之,所需热解时间延长;2、催化剂用量超过最适用量时,皂苷破坏增多,反之,所需热解时间增长。以催化剂丙二酸和丁二酸为例,人参皂苷与催化剂的最适摩尔比为1∶0.3~1∶0.5,热解最适温度为120℃,最适反应时间在4~6小时间。
本发明所提供的方法中,热解需在密闭容器如高压锅中进行,加热介质可为蒸汽、空气、二氧化碳、氮气、惰性气体或其中二至多种混合气体。使用非蒸汽作为加热介质时,容器中应加入少量水,以保持原料湿润,提高反应效率。
本发明所提供的方法中,所制备的低极性人参皂苷及其苷元为:
(1)20位羟基游离的二醇型人参皂苷
人参皂苷20-(R)-Rg3、20-(S)-Rg3、20-(R)-Rh2、20-(S)-Rh2;
(2)20位羟基游离的三醇型人参皂苷
人参皂苷20-(R)-Rg2、20-(S)-Rg2、20-(R)-Rh1和20-(S)-Rh1。
(3)20位烯键的二醇型人参皂苷
Δ20(21)-二醇型人参皂苷:Rk1、Rk2、Rs5;
Δ20(22)-二醇型人参皂苷:Rg5、Rh3、Rs4。
(4)20位烯键的三醇型人参皂苷
Δ20(21)-三醇型人参皂苷:Rg6、Rk3、Rs7,
Δ20(22)-三醇型人参皂苷:F4、Rh4、Rs6;
(5)二醇型人参皂苷苷元
原人参二醇(protopanaxadiol,PPD);
(6)三醇型人参皂苷苷元
原人参三醇(protopanaxatriol,PPT);
(7)二醇型人参皂苷苷元衍生物
3β,12β-二羟-20(21),24(25)-二烯-达玛烷[dammar-3β,12β-dihydroxyl-20(21),24(25)-diene,简称Δ20(21)-PPD]、
3β,12β-二羟-20(22),24(25)-二烯-达玛烷[dammar-3β,12β-dihydroxyl-20(22),24(25)-diene,简称Δ20(22)-PPD];
(8)三醇型人参皂苷苷元衍生物
3β,6α,12β-三羟-20(21),24(25)-二烯-达玛烷[dammar-3β,6α,12β-trihydroxyl-20(21),24(25)-diene,简称Δ20(21)-PPT]、
3β,6α,12β-三羟-20(22),24(25)-二烯-达玛烷[dammar-3β,6α,12β-trihydroxyl-20(22),24(25)-diene,简称Δ20(22)-PPT]。
本发明所提供的方法中,不同原料将得到不同的热解产物如表1所示:
表1.不同原料在不同条件下的热解产物
原料 | 条件 | 产物 |
天然二醇型人参皂甙 | 弱酸小量时 | 以20(R)-Rg3、20(S)-Rg3、Rg5Rk1为主 |
弱酸大量,或强酸小量时 | 以单糖苷20(R)-Rh2、20(S)-Rh2、Rh3和Rk2为 | |
强酸大量时 | 以环化苷元产物PD为主 | |
3位羟基游离的二醇型人参皂苷Mc C-K、Mx、C-Y和 | 弱酸 | 以20-(R)-PPD、20-(S)-PPD、Δ20(21)-PPD和△20(22)-PPD为主 |
强酸 | 以环化苷元产物PD为主 | |
天然三醇型人参皂苷Re和Rg1 | 弱酸低量时 | 为双糖苷和单糖苷的混合物20(R)-Rh2、20(S)-Rg2、Rg6、F4、20(R)-Rh1、20(S)-Rh1、Rh4和Rk3为主 |
酸高量或强酸低量时 | 以单糖苷20(R)-Rh1、20(S)-Rh1、Rh4、Rk3和苷元PT、Δ20(21)-PPT、Δ20(22)-PPT为主为 | |
强酸高量 | 以环化苷元产物PT为主 | |
6位羟基游离的三醇型人参皂苷F1 | 弱酸时 | 以20-(R)-PPT、20-(S)-PPTΔ20(21)-PPT和Δ20(22)-PPT为主 |
强酸时 | 以环化苷元产物PT为主 |
此外,还有苷元裂解物如酚类化合物、多炔类化合物等,其量随热解时酸性增强、温度升高和时间延长而增加。
本发明所提供的方法中,原料人参皂苷的转化率≥96%,主产物的总收率≥90%。
