DE1277263B - Process for the preparation of dihydromethysticin or dihydrokawain - Google Patents
Process for the preparation of dihydromethysticin or dihydrokawainInfo
- Publication number
- DE1277263B DE1277263B DES88490A DES0088490A DE1277263B DE 1277263 B DE1277263 B DE 1277263B DE S88490 A DES88490 A DE S88490A DE S0088490 A DES0088490 A DE S0088490A DE 1277263 B DE1277263 B DE 1277263B
- Authority
- DE
- Germany
- Prior art keywords
- methoxy
- pyrone
- dihydro
- dihydromethysticin
- hydrogenation
- 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.)
- Pending
Links
- RSIWXFIBHXYNFM-NSHDSACASA-N Dihydromethysticin Chemical compound C1C(OC)=CC(=O)O[C@H]1CCC1=CC=C(OCO2)C2=C1 RSIWXFIBHXYNFM-NSHDSACASA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 8
- VOOYTQRREPYRIW-LBPRGKRZSA-N Dihydrokavain Chemical compound C1C(OC)=CC(=O)O[C@H]1CCC1=CC=CC=C1 VOOYTQRREPYRIW-LBPRGKRZSA-N 0.000 title claims description 7
- VOOYTQRREPYRIW-UHFFFAOYSA-N dihydrokawain Natural products C1C(OC)=CC(=O)OC1CCC1=CC=CC=C1 VOOYTQRREPYRIW-UHFFFAOYSA-N 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002689 soil Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008034 disappearance Effects 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEAQIWGXBXCYFX-GUOLPTJISA-N Kawain Chemical compound C1C(OC)=CC(=O)O[C@H]1\C=C\C1=CC=CC=C1 XEAQIWGXBXCYFX-GUOLPTJISA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical class O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GTEXBOVBADJOQH-FWEMWIAWSA-N Methysticin Chemical compound C1C(OC)=CC(=O)O[C@H]1\C=C\C1=CC=C(OCO2)C2=C1 GTEXBOVBADJOQH-FWEMWIAWSA-N 0.000 description 3
- CGGHGWCWEAXPLK-CYBMUJFWSA-N Methysticin Natural products CC(=O)C1=CC(=O)O[C@@H](C1)C=Cc2ccc3OCOc3c2 CGGHGWCWEAXPLK-CYBMUJFWSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XEAQIWGXBXCYFX-UHFFFAOYSA-N dl-kavain Natural products C1C(OC)=CC(=O)OC1C=CC1=CC=CC=C1 XEAQIWGXBXCYFX-UHFFFAOYSA-N 0.000 description 2
- 230000002848 endoanesthetic effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OKIJSNGRQAOIGZ-UHFFFAOYSA-N Butopyronoxyl Chemical class CCCCOC(=O)C1=CC(=O)CC(C)(C)O1 OKIJSNGRQAOIGZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NQBKFULMFQMZBE-UHFFFAOYSA-N n-bz-3-benzanthronylpyrazolanthron Chemical compound C12=CC=CC(C(=O)C=3C4=CC=CC=3)=C2C4=NN1C1=CC=C2C3=C1C1=CC=CC=C1C(=O)C3=CC=C2 NQBKFULMFQMZBE-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Dihydromethysticin oder Dihydrokawain Die Erfindung betrifft ein Verfahren zur Herstellung von 4-Methoxy-6-(3',4'-methylendioxyphenyläthyl)-5,6-dihydro-oI-pyron (Dihydromethysticin) und 4-Methoxy-6-(phenyläthyl)-5, 6-dihydro-oc-pyron (Dihydrokawain).Process for the production of dihydromethysticin or dihydrokawain The invention relates to a process for the preparation of 4-methoxy-6- (3 ', 4'-methylenedioxyphenylethyl) -5,6-dihydro-ol-pyrone (Dihydromethysticin) and 4-methoxy-6- (phenylethyl) -5, 6-dihydro-oc-pyrone (dihydrokawain).
Die partielle katalytische Hydrierung von Verbindungen vom Typ des Methysticins, also von Dihydro--pyron-Verbindungen, die eine ungesättigte aliphatische Brücke enthalten, stößt häufig insofern auf Schwierigkeiten, als bei der Hydrierung nicht nur die aliphatische Doppelbindung, sondern auch die 3,4-Doppelbindung des Pyronringes angegriffen wird. The partial catalytic hydrogenation of compounds of the type des Methysticins, i.e. from dihydro- pyrone compounds, which are an unsaturated aliphatic Containing bridge often encounters difficulties insofar as hydrogenation not only the aliphatic double bond, but also the 3,4 double bond des Pyronringes is attacked.
Es ist zwar bereits bekannt (Berichte der Deutschen Chemischen Gesellschaft, Bd. 62, 1929, S. 360 bis 367), die aliphatische Doppelbindung eines-Pyronderivats vom oben beschriebenen Typ bei Zimmertemperatur katalytisch zu hydrieren. Die nach diesem Verfahren erzielten Ausbeuten lassen jedoch noch zu wünschen übrig. It is already known (reports of the German Chemical Society, Vol. 62, 1929, pp. 360 to 367), the aliphatic double bond of a pyrone derivative of the type described above to catalytically hydrogenate at room temperature. The after However, the yields achieved in this process still leave something to be desired.
