JPS62178598A - Purification of sennoside - Google Patents
Purification of sennosideInfo
- Publication number
- JPS62178598A JPS62178598A JP2006886A JP2006886A JPS62178598A JP S62178598 A JPS62178598 A JP S62178598A JP 2006886 A JP2006886 A JP 2006886A JP 2006886 A JP2006886 A JP 2006886A JP S62178598 A JPS62178598 A JP S62178598A
- Authority
- JP
- Japan
- Prior art keywords
- sennoside
- clay
- solution
- treated
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930186851 sennoside Natural products 0.000 title claims abstract description 50
- IPQVTOJGNYVQEO-KGFNBKMBSA-N sennoside A Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(C(O)=O)C=C1[C@@H]2[C@H]1C2=CC(C(O)=O)=CC(O)=C2C(=O)C2=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C=CC=C21 IPQVTOJGNYVQEO-KGFNBKMBSA-N 0.000 title claims abstract description 32
- 229940124513 senna glycoside Drugs 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title claims description 13
- 239000004927 clay Substances 0.000 claims abstract description 46
- 239000003463 adsorbent Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 241000219061 Rheum Species 0.000 claims abstract description 5
- 235000009411 Rheum rhabarbarum Nutrition 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- IPQVTOJGNYVQEO-UHFFFAOYSA-N 9-[2-carboxy-4-hydroxy-10-oxo-5-[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-9h-anthracen-9-yl]-4-hydroxy-10-oxo-5-[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-9h-anthracene-2-carboxylic acid Chemical class OC1C(O)C(O)C(CO)OC1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(C(O)=O)C=C1C2C1C2=CC(C(O)=O)=CC(O)=C2C(=O)C2=C(OC3C(C(O)C(O)C(CO)O3)O)C=CC=C21 IPQVTOJGNYVQEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229940076742 senna leaves Drugs 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229910001583 allophane Inorganic materials 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000006286 aqueous extract Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000284 extract Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008141 laxative Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 235000006693 Cassia laevigata Nutrition 0.000 abstract 1
- 241000735631 Senna pendula Species 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000001543 purgative effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000006228 supernatant Substances 0.000 description 9
- 238000003795 desorption Methods 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- IPQVTOJGNYVQEO-CXZNLNCXSA-N sennoside A Natural products O=C(O)c1cc(O)c2C(=O)c3c(O[C@H]4[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O4)cccc3[C@@H]([C@H]3c4c(c(O)cc(C(=O)O)c4)C(=O)c4c(O[C@H]5[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O5)cccc34)c2c1 IPQVTOJGNYVQEO-CXZNLNCXSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic alcohols Chemical class 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- JQVYZJIFFAHQKX-ZAULLPPESA-L calcium;3-carboxy-10-[2-carboxy-4-oxido-10-oxo-5-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-9h-anthracen-9-yl]-9-oxo-8-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-10h-anthracen-1-olate Chemical compound [Ca+2].O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(C([O-])=O)C=C1C2C1C2=CC(C([O-])=O)=CC(O)=C2C(=O)C2=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C=CC=C21 JQVYZJIFFAHQKX-ZAULLPPESA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002475 laxative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000009814 sennoside A&B Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 240000004307 Citrus medica Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZFWOUNNKSHIAFK-UHFFFAOYSA-N Sennoside D Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(CO)C=C1C2C1C2=CC(C(O)=O)=CC(O)=C2C(=O)C2=C(OC3C(C(O)C(O)C(CO)O3)O)C=CC=C21 ZFWOUNNKSHIAFK-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MGRRGKWPEVFJSH-UHFFFAOYSA-N dianthrone Natural products C12=CC=CC=C2C(=O)C2=CC=CC=C2C1=C1C2=CC=CC=C2C(=O)C2=CC=CC=C21 MGRRGKWPEVFJSH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- IPQVTOJGNYVQEO-AIFLABODSA-N sennoside B Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(C(O)=O)C=C1[C@H]2[C@H]1C2=CC(C(O)=O)=CC(O)=C2C(=O)C2=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C=CC=C21 IPQVTOJGNYVQEO-AIFLABODSA-N 0.000 description 1
- ZFWOUNNKSHIAFK-RDAFFBQNSA-N sennoside C Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC2=C1C(=O)C1=C(O)C=C(CO)C=C1[C@@H]2[C@H]1C2=CC(C(O)=O)=CC(O)=C2C(=O)C2=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C=CC=C21 ZFWOUNNKSHIAFK-RDAFFBQNSA-N 0.000 description 1
- 239000008682 sennoside C Substances 0.000 description 1
- 229940004991 sennoside b Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 るものである。[Detailed description of the invention] Industrial applications It is something that
従来の技術
センノサイドは、センナ葉、大黄等に比較的多量に含ま
れているジアンスロン配糖体であって、センノサイドＡ
およびセンノサイドＢのほか、少量のセンノサイドＣ，
Ｄ、Ｅ、Ｆなどの立体異性体がある。単離されたものは
、カルシウム塩の形で水に可溶になる。便通を促す作用
があり、下剤として有用な物質である。センナ葉や大黄
を水（アルカリを加えることらある）、含水有機溶媒等
で抽出処理すると容易に抽出されるが、抽出物そのもの
はセンノサイド以外の可溶性成分を多量に含むため、薬
効が低い。したがって、抽出物はなんらかの手段により
精製してから下剤として利用するのが普通である。Conventional technology Sennoside is a dianthrone glycoside that is contained in relatively large amounts in senna leaves, rhubarb, etc.
