DE1279683B - Process for the production of substituted ª ‡ pyrons - Google Patents
Process for the production of substituted ª ‡ pyronsInfo
- Publication number
- DE1279683B DE1279683B DES88491A DES0088491A DE1279683B DE 1279683 B DE1279683 B DE 1279683B DE S88491 A DES88491 A DE S88491A DE S0088491 A DES0088491 A DE S0088491A DE 1279683 B DE1279683 B DE 1279683B
- Authority
- DE
- Germany
- Prior art keywords
- pyrone
- magnesium
- condensation
- methoxy
- substituted
- 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
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 5
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000003935 benzaldehydes Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- DKKJNZYHGRUXBS-BQYQJAHWSA-N 5,6-Dehydrokawain Chemical compound O1C(=O)C=C(OC)C=C1\C=C\C1=CC=CC=C1 DKKJNZYHGRUXBS-BQYQJAHWSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- SAGHRZGOMJHCOS-CYBMUJFWSA-N 5,6-dehydrokawain Natural products CO[C@H]1CC(=O)OC(=C1)C=Cc2ccccc2 SAGHRZGOMJHCOS-CYBMUJFWSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DKKJNZYHGRUXBS-UHFFFAOYSA-N Desmethoxyyangonin Natural products O1C(=O)C=C(OC)C=C1C=CC1=CC=CC=C1 DKKJNZYHGRUXBS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- HZUFMSJUNLSDSZ-OWOJBTEDSA-N (e)-3-(1,3-benzodioxol-5-yl)prop-2-enal Chemical compound O=C\C=C\C1=CC=C2OCOC2=C1 HZUFMSJUNLSDSZ-OWOJBTEDSA-N 0.000 description 1
- QZMQKPGVXNSITP-UHFFFAOYSA-N 1,3-benzodioxole-4-carbaldehyde Chemical compound O=CC1=CC=CC2=C1OCO2 QZMQKPGVXNSITP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CGGHGWCWEAXPLK-CYBMUJFWSA-N Methysticin Natural products CC(=O)C1=CC(=O)O[C@@H](C1)C=Cc2ccc3OCOc3c2 CGGHGWCWEAXPLK-CYBMUJFWSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002848 endoanesthetic effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical class II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- -1 p-methoxystyryl Chemical group 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von substituierten a-Pyronen Die Erfindung betrifft ein Verfahren zur Herstellung von substituierten a-Pyronen durch Kondensation von 3,4-Methylendioxy-benzaldehyd oder eines gegebenenfalls durch eine Alkoxygruppe substituierten Benzaldehyds mit 4-Methoxy-6-methyla-pyron.Process for the preparation of substituted α-pyrones The invention relates to a process for the production of substituted a-pyrones by condensation of 3,4-methylenedioxy-benzaldehyde or one optionally through an alkoxy group substituted benzaldehyde with 4-methoxy-6-methyla-pyrone.
Es ist aus der USA.-Patentschrift 2870164 bekannt, Methysticin durch Umsetzung von 3,4-Methylendioxyzimtaldehyd mit y-Brom-t-methoxy-crotonsäuremethylester in Gegenwart von Zink herzustellen. Die bei diesem Verfahren erzielten Ausbeuten lassen jedoch zu wünschen übrig. It is known from US Pat. No. 2870164 to use methysticin Reaction of 3,4-methylenedioxycinnamaldehyde with γ-bromo-t-methoxy-crotonic acid methyl ester in the presence of zinc. The yields achieved in this process however leave a lot to be desired.
Weiterhin ist es aus dem Journal of the Chemical Society (London), 1960, S. 502 bis 506, bekannt, p-Methoxybenzaldehyd mit 4-Methoxy-6-methyla-pyron in Gegenwart von Magnesiummethylat zu kondensieren. Die nach diesem Verfahren erzielten Ausbeuten befriedigen jedoch noch nicht völlig. It is also from the Journal of the Chemical Society (London), 1960, pp. 502 to 506, known, p-methoxybenzaldehyde with 4-methoxy-6-methyla-pyrone to condense in the presence of magnesium methylate. The ones obtained by this procedure However, yields are not yet completely satisfactory.
Außerdem ist das Verfahren verhältnismäßig aufwendig, weil das als Kondensationsmittel verwendete Magnesiummethylat eigens hergestellt werden muß.In addition, the process is relatively complex because the Magnesium methylate used for the condensation agent must be specially prepared.
