CH408914A - Process for the preparation of pyridoxine - Google Patents
Process for the preparation of pyridoxineInfo
- Publication number
- CH408914A CH408914A CH536862A CH536862A CH408914A CH 408914 A CH408914 A CH 408914A CH 536862 A CH536862 A CH 536862A CH 536862 A CH536862 A CH 536862A CH 408914 A CH408914 A CH 408914A
- Authority
- CH
- Switzerland
- Prior art keywords
- methyl
- dicarboxylic acid
- hydroxypyridine
- pyridoxine
- ester
- Prior art date
Links
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 7
- 235000008160 pyridoxine Nutrition 0.000 title claims description 7
- 239000011677 pyridoxine Substances 0.000 title claims description 7
- 229940011671 vitamin b6 Drugs 0.000 title claims description 7
- -1 sodium aluminum hydride Chemical compound 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ZUFQODAHGAHPFQ-UHFFFAOYSA-N pyridoxine hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(CO)=C1O ZUFQODAHGAHPFQ-UHFFFAOYSA-N 0.000 claims description 6
- 229960004172 pyridoxine hydrochloride Drugs 0.000 claims description 6
- 235000019171 pyridoxine hydrochloride Nutrition 0.000 claims description 6
- 239000011764 pyridoxine hydrochloride Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LVJJEIJOKPHQOU-UHFFFAOYSA-N 5-hydroxy-6-methylpyridine-3,4-dicarboxylic acid Chemical class CC1=NC=C(C(O)=O)C(C(O)=O)=C1O LVJJEIJOKPHQOU-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- JXEMVHUBFNXQSY-UHFFFAOYSA-N diethyl 5-hydroxy-6-methylpyridine-3,4-dicarboxylate Chemical compound CCOC(=O)C1=CN=C(C)C(O)=C1C(=O)OCC JXEMVHUBFNXQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ASNWYVUHANWRHY-UHFFFAOYSA-N CC1=NC=C(C(=C1OCC1=CC=CC=C1)C(=O)OCC)C(=O)OCC Chemical compound CC1=NC=C(C(=C1OCC1=CC=CC=C1)C(=O)OCC)C(=O)OCC ASNWYVUHANWRHY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- KVXDYVKDICSNOV-UHFFFAOYSA-N dimethyl 5-acetyloxy-6-methylpyridine-3,4-dicarboxylate Chemical compound COC(=O)C1=CN=C(C)C(OC(C)=O)=C1C(=O)OC KVXDYVKDICSNOV-UHFFFAOYSA-N 0.000 claims description 2
- HKGQTRSBDGGXBS-UHFFFAOYSA-N dimethyl 5-hydroxy-6-methylpyridine-3,4-dicarboxylate Chemical compound COC(=O)C1=CN=C(C)C(O)=C1C(=O)OC HKGQTRSBDGGXBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
- C07D213/66—One oxygen atom attached in position 3 or 5 having in position 3 an oxygen atom and in each of the positions 4 and 5 a carbon atom bound to an oxygen, sulphur, or nitrogen atom, e.g. pyridoxal
- C07D213/67—2-Methyl-3-hydroxy-4,5-bis(hydroxy-methyl)pyridine, i.e. pyridoxine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von Pyridoxin
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Pyridoxin aus 2-Methyl-3-hydro- xy-pyradin-4, 5-dicarbonsäure oder aus in den Canboxygruppen oder in der Hydroxygruppe abgewandel- ten Derivaten davon durch chemische Reduktion, welches dadurch gekennzeichnet ist, dass als Reduk- tionsmittel Natriumaluminiumhydrid verwendet wind.
Als Ausgangsmaterial verwendbare Derivate der 2-Methyl-3-hydroxy-pyridin-4, 5-dicarbonsÏure sind z. B. deren Mono-oder Dialkylester, wie 2-Methyl- 3-hydroxy-pyridin-4, 5-dicarbonsÏure-dimethylester oder 2-Methyl-3-hydroxy-pyridin-4, 5-dicarbonsäure- diäthylester, derem Säurehalogenide oder deren Säureanhydride geeignet. Beispielhaft für Ausgangsmaterialien mit funktionell, abgewandelter Hydroxyl- gruppe sind 2-Methyl-3-acetoxy-pyridin-4, 5-dicar bonsäure-dimethylester, 2-Methyl-3-benzyloxy-pyri din-4, 5-dicarbonsäureodiäthylester oder 2-Methyl
3-benzyloxy-pyridin-4, 5-dicarbonsäure-dibenzylester.
In einer zweckmässigen Ausführungsform wird ein 2-Methyl-3-hydroxy-pyridin-4, 5-dicarbonsäureester, z. B. der Diäthylester, in einem wasserfreien, indiffe- renten Lösungsmittel, wie Tetrahydrofuran, Diäthy lenglykoldimethyläther oder Ather, gelöst und die Lösung unter Rühren einer Suspension von Natriumaluminiumhydrid in zweckmässigerweise dem gleichen organischen Lösungsmittel zugegeben. Es ist angezeigt, die Reduktion unter Ausschluss von Feuchtigkeit oder Luftsauerstoff, z. B. in einer StickstoffatmosphÏre, vor sich gehen w lassen. Die Reduktion ist nach mehreren Stunden beendet.
