DE418218C - Process for the preparation of ketones of the pyridine series - Google Patents

Process for the preparation of ketones of the pyridine series

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Publication number
DE418218C
DE418218C DEC34182D DEC0034182D DE418218C DE 418218 C DE418218 C DE 418218C DE C34182 D DEC34182 D DE C34182D DE C0034182 D DEC0034182 D DE C0034182D DE 418218 C DE418218 C DE 418218C
Authority
DE
Germany
Prior art keywords
ketones
preparation
pyridine series
pyridine
oxymethylene
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
Application number
DEC34182D
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German (de)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHEM FAB VORM E SCHERING
Original Assignee
CHEM FAB VORM E SCHERING
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by CHEM FAB VORM E SCHERING filed Critical CHEM FAB VORM E SCHERING
Priority to DEC34182D priority Critical patent/DE418218C/en
Application granted granted Critical
Publication of DE418218C publication Critical patent/DE418218C/en
Expired legal-status Critical Current

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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
    • C07D213/24—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Description

Verfahren zur Darstellung von Ketonen der Pyridinreihe. C 1 a i s e n und Fischer (Ber. d. deutsch. chem. Ges. 21 [tSSS], S. 1138) geben an, daß die ätherische Lösung von 0xymetliylenacetophenon (Benzoylaldehyd) C,HS CO . CH: CH (OH) beim Vermischen init einer solchen von Ammoniumacetat in Eisessig und mehrtägigem Stehen die Ammoniakverbindung des Aldehyds, die sich nach neueren Untersuchun--en als Bio-ß-bcnzoylvinylamin der Formel: CGH5 . CO- CH: CH # NH # CH: CH # CO. CCHg erwiesen hat, ausscheidet. Angaben über die Mengenverhältnisse und über etwaige andere Reaktionsprodukte fehlen: Es wurde nun die überraschende -Beobachtung gemacht, daß bei Anwendung eines Überschusses von Ammoniumacetat aus dem Filtrat als Hauptprodukt der Reaktion sich eine neue Base gewinnen läßt, die sich als 2-Phenyl-5-benzoylpyridinerweist und demnachaus 2Mo1. Osytnethylenverbiiidung und t AIo1. Ammoniak unter Abspaltung von 3 Mol. 'Wasser gebildet wird. In ähnlicher Weise erhält man aus Oxymetliylenverbindungen anderer Ketone bzw. deren Salzen vom Typus R # CO . CH: CH (OH) (R = Alkyl oder Aryl) Ketone der Pyridinreihe von der Formel: In manchem Falle, z. B. bei der Herstellung von 2-Methyl-5-acetylpyridin (vgl. K n u d s e n, Ber. d. deutsch. .chem. Ges. 25 [r892], S. i988), unterbleibt die Bildung einer Ammoniakvcrbindung.Process for the preparation of ketones of the pyridine series. C 1 ais en and Fischer (Ber. D. German. Chem. Ges. 21 [tSSS], p. 1138) state that the ethereal solution of oxymethyl acetophenone (benzoyl aldehyde) C, HS CO. CH: CH (OH) when mixing with one of ammonium acetate in glacial acetic acid and standing for several days, the ammonia compound of the aldehyde, which, according to recent studies, turns out to be bio-β-benzoylvinylamine of the formula: CGH5. CO- CH: CH # NH # CH: CH # CO. CCHg has been proven to be ruled out. Information on the proportions and any other reaction products are missing: The surprising observation has now been made that when an excess of ammonium acetate is used from the filtrate as the main product of the reaction, a new base can be obtained, which can be obtained as 2-phenyl-5- benzoylpyridine and therefore 2Mo1. Ethylene compound and t AIo1. Ammonia is formed with elimination of 3 moles of water. In a similar way, other ketones or their salts of the type R # CO are obtained from oxymethylene compounds. CH: CH (OH) (R = alkyl or aryl) ketones of the pyridine series of the formula: In some cases, e.g. B. in the preparation of 2-methyl-5-acetylpyridine (cf. K Nudsen, Ber. D. German.. Chem. Ges. 25 [r892], p. 1988), the formation of an ammonia compound does not occur.

