DE2444519C2 - Process for the preparation of 1,2-dihydro-2-oxo-4-methyl-quinoline derivatives - Google Patents
Process for the preparation of 1,2-dihydro-2-oxo-4-methyl-quinoline derivativesInfo
- Publication number
- DE2444519C2 DE2444519C2 DE19742444519 DE2444519A DE2444519C2 DE 2444519 C2 DE2444519 C2 DE 2444519C2 DE 19742444519 DE19742444519 DE 19742444519 DE 2444519 A DE2444519 A DE 2444519A DE 2444519 C2 DE2444519 C2 DE 2444519C2
- Authority
- DE
- Germany
- Prior art keywords
- dihydro
- oxo
- methyl
- preparation
- acetic acid
- 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
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
Description
CH3-C-CH2-C-CH 3 -C-CH 2 -C-
bedeutet, dadurch gekennzeichnet, daß man 1 Mol m-Phenylendiamin mit 1 Mol bzw. 2 Mol Diketen umsetztmeans, characterized in that 1 mol of m-phenylenediamine with 1 mol or 2 mol Diketen converts
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Umsetzung in 10%iger wäßriger Essigsäure stattfindet.2. The method according to claim 1, characterized in that the reaction in 10% aqueous Acetic acid takes place.
3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Umsetzung in organischen Lösungsmitteln unter Zusatz von etwa 5% Eisessig durchgeführt wird.3. The method according to claim 1 and 2, characterized in that the reaction in organic Solvents with the addition of about 5% glacial acetic acid is carried out.
4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die Umsetzung unterhalb von 1000C stattfindet.4. The method of claim 1 to 3, characterized in that the reaction takes place below 100 0 C.
kann auch in organischen Lösungsmitteln, in denen die Ausgangsmaterialien löslich sind (z. B. Methanol, Butylacetat, Tetrachlorkohlenstoff, Toluol) unter Zusatz von vorzugsweise etwa 5% Eisessig oder auch Eisessig allein, bei Temperaturen unterhalb 1000C, ohne Anwendung von Druck, auch unter Umständen unter Rückfluß, durchgeführt werden. Vorzugsweise wird dss Umsetzung bei 60 bis 65° C durchgeführt werden.can also be used in organic solvents in which the starting materials are soluble (e.g. methanol, butyl acetate, carbon tetrachloride, toluene) with the addition of preferably about 5% glacial acetic acid or glacial acetic acid alone, at temperatures below 100 ° C., without applying pressure, may also be carried out under reflux. The reaction is preferably carried out at from 60 to 65.degree.
In einem SulFierkolben, ausgerüstet mit Ankerrührer, Rückflußkühler, Tropftrichter, Thermometer ur,d Wasserbad, werden 43,2 g mindestens 98%iges 1,3-Phenylendiamin (F60-62°C) und 100 ml 10%ige Essigsäure eingefüllt und bei Raumtemperatur unter Rühren 35,2 g Diketen im Verlaufe von etwa 20 Minuten eingetropft Man läßt die Temperatur unter Zuhilfenahme der Reaktionswärme auf 60-650C steigen und läßt nach beendeter Diketen-Zugabe noch 1 Stunde bei 60-650C nachreagieren.A SulFier flask equipped with anchor stirrer, reflux condenser, dropping funnel, thermometer and water bath is filled with 43.2 g of at least 98% 1,3-phenylenediamine (60-62 ° C.) and 100 ml of 10% acetic acid and at room temperature g with stirring 35.2 diketene in the course of about 20 minutes is added dropwise the temperature is allowed to rise with the aid of the heat of reaction to 60-65 0 C and can after completed addition of diketene for 1 hour at 60-65 0 C to react further.
Nach Abkühlen auf etwa 15°C wird abgenutscht und im Vakuum bei 60-700C bis zur Gewichtskonstanz getrocknet, Es werden 49,2 g gelb verfärbtes 1,2-Dihy-After cooling to about 15 ° C is filtered with suction and dried to constant weight in vacuo at 60-70 0 C, are 49.2 g of yellow-discolored 1,2-dihydroxyacetone
dro-2-oxo-4-methyl-7-aminochinolin mit einem Schmelzpunkt von 268 bis 269° C erhalten, was einerdro-2-oxo-4-methyl-7-aminoquinoline with a melting point of 268 to 269 ° C, what a
Ausbeute von 70,7%, berechnet auf m-Phenylendiamin, entsprichtYield of 70.7%, calculated on m-phenylenediamine, corresponds
Nach einmaligem Umkristallisieren aus Dimethylformamid/H2O (1 :1) bzw. 50%iger Essigsäure ist das Produkt farblos und weist einen Schmelzpunkt von 274,6-275,40C bzw. 274,0-274,80C auf.A single recrystallization from dimethylformamide / H 2 O (1: 1) and 50% acetic acid, the product is colorless and has a melting point of 274.6 to 275.4 0 C and from 274.0 to 274.8 0 C to .
