DE406209C - Process for the preparation of pyrrolidine derivatives - Google Patents

Process for the preparation of pyrrolidine derivatives

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Publication number
DE406209C
DE406209C DEC32373D DEC0032373D DE406209C DE 406209 C DE406209 C DE 406209C DE C32373 D DEC32373 D DE C32373D DE C0032373 D DEC0032373 D DE C0032373D DE 406209 C DE406209 C DE 406209C
Authority
DE
Germany
Prior art keywords
parts
derivatives
preparation
pyrrolidine derivatives
benzaldehyde
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
DEC32373D
Other languages
German (de)
Inventor
Dr Max Dohrn
Dr Hans Horsters
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 DEC32373D priority Critical patent/DE406209C/en
Application granted granted Critical
Publication of DE406209C publication Critical patent/DE406209C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

Verfahren zur Darstellung von Pyrrolidinderivaten. Nach vorliegender Erfindung kann man zu neuen und therapeutisch wirksamen Pyrrolidinderivaten gelangen, wenn man acidylierte Brenztraubensäureester bzw. Oxalessigester mit 2-Aminopyridin oder dessen Abkömmlingen und Benzaldehyd oder dessen Abkömmlingen bei höheren Temperaturen kondensiert.Process for the preparation of pyrrolidine derivatives. According to the present Invention can lead to new and therapeutically effective pyrrolidine derivatives, if you have acidylated pyruvic acid esters or oxaloacetic esters with 2-aminopyridine or its derivatives and benzaldehyde or its derivatives at higher temperatures condensed.

Es sind Pyrrolidinderivate bekannt, die man durch Kondensation von acidylierten Brenztraubensäureestern mit Anilin oder substituierten Anilinen und Benzaldehyd oder dessen Abkömmlingen erhält, doch war nicht vorauszusehen, daß bei Ersatz der genannten Aminoverbindungen durch 2-Aminopyridiii und dessen#Abkömmlinge die Reaktion ähnlich und in so glatter Weise verlaufen würde, da die Aminopyridine in vielen Fällen wie Iminokörper reagieren (vgl. z. B. Berichte 54 (i921, S.814). Es kommt hinzu, daß die nach dem vorliegenden Verfahren erhältlichen Verbindungen den bekannten Pyrrolidinderivaten in therapeutischer Beziehung überlegen sind. Beispiele: i. Man erhitzt 424 Teile Benzaldehyd mit 376 Teilen 2-Aminopyridin i Stunde dang auf foo°, fügt darauf 3ooo Teile Benzol zu und gibt zu dieser Lösung 744 Teile Acetylbrenztraubensäureäthylester. Wenn die von selbst einsetzende Reaktion abgeklungen ist, erhitzt man weiter 3 bis 4 Stunden zum Sieden. Die atisl;ristallisierte Masse saugt man ab, trocknet und reinigt das erhaltene i-Pyridyl-2-phenyl-3-acetyl-4, 5-diketopyrrolidin durch Umfällen aus Natriumcarbonat. Aus den benzolischen Mutterlaugen lassen sich weitere Mengen des Kondensationsprodukts gewinnen.There are known pyrrolidine derivatives that can be obtained by condensation of acidylated pyruvic acid esters with aniline or substituted anilines and Benzaldehyde or its derivatives, but it was not foreseeable that Replacement of the amino compounds mentioned by 2-aminopyridiii and its derivatives the reaction would proceed similarly and in as smoothly a manner as the aminopyridines in many cases react like imino bodies (see e.g. Reports 54 (1921, p.814). In addition, the compounds obtainable by the present process are superior to the known pyrrolidine derivatives in therapeutic terms. Examples: i. 424 parts of benzaldehyde are heated with 376 parts of 2-aminopyridine for one hour to foo °, then add 300 parts of benzene and add 744 parts of ethyl pyruvate to this solution. When the reaction, which started by itself, has subsided, heating is continued for 3 to 4 hours to simmer. The crystallized mass is sucked off, dried and purifies the i-pyridyl-2-phenyl-3-acetyl-4, 5-diketopyrrolidine obtained by reprecipitation from sodium carbonate. Further amounts can be obtained from the benzene mother liquors win the condensation product.

Die Verbindung kristallisiert in feinen weißen Nadeln vom Schmp.245° und ist in Wasser und organischen Lösungsmitteln, außer Alkohol und Chloroform, schwerlöslich.The compound crystallizes in fine white needles with a melting point of 245 ° and is in water and organic solvents, except alcohol and chloroform, hardly soluble.

2. Man löst 136 Teile der Benzylidenv erbindung des 2-Aminopyridins in Soo Teilen Benzol und setzt 95 Teile Benzoylbrenztraubensäureester zu. Unter starker Selbsterwärmung scheiden sich hellgelbe Kristallmassen ab. Zur Vervollständigung der Reaktion erhitzt man noch 8 Stunden zum Sieden. Beim Erkalten kristallisiert das Reaktionsprodukt aus. Zur Reinigung löst man es in 2oprozentiger Natriumcarbonatlösung und fällt mit Essigsäure. Das hellgelbe Kondensationsprodukt schmilzt bei 22o°.2. 136 parts of the benzylidene compound of 2-aminopyridine are dissolved in 50 parts of benzene and 95 parts of benzoylpyruvic acid ester are added. Under strong self-heating, light yellow crystal masses separate. To complete the reaction is heated to boiling for a further 8 hours. Crystallizes on cooling the reaction product from. To clean it, dissolve it in 2 percent sodium carbonate solution and falls with acetic acid. The light yellow condensation product melts at 220 °.

