CH309832A - Process for the production of a coumarin derivative. - Google Patents
Process for the production of a coumarin derivative.Info
- Publication number
- CH309832A CH309832A CH309832DA CH309832A CH 309832 A CH309832 A CH 309832A CH 309832D A CH309832D A CH 309832DA CH 309832 A CH309832 A CH 309832A
- Authority
- CH
- Switzerland
- Prior art keywords
- parts
- coumarin
- production
- oxy
- coumarin derivative
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical group 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- -1 propylmagnesium halide Chemical class 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
- C07D311/44—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3
- C07D311/46—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3 unsubstituted in the carbocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
Description
Verfahren zur Herstellung eines Cumarinderivates. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 3-(1'- Phenyl-n-butyl)-4-oxy-cumarin, das dadurch gekennzeichnet ist, dass man auf 3-Benzoyl- 4-oxy-eumarin Propyllithium oder ein Propyl- inagiiesiumhalogenid einwirken lässt, die erhal tene Organometallverbindung hydrolytisch zer setzt,
aus dem entstandenen Carbinol Wasser abspaltet und das gebildete Reaktionsprodukt hydriert.
Das Verfahren kann im einzelnen gemäss den Anraben in der Hauptpatentschrift dureligeführt. werden.
Beispiel: In eine aus 4 Gewiehtsteilen Magnesium und 20,5 Cxewiehtsteilen n-Propylbromid in etwa. .100 Raumteilen absolutem Äther wie üblich bereitete n-Propylmagnesiumbromid- lösLingr weiden unter Rühren 13,3 CTewichts- teile 3-Berizoyl-4-oxy-cumarin eingetragen und noch 3 Stunden unter Rühren am Rückfluss ",
gekocht.. blau fügt ein Gemisch von 15 Raum teilen konzentrierter Salzsäure und 400 Raum teilen Wasser zu. Die Ätherschicht. wird mit 200 Raumteilen 3n-Natronlauge ausgeschüttelt, die wässerig-alkalische Schicht mit 50 Raum teilen Toluol gewaschen und hernach mit konzentrierter Salzsäure vorsichtig ange säuert.
Das hierbei ausfallende Öl wird in 200 Raumteilen Toluol aufgenommen, die Toluollösuüg, kurz mit Chlorcaleium getrock net, nach Abfiltrieren des Trockenmittels mit <B>100</B> mir p-Toluolsulfonsäure versetzt und am Wasserscheider so lange am Rückfluss gekocht, bis sich keine Wassertröpfchen mehr abschei den. Die Toluollösung wird im Vakuum bei 40-50 C zur Trockne eingedampft und der Rückstand in 100 Raumteilen Alkohol gelöst.
Hierbei scheiden sich geringe Mengen unver ändertes 3-Benzo5-1-4-oxy-cumarin ab, die durch Filtrieren entfernt werden. Die unge sättigte Verbindung 3-[1'-Phenyl-n-buten- (1')-yl]-4-oxy-cumarin wird nicht isoliert, sondern in der alkoholischen Lösung direkt unter Zusatz von wenig Palladiumkohle hydriert.. In kurzer Zeit erfolgt die für die Doppelbindung berechnete Wasserstoffauf nahme.
Nach Abfiltrieren des Katalysators, Abdampfen des Alkohols im Vakuum und Umkristallisieren aus Toluol erhält man das 3-(1'-Phenyl-n-butyl)-4-oxy-cumarin in weissen' Kristallen vom Schmelzpunkt 201--202 C.
Process for the production of a coumarin derivative. The present patent relates to a process for the preparation of 3- (1'-phenyl-n-butyl) -4-oxy-coumarin, which is characterized in that propyllithium or a propyl is used on 3-benzoyl-4-oxy-eumarin - lets the inorganic halide act, hydrolytically decomposing the organometallic compound obtained,
splitting off water from the resulting carbinol and hydrogenating the reaction product formed.
The process can be carried out in detail according to the indications in the main patent specification. will.
Example: In one of 4 parts by weight of magnesium and 20.5 parts by weight of n-propyl bromide approximately. .100 parts by volume of absolute ether, prepared as usual, n-propylmagnesium bromide solubles are added with stirring 13.3 parts by weight of 3-berizoyl-4-oxycoumarin and refluxed for 3 hours with stirring ",
cooked .. blue adds a mixture of 15 parts of concentrated hydrochloric acid and 400 parts of water. The ether layer. is extracted with 200 parts by volume of 3N sodium hydroxide solution, the aqueous-alkaline layer is washed with 50 parts by volume of toluene and then carefully acidified with concentrated hydrochloric acid.
The oil that precipitates out is taken up in 200 parts by volume of toluene, the toluol solution, briefly dried with chlorcaline, after filtering off the desiccant, treated with <B> 100 </B> p-toluene sulfonic acid and refluxed on the water separator until none Separate more water droplets. The toluene solution is evaporated to dryness in vacuo at 40-50 ° C. and the residue is dissolved in 100 parts by volume of alcohol.
Small amounts of unchanged 3-Benzo5-1-4-oxy-coumarin separate out and are removed by filtration. The unsaturated compound 3- [1'-phenyl-n-buten- (1 ') - yl] -4-oxy-coumarin is not isolated, but hydrogenated in the alcoholic solution directly with the addition of a little palladium carbon .. In a short time the hydrogen uptake calculated for the double bond takes place.
After filtering off the catalyst, evaporating the alcohol in vacuo and recrystallizing from toluene, 3- (1'-phenyl-n-butyl) -4-oxy-coumarin is obtained in white crystals with a melting point of 201-202 C.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH309832T | 1952-05-16 | ||
| CH307800T | 1952-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH309832A true CH309832A (en) | 1955-09-15 |
Family
ID=25735448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH309832D CH309832A (en) | 1952-05-16 | 1952-05-16 | Process for the production of a coumarin derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH309832A (en) |
-
1952
- 1952-05-16 CH CH309832D patent/CH309832A/en unknown
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