Es wurde nun überraschenderweise gefunden, daß man substituierte a-Pyrone durch Kondensation von 3,4-Methylendioxy-benzaldehyd oder eines gegebenenfalls durch eine Alkoxygruppe substituierten Benzaldehyds mit 4-Methoxy-6-methyl-<1-pyron in methanolischer Lösung und in Gegenwart von Magnesiummethylat als Kondensationsmittel in einfacher Weise und höheren Ausbeuten dadurch erhält, daß man die Kondensation durch Zugabe von. metallischem Magnesium zu der gegebenenfalls wasserhaltigen Lösung aus dem Aldehyd und dem a-Pyron bei einer 50 C nicht übersteigenden Temperatur durchführt. It has now surprisingly been found that substitution was made a-pyrones by condensation of 3,4-methylenedioxy-benzaldehyde or optionally one benzaldehyde substituted by an alkoxy group with 4-methoxy-6-methyl- <1-pyrone in methanolic solution and in the presence of magnesium methylate as a condensing agent obtained in a simple manner and higher yields by the fact that the condensation by adding. metallic magnesium to the optionally water-containing solution from the aldehyde and the a-pyrone at a temperature not exceeding 50 ° C.
Dieses Ergebnis war nicht ohne weiteres voraussehbar und beruht möglicherweise darauf, daß das sich »in in situ« bildende Magnesiummethylat die Kondensation der Reaktionspartner in erhöhtem Maße fördert. This result was not easily foreseeable and is possibly based that the magnesium methylate which forms "in situ" causes the condensation of the Promotes reaction partner to an increased extent.
Das Magnesium wird zweckmäßigerweise in Form von Grieß oder Spänen zugesetzt. Die Zugabe des Magnesiums erfolgt kontinuierlich oder portionsweise. Vorzugsweise liegt die Temperatur des Reaktionsgemisches bei der Zugabe des Magnesiums bei 40C, und die Kondensation wird vorzugsweise in Gegenwart einer Spur von Jod durchgeführt. Die Kondensation verläuft exotherm, und die immer stärker werdende Reaktion kann durch Zugabe von z B. 1 bis 2°lo Wasser Tetrahydrofuran, Benzol oder Toluol und/oder durch Kühlen unter Kontrolle gehalten werden, so daß die Temperatur 50 C nicht übersteigt. Gegen das Ende der Umsetzung wird das Reaktionsgemisch zweckmäßigerweise 30 Minuten auf dem Wasserbad erwärmt, wobei die Temperatur 50"C nicht übersteigt. The magnesium is expediently in the form of semolina or shavings added. The magnesium is added continuously or in portions. The temperature of the reaction mixture is preferably at the point at which the magnesium is added at 40C, and the condensation is preferably in the presence of a trace of iodine carried out. The condensation is exothermic, and the ever increasing Reaction can be carried out by adding, for example, 1 to 2 ° lo water tetrahydrofuran, benzene or Toluene and / or kept under control by cooling so that the temperature Does not exceed 50 C. Towards the end of implementation, that will Reaction mixture expediently Heated on the water bath for 30 minutes, the temperature not exceeding 50 ° C.
Die nach dem erfindungsgemäßen Verfahren hergestellten Verbindungen wirken als Antiphlogisticum und Endoanästheticum und als schlafinduzierendes Mittel. The compounds prepared by the process of the invention act as an anti-inflammatory and endo-anesthetic and as a sleep-inducing agent.
Die folgenden Beispiele erläutern das erfindung gemäße Verfahren. The following examples explain the process according to the invention.
Beispiel 1 4-Methoxy-6gp-methoxystyryl)-a-pyron 50 g p-Methoxybenzaldehyd und 50 g 4-Methoxy 6-methyl-a-pyron werden in 500 ccm Methanol durch leichtes Erwärmen gelöst. Zu dieser Lösung werden portionsweise 20g Magnesiumspäne unter Zugabe eines Jod kristalls zugegeben. Hierbei tritt sofort unter Erwärmung des Reaktionsgemisches eine Wasserstoffentwicklung ein. Die portionsweise Zugabe der Magnesiumspäne erfolgt in der Weise. daß die Temperatur nicht über 4Q"C hinausgeht. Nach etwa 3 Stunden ist die Kondensation beendet, und das Reaktionsgemisch ist dann gelbbraun gefärbt. An schließend wird das Ganze abgekühlt und mit der dünnter Säure (Salzsäure oder Essigsäure) neutrEdisiert, mit 200 ccm Wasser verdünnt und 3- bis 4mal mit Chloroform ausgeschüttelt. Die vereinigten Chloroformextrakte werden des öfteren mit destilliertem Wasser gewaschen, über Magnesiumsulfat getrocknet und im Vakuum eingedampft. Der sirupöse Rückstand wird hierauf in Methanol aufgenommen, mit Kohle geschüttelt, diese abfiltriert und das Filtrat im Eisschrank zur Kristallisation gebracht. Es bildet sich ein gelber amorpher Niederschlag, aus dem durch nochmalige Umkristallisation aus Methanol das 4Methoxy-6-(p-methoxystyryl)-a-pyron in Form schöner gelblicher Kristalle vom F. = 155° C erhalten wird. Example 1 4-Methoxy-6gp-methoxystyryl) -a-pyrone 50 g of p-methoxybenzaldehyde and 50 g of 4-methoxy 6-methyl-a-pyrone are dissolved in 500 cc of methanol by gentle heating solved. To this solution, 20 g of magnesium shavings are added in portions with the addition of a Iodine crystals added. This occurs immediately with heating of the reaction mixture an evolution of hydrogen. The magnesium shavings are added in portions in the way. that the temperature does not exceed 40 "C. After about 3 hours the condensation has ended and the reaction mixture is then yellow-brown in color. Then the whole thing is cooled down and treated with the dilute acid (hydrochloric acid or Acetic acid) neutralized, diluted with 200 ccm of water and 3 to Shaken out 4 times with chloroform. The combined chloroform extracts are des washed several times with distilled water, dried over magnesium sulfate and evaporated in vacuo. The syrupy residue is then taken up in methanol, Shaken with charcoal, this filtered off and the filtrate in the refrigerator for crystallization brought. A yellow amorphous precipitate forms, from which repeated Recrystallization from methanol, the 4-methoxy-6- (p-methoxystyryl) -a-pyrone in the form beautiful yellowish crystals with a temperature of 155 ° C are obtained.
