DE1931946C3 - Process for the preparation of 1-hydroxymethyl-1.2.3.4-tetrahydrofluoranthene - Google Patents
Process for the preparation of 1-hydroxymethyl-1.2.3.4-tetrahydrofluorantheneInfo
- Publication number
- DE1931946C3 DE1931946C3 DE19691931946 DE1931946A DE1931946C3 DE 1931946 C3 DE1931946 C3 DE 1931946C3 DE 19691931946 DE19691931946 DE 19691931946 DE 1931946 A DE1931946 A DE 1931946A DE 1931946 C3 DE1931946 C3 DE 1931946C3
- Authority
- DE
- Germany
- Prior art keywords
- tetrahydrofluoranthene
- hydroxymethyl
- preparation
- dimethyl sulfoxide
- hours
- 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 4
- UJWLWGABUNFRKJ-UHFFFAOYSA-N 1,2,3,4-tetrahydrofluoranthen-1-ylmethanol Chemical compound C1=CC=CC2=C3C(CO)CCC(CC=C4)=C3C4=C21 UJWLWGABUNFRKJ-UHFFFAOYSA-N 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HWEWZSACZIURKQ-UHFFFAOYSA-N 1,2,3,4-tetrahydrofluoranthene Chemical compound C1=CCC(CCC2)=C3C2=C(C=CC=C2)C2=C31 HWEWZSACZIURKQ-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- -1 1 - Hydroxymethyl Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-Toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006049 ring expansion reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M Benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N Phenylisocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von l-Hydroxymethyl-KZ^-tetrahydrofluoranthen der Formel IThe invention relates to a process for the preparation of l-hydroxymethyl-KZ ^ -tetrahydrofluoranthene of formula I.
CH2OHCH 2 OH
das dadurch gekennzeichnet ist, daß man 1,2,3,4-Tetrahydrofluoranthen mit Par?formaldehyd unter Luftttusschluß in Anwesenheit katalytischer Mengen starker Basen in Pyridin, Chinolin oder anderen aprotischen polaren Lösungsmitteln bei 0 bis 30 C 0,5 bis 2 Stunden reagieren läßt und das gebildete 1-Hytlroxymethyl-l,2,3,4-tetrahydrofluoranthen in üblicher Weise, wie Ausfällen z. B. mit Wasser und Filtration des Niederschlags isoliert.which is characterized in that 1,2,3,4-tetrahydrofluoranthene with par? formaldehyde with the exclusion of air in the presence of catalytic amounts stronger Bases in pyridine, quinoline or other aprotic polar solvents at 0 to 30 C 0.5 Allowed to react for up to 2 hours and the 1-hydroxymethyl-1,2,3,4-tetrahydrofluoranthene formed in the usual way, such as failures z. B. isolated with water and filtration of the precipitate.
Die bislang nicht bekannte Verbindung 1 wird dabei in hoher Ausbeute (95 bzw. 90%) und Reinheit erhalten.The previously unknown compound 1 is obtained in high yield (95 or 90%) and purity receive.
Bei einer anderen Ausführungsform verwendet man Dimethylsulfoxid (DMSO) als Reaktionsmedium. Man erhiilt hierbei I in Form seines Monoaddukts mit DMSO (Ausbeute: IiW0). Aus dem Addukt kann die DMSO-freie Verbindung durch Erhitzen im Vakuum hergestellt werden.In another embodiment, dimethyl sulfoxide (DMSO) is used as the reaction medium. This gives I in the form of its monoadduct with DMSO (yield: IiW 0 ). The DMSO-free compound can be produced from the adduct by heating it in vacuo.
mitWith
1 - Hydroxymethyl -1.2.3,4- tetrahydrofi uoran then 11) bildet aus Petroläther oder Methanol Wasser farblose Kristalle vom Schmelzpunkt 85 C.1 - Hydroxymethyl -1.2.3,4- tetrahydrofi uoran then 11) From petroleum ether or methanol, water forms colorless crystals with a melting point of 85 C.