and sennoside B, as well as small amounts of sennoside C,
There are stereoisomers such as D, E, and F. Isolated, it becomes soluble in water in the form of calcium salts. It has the effect of promoting bowel movements and is a useful substance as a laxative. Senna leaves and rhubarb are easily extracted using water (alkali may be added) or a water-containing organic solvent, but the extract itself contains large amounts of soluble components other than sennosides, so its medicinal efficacy is low. Therefore, the extract is usually purified by some means before being used as a laxative.
センノサイドの精製法としては、従来次のような方法が
知られている。The following methods are conventionally known as methods for purifying sennosides.
■ 粗センノサイドを第四級アンモニウム塩で処理し、
センノサイドを水に難溶性の塩として分離する方法（特
公昭５３−２５００３号）
■ 粗センノサイドを含水ｎ−ブタノールで処理し、更
に（Ｌｔ、Ｈｒ ７ ルコ−ル％ｎ ？’ ：／Ｊ？浄
中入力烙（待Ｖｎ！’４４９−１１１’＋ ９０号）
■ 巨大網状構造を有する非極性合成吸着樹脂を用いる
方法（特開昭５４−１４０７０９号）
しかしながら、これら従来の精製法はいずれも満足でき
るものではなかった。すなわち、上記■の方法は高価な
第四級アンムニウム塩を多量に必要とするばかりでなく
脱塩のためのイオン交換樹脂も必要であるから、精製コ
ストは著しく高いものとなる。また■の方法は、ｎ−ブ
タノールおよびセンノサイドの損失が多大であり、■の
方法も、多量の吸着樹脂と再生用有機溶媒を必要とし且
つそれらの劣化・損失が精製コストを高くするのが欠点
である。更にこれらの精製法によるときは、センノサイ
ドの純度が普通４０〜６０％程度にしかならず、精製度
をさらに高めようとするとセンノサイドの損失がふえ、
精製品が著しく高価なものになってしまうという問題が
あった。■ Treat crude sennoside with quaternary ammonium salt,
Method for separating sennoside as a salt hardly soluble in water (Special Publication No. 53-25003) ■ Crude sennoside is treated with water-containing n-butanol, and further treated with (Lt, Hr 7 alcohol%n?' :/J? Nakainu Hikaru (Waiting Vn! '449-111'+ No. 90) ■ Method using non-polar synthetic adsorption resin having a giant network structure (Japanese Patent Application Laid-open No. 140709/1983) However, none of these conventional purification methods are satisfactory. In other words, method ① above not only requires a large amount of expensive quaternary ammunium salt, but also requires an ion exchange resin for desalting, so the purification cost is extremely high. In addition, method (2) causes a large loss of n-butanol and sennoside, and method (2) also requires a large amount of adsorption resin and organic solvent for regeneration, and their deterioration and loss increase purification costs. Moreover, when using these purification methods, the purity of sennoside is usually only about 40 to 60%, and if you try to further increase the degree of purification, the loss of sennoside increases.
There was a problem in that the refined product became extremely expensive.
