CH291985A - Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. - Google Patents
Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole.Info
- Publication number
- CH291985A CH291985A CH291985DA CH291985A CH 291985 A CH291985 A CH 291985A CH 291985D A CH291985D A CH 291985DA CH 291985 A CH291985 A CH 291985A
- Authority
- CH
- Switzerland
- Prior art keywords
- benz
- keto
- indole
- tetrahydro
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- CAXVDGQDGNZJKF-UHFFFAOYSA-N 3,4-dihydro-1h-benzo[cd]indol-5-one Chemical compound C1=CC(C(=O)CC2)=C3C2=CNC3=C1 CAXVDGQDGNZJKF-UHFFFAOYSA-N 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CAWUZNPMHOPWST-UHFFFAOYSA-N O=C1C2CC(C=3CCNC1=3)=CC=C2 Chemical compound O=C1C2CC(C=3CCNC1=3)=CC=C2 CAWUZNPMHOPWST-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 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
- 229920001778 nylon Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/90—Benzo [c, d] indoles; Hydrogenated benzo [c, d] indoles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Indole Compounds (AREA)
Description
Verfahren zur Herstellung von 5-Keto-1,3,4,5-tetrahydro-benz(ed)indol. Im Hauptpatent ist ein Verfahren zur Her stellung von 5-Keto-1,3,4,5-tetralrydro-benz- (cd)indol beschrieben. Es hat sich nun gezeigt; dass beim Verarbeiten von grösseren Substanz mengen nach den in der Hauptpatentschriff beschriebenen Arbeitsweisen nicht immer die gleich guten Ausbeuten erhalten werden.
Es wurde nun gefunden, dass die Umlage rung des 5-Oxy -benz(ed)iridolins zum 5-Keto- 1,3,4,5-tetr.Lliydro-benz(cd)indol auch mit grö- 13eren Substanzmengen stets in vorzüglicher Ausbeute durchgeführt werden kann, wenn man erfindungsgemälä das 5-Oxy-benz(cd)indo- lin in einer Wasserstoffatmosphäre in Gegen wart eines Hydrierungskatalysators und von Lösungsmittel erhitzt.
<I>Beispiel:</I> In ein 1000 Volumenteile fassendes Reak- tionsg ef ö ss,versehenmit Rührer, G aseinleitungs- rohr und einem ca. 100 Volumenteile fassenden Extraktionsapparat nach Soxhlet (mit letzterem ist ein mit Wasser gekühlter Rückflusskühler verbunden), werden 4 Gewichtsteile 10%iger Palladiumkohle-Katalysator, 400 Volumenteile Tetralin,100 Volumenteile Xy 1o1 und 50 Volu menteile Benzol gebracht.
In die Extraktions hülse des Soxhlet-Apparates werden 4 Ge wichtsteile reines, frisch hergestelltes 5-Oxy- benz(ed)indolin und 80 Volumenteile Nylol gebracht. Unter Rühren und ständigem Ein- leiten von Wasserstoff wird das Reaktions gefäss während 8 Stunden in einem Ölbad von 200--A0 erhitzt. Bei dieser Arbeitsweise wird die Substanz im Soxhlet-Apparat nach und nach heraus gelöst und in Gegenwart des Katalysators umgelagert.
Durch Filtration der heissen Mischung wird der Katalysator entfernt. Nach Auswaschen mit heissem Xylol wird das Filtrat unter ver mindertem Druck bei einer maximalen Ölbad temperatur von 120-130 eingedampft. Aus der zurückbleibenden dunklen Kristallmasse kann leicht reines 5-Keto-1,3,4,5-tetrahydro- benz(cd)indol in ausgezeichneter Ausbeute isoliert werden.
Die Reinigung kann wie in Beispiel 1 des Hauptpatentes oder durch Umkristallisieren aus Benzol-Petroläther durchgeführt werden.
Das 5-Oxy-benz(cd)indolin kann auch auf andere Art in kleinen Anteilen nach und nach in das Reaktionsgefäss gebracht werden, bei spielsweise mit Hilfe einer Zuführungsschnecke an Stelle des Soxhlet-Apparates.
An Stelle des hier verwendeten Lösungs- mittelgemisches kann z. B. auch reines p-Cymol verwendet werden.
Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (ed) indole. In the main patent, a process for the manufacture of 5-keto-1,3,4,5-tetralrydro-benz (cd) indole is described. It has now been shown; that when processing larger amounts of substance according to the procedures described in the main patent specification, the same good yields are not always obtained.
It has now been found that the rearrangement of the 5-oxy-benz (ed) iridoline to the 5-keto-1,3,4,5-tetr.Lliydro-benz (cd) indole is always excellent, even with larger amounts of substance Yield can be carried out if, according to the invention, the 5-oxy-benz (cd) indoline is heated in a hydrogen atmosphere in the presence of a hydrogenation catalyst and a solvent.
<I> Example: </I> In a 1000 parts by volume reaction vessel equipped with a stirrer, gas inlet pipe and a 100 parts by volume Soxhlet extraction apparatus (the latter is connected to a water-cooled reflux condenser), 4 parts by weight of 10% palladium-carbon catalyst, 400 parts by volume of tetralin, 100 parts by volume of Xy 1o1 and 50 parts by volume of benzene are brought.
4 parts by weight of pure, freshly made 5-oxybenz (ed) indoline and 80 parts by volume of nylon are placed in the extraction sleeve of the Soxhlet apparatus. The reaction vessel is heated for 8 hours in an oil bath at 200 - A0 while stirring and constantly passing in hydrogen. With this procedure, the substance is gradually dissolved out in the Soxhlet apparatus and rearranged in the presence of the catalyst.
The catalyst is removed by filtering the hot mixture. After washing with hot xylene, the filtrate is evaporated under reduced pressure at a maximum oil bath temperature of 120-130. Pure 5-keto-1,3,4,5-tetrahydrobenz (cd) indole can easily be isolated in excellent yield from the dark crystal mass that remains.
The purification can be carried out as in Example 1 of the main patent or by recrystallization from benzene petroleum ether.
The 5-oxy-benz (cd) indoline can also be gradually introduced into the reaction vessel in small portions in other ways, for example with the aid of a feed screw instead of the Soxhlet apparatus.
Instead of the solvent mixture used here, z. B. also pure p-cymene can be used.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH286498T | 1950-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH291985A true CH291985A (en) | 1953-07-15 |
Family
ID=4530162
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH286498D CH286498A (en) | 1950-04-03 | 1950-04-03 | Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. |
| CH291985D CH291985A (en) | 1950-04-03 | 1951-03-02 | Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH286498D CH286498A (en) | 1950-04-03 | 1950-04-03 | Process for the preparation of 5-keto-1,3,4,5-tetrahydro-benz (cd) indole. |
Country Status (4)
| Country | Link |
|---|---|
| CH (2) | CH286498A (en) |
| DE (1) | DE869342C (en) |
| FR (1) | FR1045654A (en) |
| GB (1) | GB702768A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE542760A (en) * | 1954-11-12 |
-
1950
- 1950-04-03 CH CH286498D patent/CH286498A/en unknown
-
1951
- 1951-03-02 CH CH291985D patent/CH291985A/en unknown
- 1951-03-10 DE DE1951H0007996 patent/DE869342C/en not_active Expired
- 1951-04-02 FR FR1045654D patent/FR1045654A/en not_active Expired
- 1951-04-02 GB GB7610/51A patent/GB702768A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR1045654A (en) | 1953-11-30 |
| CH286498A (en) | 1952-10-31 |
| DE869342C (en) | 1953-03-05 |
| GB702768A (en) | 1954-01-20 |
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