Die vorliegende Erfindung betrifft den Gegenstand der Ansprüche.The present invention relates to the subject matter of the claims.
Es ist bekannt, l,2-Dihydro-2-oxo-4-methyl-7-aminochinolin aus m-Phenylendiamin und Acetessigester durch 19stündiges Erhitzen im Autoklaven auf 1300C in 45-60%iger Ausbeute herzustellen (C. 1938, II, 4240).It is known, l, 2-dihydro-2-oxo-4-methyl-7-aminoquinoline of m-phenylene diamine and ethyl acetoacetate by 19stündiges heating in an autoclave at 130 0 C in 45-60% yield to produce (C. 1938 II , 4240).
Es wurde nun gefunden, daß zur Herstellung von l,2-Dihydro-2-oxo-4-methyl-7-amino-chinolin oder 1,2-dihydro^-oxo^-methyl^-acetessigsäureamido-chinolin statt Acetessigester direkt Diketen verwendet weiden kann, wobei das Verfahren bei bedeutend niedrigeren Temperaturen und ohne Druck durchgeführt werden kann und trotzdem überraschend gute Ausbeuten erzielt werden (70-83%).It has now been found that l, 2-dihydro-2-oxo-4-methyl-7-amino-quinoline or 1,2-dihydro ^ -oxo ^ -methyl ^ -acetoacetic acid amido-quinoline instead of acetoacetic ester directly diketene can be used, the process being significant lower temperatures and without pressure can be carried out and still surprisingly good Yields can be achieved (70-83%).
Zur Herstellung von l,2-Dihydro-2-oxo-4-methyl-7-amino-chinolin setzt man 1 Mol m-Phenylidinamin mit etwa 1 Mol Diketen um, während zur Herstellung vonFor the production of 1,2-dihydro-2-oxo-4-methyl-7-amino-quinoline 1 mole of m-phenylidinamine is reacted with about 1 mole of diketene, while for the preparation of
1,2- Dihydro^-oxo^-methyl^-acetessigsäureamidochinolin. 1 Mol m-Phenylendiamin mit etwa 2 Mol Diketen umgesetzt wird.1,2-Dihydro ^ -oxo ^ -methyl ^ -acetoacetic acid amidoquinoline. 1 mole of m-phenylenediamine is reacted with about 2 moles of diketene.
Das Verfahren wird zweckmäßig in Wasser unter Zusatz von Essigsäure als Katalysator, vorzugsweise in 10%iger Essigsäure durchgeführt. Die obige ReaktionThe process is advantageously carried out in water with the addition of acetic acid as a catalyst, preferably in 10% acetic acid carried out. The above reaction
In einem Sulfierkolben, ausgerüstet mit Ankerrührer, Rückflußkühler, Tropftrichter, Thermometer und Wasserbad, werden 129,6 mindestens 98%iges 1,3-Phenylendiamin (F 60-620C), 750 ml 10%ige Essigsäure einge-In a sulfonation flask, equipped with anchor stirrer, reflux condenser, dropping funnel, thermometer, and water bath, 129.6 least 98% are 1,3-phenylenediamine einge- strength (F 60-62 0 C), 750 ml 10% acetic acid
füllt und bei Raumtemperatur unter Rühren 211,2 g Diketen im Verlaufe von 1 bis Vh Stunden zugetropft man läßt die Temperatur unter Zuhilfenahme der Reaktionswärme auf 60 bis 65° C steigen. Nach beendeter Diketen-Zugabe wird noch 1 Stunde bei 60-650C nachreagieren gelassen und dann auf etwa 15° C abgekühlt.and 211.2 g of diketene are added dropwise at room temperature with stirring over a period of 1 to 1 hour, the temperature is allowed to rise to 60 to 65 ° C. with the aid of the heat of reaction. After completion of the addition of diketene for 1 hour at 60-65 0 C is allowed to react further and then cooled to about 15 ° C.
