DE536891C - Process for the preparation of pyridine derivatives - Google Patents
Process for the preparation of pyridine derivativesInfo
- Publication number
- DE536891C DE536891C DEK115847D DEK0115847D DE536891C DE 536891 C DE536891 C DE 536891C DE K115847 D DEK115847 D DE K115847D DE K0115847 D DEK0115847 D DE K0115847D DE 536891 C DE536891 C DE 536891C
- Authority
- DE
- Germany
- Prior art keywords
- aminopyridine
- preparation
- pyridine
- pyridylpyridinium
- pyridine derivatives
- 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
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
- C07D213/22—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 containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- 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
- C07D213/16—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 containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Darstellung von Pyridinderivaten Es wurde gefunden, daß man zu einem neuen, technisch wertvollen Derivat des Pyridins gelangen kann, wenn man Thionylchlorid auf Pyridin einwirken Mt. Dabei verbindet sich i Mol. Pyridin mit einem zweiten in der Weise, daß zwischen dem -#-Kohlenstoffatom des einen und dem Stickstoffatom des anderen :eine Bindung entsteht. Der neue Stoff, dem wir die Formel zuschreiben, ist als ¢-Pyridylpyridiniumdichlorid zu bezeichnen.Process for the preparation of pyridine derivatives It has been found that a new, technically valuable derivative of pyridine can be obtained by acting on pyridine with thionyl chloride. One mole of pyridine combines with a second in such a way that between the - # -Carbon atom of one and the nitrogen atom of the other: a bond is formed. The new substance to which we have the formula is to be referred to as ¢ -pyridylpyridinium dichloride.
Unterwirft man das -¢-Pyridylpyridiniumdichlorid der Einwirkung von alkalisch reagierenden Mitteln, wie Alkali- oder Erdalkalilaugen, Ammoniak oder organischen Aminen, so wird :es zu ¢-Aminopyridin und Glutaconaldehyd aufgespalten. Der Glutaconaldehyd pflegt in den alkalischreagierendenReaktionsmitteln weiteren Veränderungen unterworfen zu sein. Verwendet man z. B. zur Spaltung heiße Alkalilauge, so wird der Aldehyd zu :einem Harz kondensiert. Bei Verwendung von Anilin bildet sich das salzsaure Glutacondianil der Formel H:; C,3.N=CH-CH=CH-CH =CH-NH#C,H;#HCI. Die Aufspaltung des ¢-Pyridylpyridiniumdichlorids zum q.-Aminopyridin läßt sich auch in der Weise bewirken, daß man zunächst Alkali in der Kälte darauf einwirken läßt und nachträglich mit Säuren erhitzt.Subjecting the - ¢ -Pyridylpyridiniumdichlorid to the action of alkaline reacting agents, such as alkali or alkaline earth solutions, ammonia or organic amines, then: it is split into ¢ -aminopyridine and glutaconaldehyde. The glutaconaldehyde maintains other substances in the alkaline reactants To be subject to change. If you use z. B. for splitting hot alkali lye, so the aldehyde is condensed to: a resin. Forms when using aniline the hydrochloric acid glutacondianil of the formula H :; C, 3.N = CH-CH = CH-CH = CH-NH # C, H; #HCI. The splitting of the ¢ -pyridylpyridinium dichloride to give the q.-aminopyridine can be also cause it to act in such a way that alkali is first acted on it in the cold leaves and subsequently heated with acids.
Aus dem Reaktionsgemisch kann man das Aminopyridin durch E.trahieren mit den üblichen Lösemitteln, durch Wasserdampfdestillation oder durch Trockendestillation gewinnen.The aminopyridine can be extracted from the reaction mixture by E. with the usual solvents, by steam distillation or by dry distillation to win.
Das q.-Aminopyridin war bisher nur mittels umständlicher Verfahren durch Totalsynthese zugänglich. Demgegenüber bedeutet das vorliegende Verfahren im Hirnblick auf seine Einfachheit und Ergiebigkeit :einen bemerkenswerten technischen Fortschritt. Beispiel i i oo Gewichtsteile Pyridin werden mit 3oo Gewichtsteilen Thionylchlorid 5 Stunden auf dem Wasserbad erhitzt; das überschüssige Thionylchlorid wird unter vermindertem Druck abdestilliert. Das Reaktionsprodukt hinterbleibt als ein dunkler Kuchen, der mit wenig Äthylalkohol angerieben und eiskalt abgesaugt wird.The q.-aminopyridine was previously only available by means of cumbersome procedures accessible by total synthesis. In contrast, the present method means in the brain's eye on its simplicity and productivity: a remarkable technical one Progress. Example 100 parts by weight of pyridine are mixed with 300 parts by weight Thionyl chloride heated on a water bath for 5 hours; the excess thionyl chloride is distilled off under reduced pressure. The reaction product remains as a dark cake, rubbed with a little ethyl alcohol and vacuumed ice cold will.
