DE2166862C3 - Process for the preparation of 2-benzylfluoranthene - Google Patents
Process for the preparation of 2-benzylfluorantheneInfo
- Publication number
- DE2166862C3 DE2166862C3 DE19712166862 DE2166862A DE2166862C3 DE 2166862 C3 DE2166862 C3 DE 2166862C3 DE 19712166862 DE19712166862 DE 19712166862 DE 2166862 A DE2166862 A DE 2166862A DE 2166862 C3 DE2166862 C3 DE 2166862C3
- Authority
- DE
- Germany
- Prior art keywords
- parts
- fluoranthene
- dihydrofluoranthene
- organic phase
- benzylfluoranthene
- 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
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- CKDLQLNLJCZJPA-UHFFFAOYSA-N 2-benzylfluoranthene Chemical compound C=1C(=C23)C4=CC=CC=C4C3=CC=CC2=CC=1CC1=CC=CC=C1 CKDLQLNLJCZJPA-UHFFFAOYSA-N 0.000 title description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- GVEPBJHOBDJJJI-UHFFFAOYSA-N Fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 10
- MBXXMPNBVQQJEL-UHFFFAOYSA-N 2,3-dihydrofluoranthene Chemical compound C12=CC=CC=C2C2=CCCC3=CC=CC1=C32 MBXXMPNBVQQJEL-UHFFFAOYSA-N 0.000 claims description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229940095076 benzaldehyde Drugs 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M Benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OWGXJHNDSSLDER-UHFFFAOYSA-N 1,2,3,3a-tetrahydrofluoranthene Chemical compound C12=CC=CC=C2C2=CC=CC3CCCC1=C32 OWGXJHNDSSLDER-UHFFFAOYSA-N 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N Decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von 2-Benzylfluoranthen aus 2.3-Dihydrofluoranthen durch Reaktion mit Benzaldehyd entsprechend dem vorstehenden Patentanspruch.The invention relates to a process for the preparation of 2-benzylfluoranthene from 2,3-dihydrofluoranthene by reaction with benzaldehyde according to the preceding claim.
2.3-Dihydrofluoranthen wird nach dem Verfahren der DT-PS 21 14 219 aus Fluoranthen dadurch erhalten, daß man Fluoranthen in Kohlenwasserstoffen bei 100 bis 1400C unter Stickstoffschutz mit Natrium behandelt, das Reaktionsprodukt anschließend mit einem Überschuß an alkoholischer Säure zerlegt, die organische Phase abtrennt, und das Reaktionsprodukt in bekannter Weise aufarbeitet. Die vom Wasser und durch Destillation vom Lösemittel befreite organische Phase enthält außer 80% an 2.3-Dihydrofluoranthen zu je 10% Fluoranthen und Tetrahydrofluoranthen.2,3-Dihydrofluoranthene is obtained from fluoranthene according to the process of DT-PS 21 14 219 by treating fluoranthene in hydrocarbons at 100 to 140 ° C. with sodium under nitrogen protection, then separating the reaction product with an excess of alcoholic acid, the organic phase separated off, and the reaction product worked up in a known manner. The organic phase freed from the water and from the solvent by distillation contains, in addition to 80% of 2,3-dihydrofluoranthene, 10% each of fluoranthene and tetrahydrofluoranthene.
Es wurde nun überraschender Weise gefunden, daß man 2-Benzy!fluoranthen isomerenfrei und in sehr guten Ausbeuten erhalten kann, wenn man die durch Destillation vom Lösemittel befreite organische Phase aus der vorstehend geschilderten Herstellung von 2.3-Dihydrofluoranthen, ausgehend von Fluoranthen, die 2.3-Dihydrofluoranthen zu etwa 80% enthält in Gegenwart von Dimethylsulfoxid als Lösungsmittel und Benzyltrimethylammoniumhydroxid (35%) mit Benzaldehyd versetzt, unter Stickstoff auf 600C erhitzt, aus dem Reaktionsprodukt nach Ansäuern und Ausfällen mit Wasser die organische Phase abtrennt und nach an sich bekannten Verfahren aufarbeitet.It has now been found, surprisingly, that 2-benzy! Fluoroanthene can be obtained isomer-free and in very good yields if the organic phase, freed from solvent by distillation, is obtained from the above-described preparation of 2,3-dihydrofluoranthene, starting from fluoranthene, the 2.3- Dihydrofluoranthene contains about 80% in the presence of dimethyl sulfoxide as solvent and benzyltrimethylammonium hydroxide (35%), mixed with benzaldehyde, heated to 60 ° C. under nitrogen, the organic phase is separated off from the reaction product after acidification and precipitation with water and worked up according to methods known per se .