Das ausgefällte Produkt wird abgenutscht und im Vakuum bei 60 bis 7O0C bis zur Gewichtskonstanz getrocknet Es werden 257 g rohes, fast farblosesThe precipitated product is filtered off and dried in vacuo at 60 to 7O 0 C and dried to constant weight are 257 g of crude, nearly colorless
1,2-Dihydro-3-oxo-4-methyl-7-acetoacetamino-chinolin
mit einem Schmelzpunkt von etwa 2380C erhalten, was
einer Ausbeute von 83%, berechnet auf m-Phenylendiamin, entspricht.
Nach einmaligem Umkristallisieren aus 67%iger1,2-dihydro-3-oxo-4-methyl-7-acetoacetamino-quinoline having a melting point of about 238 0 C, which corresponds to a yield of 83% calculated on m-phenylenediamine.
After recrystallizing once from 67%
Essigsäure beträgt der Schmelzpunkt 246,0 bis 247,00C,Acetic acid has a melting point of 246.0 to 247.0 0 C,
nach nochmaliger Umkristallisation aus der verdünntenafter repeated recrystallization from the diluted
Essigsäure verändert sich der Schmelzpunkt nicht mehr.Acetic acid no longer changes the melting point.
Die erfindungsgemäß hergestellten 1,2-Dihydro-The 1,2-dihydro-
chinolin-Derivate sind wertvolle Zwischenprodukte.quinoline derivatives are valuable intermediates.
insbesondere auf dem pharmazeutischen Sektor oder zur Herstellung von Spezial-Pigmenten.especially in the pharmaceutical sector or for the production of special pigments.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1349373A CH577973A5 (en) | 1973-09-20 | 1973-09-20 | 4-Methyl-7-substd.-2(1H)-quinolones prepn. - by reacting 1,3-phenylenediamine with diketene |
| CH1349273A CH572471A5 (en) | 1973-09-20 | 1973-09-20 | 4-Methyl-7-substd.-2(1H)-quinolones prepn. - by reacting 1,3-phenylenediamine with diketene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2444519A1 DE2444519A1 (en) | 1975-03-27 |
| DE2444519C2 true DE2444519C2 (en) | 1982-08-26 |
Family
ID=25712387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19742444519 Expired DE2444519C2 (en) | 1973-09-20 | 1974-09-18 | Process for the preparation of 1,2-dihydro-2-oxo-4-methyl-quinoline derivatives |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5058080A (en) |
| AT (1) | AT337184B (en) |
| CA (1) | CA1042894A (en) |
| CS (1) | CS182266B2 (en) |
| DD (1) | DD113536A5 (en) |
| DE (1) | DE2444519C2 (en) |
| FR (1) | FR2244763B1 (en) |
| GB (1) | GB1420530A (en) |
| IT (1) | IT1035085B (en) |
| LU (1) | LU70958A1 (en) |
| NL (1) | NL7412463A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2467511A1 (en) * | 2001-12-11 | 2003-06-19 | Bernd Lamatsch | Process for the preparation of 4-methyl-7-aminoquinolones |
-
1974
- 1974-09-12 JP JP10590474A patent/JPS5058080A/ja active Pending
- 1974-09-13 GB GB4001374A patent/GB1420530A/en not_active Expired
- 1974-09-16 CS CS633874A patent/CS182266B2/en unknown
- 1974-09-18 DE DE19742444519 patent/DE2444519C2/en not_active Expired
- 1974-09-18 DD DD18117974A patent/DD113536A5/xx unknown
- 1974-09-18 IT IT5307374A patent/IT1035085B/en active
- 1974-09-20 CA CA209,659A patent/CA1042894A/en not_active Expired
- 1974-09-20 FR FR7431844A patent/FR2244763B1/fr not_active Expired
- 1974-09-20 LU LU70958A patent/LU70958A1/xx unknown
- 1974-09-20 NL NL7412463A patent/NL7412463A/en not_active Application Discontinuation
- 1974-09-20 AT AT759274A patent/AT337184B/en not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| NICHTS-ERMITTELT |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1420530A (en) | 1976-01-07 |
| DE2444519A1 (en) | 1975-03-27 |
| NL7412463A (en) | 1975-03-24 |
| AT337184B (en) | 1977-06-10 |
| CS182266B2 (en) | 1978-04-28 |
| FR2244763B1 (en) | 1979-03-16 |
| DD113536A5 (en) | 1975-06-12 |
| FR2244763A1 (en) | 1975-04-18 |
| ATA759274A (en) | 1976-10-15 |
| LU70958A1 (en) | 1975-05-28 |
| JPS5058080A (en) | 1975-05-20 |
| IT1035085B (en) | 1979-10-20 |
| CA1042894A (en) | 1978-11-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| D2 | Grant after examination | ||
| 8339 | Ceased/non-payment of the annual fee |