CN115260001B - (1s,2s,4r)-二戊烯-1,2-二醇的制备方法 - Google Patents
(1s,2s,4r)-二戊烯-1,2-二醇的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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Abstract
发明涉及制备色谱技术领域。针对(1S,2S,4R)‑二戊烯‑1,2‑二醇难以从天然产物中分离、纯化的问题，本发明提供制备(1S,2S,4R)‑二戊烯‑1,2‑二醇的方法，豆渣粉末乙醇提取后，采用石油醚、乙酸乙酯和正丁醇依次萃取后得到的正丁醇萃取物，将豆渣正丁醇萃取物上样到大孔吸附树脂，然后分别通过不同浓度的乙醇水溶液洗脱，取特定浓度的乙醇水溶液洗脱液，浓缩后经亲水柱色谱分离即可得到纯度很高的(1S,2S,4R)‑二戊烯‑1,2‑二醇。本发明所述制备方法具有操作简便，制备快速、条件温和的优点。
Description
技术领域
发明涉及制备色谱技术领域，具体涉及(1S,2S,4R)-二戊烯-1,2-二醇的制备方法。
背景技术
单萜类物质广泛应用于制药、化妆品、农业和食品工业。R-(+)-柠檬烯是柑橘油的主要成分，已被用于化妆品、食品和饮料工业和清洁材料。(1S,2S,4R)-二戊烯-1,2-二醇是R-(+)-柠檬烯的一种生物转化产物，(1S,2S,4R)-二戊烯-1,2-二醇具有显著的抗炎、抗菌和抗肿瘤活性。开展(1S,2S,4R)-二戊烯-1,2-二醇的制备与纯化研究对于(1S,2S,4R)-二戊烯-1,2-二醇的综合利用具有重要意义。
目前关于(1S,2S,4R)-二戊烯-1,2-二醇的制备技术报道的很少，有人用1Kg利比里亚风疹(Lippia rubella，一种植物)干燥、粉碎并用乙醇渗滤提取8次。90g乙醇提取物悬浮于水中，并依次采用有机溶剂进行液-液分配萃取，得到正己烷部分(5.9g)、二氯甲烷部分(1.8g)、乙酸乙酯部分(21.2g)和正丁醇部分(29.1g)。采用四元系统正己烷-乙酸乙酯-甲醇-水依次以1:1:1:1(A)、5:6:5:6(B)、4:6:4:6(C)、3:6:3:6(D)、2:6:2:6(F)和1:6:1:6(G)的6个比例进行高速逆流色谱分离纯化实验。高速逆流色谱柱首先装入溶解系统G的上层有机相，它在整个分离过程中作为固定相。设置旋转后，溶剂系统G的下层水相用作第一步梯度分离的流动相。以2ml/min的速度沿头尾方向泵送(反相洗脱模式)。在达到色谱柱的流体动力学平衡后，注入样品。在梯度的每个步骤(从G到A)中收集20个4mL级分，总共提供120个级分。其中级分83-91合并后得到(1S,2S,4R)-二戊烯-1,2-二醇(期刊名RevistaBrasileira de Farmacognosia题目：Absolute Stereochemistry of AntifungalLimonene-1,2-diols from Lippia rubella；网址：https://doi.org/10.1007/s43450-020-00081-x)。
高速逆流色谱是高速逆流色谱(high speed countercurrent chromatography,HSCCC)是20世纪80年代发展起来的一种连续高效的液-液分配色谱分离技术。它利用两相溶剂体系在高速旋转的螺旋管内建立起一种特殊的单向性流体动力学平衡，当其中一相作为固定相，另一相作为流动相，在连续洗脱的过程中能保留大量固定相。上述分离纯化过程复杂，对设备要求较高，分离成本较高。
目前，大孔吸附树脂是富集与纯化天然产物常用的分离手段。大孔吸附树脂是以苯乙烯为单体，二乙烯苯为交联剂，甲苯、二甲苯为致孔剂，偶氮二异丁腈为引发剂制备的一类多孔骨架结构。它们具有良好的大孔网状结构、较大的比表面积以及稳定的理化性质，已经成功应用于植物单萜类成分的富集。然而直接利用大孔吸附树脂纯化技术很难一步实现(1S,2S,4R)-二戊烯-1,2-二醇的制备。
发明内容
针对(1S,2S,4R)-二戊烯-1,2-二醇难以从天然产物中分离、纯化的上述问题，本发明提供制备(1S,2S,4R)-二戊烯-1,2-二醇的方法，将豆渣正丁醇萃取物上样到大孔吸附树脂，然后分别通过不同浓度的乙醇水溶液洗脱，取特定浓度的乙醇水溶液洗脱液，浓缩后经亲水柱色谱分离即可得到纯度很高的(1S,2S,4R)-二戊烯-1,2-二醇。本发明所述制备方法具有操作简便，条件温和等优点。
本发明的技术方案如下：
一种制备(1S,2S,4R)-二戊烯-1,2-二醇的方法，包括以下步骤：
(1)将豆渣粉末用乙醇浸提，提取液经减压挥发掉乙醇后，加入石油醚萃取，分离去除石油醚萃取液，加入乙酸乙酯萃取，分离去除乙酸乙酯萃取液，加入正丁醇萃取，分离得到豆渣正丁醇萃取液；
(2)将豆渣正丁醇萃取液加入水中，并超声均匀，得样品溶液Ⅰ；