発明が解決しようとする問題点
本発明は、従来のセンノサイド精製法が上述のような欠
点を持つものであったことに鑑み、より高純度のセンノ
サイドをより高収率で、しかもより低いコストで得られ
る新規なセン７サイドの精製法を提供しようとするもの
である。Problems to be Solved by the Invention In view of the fact that the conventional sennoside purification method had the above-mentioned drawbacks, the present invention aims to produce sennoside of higher purity at a higher yield and at a lower cost. The present invention aims to provide a novel method for purifying the obtained Sen7side.
辿逓縛じ］ぢ欠するための千ｆ２
本発明が提供するセン７サイドの精製法は、精製しよう
とするｍセンノサイドをまず酸性の水溶液にして粘土系
吸着剤に接触させ、吸着剤にセン７サイドを選択的に吸
着させる。The method for purifying sen7side provided by the present invention is to first make the m-sennoside to be purified into an acidic aqueous solution and bring it into contact with a clay-based adsorbent. 7 sides are selectively adsorbed.
次いで吸着されなかった不純物を含む被処理液と粘土系
吸着剤とを分離し、粘土系吸着剤よりセンノサイドを脱
着させて回収するものである。Next, the liquid to be treated containing unadsorbed impurities and the clay-based adsorbent are separated, and the sennosides are desorbed from the clay-based adsorbent and recovered.
粘土系１吸着剤には種々のものがあるが、この方法で用
いる粘土系吸着剤として好適なものは、モンモリロナイ
ト、ハロイサイト、アロフェン、アタパルジャイト、パ
リフルスカイト、酸性白土、活性白土などであり、これ
らの中でも、酸性白土および活性白土は吸着能がすぐれ
、かつ安価で入手ら容易なので、特に好ましい。There are various types of clay-based adsorbents, but suitable clay-based adsorbents for use in this method include montmorillonite, halloysite, allophane, attapulgite, parifulskite, acid clay, and activated clay. Among these, acid clay and activated clay are particularly preferred because they have excellent adsorption ability, are inexpensive, and are easily available.
粗センノサイドの酸性水溶液を粘土系吸着剤に接触させ
たときに起こる吸着は、センノサイドをよく吸着するが
センノサイド以外の植物体成分はほとんど吸着しない選
択的吸着である。このような選択的吸着は、被処理液が
中性ないしアルカリ性のときは生じない。粘土系吸着剤
によるセンノサイドの選択的吸着は、巨大網状構造を有
する非極性吸着樹脂やイオン交換樹脂による吸着の場合
とＭ似の、粘土粒子内部における吸着と陰イオン交換に
よるものと思われるが、吸着やイオン交換を行う極性基
の相違に基づき、非極性吸着樹脂やイオン交換樹脂によ
る吸着と比べるとはるかに強い選択性を示す。したがっ
て、粗センノサイドの酸性溶液を粘土系吸着剤に接触さ
せたのち粘土系吸着剤と被処理液とを分離すれば、セン
ノサイドと大部分の不純物との分離が行われる。The adsorption that occurs when an acidic aqueous solution of crude sennoside is brought into contact with a clay-based adsorbent is a selective adsorption in which sennoside is well adsorbed, but plant components other than sennoside are hardly adsorbed. Such selective adsorption does not occur when the liquid to be treated is neutral or alkaline. The selective adsorption of sennosides by clay-based adsorbents is thought to be due to adsorption and anion exchange inside clay particles, similar to the adsorption by nonpolar adsorption resins and ion exchange resins with large network structures. Based on the difference in polar groups that perform adsorption and ion exchange, it exhibits much stronger selectivity than adsorption using nonpolar adsorption resins or ion exchange resins. Therefore, by bringing an acidic solution of crude sennoside into contact with a clay-based adsorbent and then separating the clay-based adsorbent from the liquid to be treated, sennoside and most of the impurities can be separated.
本発明の方法により精製することので鰺る粗センノサイ
ドは、センナ葉、大黄等から得られたセンノサイド含有
抽出液もしくは抽出物、およびこれらの精製物であって
さらに精製を必要とするものである。精製処理を行うに
当ってはこれを適当な濃度の水溶液とし、酸（たとえば
希塩酸、希硫酸、希硝酸など）を加えて、ｐｔ−ｒを望
ましくは１．０〜６．０に調整する。なお含水有機溶媒
を用いた抽出液の場合は、有機溶媒を完全に除いておく
。The crude sennosides that can be purified by the method of the present invention are sennoside-containing extracts or extracts obtained from senna leaves, rhubarb, etc., and purified products thereof, which require further purification. In carrying out the purification treatment, this is made into an aqueous solution of an appropriate concentration, and an acid (for example, dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, etc.) is added to adjust the pt-r to preferably 1.0 to 6.0. In the case of an extract using a water-containing organic solvent, the organic solvent should be completely removed.