本发明所提供的方法中,所制备的产物可以以低极性人参皂苷混合物的形式、经常规方法干燥后,直接用于医药品、化妆品和健康功能食品领域;也可结合分离纯化技术,大批量地制备权利要求2所述的各种低极性人参皂苷单体。经纯化后的低极性人参皂苷单体或其混合物可与各种法定的药用或食品的赋型剂和配合剂配伍制备成各种剂型,用于医药品、化妆品和健康功能食品领域;也可作为合成其它生物活性化合物的原料。
本发明所提供的方法中,所述方法同样适用于人参皂苷以外的其它三萜类皂苷如三七皂苷(Notoginsenosides)、绞股蓝皂苷(Gypenosides)、越南人参皂苷(Vietnamese ginsenosides)、桦叶烯四醇(Betulafolientetraol)、桦叶烯四醇A(Betulafolientetraol A)、桦叶烯五醇(Betulafolienpentaol)、达玛烯二醇(Dammarenediol)、达玛-24-3β,20-二醇-3-乙酸酯(Dammar-24-ene-3β,20-diol-3-acetate)、羟基达玛烯酮(Hydroxyldammarenone)、奥寇梯木酮(Octillone)、龙脑香环氧二醇(Kapurol)、龙脑香环氧醇酮(Kapurone)、龙脑香二醇酮(Dryobalanone)、龙脑香醇酮酸(Dryobalanonoloic acid)等。自这些三萜皂苷或含有这些三萜皂苷的植物如(包括植物的任何部位和任何存在形式如组织块、粉末或其提取物等)或含这些三萜皂苷的植物培养物为起始原料,制备相应的低极性三萜皂苷或三萜皂苷的苷元。
本发明明确了人参皂苷高温热解所需的催化剂,解决了红参炮制天然人参皂苷高温热解转化的必须或必要条件,为大量制备低极性人参皂苷提供了一个简便而高效的方法。使用本发明提供的方法制备低极性人参皂苷及其衍生物,其工艺简便、质量可控、原料的苷元转化率高(≥96%),主产物苷元总收率高(≥90%),成本低。在联用分离纯化技术的基础上,可大批量地制备各类低极性人参皂苷单体。
具体实施方式:
实施例1
二醇型人参皂苷(25g)与45%的丙二酸水溶液(5ml)浸湿混匀,置于高压灭菌锅中,120℃热解5小时。热解产物(HPLC分析表明,热解转化率≥96%,主产物为20-(R)-Rg3、20-(S)-Rg3、Rg5和Rk1)中,加入100mL水溶液形成悬浊液,用二氯甲烷萃取3次,减压除去水相中二氯甲烷后,再向其中加入30%的乙醇1000ml,将溶解液进行吸附树脂柱层析,30%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷。减压浓缩,析出大量沉淀,过滤后获20-(R)-Rg3(2.05g);向滤液中加入1/5份的丙酮,放置12h后,析出白色沉淀,上反相制备柱进行分离(流动相为65%的乙醇)分别获20-(S)-Rg3(2.3g),Rg5(1.8g)和Rk1(1.4g)。
实施例2
三醇型人参皂苷(25g)与45%天冬氨酸水溶液(5ml)浸湿混匀,置于高压灭菌锅中,120℃热解5小时。热解产物(HPLC分析表明,热解转化率≥96%,主产物为20(R)-Rg2、20(S)-Rg2、Rg6、F4、20-(R)-Rh1、20-(S)-Rh1、Rh4和Rk3)中,加入100mL水溶液形成悬浊液,用二氯甲烷萃取3次,减压除去水相中二氯甲烷后,再向其中加入30%的乙醇1000ml,将溶解液进行吸附树脂柱层析,30%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷。减压浓缩除乙醇溶液,获白色粉末(9g);此沉淀经反相(流动相为65%的乙醇)和正相(流动相为氯仿/甲醇/水=7/3/1下层)制备柱进行分离得到20(R)Rg2(0.8g)、20(S)-Rg2(0.83g)、Rg6(1.14g)、F4(1.10g)、20(R)-Rh1(0.5g)、20(S)-Rh1(0.55g)、Rh4(1.3g)和Rk3(1.23g)。