R = BenzylR = benzyl
Die erfindungsgemäße Reaktion kann als Prototyp für die Reaktion des 2.3-Dihydrofluoranthens mit Aldehyden gelten. Sie zeigt, daß auch in Gegenwart von Nebenprodukten eine selektive Umsetzung des 2.3-Dihydrofluoranthens erfolgt.The reaction according to the invention can be used as a prototype for the reaction of 2,3-dihydrofluoranthene with Aldehydes apply. It shows that even in the presence of by-products, a selective conversion of the 2,3-dihydrofluoranthene he follows.
2-Benzylfluoranthen kann ebenso wie Fluoranthen zur Herstellung von Farbstoff-Zwischenprodukten verwendet, werden.Like fluoranthene, 2-Benzylfluoranthene can be used in the production of dye intermediates be used.
Das nachfolgende Beispiel erläutert das Verfahren der Erfindung zur Gewinnung von 2-Benzylfluoranthen.The following example illustrates the process of the invention for obtaining 2-benzylfluoranthene.
200 Teile Fluoranthen werden in 1000 Teilen Dekahydronaphthalin gelöst und bei HO0C unter heftigem Rühren und Stickstoffschutz innerhalb von 6 Stunden mit 50 Teilen Natrium versetzt. Nach Beendigung der Metallierung kühlt man auf 100C und zerlegt das Reaktionsgemisch unter Rühren und Stickstoffschutz durch langsames Zutropfen eines Gemisches aus 500 Teilen Äthanol und 120 Teilen konz. Salzsäure. Anschließend gießt man auf 500 Teile Wasser, trennt die organische Phase ab, trocknet mit Calciumchlorid und destilliert Dekalin im Vakuum bei 0,5 bis 2 mm ab.200 parts of fluoranthene are dissolved in 1000 parts of decahydronaphthalene and 50 parts of sodium are added over the course of 6 hours at HO 0 C with vigorous stirring and nitrogen protection. After the metalation has ended , the mixture is cooled to 10 ° C. and the reaction mixture is decomposed, while stirring and under nitrogen protection, by slowly adding dropwise a mixture of 500 parts of ethanol and 120 parts of conc. Hydrochloric acid. It is then poured into 500 parts of water, the organic phase is separated off, dried with calcium chloride and decalin is distilled off in vacuo at 0.5 to 2 mm.
Der Rückstand enthält laut Gaschromatogramm 80% (166 Teile) 2.3-Dihydrofluoranthen und je 10% (20 Teile) Fluoranthen und Tetrahydrofluoranthen.According to the gas chromatogram, the residue contains 80% (166 parts) of 2,3-dihydrofluoranthene and 10% (20 parts) each Fluoranthene and tetrahydrofluoranthene.
Nach Destillation im Vakuum erhält man ein Destillat, das zu je 15% (30 Teile) aus Fluoranthen und Tetrahydrofluoranthen und zu 70% (140 Teile) aus 2.3-Dihydrofluoranthen besteht.After distillation in vacuo, a distillate is obtained, each of which consists of 15% (30 parts) of fluoranthene and Tetrahydrofluoranthene and 70% (140 parts) of 2,3-dihydrofluoranthene.
10 Teile dieses Gemisches werden mit 10 Teilen Benzaldehyd, 20 Teilen Dimethylsulfoxid und 1 Teil Benzyltrimethylammoniumhydroxid (35%) 1 Stunde unter Stickstoff auf 6O0C erhitzt; man neutralisiert mit Salzsäure, gießt auf Wasser, schüttelt mit Äther aus, trennt die organische Phase ab und erhält nach Destillation im Hochvakuum 9 Teile 2-Benzylfluoranthen. 10 parts of this mixture (% 35) was heated with 10 parts of benzaldehyde, 20 parts of dimethyl sulfoxide and 1 part of benzyltrimethylammonium hydroxide for 1 hour under nitrogen at 6O 0 C; the mixture is neutralized with hydrochloric acid, poured into water, extracted with ether, the organic phase is separated off and 9 parts of 2-benzylfluoranthene are obtained after distillation in a high vacuum.
Schmelzpunkt aus Äthanol: 100,2 bis 102,40C
Elementaranalyse:Melting point from ethanol: 100.2 to 102.4 0 C
Elemental analysis:
Berechnet: C 94,48, H 5,52;Calculated: C 94.48, H 5.52;
gefunden: C 94,13, H 5,70.Found: C 94.13, H 5.70.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712166862 DE2166862C3 (en) | 1971-03-24 | Process for the preparation of 2-benzylfluoranthene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712166862 DE2166862C3 (en) | 1971-03-24 | Process for the preparation of 2-benzylfluoranthene |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2166862A1 DE2166862A1 (en) | 1976-04-08 |
| DE2166862B2 DE2166862B2 (en) | 1977-03-31 |
| DE2166862C3 true DE2166862C3 (en) | 1977-11-17 |
Family
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