被処理液と粘土系吸着剤とを接触させる方法は任意であ
るが、通常は被処理液中に粘土系吸着剤を投入して撹拌
し、その後、静置すればよい６粘土系吸着剤は、被処理
液中の固形分に対して０．５〜２０％程度を用いる（適
量はその吸着剤のＳ類や被処理液中のセンノサイドの純
度により異なる）。The method of bringing the liquid to be treated and the clay-based adsorbent into contact is arbitrary, but usually the clay-based adsorbent is added to the liquid to be treated, stirred, and then left to stand.6 Clay-based adsorbents About 0.5 to 20% of the solid content in the liquid to be treated is used (the appropriate amount varies depending on the S type of the adsorbent and the purity of sennoside in the liquid to be treated).
帛薯り九睡多稟小ψト↓τ１１六大ｄし足ｉ市面；ホＬ
本Ｉ〜耐１上 −φ上、−−シタン、遠心分離、ろ過
等により行う。It's 9 times a day, 9 years ago, 6 years ago, 11 years ago.
Book I ~ Endurance 1 Upper - φ Upper - - Performed by using citron, centrifugation, filtration, etc.
センノサイドを吸着しｔこ粘土系吸着剤よりセンノサイ
ドを脱着させるには、メタノール、エタノール等の低級
脂肪族アルコールやアセトン等の低級脂肪族ケトン等の
親水性有機溶媒、これら親水性有機溶媒と水との混合物
、アルカリ金属らしくはアルカリ土類金属の水酸化物も
しくは炭酸塩またはアンモニアを加えてアルカリ性にし
た水などを、粘土系吸着剤の約１０〜５０倍量、接触さ
せればよい。In order to adsorb and desorb sennosides from a clay-based adsorbent, hydrophilic organic solvents such as lower aliphatic alcohols such as methanol and ethanol and lower aliphatic ketones such as acetone, and the combination of these hydrophilic organic solvents and water are used. A mixture of hydroxides or carbonates of alkali metals, such as alkaline earth metals, or water made alkaline by adding ammonia may be brought into contact in an amount about 10 to 50 times the amount of the clay-based adsorbent.
上記吸着処理および脱着処理は、２〜３回くり返すこと
により、はぼ定量的に、センノサイドの吸・脱着を生起
させることができる。By repeating the adsorption treatment and desorption treatment 2 to 3 times, the adsorption and desorption of sennosides can be caused almost quantitatively.
吸着剤から脱着されたセンノサイドを含む脱着液がらセ
ンノサイドを回収するには、単なる濃縮によって溶媒ま
たは水を除く方法のほか、濃縮液にしたあと水酸化カル
シウム、酢酸カルシウム等を加え、更にメタノールを加
えて、セン７サイドをカルシウム塩の形で析出させる方
法などがある。To recover sennosides from the desorption solution containing sennosides that have been desorbed from the adsorbent, it is possible to remove the solvent or water by simple concentration, or to make a concentrated solution, add calcium hydroxide, calcium acetate, etc., and then add methanol. For example, there is a method in which Sen7side is precipitated in the form of a calcium salt.
発明の効果
本発明の精製法は、上述のように安価な粘土系吸着剤を
使用するものであり、しかも粘土系吸着剤を特定の条件
で使用する場合に起こる高度の選択的吸着を利用するも
のでふＬｈ・ら、従来の方法では容易には得られなかっ
たような高純度のセン７サイドが高収率で、且つ低いコ
ストで、容易に得られるという特長がある。Effects of the Invention The purification method of the present invention uses an inexpensive clay-based adsorbent as described above, and also utilizes the highly selective adsorption that occurs when the clay-based adsorbent is used under specific conditions. Monodefu Lh. et al. have the advantage that high-purity Sen7side, which cannot be easily obtained by conventional methods, can be easily obtained in high yield and at low cost.
医１瀝 以下実施例を示して本発明を説明する。Medical 1st death The present invention will be explained below with reference to Examples.
