CN109096076B - 一种查尔酮类化合物及其制备方法 - Google Patents
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Abstract
本发明公开了一种制备2,2',4,4'‑四羟基‑3‑(2”‑羟基‑3”‑甲基丁基‑3”‑烯基)查尔酮的方法，该方法的步骤为：用体积分数40～100％甲醇或乙醇水溶液浸提桑叶，将浸提液浓缩去除甲醇或乙醇后用水溶解，然后依次用石油醚、乙酸乙酯萃取，将乙酸乙酯萃取液浓缩得浸膏，浸膏经硅胶柱层析，以氯仿/甲醇为洗脱剂，收集氯仿/甲醇体积比为95/5洗脱的馏分，该馏分再经反相柱层析，以甲醇/水为洗脱剂，收集甲醇/水体积比为60/40洗脱的馏分，即得。本发明对于推动桑叶的深加工利用，提升桑叶产品附加值，促进该行业的可持续发展具有重要的意义。
Description
技术领域
本发明涉及天然产物化学领域，具体涉及一种查尔酮类化合物及其制备方法。
背景技术
桑树属于桑科常绿乔木，广泛种植于热带与亚热带地区。桑椹果实香甜可口，营养价值和保健功能较高，具有治疗白发、消炎等功效，深受广大消费者的喜爱。桑叶属于新资源蔬菜食品，口感鲜嫩，已逐渐为消费者所接受。研究发现，桑叶富含黄酮类化合物，具有抗氧化、抗癌、调节免疫等生物活性。然而，目前关于桑叶活性成分的研究极为有限，相关活性物质组成仍有待研究。
发明内容
本发明的目的是提供一种查尔酮类化合物的制备方法，具体为2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的制备方法。
本发明的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮，该化合物是从桑叶中提取分离得到，其结构式如下式(I)所示：
所述的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的制备方法包括以下步骤：用体积分数40～100％甲醇或乙醇水溶液浸提桑叶，将浸提液浓缩去除甲醇或乙醇后用水溶解，然后依次用石油醚、乙酸乙酯萃取，将乙酸乙酯萃取液浓缩得浸膏，浸膏经硅胶柱层析，以氯仿/甲醇为洗脱剂，从体积比100/0～60/40梯度洗脱，收集氯仿/甲醇体积比为95/5洗脱的馏分，该馏分再经反相柱层析，以甲醇/水为洗脱剂，从体积比10/90～100/0梯度洗脱，收集甲醇/水体积比为60/40洗脱的馏分，即得到2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮。
所述的桑叶为桑叶粉末，其是将新鲜的桑叶干燥后粉碎成粉末。
所述的用体积分数40～100％甲醇或乙醇水溶液浸提桑叶，甲醇或乙醇水溶液的用量是5～20mL/g桑叶(即每克桑叶用5-20ml甲醇或乙醇水溶液)，浸提的温度为25～80℃，浸提时间为1～72小时。
所述的将浸提液浓缩去除甲醇或乙醇后用水溶解，是将浸提液在40～80℃下浓缩除去甲醇或乙醇，再加入1～5倍体积的水溶解。
所述的依次用石油醚、乙酸乙酯萃取，是先用石油醚萃取3～12次，再用乙酸乙酯萃取3～12次。
本发明证实，所述的化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮具有良好的自由基清除能力，该化合物对DPPH自由基清除的IC50值为21.6μM。表明本发明提供的化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮具有优异的抗氧化性能，可用于制备抗氧化护肤品、药品或保健品。
与现有技术相比，本发明的优势在于：
本发明从桑叶中制备分离得到2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮，该化合物的产率为10～120mg/kg(纯度为85～95％)。本发明对于推动桑叶的深加工利用，提升桑叶产品附加值，促进该行业的可持续发展具有重要的意义。同时也为2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的制备提供了一种新的方法。
具体实施方式
以下实施例是对本发明的进一步说明，而不是对本发明的限制。
实施例1
一、2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的制备分离
1)选料：选择新鲜桑叶，清水洗涤；
2)干燥粉碎：将桑叶晒干或烘干，采用粉碎机粉碎成粉末；
3)浸提：按5mL/g桑叶粉末的投料量(即每克桑叶粉末加5mL甲醇水溶液)，往桑叶粉末中加入体积分数40％的甲醇水溶液，在25℃浸提1小时，过滤，收集过滤液；
4)有机溶剂分级：将上述过滤液在40℃下浓缩除去甲醇，得浓缩液，加入浓缩液1倍体积的水，先后用等体积的石油醚、乙酸乙酯分别萃取3次；选择乙酸乙酯相萃取液进行浓缩，将得到的浸膏用于后续纯化；
5)取乙酸乙酯相萃取液浓缩后得到的浸膏，采用硅胶柱(100～200目)层析，以氯仿/甲醇为洗脱溶剂，从体积比100/0～60/40梯度洗脱，收集氯仿/甲醇体积比为95/5洗脱的组分，再经C18反相柱层析，以甲醇/水为洗脱剂，从体积比10/90～100/0梯度洗脱，收集甲醇/水体积比为60/40洗脱的组分，在60℃蒸发浓缩干燥，即得到化合物1(2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮)。
采用该方法获得的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的产率为10～40mg/kg，纯度为85～95％。
二、化合物1(2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮)的结构鉴定
化合物1(2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮)易溶于甲醇，质谱结果表明：该化合物分子量为564。该化合物的1H NMR(500MHz，CD3OD)和13C NMR(125MHz，CD3OD)见表1。