(3)将样品溶液Ⅰ上样到大孔吸附树脂，并依次用10-30％(v/v)、40-80％(v/v)乙醇水溶液在常压下分别洗脱，取40-80％(v/v)乙醇水溶液洗脱得到的洗脱液，并蒸干溶剂，然后加入质子性溶剂溶解，超声，并采用0.22μm滤膜过滤掉杂质，得到样品溶液Ⅱ；
(4)将样品溶液Ⅱ经制备液相色谱在进行单体化合物溶液的分离，色谱柱为亲水性色谱柱，液相色谱条件，0～20min，15％ACN(v/v)，收集的洗脱液，蒸干，即可得到(1S,2S,4R)-二戊烯-1,2-二醇。
所述豆渣是指大豆豆渣。(1S,2S,4R)-二戊烯-1,2-二醇存在于豆渣之中。豆渣可以选用生产豆奶或豆腐过程中的副产品。
所述的亲水性制备色谱柱可以选用现有的产品，也可以采用以下方法制备：将氨基硅胶微球、对苯二甲醛与间苯二胺在N,N-二甲基甲酰胺溶剂中，在80-120℃条件下反应8-24h，用乙醇清洗后装柱得到。硅胶微球上的氨基与对苯二甲醛上的醛基反应，再与间苯二胺上的胺基反应，形成了缩醛胺型微孔有机聚合物，使得硅胶微球具有丰富的亚胺片段，可以与(1S,2S,4R)-二戊烯-1,2-二醇结构中的醇羟基产生氢键作用而实现较好色谱分离。
所述豆渣正丁醇萃取液上样到大孔吸附树脂后，优选依次用30％、50％、80％的乙醇水溶液在常压下洗脱。本发明的实验证明，50％(v/v)乙醇水溶液洗脱得到的洗脱液含有目标分子，豆渣正丁醇萃取物经大孔吸附树脂粗划段后，采用缩醛胺型微孔有机聚合物修饰的硅胶柱色谱对50％乙醇/水洗脱部分进行制备分离，能够快速制备纯化(1S,2S,4R)-二戊烯-1,2-二醇的单体化合物。
所述大孔树脂可以选用D101大孔树脂。
所述质子性溶剂可以选用甲醇、乙醇、乙酸或四氢呋喃，优选甲醇。
有益效果：本发明操作简便，能够快速分离纯化目标分子，并且条件温和，成本低。
附图说明
图1为实施例(1S,2S,4R)-二戊烯-1,2-二醇的制备色谱分离图。
图2为(1S,2S,4R)-二戊烯-1,2-二醇的结构。
图3为(1S,2S,4R)-二戊烯-1,2-二醇的13C NMR谱。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明。
实施例
一、豆渣正丁醇萃取物的制备：
将豆渣粉末用乙醇浸提，提取液经减压挥发掉乙醇后，加入石油醚萃取，分离去除石油醚萃取液，加入乙酸乙酯萃取，分离去除乙酸乙酯萃取液，加入正丁醇萃取，分离得到豆渣正丁醇萃取液；
二、样品溶液的制备：
取14g豆渣正丁醇萃取液加入圆底烧瓶中，并加入15mL水，并超声至均匀；
三、预处理
将样品溶液上样到大孔吸附树脂(D101，30mm×400mm)，并依次用1.0L 30％(v/v)、1.0L 50％(v/v)和1.0L 80％(v/v)乙醇水溶液在常压下分别洗脱；
只取50％(v/v)乙醇水溶液洗脱得到的洗脱液，移至旋蒸瓶中并减压蒸干，然后加入3mL甲醇溶解，超声，并采用0.22μm滤膜过滤掉杂质，得到甲醇样品溶液；
四、分离纯化
将亲水性制备色谱柱(采用本发明所述方法制备，10μm，10×250mm)装到制备液相色谱仪器上，将甲醇样品溶液经制备液相色谱进行单体化合物溶液的分离，液相色谱条件，0～20min，15％ACN(v/v)，收集的洗脱液，蒸干，得到产物21.7mg。
五、分析
对产物进行13C NMR谱测试(图3)，碳谱数据与参考文献报道的数据几乎完全一致，证明即可得到(1S,2S,4R)-二戊烯-1,2-二醇。
以上所述的实施例仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (5)
1.(1S,2S,4R)-二戊烯-1,2-二醇的制备方法，其特征在于：包括以下步骤：
(1)将豆渣粉末用乙醇浸提，提取液经减压挥发掉乙醇后，加入石油醚萃取，分离去除石油醚萃取液，加入乙酸乙酯萃取，分离去除乙酸乙酯萃取液，加入正丁醇萃取，分离得到豆渣正丁醇萃取液；
(2)将豆渣正丁醇萃取液加入水中，并超声均匀，得样品溶液Ⅰ；
(3)将样品溶液Ⅰ上样到大孔吸附树脂，并依次用按v/v为10-30％、40-80％乙醇水溶液在常压下分别洗脱，取v/v 40-80％乙醇水溶液洗脱得到的洗脱液，并蒸干溶剂，然后加入质子性溶剂溶解，超声，并采用0.22μm滤膜过滤掉杂质，得到样品溶液Ⅱ；所述质子性溶剂为甲醇、乙醇；
(4)将样品溶液Ⅱ经制备液相色谱在进行单体化合物溶液的分离，色谱柱为亲水性色谱柱，液相色谱条件，0～20min，v/v 15％ACN，收集的洗脱液，蒸干，即可得到(1S,2S,4R)-二戊烯-1,2-二醇。
2.根据权利要求1所述的制备方法，其特征在于：所述豆渣为大豆豆渣。
3.根据权利要求1所述的制备方法，其特征在于：所述的亲水性制备色谱柱为氨基硅胶微球、对苯二甲醛与间苯二胺在N,N-二甲基甲酰胺溶剂中80-120℃条件下反应8-24h，用乙醇清洗后装柱得到。