実施例 １
炭酸水素ナトリウム５０ｇを溶解した水１０ｅに、セン
ナ葉（センノサイドＡおよびＢ合計１．２％を含有）ｌ
ｋ、を投入し、３時間撹拌してセンノサイドを抽出した
。抽出液を分離したのち、抽出残渣に水１０ｅを加えて
２回抽出を行い、抽出液合計２５．２ Ｑを得た。この
抽出液に、希塩酸を加えてｐＨを４．０に調整し、次い
で活性白土１５ｇを添加して１時間撹拌し、センノサイ
ドを吸着させた。このあと＃置し、沈降した活性白土と
上澄液とをデカンチーシコンで分離した。Example 1 Senna leaves (containing a total of 1.2% of sennosides A and B) were added to 10e of water in which 50g of sodium hydrogen carbonate was dissolved.
k, and stirred for 3 hours to extract sennosides. After separating the extract, 10e of water was added to the extraction residue and extraction was performed twice to obtain a total of 25.2 Q of extract. Dilute hydrochloric acid was added to this extract to adjust the pH to 4.0, and then 15 g of activated clay was added and stirred for 1 hour to adsorb sennosides. Thereafter, the precipitated activated clay and the supernatant were separated using a decanterizer.
上澄液について上記と同じ活性白土処理を２回繰り返し
た後、すべての活性白土を合せてろ過、水洗したく最後
の吸着処理の上澄液、ろ液および洗浄液を合せてその中
のセンノサイドを定量したところ、セン７サイドＡおよ
び８合計量で０．０６ｇであった。）。After repeating the same activated clay treatment twice for the supernatant liquid, all the activated clay is combined, filtered, and washed with water.The supernatant liquid, filtrate, and washing liquid from the last adsorption process are combined to remove the sennosides therein. When quantitatively determined, the total amount of Sen7 Side A and 8 was 0.06 g. ).
洗浄後の活性白土を次いで８５％メタノール１ｅ中に投
入し、１時間撹拌を続けてセンノサイドを肌着させてか
ら静置した。沈降した活性白土と上澄液とをデカンテー
ションで分離し、活性白土に再度同様の脱着処理を施し
、最後に活性白土をろ過し８５％メタ／−ル１００ｍ１
で洗浄した。すべての上澄液、ろ液および洗浄液を合せ
た脱着液中のセン７サイドを定量したところ、センノサ
イドＡおよび８合計量で１１゜７ｇであった（回収率９
７．５％）。The washed activated clay was then poured into 85% methanol 1e, stirred continuously for 1 hour to coat the sennoside, and then left to stand. The precipitated activated clay and the supernatant liquid are separated by decantation, the activated clay is subjected to the same desorption treatment again, and finally the activated clay is filtered to obtain 100ml of 85% methanol.
Washed with. Sennoside A and 8 were quantified in the desorption solution containing all the supernatant, filtrate, and washing solution, and the total amount of sennoside A and 8 was 11.7 g (recovery rate 9
7.5%).
上記脱着液を１５Ｏｎ＋１になるまで４０℃以下で減圧
濃縮し、得られた濃縮液を水酸化カルシウムで中和した
のち無水メタノール１．３５ Ｑを加え、センノサイド
をセンノサイドカルシウムとして析出させた。析出物を
ろ別し、減圧下に４０°Ｃで乾燥し、黄褐色の粉末１７
．７ｇ（センノサイド八およびＢの合計含有量６５％、
原料中のセンノサイド基準の回収率９５．９％）を得た
。The desorption solution was concentrated under reduced pressure at 40° C. or below until the concentration reached 15On+1, and the resulting concentrated solution was neutralized with calcium hydroxide, and then 1.35 Q of anhydrous methanol was added to precipitate sennosides as sennoside calcium. The precipitate was filtered off and dried at 40°C under reduced pressure to give a yellowish brown powder 17.
．． 7g (total content of sennosides 8 and B 65%,
A recovery rate of 95.9% based on sennoside in the raw material was obtained.
