DE957946C - Ver drive for the preparation of 2 5-substituted 2 5 dihydrofuran derivatives - Google Patents
Ver drive for the preparation of 2 5-substituted 2 5 dihydrofuran derivativesInfo
- Publication number
- DE957946C DE957946C DENDAT957946D DE957946DA DE957946C DE 957946 C DE957946 C DE 957946C DE NDAT957946 D DENDAT957946 D DE NDAT957946D DE 957946D A DE957946D A DE 957946DA DE 957946 C DE957946 C DE 957946C
- Authority
- DE
- Germany
- Prior art keywords
- substituted
- derivatives
- preparation
- ver drive
- furan
- 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.)
- Expired
Links
- 125000004852 dihydrofuranyl group Chemical class O1C(CC=C1)* 0.000 title 1
- 150000002240 furans Chemical class 0.000 claims description 4
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-Dihydrofuran Chemical class C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N furane Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N ethoxyethane;trifluoroborane Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N Ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 229940077484 ammonium bromide Drugs 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M Lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M Sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ZYTSUANFIPZBDM-UHFFFAOYSA-N (2,5-dimethoxy-2H-furan-5-yl)methanol Chemical compound COC1OC(CO)(OC)C=C1 ZYTSUANFIPZBDM-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- BVJOXYJFOYNQRB-UHFFFAOYSA-N morpholine;hydrobromide Chemical compound Br.C1COCCN1 BVJOXYJFOYNQRB-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940075581 sodium bromide Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
AUSGEGEBEN AM 14. FEBRUAR 1957ISSUED FEBRUARY 14, 1957
K 17798 IVb/12 qK 17798 IVb / 12 q
Zusatz zum Patent 848Addendum to patent 848
Das Patent 848501 betrifft ein Verfahren zur Herstellung von 2, 5-substituierten 2, 5-Dihydrofuranderivaten aus Furan bzw. seinen Derivaten durch Oxydation unter Substituierung in 2, 5-Stel-· lung. Das Merkmal dieses Verfahrens besteht darin, daß die Oxydation auf elektrolytischem Wege in einer Lösung des Furans bzw. Furandefivats in einem organischen Lösungsmittel vorgenommen wird.The patent 848501 relates to a method for Production of 2,5-substituted 2,5-dihydrofuran derivatives from furan or its derivatives by oxidation with substitution in the 2,5-position. The feature of this procedure is in that the oxidation is carried out electrolytically in a solution of the furan or furan derivative is made in an organic solvent.
Es hat sich jetzt herausgestellt, daß dieses Verfahren in vorteilhafter Weise auch mit solchen Furanderivaten als Ausgangsmaterial durchgeführt werden kann, die in der ct-S teilung eine gegebenenfalls acetalisierte Formylgruppe tragen.It has now been found that this method in an advantageous manner with such Furan derivatives can be carried out as starting material, which in the ct-S division a optionally carry acetalized formyl group.
Die aus solchen Furanderivaten hergestellten 2, 5-substituierten 2, 5-Dihydrofuranderivate können als Zwischenprodukte bei der Herstellung von Dicarbonylverbindungen verwendet werden.The 2,5-substituted 2,5-dihydrofuran derivatives produced from such furan derivatives can used as intermediates in the manufacture of dicarbonyl compounds.
Das Herstellungsverfahren schließt sich eng an das Verfahren nach dem Hauptpatent an, indem als Elektrolyte vorwiegend Ammoniumbromid oder eine Mischung von Bromiden, z. B. Ammor niumbromid und Lithiumbromid, verwendet werden. Es lassen sich jedoch auch andere HalogenideThe manufacturing process closely follows the process according to the main patent by as electrolytes mainly ammonium bromide or a mixture of bromides, e.g. B. Ammor nium bromide and lithium bromide can be used. However, other halides can also be used
verwenden, sowohl von organischer als auch von anorganischer Art, z. B. Morpholinhydrobromid oder Bortrifluoridätherat, sowie halogenfreie Elektrolyte, wie Schwefelsäure, Nitrate, Rhodanide oder Formiate.use, both organic and inorganic, e.g. B. morpholine hydrobromide or boron trifluoride etherate, as well as halogen-free electrolytes, such as sulfuric acid, nitrates, rhodanides or formates.
Die Erfindung wird nachstehend durch einige Ausführungsbeispiele näher erläutert.The invention is explained in more detail below by means of a few exemplary embodiments.