3. 94 Teile 2-Aminopyridin werden in der Wärme mit io6Teilen Benzaldehvd zur Benzviidenverbindung kondensiert. Man gibt darauf 5oo Teile absoluten Alkohol und 188 Teile Oxalessigester zu und erwärmt 6 Stunden auf foo°. Man kristallisiert aus Alkohol um und erhält das Kondensationsprodukt in gelblichen Nadeln vom Schmelzpunkt 192°.3. 94 parts of 2-aminopyridine are mixed with 100 parts of benzaldehyde in the heat condensed to the Benzviidenverbindungen. 500 parts of absolute alcohol are then added and 188 parts of oxaloacetate and heated to foo ° for 6 hours. One crystallizes from alcohol and receives the condensation product in yellowish needles with a melting point 192 °.

.4. Man setzt zu einer benzolischen Lösung des aus 94 Teilen 2-Aniinopyridin und i 5o Teilen Piperonal hergestellten Kondensationsprodukts 5o Gewichtsteile Acetyll)renztraubensäureester und erhitzt nach Abklingen der von selbst einsetzenden Erwärmung noch 30 Minuten zum Sieden..4. One sets to a benzene solution of the 94 parts of 2-aninopyridine and i 50 parts of piperonal produced condensation product 50 parts by weight of acetyl) pyruvic acid ester and heated after the of self-initiated heating another 30 minutes to boil.

Die bei dem Erkalten sich abscheidenden Kristalle kann man aus Alkohol umkristallisieren. Sie sind löslich in Natriumcarbonat, unlöslich in verdünnten Säuren und schmelzen bei 146 bis I:1.8°.The crystals that separate out when it cools down can be obtained from alcohol recrystallize. They are soluble in sodium carbonate, insoluble in diluted Acids and melt at 146 to I: 1.8 °.

5. 14:i Teile 2-Aminochinolin werden mit Io6 Teilen Benzaldehyd eine halbe Stunde auf ioo° erhitzt. Danach gibt man iooo Teile Benzol und 186 Teile Acetylbrenztraubensäureester zu und erhitzt 4 Stunden zum Sieden. Nach längerem Stehen wird die Masse halbfest. Man verreibt mit Aceton, saugt scharf ab und reinigt durch Umkristallisieren aus wässerigem Alkohol. Das Kondensationsprodukt bildet weiße Nadeln vorn Schmelzpunkt r52°.5. 14: i parts of 2-aminoquinoline are combined with 10 6 parts of benzaldehyde Heated to 100 ° for half an hour. Then 1000 parts of benzene and 186 parts of acetylpyruvic acid ester are added and heated to boiling for 4 hours. After standing for a long time, the mass becomes semi-solid. It is triturated with acetone, sharply suctioned off and purified by recrystallization aqueous alcohol. The condensation product forms white needles at the melting point r52 °.

Claims (1)

PA TEN T-AN sPRUCFI: Verfahren zur Darstellung von Pyrrolidinderivaten, dadurch gekennzeichnet, daß man acidylierte Brenztraubensäureester bzw. Oxalessigester mit 2-Aininopyridin oder dessen Abkömmlingen und Benzaldehyd oder dessen Abkömmlingen bei höheren Temperaturen kondensiert.PA TEN T-AN sPRUCFI: Process for the preparation of pyrrolidine derivatives, characterized in that acidylated pyruvic acid esters or oxaloacetic esters are used with 2-amino pyridine or its derivatives and benzaldehyde or its derivatives condensed at higher temperatures.
DEC32373D 1922-07-20 1922-07-20 Process for the preparation of pyrrolidine derivatives Expired DE406209C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEC32373D DE406209C (en) 1922-07-20 1922-07-20 Process for the preparation of pyrrolidine derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEC32373D DE406209C (en) 1922-07-20 1922-07-20 Process for the preparation of pyrrolidine derivatives

Publications (1)

Publication Number Publication Date
DE406209C true DE406209C (en) 1924-11-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEC32373D Expired DE406209C (en) 1922-07-20 1922-07-20 Process for the preparation of pyrrolidine derivatives

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DE (1) DE406209C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039332A1 (en) * 1997-03-07 1998-09-11 The University Of North Carolina At Chapel Hill 2-aryl-naphthyridin-4-ones as antitumor agents

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039332A1 (en) * 1997-03-07 1998-09-11 The University Of North Carolina At Chapel Hill 2-aryl-naphthyridin-4-ones as antitumor agents
US5994367A (en) * 1997-03-07 1999-11-30 The University Of North Carolina At Chapel Hill Method for treating tumors using 2-aryl-naphthyridin-4-ones
US6071930A (en) * 1997-03-07 2000-06-06 The University Of North Carolina At Chapel Hill Method for treating tumors using 2-aryl-naphthyridin-4-ones
US6229016B1 (en) 1997-03-07 2001-05-08 The University Of North Carolina At Chapel Hill Method for treating tumors using 2-aryl-naphthyridin-4-ones

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