実施例 ２
７０％メタ／−ル５ｅに、実施例１で用いたものと同じ
センナ葉１に、を投入し、３時間攪拌してセンノサイド
を抽出した。抽出液を分離したのち、抽出残渣に７０％
メタノール５ｅを加えて２回抽出を行い、抽出液合計ｉ
３．ｉｅを得た。Example 2 Senna leaves 1, the same as those used in Example 1, were added to 70% methanol 5e and stirred for 3 hours to extract sennosides. After separating the extract, 70% of the extraction residue is
Extraction was performed twice by adding methanol 5e, and the total extract i
3. I got ie.
この抽出液を４０℃以下で減圧濃縮し、得られた濃縮液
に水１０ｇを加え、さらに希硫酸を加えてｐＨを２．０
に調整し、次いで酸性白土１０ｇを添加して１時間撹拌
し、センノサイドを吸着させた。このあと静置し、沈降
した酸性白土と上澄液とをデカンテーションで分離した
。上澄液について上記と同じ酸性白土処理を２回繰り返
した後、すべての酸性白土を合せてろ過、水洗した（最
後の吸着処理の上澄液、ろ液および洗浄液を合せてその
中のセンノサイドを定量したところ、センノサイドＡお
よび８合計量で０．１ｇであった。）。This extract was concentrated under reduced pressure at a temperature below 40°C, 10 g of water was added to the obtained concentrate, and diluted sulfuric acid was further added to adjust the pH to 2.0.
Then, 10 g of acid clay was added and stirred for 1 hour to adsorb sennosides. Thereafter, the mixture was allowed to stand, and the precipitated acid clay and the supernatant liquid were separated by decantation. After repeating the same acid clay treatment as above twice for the supernatant liquid, all the acid clay was combined, filtered, and washed with water. When quantified, the total amount of Sennoside A and 8 was 0.1 g.)
洗浄後の酸性白土を次いで水ｌｅ中に投入し、アンモニ
ア水を加えてｐＨを１０．０に調整し、１時間撹拌を続
けてセンノサイドを脱着させてから静置した。沈降した
酸性白土と上澄液とをデカンテーションで分離し、酸性
白土に再度同様の脱着処理を施し、最後に酸性白土をろ
過し、水洗した。すべての上澄液、ろ液および洗浄液を
合せた脱着液中のセンノサイドを定量したところ、セン
ノサイドＡおよび８合計量で１１．３ｇであった（回収
率９４．１％）。The washed acid clay was then poured into water, aqueous ammonia was added to adjust the pH to 10.0, stirring was continued for 1 hour to desorb sennosides, and the mixture was allowed to stand still. The precipitated acid clay and the supernatant liquid were separated by decantation, the acid clay was again subjected to the same desorption treatment, and finally the acid clay was filtered and washed with water. When the amount of sennoside in the desorption liquid, which was a combination of all the supernatant liquid, filtrate, and washing liquid, was quantified, the total amount of sennosides A and 8 was 11.3 g (recovery rate 94.1%).
以下実施例１と同様に繰作して、黄褐色の粉末１６．５
ｇ（センノサイドＡおよびＢの合計含有量６７％、原料
中のセンノサイド基準の回収率９２．１％）を得た。The following procedure was repeated in the same manner as in Example 1, and 16.5% of yellowish brown powder was obtained.
g (total content of sennosides A and B: 67%, recovery rate based on sennosides in the raw material: 92.1%).
注：センノサイドの定量は下記条件の高速液体クロマト
グラフィーによる。Note: Sennosides are quantified by high performance liquid chromatography under the following conditions.
カラム： ７ｚ−Ｂｏｏｄｏｌ＋ａｋ ｃｌ１１移動Ｗ
Ｉ：
Ｈ２Ｏ： ＡｃＣＮ ： Ａｃ０Ｈ＝８４ ： １
５ ： １検出：ＵＶ３４１）ｎｍ
流速： ２ｍｌ／ｍｉｎColumn: 7z-Boodol+ak cl11 movement W
I: H2O: AcCN: Ac0H=84:1
5:1 detection: UV341)nm Flow rate: 2ml/min
Claims (4)
剤に接触させ、次いで被処理液と分離した粘土系吸着剤
よりセンノサイドを脱着させて回収することを特徴とす
るセンノサイドの精製法。(1) A method for purifying sennoside, which comprises making crude sennoside into an acidic aqueous solution, bringing it into contact with a clay-based adsorbent, and then desorbing and recovering the sennoside from the clay-based adsorbent separated from the liquid to be treated.
イト、アロフェン、アタパルジャイト、パリゴルスカイ
ト、酸性白土または活性白土を用いる特許請求の範囲第
１項記載の精製法。(2) The purification method according to claim 1, in which montmorillonite, halloysite, allophane, attapulgite, palygorskite, acid clay or activated clay is used as the clay-based adsorbent.
