CH141019A - Process for the preparation of Dihydrururacilessigsäure (2.6-Dioxy-4.5-dihydroessigsäurepyrimidin). - Google Patents
Process for the preparation of Dihydrururacilessigsäure (2.6-Dioxy-4.5-dihydroessigsäurepyrimidin).Info
- Publication number
- CH141019A CH141019A CH141019DA CH141019A CH 141019 A CH141019 A CH 141019A CH 141019D A CH141019D A CH 141019DA CH 141019 A CH141019 A CH 141019A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- diethyl ester
- parts
- dioxy
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- -1 oxymethylene succinic acid diethyl ester Chemical class 0.000 claims description 2
- ZVGODTQUYAKZMK-UHFFFAOYSA-N 2-(2,4-dioxo-1h-pyrimidin-5-yl)acetic acid Chemical compound OC(=O)CC1=CNC(=O)NC1=O ZVGODTQUYAKZMK-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- ZXYAAVBXHKCJJB-UHFFFAOYSA-N uracil-5-carboxylic acid Chemical compound OC(=O)C1=CNC(=O)NC1=O ZXYAAVBXHKCJJB-UHFFFAOYSA-N 0.000 description 2
- CNIIGCLFLJGOGP-UHFFFAOYSA-N 2-(1-naphthalenylmethyl)-4,5-dihydro-1H-imidazole Chemical compound C=1C=CC2=CC=CC=C2C=1CC1=NCCN1 CNIIGCLFLJGOGP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XHLXMRJWRKQMCP-UHFFFAOYSA-N Diethyl methylsuccinate Chemical compound CCOC(=O)CC(C)C(=O)OCC XHLXMRJWRKQMCP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BTOLNVOZDUMQRF-UHFFFAOYSA-N ethyl 2-(2,4-dioxo-1h-pyrimidin-5-yl)acetate Chemical compound CCOC(=O)CC1=CNC(=O)NC1=O BTOLNVOZDUMQRF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Darstellung von Dilzydriiruracilessigsänre (2.6-Diogy- 4. 6-diliydroessigsäur epyr imidin). An die Doppelbindung des trans-ss-Ura- midomethylenbernsteinsäurediäthylester (1I), erhalten neben cis-R-Uramidometlrylenbern- steinsäurediäthylester (III) durch Konden sation von Oxymetlrylenbernsteirrsäurediäthyl- ester (I) mit Harnstoff,
wird Wasserstoff angelagert. Dadurch wird die am Kohlenstoff sitzende Doppelbindung zur freien Rotation aufgesprengt, und die Möglichkeit der Ring bildung ist als schöner Konstitutionsbeweis für die cis-trans-Figuration des UramidomP- thylenbernsteinsäurediä thylesters gegeben.
Verseift man den so erhaltenen Diäthyl- ester der Uramidoitamalsäure (IV) mit Salz säure, so wird unter Bildung von einem Mo lekül Wasser, Dihydrüruracilessigsäureätliyl- ester (V), und schliesslich nach vollständiger VerseifungDihydrüruracilessigsäure(VI) (2.6- Dioxy-4. 5-dihydroessigsäurepyrimidin) erhal ten, welches Darstellungsverfahren Gegen stand vorliegenden Patentes ist.
EMI0001.0032
<I>Beispiel:</I> 10 Teile Oxymethylenbernsteinsäuredi- äthylester werden mit 3 Teilen Harnstoff und 20 Teilen 96 %igem Alkohol auf dem Wasserbad 5 Stunden erwärmt.
Das Produkt für Vakuumexsikkator über konzentrierter Schwefelsäure getrocknet, einmal mit 5 Teilen Wasser gewaschen und wieder getrocknet, ergibt 9 Teile cis-trans-p-Uramidomethylen- bernsteinsäurediäthylester-gemisch. Der cis P- Uramidornetlrylenbernsteinsäurediäthylester wird mit 30 Teilen Äther ausgezogen, und es verbleiben 7 Teile trarrs-,9-Uramidome- thylenbernsteinsäurediäthylester. Nachdem diese mit 3,5 Teilen heissem Wasser gereinigt, werden spitze Nadeln vom<B>SD.</B> 1440 erhalten.