Das entstandene Pyridoxin kann vorteilhafterweise durch Zugabe von alko holischer Salzsäure als Hydrochlorid zur Abscheidung gebracht werden.
Beispiel
2, 5g pulverisiertes Natriumalummiumhydrid werden in 100ml abs. TetrahydroEuran suspendiert und in einer Stickstoffatmosphäre unter Rühren mit einer Lösung von 5, 06 g 2-Methyl-3-hydroxy-pyridin-4, 5-dicarbonsäureAdiäthylester in abs. Tetrahydrofuran versetzt, wobei die Temperatur zwischen 0 und 10 gehalten wurde. Nach l0-st ndigem R hren versetzt man mit 1, 5 g Wasser und anschliessend mit oa. 10 /o-iger alkoholischler Salzsäure bis zur deutlich kongosauren Reaktion. Nach 30 Minuten nubscht man vom ausgeschiedenen Niederschlag ab, kocht denselben in Äthanol auf und filtriert heiss. Das Fil- trat wind abkühlen gelassen, wobei sich Kristalle von : Pyridoxin-hydrochlorid ausscheiden.
Diese werden abgenutscht und mit Alkohol und Äther nachgewa- schen. Das as Pyridoxin-hydrochlorid schmilzt bei 202-203 . Der Mischschmelzpunkt mit einer authen tischen Probe von Pyridoxin-hydrochlorid zeigt keine Depression. Ausbeute : 70 /o.
PATENTANSPRUCH
Verfahren zur Herstellung von Pyndoxin aus 2-Methyl-3-hydroxy-pyridin-4, 5-dicarbonsäure oder aus in den Carboxygruppen oder in der Hydroxygruppe abgewandelten Derivaten davon durch chemische Reduktion, dadurch gekennzeichnet, dass als Reduktionsmittel Natriumaluminiumhydrid verwendet wird.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the preparation of pyridoxine
The present invention relates to a process for the preparation of pyridoxine from 2-methyl-3-hydroxy-pyradine-4,5-dicarboxylic acid or from derivatives thereof modified in the canboxy groups or in the hydroxyl group by chemical reduction, which is characterized that sodium aluminum hydride is used as a reducing agent.
Usable as starting material derivatives of 2-methyl-3-hydroxypyridine-4, 5-dicarboxylic acid are z. B. their mono- or dialkyl esters, such as 2-methyl-3-hydroxypyridine-4, 5-dicarboxylic acid dimethyl ester or 2-methyl-3-hydroxypyridine-4,5-dicarboxylic acid diethyl ester, their acid halides or their acid anhydrides suitable. Examples of starting materials with a functionally modified hydroxyl group are 2-methyl-3-acetoxypyridine-4,5-dicarboxylic acid dimethyl ester, 2-methyl-3-benzyloxypyridine-4,5-dicarboxylic acid diethyl ester or 2-methyl
3-benzyloxy-pyridine-4,5-dicarboxylic acid dibenzyl ester.
In an advantageous embodiment, a 2-methyl-3-hydroxypyridine-4,5-dicarboxylic acid ester, for. B. the diethyl ester, dissolved in an anhydrous, indifferent solvent such as tetrahydrofuran, Diethy lenglykoldimethyläther or ether, and the solution is added to a suspension of sodium aluminum hydride in the same organic solvent, conveniently while stirring. It is advisable to carry out the reduction with the exclusion of moisture or atmospheric oxygen, e.g. B. in a nitrogen atmosphere, w let go ahead. The reduction is complete after several hours.
The resulting pyridoxine can advantageously be deposited as the hydrochloride by adding alcoholic hydrochloric acid.
example
2.5g of powdered sodium aluminum hydride are dissolved in 100ml of abs. TetrahydroEuran suspended and in a nitrogen atmosphere with stirring with a solution of 5.06 g of 2-methyl-3-hydroxypyridine-4, 5-dicarboxylic acid diethyl ester in abs. Tetrahydrofuran was added, the temperature being kept between 0 and 10. After stirring for 10 hours, 1.5 g of water are added, followed by the above. 10 / o alcoholic hydrochloric acid up to the clearly Congo acidic reaction. After 30 minutes, the precipitate which has separated out is nebulized, the same is boiled in ethanol and filtered hot. The filtrate is left to cool, whereupon crystals of: pyridoxine hydrochloride separate out.
These are sucked off and washed with alcohol and ether. The as pyridoxine hydrochloride melts at 202-203. The mixed melting point with an authentic sample of pyridoxine hydrochloride shows no depression. Yield: 70 / o.
PATENT CLAIM
Process for the preparation of pyndoxin from 2-methyl-3-hydroxypyridine-4,5-dicarboxylic acid or from derivatives thereof modified in the carboxy groups or in the hydroxyl group by chemical reduction, characterized in that sodium aluminum hydride is used as the reducing agent.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH536862A CH408914A (en) | 1962-05-05 | 1962-05-05 | Process for the preparation of pyridoxine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH536862A CH408914A (en) | 1962-05-05 | 1962-05-05 | Process for the preparation of pyridoxine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH408914A true CH408914A (en) | 1966-03-15 |
Family
ID=4292382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH536862A CH408914A (en) | 1962-05-05 | 1962-05-05 | Process for the preparation of pyridoxine |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH408914A (en) |
-
1962
- 1962-05-05 CH CH536862A patent/CH408914A/en unknown
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