の水によりセンノサイドを脱着させる特許請求の範囲第
１項記載の精製法。(3) The purification method according to claim 1, in which sennosides are desorbed using a hydrophilic organic solvent, a water-containing organic solvent, or alkaline water.
である特許請求の範囲第１項記載の精製法。(4) The purification method according to claim 1, wherein the crude sennoside is an aqueous extract of senna leaves or rhubarb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006886A JPS62178598A (en) | 1986-02-03 | 1986-02-03 | Purification of sennoside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006886A JPS62178598A (en) | 1986-02-03 | 1986-02-03 | Purification of sennoside |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62178598A true JPS62178598A (en) | 1987-08-05 |
| JPH057400B2 JPH057400B2 (en) | 1993-01-28 |
Family
ID=12016777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006886A Granted JPS62178598A (en) | 1986-02-03 | 1986-02-03 | Purification of sennoside |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62178598A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06510412A (en) * | 1992-06-11 | 1994-11-17 | ソニー エレクトロニクス インコーポレイテッド | User-selectable responses to alerts sent from cellular phone base stations |
| US5710260A (en) * | 1991-06-25 | 1998-01-20 | Madaus Ag | Method of extracting sennosides A, B and A1 |
| JP2008266228A (en) * | 2007-04-23 | 2008-11-06 | National Agriculture & Food Research Organization | Method of saccharification and retrieval for biomass |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254689B (en) * | 2015-11-04 | 2018-12-04 | 安徽九方药物研究院有限公司 | Sennoside AB salt compound and its preparation method and application |
-
1986
- 1986-02-03 JP JP2006886A patent/JPS62178598A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710260A (en) * | 1991-06-25 | 1998-01-20 | Madaus Ag | Method of extracting sennosides A, B and A1 |
| JPH06510412A (en) * | 1992-06-11 | 1994-11-17 | ソニー エレクトロニクス インコーポレイテッド | User-selectable responses to alerts sent from cellular phone base stations |
| JP2008266228A (en) * | 2007-04-23 | 2008-11-06 | National Agriculture & Food Research Organization | Method of saccharification and retrieval for biomass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH057400B2 (en) | 1993-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20060142555A1 (en) | Process for production of steviosides from stevia rebaudiana bertoni | |
| JPS62157B2 (en) | ||
| JPH0245637B2 (en) | ||
| HU197917B (en) | Process for cleaning glycosides with anthracyclinone skeleton by selective adsorption on resins | |
| KR100944242B1 (en) | Process for production of steviosides from Stevia Rebaudiana Bertoni | |
| CN101429220A (en) | Separation and purification process for sucrose trichloride | |
| KR20110068986A (en) | Process for extraction of glucosinolates from broccoli seeds | |
| KR20130103745A (en) | Method for preparing an extract of centella asiatica | |
| CN102443619A (en) | Method for extracting chlorogenic acid and hederagenin from honeysuckle flower | |
| CN102093236B (en) | Ornithine aspartate compound and new preparation method thereof | |
| JPS62178598A (en) | Purification of sennoside | |
| JPS5852999B2 (en) | Stevioside Noseiseihou | |
| CN107032983A (en) | A kind of method that utilization macroporous absorbent resin extracts separation butanedioic acid from zymotic fluid | |
| CN110590876B (en) | High-purity stevioside and preparation method thereof | |
| JPS62126185A (en) | Production of isoflavone derivative | |
| JPS6219436B2 (en) | ||
| JP2003277282A (en) | Extract of acanthopanax senticosus harms and its production method | |
| JPS5811986B2 (en) | Method for producing steviol glycosides containing no bitter, astringent, or odor components | |
| CN115779006B (en) | Method for extracting and separating polysaccharide, saponin and organic acid from radix ranunculi ternati | |
| JPS6281325A (en) | Purification of aescin | |
| JPS5828245A (en) | Preparation of sweetening agent | |
| JPS6257637B2 (en) | ||
| KR20010068749A (en) | A manufacturing method of licorice extract suitable to production of soy sauce | |
| JPS5942862A (en) | Purification of stevia sweetening substance | |
| US6316615B1 (en) | Process for the recovery of potassium bitartrate and other products from tamarind pulp |