CN100387610C - 漆叶苷的合成方法 - Google Patents
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Abstract
本发明公开了一种以天然提取物为基本原料的漆叶苷的合成方法。本发明以柚皮苷为原料，以1，4-二氧环己烷为反应溶剂，在碱存在条件下与碘发生氧化脱氢反应生成粗产品漆叶苷。经过多步重结晶，得到精制漆叶苷。本发明操作简单，反应条件稳定，容易控制，产品易于分离纯化。产品总收率可达50～65%，纯度可达到98%以上，且生产成本较低，对环境无污染。
Description
技术领域
本发明涉及一种以天然提取物为基本原料的漆叶苷的合成方法。
背景技术
漆叶苷(Rhoifolin)，又称野漆树苷，深黄色簇状结晶(甲醇)，分子式为C27H32O14，分子量580.53，熔程为258℃-260℃。FeCl3乙醇液显灰绿色至灰红色。其存在于柑桔类植物的果皮中。化学名为芹菜素-7-鼠李糖基葡萄糖苷。其结构式为
据报道，漆叶苷具有散寒、燥湿、消炎、利气等功效，用于风寒咳嗽、喉痒痰多、呕恶痞闷等(袁旭江化橘红中酚性成分的研究，中草药，2004，35(5)，498-500)。漆叶苷还具有促经神经生长因子的合成，影响中枢神经，是醛糖还原酶抑制剂和抗氧化剂。漆叶苷还能够治疗糖尿病和神经病(R.A.Rosenbloom.Method and composition for the topical treatment of diabetic neuropathy，US6,555,573)。作为黄酮类化合物的糖苷配合物，漆叶苷也同样具有抗病毒，抗老化，抗紫外线，是良好的紫外线吸收剂。
随着社会的发展，人类疾病谱已悄然发生改变，医疗模式已由单纯的疾病治疗转变为预防、保健、治疗、康复相结合的模式，各种替代医学和传统医学正在发挥这越来越大的作用，人类“回归自然”的呼声越来越高，使传统医药备受青睐。对漆叶苷的制备目前文献所提及的方法都是从植物中提取。例如以多年生黑麦草作为原料，利用乙醚作为提取剂，索氏提取器作为反应器，提取漆叶苷等有效成分(R.A.Rosenbloom.Method and composition for the topicaltreatment of diabetic neuropathy，US6,555,573)。目前也有报道用碘/吡啶体系来实现黄烷酮配糖化合物转化为黄酮配糖化合物，且得率较好，但是吡啶价格较高，增加生产成本，而且其对人体不友好的气味，不易于工业化生产。
发明内容
本发明的目的是提供一种以天然的柚皮苷为原料，成本低，适于工业化生产的合成漆叶苷的方法。
漆叶苷的合成方法，其步骤如下：
1)将柚皮苷和碘溶于1，4-二氧环己烷中，柚皮苷与碘的摩尔比为1∶0.5～2.5，柚皮苷与1，4-二氧环己烷的质量/体积比为1∶1～1∶5，再加入碱性物质，碱性物质在总溶液中的浓度为0.05％～1％，在50～140℃条件下进行氧化脱氢反应，反应结束后，浓缩反应液，加入2倍至20倍体积水，静置，抽滤，得到漆叶苷的粗产品；
2)漆叶苷粗品用碱溶液溶解，加入醇，醇的用量为碱溶液体积的1～4倍，调节pH值4～7，析出晶体，抽滤，用1，4-二氧环己烷/水体系或二甲基甲酰胺/水体系或丙酮/水体系重结晶，静置，过滤，得到精制漆叶苷。
本发明中，步骤1)氧化反应的温度优选70～120℃。所说的碱性物质可以是氢氧化钠、氢氧化钾或氢氧化钡。步骤2)中所用的醇是含碳数为C1～C6的一元醇，二元醇或三元醇。
本发明是以具有生物活性的天然提取物柚皮苷为起始原料，与植物提取法相比，该方法成本低，脱氢氧化一步用碘/1，4-二氧环己烷体系，反应条件温和，原料易得且价格便宜，产品纯度和收率均较高；该反应条件容易控制，安全，无污染。从整个合成过程看，大部分反应溶剂可以回收，重新利用，使合成成本大大降低。
发明原理如下：
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1：
取柚皮苷70g，溶解于350ml 1，4-二氧环己烷当中，同时加入氢氧化钠2.5g，置于三口烧瓶中，并保持回流；取24.4g碘溶于150ml 1，4-二氧环己烷当中，倒入恒压滴液漏斗，缓慢滴加入上述三口烧瓶中，在105℃下氧化反应4h。反应结束后，浓缩反应液到100ml，加水至1000ml，静置12小时，过滤。用7％氢氧化钠水溶液200ml溶解，再加入200ml的乙醇，用盐酸调节pH至4。静置得沉淀，过滤。用1，4-二氧环己烷100ml加热溶解以上所得漆叶苷，再加入水，过滤得到42g干饼。重复用1，4-二氧环己烷/水重结晶2次，过滤干燥得38g纯度高于98％的漆叶苷，收率54.3％。
