CH313262A - Method for obtaining genines - Google Patents
Method for obtaining geninesInfo
- Publication number
- CH313262A CH313262A CH313262DA CH313262A CH 313262 A CH313262 A CH 313262A CH 313262D A CH313262D A CH 313262DA CH 313262 A CH313262 A CH 313262A
- Authority
- CH
- Switzerland
- Prior art keywords
- dependent
- product
- process according
- extraction
- diethyl ether
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 229930182470 glycoside Natural products 0.000 claims description 10
- 150000002338 glycosides Chemical class 0.000 claims description 10
- 229930183217 Genin Natural products 0.000 claims description 7
- 244000198134 Agave sisalana Species 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- INLFWQCRAJUDCR-IQVMEADQSA-N (1R,2S,4S,5'S,6R,7S,8R,9S,12S,13S)-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane] Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CCCCC4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@H](C)CO1 INLFWQCRAJUDCR-IQVMEADQSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000003431 steroids Chemical class 0.000 claims description 3
- 235000011624 Agave sisalana Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QOLRLLFJMZLYQJ-LOBDNJQFSA-N Hecogenin Chemical compound O([C@@H]1[C@@H]([C@]2(C(=O)C[C@@H]3[C@@]4(C)CC[C@H](O)C[C@@H]4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 QOLRLLFJMZLYQJ-LOBDNJQFSA-N 0.000 description 5
- OXLGJTRVVNGJRK-UHFFFAOYSA-N Hecogenin Natural products CC1CCC2(CC3CC4C5CCC6CC(O)CCC6(C)C5CC(=O)C4(C)C3C2C)OC1 OXLGJTRVVNGJRK-UHFFFAOYSA-N 0.000 description 5
- UVLDESQWQRMYKD-UHFFFAOYSA-N Neobotogenin Natural products CC1C(C2(C(=O)CC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 UVLDESQWQRMYKD-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 244000193174 agave Species 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000005903 Dioscorea Nutrition 0.000 description 1
- 244000281702 Dioscorea villosa Species 0.000 description 1
- 235000000504 Dioscorea villosa Nutrition 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000004879 dioscorea Nutrition 0.000 description 1
- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 description 1
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229930190071 lycoside Natural products 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Compounds Of Unknown Constitution (AREA)
Description
Verfahren zur Gewinnung von Geninen Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Gewinnung von Steroid- Sapogeninen aus Rohglykosiden. Geeignete Rohglykosidgemische werden z. B. aus Agave- arten, wie Agave sisalana oder Agave four- eroydes, insbesondere aus dem Abfall bei der Sisalfaser-Isolierung, erhalten. Zur Gewin nung der Genine, wie z.
B. des Hecogenins, wurde bis anhin auf das Rohglykosidgemisch eine Säure, wie z. B. Salzsäure oder Schwe felsäure, einwirken gelassen, der dabei auf tretende Rückstand mit Alkali, wie z. B. alkoholischem Alkalihydroxyd, behandelt, das Reaktionsgeniiseh hernach mit Tierkohle ver setzt, alkalisch abfiltriert und aus dem R.üek- stand das Genin, z. B. Hecogenin, extrahiert.
Es wurde nun gefunden, dass man die Ge nire ohne Verwendung von Adsorbentien, wie Tierkohle, bei der. alkalischen Filtration in reiner Form erhalten kann. Das Verfah ren gemäss der Erfindung ist, dadurch ge kennzeichnet, dass man auf das durch De- handlung von Steroid-Sapogenine enthalten den Roh-lykosiden mit Säuren erhaltene Pro dukt ein Erdalkalihydroxy d, insbesondere Kalkmilch, einwirken lässt, aus dein R.eak- lionsgemisch den unlöslichen Anteil abtrennt und diesen mit organischen Lösungsmitteln extrahiert.
Vorzugsweise geht man von einem solchen Produkt aus, das durch Behandlung von Rohglykosiden mit. Säuren und naehträg- lieh mit AlkalihvdroYyden und Ansäuern erhalten wird. Die verfahrensgemässe Un i setzung mit einem Eraalkalihydroxvd liefert ein leicht filtrierbares Produkt. Als Extrak tionsmittel eignet sich insbesondere Diäthyl- ä.ther, ferner z. B. auch Äthylenchlorid, Tetrachlorkohlenstoff oder Benzol.
