DE706692C - Verfahren zur Herstellung von in 6-Stellung nicht substituierten ª‰-Derivaten des Pyridins - Google Patents
Verfahren zur Herstellung von in 6-Stellung nicht substituierten ª‰-Derivaten des PyridinsInfo
- Publication number
- DE706692C DE706692C DEB181699D DEB0181699D DE706692C DE 706692 C DE706692 C DE 706692C DE B181699 D DEB181699 D DE B181699D DE B0181699 D DEB0181699 D DE B0181699D DE 706692 C DE706692 C DE 706692C
- Authority
- DE
- Germany
- Prior art keywords
- pyridine
- derivatives
- substituted
- preparation
- syntheses
- 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
- 238000000034 method Methods 0.000 title claims description 3
- 150000003222 pyridines Chemical class 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title description 2
- 150000002576 ketones Chemical class 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 235000005911 diet Nutrition 0.000 claims description 2
- 241000995602 Nionia Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000037213 diet Effects 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical class O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940118019 malondialdehyde Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NNBYTRDSKTZTGA-UHFFFAOYSA-N 1-(2-methylpyridin-3-yl)ethanone Chemical compound CC(=O)C1=CC=CN=C1C NNBYTRDSKTZTGA-UHFFFAOYSA-N 0.000 description 1
- VNCAJINVSUVLQL-NSHDSACASA-N 2-methyl-3-[(2s)-1-methylpyrrolidin-2-yl]pyridine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1C VNCAJINVSUVLQL-NSHDSACASA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 ether acetals Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
-
- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pyridine Compounds (AREA)
Description
- Verfahren zur Herstellung von in 6-Stellung nicht substituierten ß-Derivaten des Pyridins Es wurde gefunden, daß der im freien Zustande unbekannte und daher r zu Synthesen bisher nicht herangezogene unsubstituierte Malondialdehy d (bzw. das ihm tautomere ß-Oxyacrolein) sich überraschenderweise in Form seines Diäthylacetals mitAmmoniakverbindungen von Ketonen mit einer reaktionsfähigen Methylengruppe - R' # C O # C H2 R" sei die allgemeine Formel der Ketone und darin R' ein beliebiger Kohlenwasserstoffrest, R" eine aktivierende Gruppe, wie Carbonyl, Carboxyl, Cyan o. dgl. - leicht zu ß-Derivaten des Pyridins kondensieren läßt, etwa im Sinne des folgenden Schemas: Diese ß-Derivate sind im Gegensatz zu den Produkten anderer Pyridinsynthesen, die unter Verwendung von Oxyketonen durchgeführt werden, in 6-Stellung nicht substituiert.
- Die bisher bekannten Synthesen ähnlicher Art sind mit i, 3-Ketaldehyden b@zw. z, 3-Diketonen durchgeführt worden; ihre Produkte sind daher Pyridinabkömmlinge, die außer in 3-Stellung noch in 6- bzw. 4- und 6-Stellung substituiert sind. Die Verwendung eines i, 3-Dialdehyds war bisher nicht bekannt; besonders war der Malondialdehyd nie zu Synthesen herangezogen worden. Dieser ist in freier Form auch nicht darstellbar. Es bedeutet diesem Tatbestand gegenüber einen Fortschritt, daß nunmehr der Malondialdehyd in Form des ätheracetales seines Enols zu solchen Umsetzungen herangezogen werden kann. Dadurch ist es möglich, bisher unbekannte, zu vielen weiteren Synthesen befähigte 2, 3-Derivate des Pyridins herzustellen.
- Die Umsetzung erfolgt durch bloßes Erhitzen der Komponenten mit oder ohne Verwendung eines Lösungsmittels.
- Die erhaltenen Produkte sollen therapeutische Verwendung finden.
heispiele I. 13,.I Ge«iclitsteile @-Amin@crot@@usüure- äthylester werden mit I7.5 Gewichtsteilen p-ltholyacroleindiätliylacetal Tage lang auf dein Wasserbade erhitzt. Das Reaktinns- gemisch wird mit verdünnter Salzsäure be- handelt, die dabei erhaltene salzsaure Lösung mit Soda alkalisch gemacht, mit Äther aus- geschüttelt und der ätherische Auszug nach dem Abdampfen des .iili@rs der D"stillatiori unterworfen. Der bei der Umsetzung ent- standene 2-Metliylnicotinsättre,*ithylester geht bei 225 bis 23o"iiber. Atisbetite gegen &i°'" der Theorie. 2. io Gewichtsteile Acetyla.cetonamin wer- den mit r7.; Gewichtsteilen @ß-_@thox.vacrolciii- diäthylacetal 36 Stunden lang im Olbade auf i 5o bis 16u-- erhitzt. Das erhaltene Reak- tionsgemiscb wird mit verdünnter Salzsätiro ausgezogen. die salzsaure Lösung alkalisch gemacht und ausge:ithert und "er Ätheraus- - 3. Wie nach Beispiel r, aber unter Verwendung vors 2o Raumteilen Alkohol als Lösungsmittel. Vor der weiteren Aufarbeitung wird der Alkohol abdestilliert.
Claims (1)
- PATENTANSPRUCH:
Verfahren zur Herstellung von in 6-Stellung nicht substituierten /3-Deri- vaten des Pvridins, dadurch gekenn- zeichnet, daß das Diäthvlacetal des nicht substituierten llalon<iial(ielivds mit Am- nioniakverbindungen von Ketonen der all- l;eItteiüen Formel R'# C O # C H, R", worin ft' eitil)elie#bigerKoliienwasserstoffrest und R' eine aktivierende Gruppe ist, umge- setzt wird.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB181699D DE706692C (de) | 1938-02-01 | 1938-02-01 | Verfahren zur Herstellung von in 6-Stellung nicht substituierten ª‰-Derivaten des Pyridins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB181699D DE706692C (de) | 1938-02-01 | 1938-02-01 | Verfahren zur Herstellung von in 6-Stellung nicht substituierten ª‰-Derivaten des Pyridins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE706692C true DE706692C (de) | 1941-06-03 |
Family
ID=7009152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB181699D Expired DE706692C (de) | 1938-02-01 | 1938-02-01 | Verfahren zur Herstellung von in 6-Stellung nicht substituierten ª‰-Derivaten des Pyridins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE706692C (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE936448C (de) * | 1952-02-02 | 1955-12-15 | Riedel De Haeen Ag | Verfahren zur Herstellung von 2, 6-Dimethyl-pyridin-carbonsaeure-(3) |
-
1938
- 1938-02-01 DE DEB181699D patent/DE706692C/de not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE936448C (de) * | 1952-02-02 | 1955-12-15 | Riedel De Haeen Ag | Verfahren zur Herstellung von 2, 6-Dimethyl-pyridin-carbonsaeure-(3) |
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