Ferner wird in der USA.-Patentschrift 2 870 164 die Hydrierung von Methysticin zum Dihydromethysticin bei Zimmertemperatur und unter Druck beschrieben. Auch die hier erzielten Ausbeuten befriedigen nicht. In addition, US Pat. No. 2,870,164 describes the hydrogenation of Methysticin to dihydromethysticin at room temperature and under pressure is described. The yields achieved here are also unsatisfactory.
Es wurde nun überraschenderweise gefunden, daß man 4 - Methoxy - 6 - (3',4' - methylendioxyphenyläthyl)-5,6-dihydro-a-pyron (Dihydromethysticin) oder 4-Methoxy-6- (phenyläthyl) - 5,6 - dihydro-ol-pyron (Dihydrokawain) durch Hydrierung von 4-Methoxy-6 - (3',4' - methylendioxystyryl) - 5,6 - dihydro-x-pyron oder 4-Methoxy-6-styryl-5,6-dihydro-a-pyron in Gegenwart von Methanol und kolloidalem Palladium als Katalysator in besseren Ausbeuten dadurch erhält, daß man eine methanolische Lösung verwendet, die einen Teil des zu hydrierenden o ;-Pyrons als Bodenkörper enthält, und die Hydrierung bis zum Verschwinden des Bodenkörpers bei einer Temperatur von -10 bis -5"C durchführt oder einleitet und die Temperatur nicht über +15°C ansteigen läßt. It has now been found, surprisingly, that 4 - methoxy - 6 - (3 ', 4' - methylenedioxyphenylethyl) -5,6-dihydro-a-pyrone (dihydromethysticin) or 4-methoxy-6- (phenylethyl) -5,6-dihydro-ol-pyrone (dihydrokawain) by hydrogenation of 4-methoxy-6 - (3 ', 4' - methylenedioxystyryl) - 5,6 - dihydro-x-pyrone or 4-methoxy-6-styryl-5,6-dihydro-a-pyrone in the presence of methanol and colloidal palladium as a catalyst in better Yields obtained by using a methanolic solution that has a Contains part of the o; -pyron to be hydrogenated as a soil body, and the hydrogenation until the body of the soil disappears at a temperature of -10 to -5 "C. or initiates and does not allow the temperature to rise above + 15 ° C.
Bei dem erfindungsgemäßen Verfahren verläuft die partielle Hydrierung praktisch quantitativ. Die Ausbeuten betragen beispielsweise 95 bis 98 01o der Theorie. Die 3,4-Doppelbindung des o ;-Pyronringes wird somit bei der Hydrierung nicht angegriffen, und auch eine Spaltung des Pyronringes tritt nicht ein. Ein solcher Reaktionsverlauf des erfindungsgemäßen Verfahrens war nicht ohne weiteres voraussehbar. In the process according to the invention, the partial hydrogenation takes place practically quantitative. The yields are, for example, 95 to 98,010 of theory. The 3,4 double bond of the o; pyrone ring is therefore not attacked during the hydrogenation, and the pyrone ring does not split either. Such a course of reaction of the process according to the invention was not readily foreseeable.
Das Dihydrokawain wirkt als Antiphlogisticum und Endoanästheticum, das Dihydromethysticin als schlafinduzierendes Mittel und ebenfalls als Endoanästheticum. The Dihydrokawain acts as an anti-inflammatory and endo-anesthetic, the dihydromethysticin as sleep-inducing agent and also as an endo-anesthetic.
Die folgenden Beispiele erläutern das erfindungsgemäße Verfahren. The following examples explain the process according to the invention.
Beispiel 1 300 g 4- Methoxy-6- (3',4' - methylendioxystyryl)-5,6-dihydro-a-pyron (Methysticin) werden in 10 1 Methanol gegeben, und das Ganze wird im Kühlschrank auf -10 bis -5"C gebracht. Zu der abgekühlten Lösung, die 4-Methoxy-6-(3',4'-methylendioxystyryl)-5,6-dihydro-a-pyron (Methysticin) als Bodenkörper ungelöst enthält, werden 50 ccm Palladium-Lösung nach P a a 1 zugegeben, und dann wird mit Wasserstoff auf dem Schüttelapparat so lange hydriert, bis sich der Bodenkörper gerade gelöst hat. Example 1 300 g of 4-methoxy-6- (3 ', 4' - methylenedioxystyryl) -5,6-dihydro-a-pyrone (Methysticin) are put in 10 1 of methanol, and the whole thing is in the refrigerator brought to -10 to -5 "C. To the cooled solution, the 4-methoxy-6- (3 ', 4'-methylenedioxystyryl) -5,6-dihydro-a-pyrone (Methysticin) contains undissolved sediment, 50 ccm of palladium solution are added P a a 1 is added, and then hydrogen on the shaker for so long hydrates until the soil has just loosened.