Die Ausbeute beträgt 91 g. Die Verbindung ergibt eine gelbbraune Schwefelsäurereaktion. The yield is 91 g. The connection results in a yellow-brown Sulfuric acid reaction.
Beispiel 2 Methoxy-6-(3',4'-methylendioxystyryl)-5,6dehydro-a-pyron-(5,6-Dehydrnmethysticin) 15 g 3, SMethylendioxybenzaldehyd (Piperonal) werden zusammen mit 14 g SMethoxy-6-methyla-pyron in 150 ccm Methanol gelöst, und dann werden portionsweise 6 g Magnesiumspäne mit einem Jodkristall in der Weise zugegeben, daß die Reaktionstemperatur etwa bei 40"C gehalten wird. Anschließend wird das erhaltene Gemisch analog Beispiel 1 aufgearbeitet und gereinigt. Es werden 23 g 5, SDehydromethysticin vom F. = 233"C in Form zitronengelber Kristalle erhalten. Die Verbindung ergibt eine dunkelbraune Schwefelsäurereaktion.Example 2 methoxy-6- (3 ', 4'-methylenedioxystyryl) -5,6dehydro-a-pyrone- (5,6-dehydrnmethysticin) 15 g of 3, S methylenedioxybenzaldehyde (piperonal) are dissolved together with 14 g of S methoxy-6-methyla-pyrone in 150 cc of methanol, and then 6 g of magnesium turnings with an iodine crystal are added in portions in such a way that the reaction temperature is kept at about 40 ° C The mixture obtained is then worked up and purified analogously to Example 1. 23 g of 5, S-hydromethysticin with a F. = 233 ° C. are obtained in the form of lemon-yellow crystals. The compound gives a dark brown sulfuric acid reaction.
Beispiel 3 4-Methoxy-6-styryl-5,6-dehydro-a-pyron (5,6-Dehydrokawain) 10,6 g (0,1 Mol) Benzaldehyd und 14 g (0,1 Mol) 4-Methoxy-6-methyl-a-pyron werden in 120 com Methanol gelöst und mit 4 g Magnesiumspänen gemäß Beispiel 1 kondensiert und anschließend das Reaktionsgemisch in analoger Weise aufgearbeitet. Nach der Umkristallisation aus Methanol werden 13,5 g 5,6-Dehydrokawain in Form von schönen gelblichen Stäbchen vom F. = 138"C erhalten. Die Verbindung ergibt eine rotbraune Schwefelsäurereaktion.Example 3 4-methoxy-6-styryl-5,6-dehydro-a-pyrone (5,6-dehydrokawain) 10.6 g (0.1 mol) of benzaldehyde and 14 g (0.1 mol) of 4-methoxy-6-methyl-a-pyrone are dissolved in 120 com of methanol and condensed with 4 g of magnesium turnings according to Example 1 and then the reaction mixture worked up in an analogous manner. After recrystallization from methanol, 13.5 g of 5,6-dehydrokawain are obtained in the form of beautiful yellowish rods with a melting point of 138 ° C. The compound gives a red-brown sulfuric acid reaction.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES88491A DE1279683B (en) | 1963-11-29 | 1963-11-29 | Process for the production of substituted ª ‡ pyrons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES88491A DE1279683B (en) | 1963-11-29 | 1963-11-29 | Process for the production of substituted ª ‡ pyrons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1279683B true DE1279683B (en) | 1968-10-10 |
Family
ID=7514483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES88491A Pending DE1279683B (en) | 1963-11-29 | 1963-11-29 | Process for the production of substituted ª ‡ pyrons |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1279683B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 DES88491A patent/DE1279683B/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 |
|---|---|---|---|---|
| WO1999025716A3 (en) * | 1997-11-14 | 1999-07-15 | Schwabe Willmar Gmbh & Co | Pyranones, method for the production and use thereof |
| US6288109B1 (en) | 1997-11-14 | 2001-09-11 | Dr. Willmar Schwabe Gmbh & Co. | Pyranones, method for the production and use thereof |
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