Beispiel ιExample ι
ίο Zu einer Lösung von 5 g Ammoniumbromid in 270 ecm Methanol werden 35,5gFürfuroldhnethylacetal zugesetzt. Die Mischung wird auf etwa —Ί50 abgekühlt und mit einer Klemmspannung von etwa 5 Volt so lange elektrolysiert, bis eine Elektrizitätsmenge von 14 Amperestunden die Lösung passiert hat. Die Elektrolyse wird dann unterbrochen und die noch kalte Reaktionsmischung in eine Lösung von Natriummethylat (1,20 g Natrium in 30 ecm Methanol) gegossen. Nach demίο To a solution of 5 g of ammonium bromide in 270 ecm of methanol, 35.5 g of Fururoldhnethylacetal are added. The mixture is cooled to about 0 -Ί5 and electrolyzed with a clamping voltage of about 5 volts until a quantity of electricity of 14 ampere hours, the solution has passed. The electrolysis is then interrupted and the still cold reaction mixture is poured into a solution of sodium methylate (1.20 g of sodium in 30 ecm of methanol). After this
ao Abdestillieren von Methanol und Ammoniak im Vakuum wird das gebildete Natriumbromid aus dem Destillationsrückstand durch Zusatz von 200 ecm Äther ausgefällt, und dann wird filtriert. Nach dem Abdunsten des Äthers aus dem Filtratao distilling off methanol and ammonia in vacuo, the sodium bromide formed is removed the distillation residue is precipitated by adding 200 ecm of ether, and then it is filtered. After the ether has evaporated from the filtrate
»5 wird im Vakuum destilliert. Man erhält 41,8 g 2, 5-Diimethoxy-2, S-diihydroifurfuroldimethylacetal, dessen Kochpunkt bei 13 mm Hg bei 107 bis iio° liegt.»5 is distilled in vacuo. 41.8 g are obtained 2, 5-Diimethoxy-2, S-diihydroifurfuroldimethylacetal, its boiling point at 13 mm Hg at 107 to 10 ° lies.
14,7 g4-IsopropyIfurfuroldimethylacetal, 270 ecm Methanol und 5 g Ammoniumbromid werden gemäß Beispiel 1 unter Anwendung einer Elektrizitätsmenge von 4,4 Arnperestunderi elektrolysiert. Durch die Aufarbeitung erhält man 14,7 g 2, 5-Dimethoxy-4-isopropyl-2, 5-dihydrofurfuroldimethylacetal, dessen Kochpunkt bei o, I1 mm Hg bei 64 bis 65,5° liegt.14.7 g of 4-isopropylfurfuroldimethylacetal, 270 ecm of methanol and 5 g of ammonium bromide are electrolyzed according to Example 1 using an amount of electricity of 4.4 Amperestunderi. By working up, 14.7 g of 2 receives, 5-dimethoxy-4-isopropyl-2, 5-dihydrofurfuroldimethylacetal, whose boiling point is at o, I 1 mm Hg at 64 to 65.5 °.
30 g Furfurol, 250 ecm Methanol und 5 g Bortrifluoridätherat werden gemäß Beispiel 1 unter Anwendung einer Elektriziitäts-menge von 20 Ampere&tunden elektrolysiert. Durch Aufarbeitung erhält man 47,1 g eines Produktes, dessen Kochpunkt bei 10 mm Hg bei 94 bis iio° liegt und das vorwiegend aus 2, 5"Dimethoxy-2, 5-dihydrofurfuroldimethylacetal besteht, verunreinigt durch etwas 2, 5-Dimethoxy-2, 5-dihydrofurfurol.30 g of furfural, 250 ecm of methanol and 5 g of boron trifluoride etherate are according to Example 1 using an amount of electricity of 20 amps electrolyzed. Work-up gives 47.1 g of a product whose boiling point at 10 mm Hg it is 94 to 10 ° and that predominantly from 2.5 "dimethoxy-2,5-dihydrofurfural dimethylacetal consists, contaminated by some 2, 5-dimethoxy-2, 5-dihydrofurfurol.
Claims (1)
Deutsche ' Auslegeschrift K 6143 IVc/12 q.Considered publications:
German 'Auslegeschrift K 6143 IVc / 12 q.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE957946C true DE957946C (en) | 1957-01-24 |
Family
ID=582412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT957946D Expired DE957946C (en) | Ver drive for the preparation of 2 5-substituted 2 5 dihydrofuran derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE957946C (en) |
-
0
- DE DENDAT957946D patent/DE957946C/en not_active Expired
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