Man gelangt zu dem gleichen Produkt, wenn man anstatt 5 Stunden auf dem Wasserbad zu erwärmen, 2 bis 3 Tage bei gewöhnlicher Temperatur stehenläßt. Man kann auch das Thionylchlorid in :einem Lösungsmittel, z. B. Benzol, zweckmäßig unter Erwärmen, auf das Pyridin einwirken lassen. Die Ausbeute nähert sich dem berechneten Wert. Durch Umkristallisieren kann man das gebildete 4-Pyridylpyridiniumdichlorid in einer in farblosen Rhomboedern kristallisierenden Modifikation-vom -Schmelzpunkt 17i bis 172° und in :einer anderen Modifikation vom Schmelzpunkt 151 bis 152° erhalten. Die letztgenannte Form geht bei längerem Stehen und beim Umkristallisieren aus heißer Salzsäure in die erstgenannte, offenbar beständigere Form über. In Wasser ist das Pyridylpyridiniumdichlorid leicht löslich, durch siedendes Wasser wird es zersetzt. ,Seine alkalisch-wäßrige Lösung färbt sich sofort orange und scheidet bei längerem Stehen eine rote Substanz ab. Die hochschmelzende Form liefert ein bei i8o bis 181° schmelzendes Pikrat.You get the same product if you instead of 5 hours to warm in the water bath, leave to stand for 2 to 3 days at ordinary temperature. You can also use the thionyl chloride in: a solvent, e.g. B. benzene, appropriate while warming, let the pyridine act. The yield approaches the calculated one Value. The 4-pyridylpyridinium dichloride formed can be obtained by recrystallization in a modification from the melting point that crystallizes in colorless rhombohedra 17i to 172 ° and in: another modification from melting point 151 to 152 ° obtained. The latter form becomes hotter when standing for a long time and when recrystallizing Hydrochloric acid in the former, apparently more stable form. It is in water Pyridylpyridinium dichloride easily soluble, it is decomposed by boiling water. , Its alkaline-aqueous solution turns orange immediately and separates with longer Are a red substance sticking out. The high-melting form provides a temperature between 180 and 181 ° melting picrate.
Erhitzt man i oo g gereinigtes 4-Pyridylpyridiniumdichlorid mit etwa 3oo Gewichts teilen konzentrierten wäßrigen Ammoniaks im Autoklaven 8 Stunden auf 15o bis 16o°, dampft das Reaktionsprodukt weitgehend ein und destilliert nach Zugabe von Alkali. mit überhitztem Wasserdampf, so erhält man durch Eindampfen des Destillats das rohe 4-Aminopyridin, gegebenenfalls nach Neutralisieren mit Säure in Form seines Salzes. Durch Umkristallisieren können etwa 25 Teile reines 4Aminopyridin gewonnen werden.One heats 100 g of purified 4-pyridylpyridinium dichloride with about 300 weight divide concentrated aqueous ammonia in the autoclave for 8 hours 15o to 16o °, the reaction product largely evaporates and distilled after addition of alkali. with superheated steam, it is obtained by evaporating the distillate the crude 4-aminopyridine, optionally after neutralization with acid in the form of his Salt. About 25 parts of pure 4-aminopyridine can be obtained by recrystallization will.
Ersetzt man im obigen Beispiel die Ammoniaklösung durch 5ooccm 33%iger Natronlauge oder durch Kalkmilch vors entsprechendem Gehalt, so gelangt man zu ähnlichen Ergebnissen.In the above example, if the ammonia solution is replaced by 50 cm 33% strength Caustic soda or milk of lime before the appropriate content, one arrives at similar ones Results.
Das 4-Aminopyridin wird auch erhalten, wenn man z. B. 30 g 4-Pyridylpyridiniumdichlorid mit der gleichen Gewichtsmenge Kaliumhydroxyd und etwas Calciumoxyd etwa eine Viertelstunde auf 200° erhitzt und dann wie oben mit überhitztem Wasserdampf destilliert. Man erhält etwa 4 bis 5 g 4-Aminopyridin. Beispiel 2 5 g reines Pyridylpyridiniumdichlorid werden mit 2o ccm gesättigter wäßriger Methylaminlösung 8 Stunden auf i 5o° erhitzt. Durch Ausäthern wird ein Basengemisch erhalten, aus dem durch fraktionierte Kristallisation neben 4-Aminopyridin auch 4-Methylaminopyridin vom bekannten Schmelzpunkt I16 bis i 18° erhalten wird.The 4-aminopyridine is also obtained when z. B. 30 g of 4-pyridylpyridinium dichloride with the same weight of potassium hydroxide and some calcium oxide heated to 200 ° for about a quarter of an hour and then distilled with superheated steam as above. About 4 to 5 g of 4-aminopyridine are obtained. Example 2 5 g of pure pyridylpyridinium dichloride are heated to 15 ° for 8 hours with 20 cc of saturated aqueous methylamine solution. A base mixture is obtained by etherification, from which, by fractional crystallization, not only 4-aminopyridine but also 4-methylaminopyridine with a known melting point of 16 to 18 ° is obtained.