实施例2：
取柚皮苷70g，碘30.5g溶解于400ml 1，4-二氧环己烷当中，加入氢氧化钾3.2g，恒温水浴95℃，氧化反应7h。反应结束后，反应液如实施例1浓缩加水，静置过夜，过滤，得到粗产品漆叶苷。然后加入3％氢氧化钠水溶液200ml溶解，再加入200ml的甲醇，用硫酸调节pH＝6。静置得沉淀，过滤。用1，4-二氧环己烷加热溶解以上所得漆叶苷，再加入水，过滤干燥，得到46g纯度高于98％的漆叶苷，收率65.7％。
实施例3：
取柚皮苷70g，溶解于250ml 1，4-二氧环己烷中，再加入3.0g氢氧化钠置于1000ml三口瓶当中，恒温水浴60℃。取30.5g碘溶解于150ml 1，4-二氧环己烷中，先往三口瓶中加入50ml碘的1，4-二氧环己烷溶液，剩下的碘的1，4-二氧环己烷溶液分三次加入到三口瓶中，大约每隔1小时加一次。反应结束后，反应液按实施例1浓缩加水，静置过夜，过滤得到粗品。用100ml二甲基甲酰胺加热溶解以上所得漆叶苷，过滤，再加入水至500ml，静置过滤。然后加入5％氢氧化钠水溶液500ml溶解，再加入500ml的甘油，用硫酸调节pH＝5。静置得沉淀，过滤。得到26g纯度高于98％的漆叶苷，收率37.2％。
实施例4：
取柚皮苷70Kg，溶解于250L 1，4-二氧环己烷中，加入氢氧化钠2.0Kg，恒温水浴90℃。取37.5Kg碘溶解于200L 1，4-二氧环己烷当中，分四次加入到柚皮苷的1，4-二氧环己烷溶液中，每1.5小时添加一次。浓缩反应液到100L，加水到1000L，静置。得到的粗产品加入4％氢氧化钠的水溶液100L溶解，加乙醇100L，用盐酸调节至pH＝5。静置得沉淀，过滤。用丙酮100L加热溶解以上所得漆叶苷，加入水500L，过滤。重复用丙酮/水体系重结晶，所得的漆叶苷质量为38Kg，纯度高于98％，收率54.2％。
Claims (3)
1.漆叶苷的合成方法，其步骤如下：
1)将柚皮苷和碘溶于1，4-二氧环己烷中，柚皮苷与碘的摩尔比为1∶0.5～2.5，柚皮苷与1，4-二氧环己烷的质量/体积比为1∶1～1∶5，再加入碱性物质，碱性物质在总溶液中的浓度为0.05％～1％，在50～140℃条件下进行氧化脱氢反应，反应结束后，浓缩反应液，加入2倍至20倍体积水，静置，抽滤，得到漆叶苷的粗产品，所说的碱性物质是氢氧化钠、氢氧化钾或氢氧化钡；
2)漆叶苷粗品用碱溶液溶解，加入醇，醇的用量为碱溶液体积的1～4倍，调节pH值4～7，析出晶体，抽滤，用1，4-二氧环己烷/水体系或二甲基甲酰胺/水体系或丙酮/水体系重结晶，静置，过滤，得到精制漆叶苷。
2.根据权利要求1所述的漆叶苷合成方法，其特征在于步骤1)氧化反应的温度为70～120℃。
3.根据权利要求1所述的漆叶苷合成方法，其特征在于步骤2)中所用的醇是含碳数为C1～C6的一元醇，二元醇或三元醇。
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| CN102633850A (zh) * | 2010-08-16 | 2012-08-15 | 江西山香药业有限公司 | 野漆树苷的提取方法及其制备药物用途 |
| CN101897715B (zh) * | 2010-08-16 | 2012-07-11 | 江西山香药业有限公司 | 女贞苷、野漆树苷组合物及其制备药物用途 |
| CN103012524B (zh) * | 2012-12-31 | 2015-02-25 | 浙江大学 | 一种半合成制备漆叶苷的方法 |
| CN103833810A (zh) * | 2014-02-12 | 2014-06-04 | 李玉山 | 一种野漆树苷的制备新技术 |
| CN113583063A (zh) * | 2021-08-18 | 2021-11-02 | 陕西嘉禾生物科技股份有限公司 | 一种利用柚皮苷合成大波斯菊苷的方法 |
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| JPH09121829A (ja) * | 1995-11-08 | 1997-05-13 | Japan Tobacco Inc | たばこ香喫味改良剤 |
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