Der trans-f-Uramidonrethylenbernstein- säurediäthylester wird in 175 Teilen 60 %igern Alkohol gelöst und bei Gegenwart von 21 Teilen Nickelkatalysator unter einem Druck von V/ro Atmosphären (absolut), und gleich zeitigem Schütteln, 21j;; Stunden Wasserstoff eingeleitet. Vom Katalysator abfiltriert und die klare Lösung auf dein Wasserbad ein gedampft.
Ergibt 6,65 Teile Uramidoitamal- säurediätlrylester, der nach völligem Trocknen aus heissem Benzol, nach einigen Tagen grosse, farblose Tafeln vom Sp. 62 0 bildet.
Das Rohprodukt wird mit gleichen Teilen 25 %iger Salzsäure zweimal auf dem Wasser bad zur Verseifung und Ringbildung einge dampft. Einmal aus 2,1 Teilen Wasser heiss gereinigt, ergibt 4,2 Teile Dihydrüruracil- essigsäure (2.6-Dioxy-4.5-dihydroessigsäure- pyrimidin), in Form von kleinen, farblosen Nädelchen. Sp. 247-250 0.
Process for the preparation of Dilzydriiruracilessigsänre (2.6-Diogy-4. 6-Diliydroessigsäurepyr imidin). On the double bond of the trans-ß-uramido methylsuccinic acid diethyl ester (1I), in addition to cis-R-uramidomethylsuccinic acid diethyl ester (III), by condensation of oxymethylsuccinic acid diethyl ester (I) with urea,
hydrogen is deposited. As a result, the double bond on the carbon is broken open for free rotation, and the possibility of ring formation is provided as a nice proof of the constitution for the cis-trans figuration of the uramidomPthylenesuccinic acid diethyl ester.
If the diethyl ester of uramidoitamic acid (IV) obtained in this way is saponified with hydrochloric acid, one molecule of water, dihydric uracilacetic acid ethyl ester (V), and finally, after complete saponification, dihydric uracilic acid (VI) (2.6-dioxy-4.5 -dihydroessigsäurepyrimidin) th, which method of preparation is the subject of the present patent.
EMI0001.0032
<I> Example: </I> 10 parts of oxymethylene succinic acid diethyl ester are heated with 3 parts of urea and 20 parts of 96% alcohol on a water bath for 5 hours.
The product dried over concentrated sulfuric acid for a vacuum desiccator, washed once with 5 parts of water and dried again, yields 9 parts of cis-trans-p-uramidomethylene succinic acid diethyl ester mixture. The cis P-uramidomethylsuccinic acid diethyl ester is extracted with 30 parts of ether, and 7 parts of solid 9-uramidomethylsuccinic acid diethyl ester remain. After cleaning these with 3.5 parts of hot water, sharp needles from <B> SD. </B> 1440 are obtained.
The trans-f-uramidonrethylene succinic acid diethyl ester is dissolved in 175 parts of 60% alcohol and, in the presence of 21 parts of nickel catalyst, under a pressure of v / ro atmospheres (absolute), and shaking at the same time, 21%; Hours of hydrogen initiated. The catalyst was filtered off and the clear solution was evaporated onto your water bath.
Yields 6.65 parts of uramidoitamalic acid dietarylryl ester which, after drying completely from hot benzene, forms large, colorless tablets of Sp. 62 0 after a few days.
The crude product is evaporated twice on the water bath with equal parts of 25% hydrochloric acid for saponification and ring formation. Once cleaned with hot water from 2.1 parts of water, this gives 4.2 parts of dihydric acetic acid (2,6-dioxy-4,5-dihydroacetic acid pyrimidine) in the form of small, colorless needles. Sp. 247-250 0.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH141019T | 1928-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH141019A true CH141019A (en) | 1930-07-15 |
Family
ID=4397989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH141019D CH141019A (en) | 1928-03-20 | 1928-03-20 | Process for the preparation of Dihydrururacilessigsäure (2.6-Dioxy-4.5-dihydroessigsäurepyrimidin). |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH141019A (en) |
-
1928
- 1928-03-20 CH CH141019D patent/CH141019A/en unknown
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