Claims (1)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK115847D DE536891C (en) | 1929-07-24 | 1929-07-24 | Process for the preparation of pyridine derivatives |
| AT129317D AT129317B (en) | 1929-07-24 | 1930-07-19 | Process for the preparation of pyridine derivatives. |
| CH150299D CH150299A (en) | 1929-07-24 | 1930-07-21 | Process for the preparation of 4-aminopyridine. |
| GB22220/30A GB346246A (en) | 1929-07-24 | 1930-07-23 | Process for the manufacture of pyridine derivatives |
| CH161222D CH161222A (en) | 1929-07-24 | 1931-07-22 | Process for the preparation of 4-oxypyridine. |
| AT140850D AT140850B (en) | 1929-07-24 | 1931-07-22 | Process for the preparation of pyridine derivatives. |
| CH158825D CH158825A (en) | 1929-07-24 | 1931-07-22 | Process for the preparation of 4-oxypyridine. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK115847D DE536891C (en) | 1929-07-24 | 1929-07-24 | Process for the preparation of pyridine derivatives |
| US161222XA | 1930-07-23 | 1930-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE536891C true DE536891C (en) | 1931-10-28 |
Family
ID=34066205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK115847D Expired DE536891C (en) | 1929-07-24 | 1929-07-24 | Process for the preparation of pyridine derivatives |
Country Status (4)
| Country | Link |
|---|---|
| AT (2) | AT129317B (en) |
| CH (2) | CH150299A (en) |
| DE (1) | DE536891C (en) |
| GB (1) | GB346246A (en) |
-
1929
- 1929-07-24 DE DEK115847D patent/DE536891C/en not_active Expired
-
1930
- 1930-07-19 AT AT129317D patent/AT129317B/en active
- 1930-07-21 CH CH150299D patent/CH150299A/en unknown
- 1930-07-23 GB GB22220/30A patent/GB346246A/en not_active Expired
-
1931
- 1931-07-22 CH CH158825D patent/CH158825A/en unknown
- 1931-07-22 AT AT140850D patent/AT140850B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CH150299A (en) | 1931-10-31 |
| CH158825A (en) | 1932-12-15 |
| GB346246A (en) | 1931-04-09 |
| AT129317B (en) | 1932-07-25 |
| AT140850B (en) | 1935-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE536891C (en) | Process for the preparation of pyridine derivatives | |
| DE817911C (en) | Process for the preparation of pyridine-3-carboxamides which are basically substituted in the 6-position | |
| DE2302970C3 (en) | Process for the preparation of 4- (1-substituted-4-piperidylidene) -4H-benzo [4,5] cyclohepta [1,2-b] thiophene-10 (9H) -ones | |
| DE673949C (en) | Process for the preparation of basic substituted indoles | |
| DE565320C (en) | Process for the preparation of pyridine derivatives | |
| DE60077C (en) | Process for the preparation of p-oxy-m-nitrobenzaldehyde and p-mefhoxy-mnitrobenzaldehyde from p-chlorobenzaldehyde | |
| DE503031C (en) | Process for the preparation of the N-oxyethyl derivatives of core substitution products of -amino-1-oxybenzene | |
| DE629699C (en) | Process for the preparation of benzene series diamino alcohols | |
| DE396507C (en) | Process for the preparation of pyrazolone derivatives | |
| DE671841C (en) | Process for the preparation of N-alkyl and N-aralkyl compounds of aminoethylphedrine | |
| DE641270C (en) | Process for the preparation of pyridinium ethanols substituted by heterocyclic radicals | |
| DE952634C (en) | Process for the preparation of compounds of the pyridine series | |
| DE213713C (en) | ||
| DE629054C (en) | Process for the production of pellets of tertiary aliphatic amino acids | |
| DE611054C (en) | Process for the preparation of paradiketocamphane carboxylic acid and of ketooxycamphane carboxylic acid | |
| DE169358C (en) | ||
| DE871010C (en) | Process for the preparation of amines or acetylamines of the cyclopentanopolyhydrophenanthrene series | |
| DE662646C (en) | Process for the preparation of oxycinnamic acids | |
| DE504241C (en) | Process for the preparation of 6-amino-2-oxynaphthalene-3-carboxylic acid and its nitrogen-substituted derivatives | |
| AT200577B (en) | Process for the preparation of new 2-amino-4-oxo-3,4-dihydro- (or 3,4,5,6-tetrahydro-) pyridenes which are disubstituted in the 3-position by hydrocarbon radicals having 2-10 carbon atoms | |
| DE715023C (en) | Process for the preparation of haloalkylamines | |
| DE481285C (en) | Process for the preparation of halogen derivatives of lupinine | |
| DE528268C (en) | Process for the preparation of porphyrins | |
| DE613736C (en) | Process for the preparation of compounds of the hydrouracil series | |
| DE365367C (en) | Process for the preparation of 2-oxy-1-arylaminonaphthalenes |