Um die Genine in möglichst reiner Form zu gewin nen, empfiehlt es sich, die Extraktion frak tioniert durchzuführen, z. B. mit verschiede nen Lösungsmitteln. Eine besondere Ausfüh rungsform besteht darin, dass man zuerst mit Petroläther Verunreinigungen, und dann mit Diäthyläther das Genin, z. B. Hecogenin, extrahiert.
Die Erfindung wird in den nachstehenden Beispielen näher beschrieben. Zwischen Ge wichtsteil und Volumteil besteht die gleiche Beziehung wie zwischen Gramm und Kubik zentimeter. Die Temperaturen sind in Cel siusgraden angegeben. Beispiel <I>1</I> 500 Gewichtsteile trockener Rohglykosid- schlaiyvn (z.
B. aus Sisalwaste-Presssaft nach bekannter Vorschrift gewonnen [Chemistry Industrv 1952 S. -126]) werden mit 1500 Vo- lumteilen Wasser und 500 Volumteilen kon zentrierter Salzsäure einige Stunden zum Ko chen erhitzt. Nach dem Erkalten nutseht man ab, kocht den Filterkuchen mit 1000 Volum- teilen 10 o/miger Natronlauge während 2 Stun den, säuert an und saugt nach dem Erkalten ab.
Das Reaktionsprodukt suspendiert man in heissem Wasser, versetzt mit Kalkmilch bis zur stark alkalischen Reaktion, saugt wie derum ab und trocknet die braune Masse, In einem Extraktor wird dann diese zuerst mit Petroläther behandelt, bis er farblos ab läuft, und dann erschöpfend mit Äther extrahiert. Je nach der Qualität des Rohgly- kosids krystallisiert das Hecogenin in reiner Form oder mit etwas andern Gxeninen ver- miseht, direkt aus.
Beispiel <I>2</I> 200 Voluniteile Glykosidschlanim, wie er nach obiger Literaturangabe durch Fermen tation von Sisalpresssaft erhalten wird, kocht. man einige Stunden mit 50 Volumteilen kon zentrierter Salzsäure und arbeitet das Reak tionsprodukt wie in Beispiel 1 auf. Nach der C eichen Vorschrift wird nun mit Kalkmilch behandelt und der Schlamm dann erschöp fend mit Äther extrahiert, wobei vorteil- hafterweise die ersten, gefärbten Extrakt anteile, die nur wenig Genin enthalten, ge sondert aufgefangen werden.
Aus den spä teren nicht oder nur sehr schwach gefärbten Extraktfraktionen kristallisiert das Heco- genin, gegebenenfalls mit .etwas andern Ge- ninen, aus.
<I>Beispiel 3</I> Trockener Sisal-Rohglykosidsehlamm wird wie in Beispiel 1 angegeben, mit Salzsäure gekocht. Nach dem Abfiltrieren des braunen Schlammes wird dieser in Wasser suspen diert und nach Zusatz von Bariumhydroxyd bis zur stark alkalischen Reaktion einige Stunden gekocht. Nach dem Erkalten saugt man den Niederschlag ab, trocknet ihn und extrahiert ihn wie in Beispiel 1 und 2 be schrieben ist.
Beispiel Trockene Knollen von Dioscorea ma- erostachya werden mit Methanol erschöpfend extrahiert. Den harzigen 1VIethanolrüekstand löst man in 3 Volumteilen Methanol und 1 Volumteil konzentrierter Salzsäure, kocht während 2 Stunden am und giesst in Wasser.
Das braune Pulver wird ab gesogen, in Wasser suspendiert und mit Kalkmilell bis zur alkalischen Reaktion ver setzt, wobei vorteilhaft erwärmt. wird. -Man saugt ab, trocknet und extrahiert mit Äther. Aus dem Extrakt fällt das Diosgenin, even- tuell vermischt mit andern Geninen, in schö nen Kristallen aus.
Process for the production of genins The present invention relates to a process for the production of steroid sapogenins from crude glycosides. Suitable raw glycoside mixtures are z. B. from agave species such as Agave sisalana or Agave foureroydes, in particular from the waste in the sisal fiber insulation. To win the Genine such.
B. of hecogenin, an acid, such as, for example, was previously applied to the raw glycoside mixture. B. hydrochloric acid or sulfuric acid, allowed to act, the resulting residue with alkali, such as. B. alcoholic alkali hydroxide, treated, the reaction geniiseh afterwards ver with animal charcoal, filtered off alkaline and from the R.üek- stand the genin, z. B. hecogenin extracted.