Die Endtemperatur bei der Hydrierung darf nicht über 15"C ansteigen. Nach dem Abkühlen wird 20 g Kohlepulver zugesetzt, geschüttelt und das Gemisch filtriert. Das klare Filtrat wird bis zur Hälfte eingeengt; anschließend läßt man im Kühlschrank auskristallisieren. The final temperature during the hydrogenation must not exceed 15 ° C. After cooling, 20 g of powdered carbon are added, shaken and the mixture is filtered. The clear filtrate is concentrated by half; then leave in the refrigerator crystallize.
Die Ausbeute an 4-Methoxy-6-(3',4'-methylendioxyphenyläthyl) - 5,6 - dihydro- oc-pyron (Dihydromethysticin) beträgt 290 bis 295 g. Die Verbindung schmilzt bei 116 bis 117"C und ergibt eine weinrote Schwefelsäurereaktion. The yield of 4-methoxy-6- (3 ', 4'-methylenedioxyphenylethyl) - 5.6 - dihydro- oc-pyrone (dihydromethysticin) is 290 to 295 g. The connection is melting at 116 to 117 "C and gives a wine-red sulfuric acid reaction.
Beispiel 2 100 g 4-Methoxy-6-styryl- 5,6- dihydro-nc-pyron (Kawain) werden in 500ccm Methanol gegeben, und das Ganze wird im Kühlschrank auf -10 bis -5"C gebracht. Zu der abgekühlten Lösung, die 4-Methoxy- 6-styryl- 5,6 - dihydro - - pyron (Kawain) als Bodenkörper ungelöst enthält, werden 20 ccm Palladium-Lösung nach P a a 1 zugegeben, und dann wird mit Wasserstoff so lange bei der angegebenen Temperatur hydriert, bis sich der Bodenkörper gerade gelöst hat. Da zu Anfang die Hydrierung schnell einsetzt, ist es angebracht, den einzuleitenden Wasserstoff ebenfalls aus -10 bis 5OC zu kühlen. Nach dem Abkühlen wird 20 g Kohlepulver zugesetzt, geschüttelt und das Gemisch filtriert. Das klare Filtrat wird bis zur Hälfte eingeengt; anschließend läßt man im Kühlschrank auskristallisieren. Example 2 100 g of 4-methoxy-6-styryl-5,6-dihydro-nc-pyrone (Kawain) are placed in 500ccm of methanol, and the whole thing is in the refrigerator to -10 to -5 "C. To the cooled solution, the 4-methoxy-6-styryl-5,6 - dihydro - - If pyron (Kawain) contains undissolved soil, 20 ccm of palladium solution become after P a a 1 added, and then with hydrogen for so long hydrogenated at the specified temperature until the soil has just loosened. Since the hydrogenation starts quickly at the beginning, it is advisable to initiate the To cool hydrogen also from -10 to 5OC. After cooling, 20 g of carbon powder is added added, shaken and the mixture filtered. The clear filtrate is up to Half constricted; then allowed to crystallize in the refrigerator.
Die Ausbeute an 4-Methoxy-6-(phenyläthyl)-5,6-dihydro-ozpyron (Dihydrokawain) beträgt 98,5 g. Die Verbindung schmilzt nach dem Umkristallisieren aus Äther und Petroläther (7:3) bei 58 bis 60"C und ergibt eine negative Schwefelsäurereaktion. The yield of 4-methoxy-6- (phenylethyl) -5,6-dihydro-ozpyron (Dihydrokawain) is 98.5 g. The compound melts after recrystallization from ether and Petroleum ether (7: 3) at 58 to 60 "C and gives a negative sulfuric acid reaction.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES88490A DE1277263B (en) | 1963-11-29 | 1963-11-29 | Process for the preparation of dihydromethysticin or dihydrokawain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES88490A DE1277263B (en) | 1963-11-29 | 1963-11-29 | Process for the preparation of dihydromethysticin or dihydrokawain |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1277263B true DE1277263B (en) | 1968-09-12 |
Family
ID=7514482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES88490A Pending DE1277263B (en) | 1963-11-29 | 1963-11-29 | Process for the preparation of dihydromethysticin or dihydrokawain |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1277263B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2096877A1 (en) * | 1970-07-09 | 1972-03-03 | Hexachimie | |
| WO1999025716A3 (en) * | 1997-11-14 | 1999-07-15 | Schwabe Willmar Gmbh & Co | Pyranones, method for the production and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2870164A (en) * | 1956-09-19 | 1959-01-20 | Riker Laboratories Inc | Process for making d, l-methysticin and d, l-dihydromethysticin |
-
1963
- 1963-11-29 DE DES88490A patent/DE1277263B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2870164A (en) * | 1956-09-19 | 1959-01-20 | Riker Laboratories Inc | Process for making d, l-methysticin and d, l-dihydromethysticin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2096877A1 (en) * | 1970-07-09 | 1972-03-03 | Hexachimie | |
| WO1999025716A3 (en) * | 1997-11-14 | 1999-07-15 | Schwabe Willmar Gmbh & Co | Pyranones, method for the production and use thereof |
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