实施例3
二醇型人参皂苷(25g)与9mol/L的硫酸(5ml)浸湿混匀,置于高压灭菌锅中,120℃热解5小时。热解产物(HPLC分析表明,热解转化率≥96%,产物为侧链环化的人参二醇PD和少量的20(R)-Rh2、20(S)-Rh2、Rh3和Rk2)中,加入1000mL水溶解,进行吸附树脂柱层析30%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷。减压除乙醇,析出大量沉淀(6.4g)。此沉淀经反相制备柱进行分离(流动相为65%的乙醇)得到PD(2.3g)、Δ20(22)-PPD(0.4g)、20-(R)-Rh2(0.38g)、20-(S)-Rh2(0.34g)、Rh3(0.44g)和Rk2(0.51g)。
实施例4
二醇型人参皂苷(25g)与50%甲酸水溶液(5mL)浸湿混匀,置于高压灭菌锅中,120℃热解5小时。热解产物的HPLC分析表明,热解转化率≥96%,产物主要为20(R)-Rh2、20(S)-Rh2、Rh3、Rk2和PD中。加入1000mL水溶解,进行吸附树脂柱层析30%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷。减压除去收集液中的乙醇,析出大量沉淀(8.9g)。此沉淀经反相制备柱进行分离(流动相为65%的乙醇)分别得到20(R)-Rh2(1.8g)、20(S)-Rh2(1.4g)、Rh3(1.7g)、Rk2(1.9g)和人参二醇(1.3g)。
实施例5
人参皂甙C-K(5.0g)与45%葡萄糖醛酸(5mL)浸湿混匀,置于高压灭菌锅中,120℃热解5小时;热解产物的HPLC分析表明,转化率≥96%,产物主要为20-(R)-PPD、20-(S)-PPD、Δ20(21)-PPD和Δ20(22)-PPD。后者中,加入1000mL 40%的乙醇溶解,进行吸附树脂柱层析(40%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷)。减压除去收集液中的乙醇,析出大量沉淀(6.4g)。沉淀经硅胶层析(洗脱剂为石油醚/乙酸乙酯=8/1)分离纯化分别获得20-(R)-PPD(0.74g)、20-(S)-PPD(0.64g)、Δ20(21)-PPD(0.54g)和Δ20(22)-PPD(0.71g)。
实施例6
人参皂苷F1(5.0g)与68%甘氨酸(5mL)湿混匀,置于高压灭菌锅中,120℃热解5小时;热解产物的HPLC分析表明,转化率≥96%,产物主要为20-(R)-PPT、20-(S)-PPT、Δ20(21)-PPT和Δ20(22)-PPT。后者中加入1000mL水溶解,进行吸附树脂柱层析,30%的乙醇洗脱除杂后,用90%的乙醇洗脱回收低极性皂苷。减压除收集液中乙醇,析出大量沉淀(6.4g)。沉淀经硅胶层析(洗脱剂为石油醚/乙酸乙酯=8/1),分别为20-(R)-PPD(0.71g)、20-(S)-PPD(0.66g)、Δ20(21)-PPD(0.52g)和Δ20(22)-PPD(0.73g)。
Claims (10)
1、一种催化热解制备低极性人参皂苷及其苷元的方法,低极性人参皂苷及其苷元为:
(1)20位羟基游离的二醇型人参皂苷:
人参皂苷20-(R)-Rg3、20-(S)-Rg3、20-(R)-Rh2和20-(S)-Rh2;
(2)20位羟基游离的三醇型人参皂苷:
20-(R)-Rg2、20-(S)-Rg2、20-(R)-Rh1和20-(S)-Rh1;
(3)20位烯键的二醇型人参皂苷:
(4)20位烯键的三醇型人参皂苷:
(5)二醇型人参皂苷苷元
原人参二醇;
(6)三醇型人参皂苷苷元
原人参三醇;
(7)二醇型人参皂苷苷元衍生物
3β,12β-二羟-20(21),24(25)-二烯-达玛烷、
3β,12β-二羟-20(22),24(25)-二烯-达玛烷;
(8)三醇型人参皂苷苷元衍生物:
3β,6α,12β-三羟-20(21),24(25)-二烯-达玛烷、