It has now been found that the Ge nire without the use of adsorbents, such as animal charcoal, in the. alkaline filtration can be obtained in pure form. The method according to the invention is characterized in that an alkaline earth hydroxide, in particular milk of lime, is allowed to act on the product obtained by treating steroid sapogenins containing the crude lycosides with acids, from which R.eak- ion mixture separates the insoluble fraction and this extracted with organic solvents.
It is preferable to start from such a product that is obtained by treating raw glycosides. Acids and additive borrowed with alkali hydroxides and acidification is obtained. The process according to the mixture with an Eraalkalihydroxvd provides an easily filterable product. Diethyl ether is particularly suitable as extraction agent, and also z. B. also ethylene chloride, carbon tetrachloride or benzene.
In order to win the genins in the purest possible form, it is advisable to carry out the extraction fractionated, eg. B. with various solvents. A special Ausfüh insurance form is that you first with petroleum ether impurities, and then the Genin with diethyl ether, z. B. hecogenin extracted.
The invention is described in more detail in the examples below. The relationship between part by weight and part by volume is the same as that between grams and cubic centimeters. The temperatures are given in degrees Celsius. Example <I> 1 </I> 500 parts by weight of dry raw glycoside flakes (e.g.
B. obtained from sisal waste press juice according to known regulations [Chemistry Industrv 1952 p. -126]) are heated to boiling with 1500 parts by volume of water and 500 parts by volume of concentrated hydrochloric acid for a few hours. After cooling, it is removed, the filter cake is boiled with 1000 parts by volume of 10% sodium hydroxide solution for 2 hours, acidified and, after cooling, suctioned off.
The reaction product is suspended in hot water, milk of lime is added until it has a strongly alkaline reaction, and the brown mass is then suctioned off again and dried.In an extractor, this is first treated with petroleum ether until it runs colorless, and then extracted exhaustively with ether . Depending on the quality of the raw glycoside, the hecogenin crystallizes out in its pure form or in the presence of some other glycoside, directly.
Example <I> 2 </I> 200 parts by volume of glycoside slime, as obtained from the above literature by fermentation of sisal press juice, boils. one for a few hours with 50 parts by volume of concentrated hydrochloric acid and works up the reaction product as in Example 1. According to the C eich prescription, milk of lime is used and the sludge is then extracted exhaustively with ether, the first, colored extract components, which contain only a little genin, being advantageously collected separately.
The hecogenin crystallizes out of the later uncolored or only very weakly colored extract fractions, possibly with slightly different genes.
<I> Example 3 </I> Dry raw sisal glycoside lamb is cooked with hydrochloric acid as indicated in Example 1. After filtering off the brown sludge, it is suspended in water and, after adding barium hydroxide, boiled for a few hours until a strongly alkaline reaction. After cooling, the precipitate is filtered off with suction, dried and extracted as described in Examples 1 and 2.
Example Dry bulbs of Dioscorea marerostachya are exhaustively extracted with methanol. The resinous 1VIethanolrückstand is dissolved in 3 parts by volume of methanol and 1 part by volume of concentrated hydrochloric acid, boiled for 2 hours and poured into water.
The brown powder is sucked off, suspended in water and ver with lime milk until an alkaline reaction, heated advantageously. becomes. -Man sucks off, dries and extracts with ether. The diosgenin precipitates out of the extract, possibly mixed with other genins, in beautiful crystals.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH313262T | 1952-12-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH313262A true CH313262A (en) | 1956-03-31 |
Family
ID=4495127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH313262D CH313262A (en) | 1952-12-15 | 1952-12-15 | Method for obtaining genines |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH313262A (en) |
| DE (1) | DE946898C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2991282A (en) * | 1956-10-15 | 1961-07-04 | Rubin Martin | Production of hecogenin and tigogenin from plant material |
-
1952
- 1952-12-15 CH CH313262D patent/CH313262A/en unknown
-
1953
- 1953-12-11 DE DEC8597A patent/DE946898C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2991282A (en) * | 1956-10-15 | 1961-07-04 | Rubin Martin | Production of hecogenin and tigogenin from plant material |
Also Published As
| Publication number | Publication date |
|---|---|
| DE946898C (en) | 1956-08-09 |
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