表1化合物1的13C与1H谱化学位移
综上所述，鉴定该化合物1的结构式如式(I)所示，名称为：2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮，该化合物易溶于甲醇。
实施例2
1)选料：选择新鲜桑叶，清水洗涤；
2)干燥粉碎：将桑叶晒干或烘干，采用粉碎机粉碎成粉末；
3)浸提：按20mL/g桑叶粉末的投料量(即每克桑叶粉末加20mL甲醇水溶液)，往桑叶粉末中加入体积分数100％的甲醇水溶液(即完全是甲醇)，在80℃浸提72小时，过滤，收集过滤液；
4)有机溶剂分级：将上述过滤液在60℃浓缩除去甲醇，得浓缩液，加入浓缩液5倍体积的水，先后用等体积的石油醚、乙酸乙酯分别萃取12次；选择乙酸乙酯相萃取液进行浓缩，将得到的浸膏用于后续纯化；
后续纯化步骤与实施例1相同，由此得到化合物1并鉴定为2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮。
采用该方法获得的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的产率为70～120mg/kg，纯度为85～95％。
实施例3
1)选料：选择新鲜桑叶，清水洗涤；
2)干燥粉碎：将桑叶晒干或烘干，采用粉碎机粉碎成粉末；
3)浸提：按20mL/g桑叶粉末的投料量(即每克桑叶粉末加20mL乙醇水溶液)，往桑叶粉末中加入体积分数40％的乙醇水溶液，在55℃浸提24小时，过滤，收集过滤液；
4)有机溶剂分级：将上述过滤液在60℃浓缩除去乙醇，得浓缩液，加入浓缩液3倍体积的水，先后用等体积的石油醚、乙酸乙酯分别萃取6次；选择乙酸乙酯相萃取液进行浓缩，将得到的浸膏用于后续纯化；
后续纯化步骤与实施例1相同，得到化合物1并鉴定为2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮。
采用该方法获得的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的产率为30～80mg/kg，纯度为85～95％。
实施例4
1)选料：选择新鲜桑叶，清水洗涤；
2)干燥粉碎：将桑叶晒干或烘干，采用粉碎机粉碎成粉末；
3)浸提：按5mL/g桑叶粉末的投料量(即每克桑叶粉末加5mL乙醇水溶液)，往桑叶粉末中加入体积分数100％的乙醇水溶液(即是乙醇)，在80℃浸提48小时，过滤，收集过滤液；
4)有机溶剂分级：将上述过滤液在80℃浓缩除去乙醇，得浓缩液，加入浓缩液1倍体积的水，先后用与等体积的石油醚、乙酸乙酯分别萃取6次；选择乙酸乙酯相萃取液进行浓缩，将得到的浸膏用于后续纯化；
后续纯化步骤与实施例1相同，得到化合物1并鉴定为2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮。
采用该方法获得的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮的产率为50～100mg/kg，纯度为85～95％。
实施例5
DPPH是一种稳定的长寿命自由基，当有自由基清除剂存在时，由于与其单电子配对而使DPPH光吸收减弱，借此评价物质清除自由基的能力，从而评定其抗氧化能力。本发明通过DPPH自由基中和试验，测定吸光度，检测化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮对DPPH自由基清除能力，以评价该化合物的抗氧化能力，所述的测试方法具体包括以下步骤：
将1,1-二苯基-2-三硝基苯肼(DPPH)溶于无水乙醇配制成浓度为0.2mM的溶液；将化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮溶于无水乙醇；取80μL的2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮乙醇溶液和160μL浓度为0.2mM的DPPH乙醇溶液混合，避光室温下放置30min，在光吸收酶标仪(SpectraMax 190,Molecular Devices,USA)于517nm波长下测定吸光度值。结果表明，化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮对DPPH自由基清除的IC50值为21.6μM。表明本发明提供的化合物2,2',4,4'-四羟基-3-(2″-羟基-3″-甲基丁基-3″-烯基)查尔酮具有优异的抗氧化性能，可用于制备抗氧化护肤品、药品或保健品。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.一种制备2,2',4,4'-四羟基-3-(2”-羟基-3”-甲基丁基-3”-烯基)查尔酮的方法，其特征在于，包括以下步骤：用体积分数40～100％甲醇或乙醇水溶液浸提桑叶，将浸提液浓缩去除甲醇或乙醇后用水溶解，然后依次用石油醚、乙酸乙酯萃取，将乙酸乙酯萃取液浓缩得浸膏，浸膏经硅胶柱层析，以氯仿/甲醇为洗脱剂，从体积比100/0～60/40梯度洗脱，收集氯仿/甲醇体积比为95/5洗脱的馏分，该馏分再经反相柱层析，以甲醇/水为洗脱剂，从体积比10/90～100/0梯度洗脱，收集甲醇/水体积比为60/40洗脱的馏分，即得到2,2',4,4'-四羟基-3-(2”-羟基-3”-甲基丁基-3”-烯基)查尔酮；
所述的桑叶为桑叶粉末，其是将新鲜的桑叶干燥后粉碎成粉末；
所述的用体积分数40～100％甲醇或乙醇水溶液浸提桑叶，甲醇或乙醇水溶液的用量是5～20mL/g桑叶，浸提的温度为25～80℃，浸提时间为1～72小时；
所述的将浸提液浓缩去除甲醇或乙醇后用水溶解，是将浸提液在40～80℃下浓缩除去甲醇或乙醇，再加入1～5倍体积的水溶解；
所述的依次用石油醚、乙酸乙酯萃取，是先用石油醚萃取3～12次，再用乙酸乙酯萃取3～12次；
所述的2,2',4,4'-四羟基-3-(2”-羟基-3”-甲基丁基-3”-烯基)查尔酮，其结构式如下式(I)所示：
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