Die erwähnten Ketonen sollen zur Herstellung therapeutisch wirksamer Präparate dienen. Beispiele.The mentioned ketones are said to be therapeutically effective for the production Serving preparations. Examples.

t. Darstellung von 2-Phrnyl-5-benzoylpyridin. Zu einer ätherischen Lösung von aus S 5 g Natriumsalz hergestelltem Oxy mc#tIiylciutc-etophenon gibt man in kleinen Anteilen eine übersättigte Lösung von 30 g Ammoniumacetat in Eisessig und läßt 2 bis 3 Tage verschlossen stehen. Von der Ausgeschiedenen Atnmoniakvcrbindung des Oxymethylenacetoplicnons wird dann abgesaugt; das Filtrat läßt man verdunsten, wobei sich die Pyridinbase abscheidet. Aus Alkohol umkristallisiert bildet si f rT@tc Blättehen-L@com Schmelzpunkt 87-,88°, die unlöslich in 'Wasser, schwer löslich in kaltem, leicht löslich in heiP,em Alkohol, unlösiicli in Pctroläthcr,-sonst iin allgemeinen leicht löslich in organischen Lösungsmitteln sind. Das in Wasser schwer lösliche Chlorhydrat schmilzt b.ei__ ao@°,.rdas Oxtnl bei 183 bis 18q.. - -2. Dai``st'el`lüüg"'v'ö"ri 2-Metliyl-5-acetylpyridin. Zu einer übersättigten Lösung von 5o g Ammoniumacetat in Eisessig gibt man in kleinen Anteilen too g gepulvertes Natrium. formylaceton unter Kühlung und läßt 2 Tagc stehen. Man fügt dann Wasser bis zur Lösung. des ausgeschiedenen Natriumacetats hinzu, dann Natronlauge bis zur alkalischen Reaktion und schüttelt mit Äther aus. Dieser enthält neben etwas Triacetylbenzol die Base, die man durch Destillation oder über das Quecksilberchloriddoppelsalz reinigt.t. Preparation of 2-phrnyl-5-benzoylpyridine. A supersaturated solution of 30 g of ammonium acetate in glacial acetic acid is added in small portions to an ethereal solution of oxy mc # tiylciutc-etophenone prepared from 5 g of sodium salt and left to stand for 2 to 3 days. The released ammonia compound of the oxymethylene acetophenone is then suctioned off; the filtrate is allowed to evaporate, the pyridine base separating out. Recrystallized from alcohol it forms a melting point of 87-88 °, which is insoluble in water, sparingly soluble in cold, easily soluble in hot alcohol, insoluble in polyether, otherwise generally easily soluble stuffs are gsmit in organic Lösun. The hydrochloride, which is sparingly soluble in water, melts at 183 to 18q .. - -2. Dai``st'el`lüüg "'v'ö" ri 2-methyl-5-acetylpyridine. To a supersaturated solution of 50 g of ammonium acetate in glacial acetic acid, too g of powdered sodium is added in small portions. formyl acetone with cooling and allowed to stand for 2 days. Water is then added to the solution. of the precipitated sodium acetate, then sodium hydroxide solution until it has an alkaline reaction and shakes out with ether. In addition to some triacetylbenzene, this contains the base, which is purified by distillation or with the double salt of mercury chloride.

Claims (1)

PATGNT-ANsPRUCH: Verfahren zur Darstellung von Ketonen der Pyridinreilte, dadurch gekennzeichnet, daß man auf Oxymethylenverbindungen von Ketonen bzw. deren Salzen vom Typus: R # CO # CH : CH (OH) (R = Alkyl oder Aryl) Ainmoniumacetat im L'berschuß, in Gegenwart von Eisessig, einwirken läßt, etwa gebildete Ammoniakverbindung des Oxymethylenketons abtrennt und das entstandene Pyridylketon nach üblichen Methoden abscheidet.PATGNT CLAIM: Process for the preparation of ketones of the pyridine range, characterized in that one on oxymethylene compounds of ketones or their Salts of the type: R # CO # CH: CH (OH) (R = alkyl or aryl) ammonium acetate im The excess, in the presence of glacial acetic acid, allows any ammonia compound formed separates the oxymethylene ketone and the resulting pyridyl ketone by conventional methods separates.
DEC34182D 1923-11-23 1923-11-23 Process for the preparation of ketones of the pyridine series Expired DE418218C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEC34182D DE418218C (en) 1923-11-23 1923-11-23 Process for the preparation of ketones of the pyridine series

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEC34182D DE418218C (en) 1923-11-23 1923-11-23 Process for the preparation of ketones of the pyridine series

Publications (1)

Publication Number Publication Date
DE418218C true DE418218C (en) 1925-08-28

Family

ID=7021188

Family Applications (1)

Application Number Title Priority Date Filing Date
DEC34182D Expired DE418218C (en) 1923-11-23 1923-11-23 Process for the preparation of ketones of the pyridine series

Country Status (1)

Country Link
DE (1) DE418218C (en)

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