4.根据权利要求1所述的制备方法，其特征在于：所述样品溶液Ⅰ上样到大孔吸附树脂后，依次用30％、50％的乙醇水溶液在常压下洗脱，保留v/v为50％的乙醇水溶液洗脱得到的洗脱液。
5.根据权利要求1所述的制备方法，其特征在于：所述大孔吸附树脂为D101大孔吸附树脂。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402544A (zh) * | 2008-11-14 | 2009-04-08 | 沈阳万爱普利德医药科技有限公司 | 一种高纯度β-榄香烯原料药的工业化生产方法 |
| CN106726867A (zh) * | 2016-11-17 | 2017-05-31 | 东莞波顿香料有限公司 | 一种椴树花提取物的提取方法及该提取物的应用 |
| CA3121924A1 (en) * | 2018-12-14 | 2020-06-18 | Techson Industry Company Limited | Method for preparing cannabidiol by seperation and purification using high-speed countercurrent chromatography |
| WO2022052394A1 (zh) * | 2020-09-14 | 2022-03-17 | 浙江大学 | 一种飞燕草素酰基化花色苷的制备方法 |
-
2022
- 2022-08-15 CN CN202210975414.0A patent/CN115260001B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402544A (zh) * | 2008-11-14 | 2009-04-08 | 沈阳万爱普利德医药科技有限公司 | 一种高纯度β-榄香烯原料药的工业化生产方法 |
| CN106726867A (zh) * | 2016-11-17 | 2017-05-31 | 东莞波顿香料有限公司 | 一种椴树花提取物的提取方法及该提取物的应用 |
| CA3121924A1 (en) * | 2018-12-14 | 2020-06-18 | Techson Industry Company Limited | Method for preparing cannabidiol by seperation and purification using high-speed countercurrent chromatography |
| WO2022052394A1 (zh) * | 2020-09-14 | 2022-03-17 | 浙江大学 | 一种飞燕草素酰基化花色苷的制备方法 |
Non-Patent Citations (5)
| Title |
|---|
| Biotransformation of (R)-(+)-and (S)-(-)-limonene by fungi and the use of solid phase microextraction for screening;Jan C.R.等;《Photochemistry》;20011231;第199-208页 * |
| Epoxide hydrolase activity in the aqueous extracts of vegetable flours and application to the stereoselective hydrolysis of limonene oxide;Claudia Sanfilippo等;《Molecular Catalysis》;20220818;第1-6页 * |
| Suzana Guimarães Leitão等.Absolute Stereochemistry of Antifungal Limonene-1,2-diols from Lippia rubella.《Revista Brasileira de Farmacognosia》.2020,第1-7页. * |
| Tiago Daniel Madureira de Medeiros等.Extraction and purification of limonene-1,2-diol obtained from the fungal biotransformation of limonene.《Separation and Purification Technology》.2020,第1-6页. * |
| 胜红蓟内生真菌转化柠檬烯产物的抑菌活性;裴真巧等;《华侨大学学报（自然科学版）》;20221202;第44卷(第01期);第87-93页 * |
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