3β,6α,12β-三羟-20(22),24(25)-二烯-达玛烷;
其特征在于:以人参皂苷或任何含有人参皂苷的植物为原料,以酸为催化剂,经110~180℃高温蒸制0.5~10小时。
2、按照权利要求1所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:人参皂苷与催化剂的摩尔比为1∶0.01~1∶1;催化剂的使用方式为将制备成水溶液的催化剂与原料浸润混合后蒸制。
3、按照权利要求1所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于所用催化剂为多元有机酸、一元有机酸、无机酸中的一种或二种以上的混合。
4、按照权利要求3所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于所述多元有机酸选自草酸、丙二酸、丁二酸、丁烯二酸、酒石酸、苹果酸、柠檬酸、己二酸、苯二甲酸、天冬氨酸、谷氨酸。
5、按照权利要求3所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于所述一元有机酸选自氨基酸、糖醛酸、甲酸、冰醋酸、乳酸、丙酸、丁酸、戊酸、苯甲酸、水杨酸、磺基水杨酸、苯磺酸、一氟乙酸、二氟乙酸、三氟乙酸、一氯乙酸、二氯乙酸、三氯乙酸。
6、按照权利要求3所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于所述无机酸选自硼酸、盐酸、硫酸、磷酸。
7、按照权利要求1所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:所用原料为含人参皂苷的任何植物及其组织培养物,所述植物以植物的任何部位和任何形式存在,或任何纯度的天然人参皂苷、3位羟基游离的二醇型人参皂苷、6位羟基游离的三醇型人参皂苷的单体人参皂苷或二种以上单体人参皂苷的混合。
8、按照权利要求7所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:所述天然人参皂苷为Rb1、Rb2、Rb3、Rc、Rd、Rg1、Re或Rf。
9、按照权利要求7所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:所述3位羟基游离的二醇型人参皂苷为20-O-β-D-葡萄糖-20(S)-原人参二醇、20-O-α-L-阿拉伯糖(1→6)-β-D-葡萄糖-20(S)-原人参二醇、20-O-α-L-阿拉伯糖(1→6)-β-D-葡萄糖-20(S)-原人参二醇或20-O-β-D-木糖-β-D-葡萄糖-20(S)-原人参二醇。
10、按照权利要求7所述催化热解制备低极性人参皂苷及其苷元的方法,其特征在于:所述6位羟基游离的三醇型人参皂苷为20-O-β-D-葡萄糖-20(S)-原人参二醇。
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CN1122042C (zh) * | 2000-10-10 | 2003-09-24 | 海南亚洲制药有限公司 | 稀有人参皂甙的制备方法 |
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CN103665078B (zh) * | 2013-12-18 | 2016-06-08 | 成都医路康医学技术服务有限公司 | 一种17α-羟基甾体酯的制备方法 |
CN104593178A (zh) * | 2014-11-19 | 2015-05-06 | 吉林农业大学 | 一种含有人参稀有皂苷的多功能手工皂 |
CN104593178B (zh) * | 2014-11-19 | 2017-11-28 | 吉林农业大学 | 一种含有人参稀有皂苷的多功能手工皂 |
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