Elementaranalyse:Elemental analysis:
Berechnet ... C 86.41, H 6,82%;Calculated ... C 86.41, H 6.82%;
gefunden .... C 86.53, H 7,19%.found .... C 86.53, H 7.19%.
Das Monoaddukt mit DMSO schmilzt bei 112 bis
1130C.
Elementaranalyse:The monoadduct with DMSO melts at 112 to 113 0 C.
Elemental analysis:
Berechnet ... C 72,58. H 7,05, S 10.20%:
gefunden .... C 72,67, H 6,72, S 10.04%.Calculated ... C 72.58. H 7.05, S 10.20%:
found .... C 72.67, H 6.72, S 10.04%.
Die Konstitutionsbestimmung von I erfolgte mit chemischen und spektroskopischen Methoden. Beweisend sind die Bildungsweise, die Elementaranalyse und die Ringerweiterung beim Erhitzen mit Phosphorsäure zum bekannten 1,10-Trimethylenphenanthren(III). The constitution of I was determined using chemical and spectroscopic methods. Proof are the mode of formation, the elemental analysis and the ring expansion when heated with phosphoric acid to the known 1,10-trimethylene phenanthrene (III).
Die hergestellte Verbindung ist mannigfachen Umsetzungen zugänglich und besitzt besonders als Zwischenprodukt Tür die Herstellung von pharmakologisch wirksamen Substanzen, z. B. von Aminoderivaten, wie des /y-Phenyläthylamin-Derivats. von der allgemeinen Formel IV Interesse:The compound produced is amenable to various reactions and is particularly useful as an intermediate For the production of pharmacologically active substances, e.g. B. of amino derivatives, like the / y-phenylethylamine derivative. of the general formula IV interest:
H2 H 2
H 2
(In Formel IV stehen(Stand in Formula IV
Alkyl-, Aryl- oder Aralkylgruppen.)Alkyl, aryl, or aralkyl groups.)
Als Beispiele für die vielseitigen Reaktionsmöglichkeiten von 1 seien die Veresterungen mit Essigsäureanhydnd. Ameisensäure. Tosylchlorid. ThionylchloridAs examples of the versatile response options of 1 are the esterifications with acetic anhydride. Formic acid. Tosyl chloride. Thionyl chloride
und Phenylisocyanat sowie die bereits erwähnte Ringerweiterung (beim Erhitzen mit Phosphorsäure) zu dem auf anderem Wege schwer zugänglichen 1.10-Trimethylenphenanthren (III). vgl E. C 1 a r »Polycyclicand phenyl isocyanate as well as the already mentioned ring expansion (when heated with phosphoric acid) 1.10-trimethylene phenanthrene, which is difficult to access in any other way (III). see E. C 1 a r »Polycyclic
Hydrocarbons«, 1964, Bd. 2, S. 394) erwähnt. Alle diese Reaktionen verlaufen praktisch quantitativ und sind leicht durchführbar.Hydrocarbons ", 1964, Vol. 2, p. 394) mentioned. All these reactions are practically quantitative and are easy to do.
Die nachstehenden Beispiele erläutern das vorliegende Verfahren.The following examples illustrate the present process.
10 Teile 1,2,3,4-Tetrahydrofluoranthen werden in 15 Teilen Pyridin gelöst und mit 1,6 Teilen Paraformaldehyd versetzt. Anschließend gibt man bei 10 C nach Stickstoffspülung 0,1 Teil Benzyl-trimethyl-ammoniumhydroxid hinzu. Nach 2 Stunden fügt man 0,2 Teile Eisessiü hinzu, versetzt mit Wasser, saugt ab und erhält I - Hydroxymethyl - 1,2,3,4 - tetrahydrofluoranthen vom Schmelzpunkt 83 bis 85 C (97% der Theorie).10 parts of 1,2,3,4-tetrahydrofluoranthene are dissolved in 15 parts of pyridine and 1.6 parts of paraformaldehyde offset. Then 0.1 part of benzyltrimethylammonium hydroxide is added at 10 ° C. after purging with nitrogen added. After 2 hours, 0.2 part of Eisessiü is added, water is added, the mixture is filtered off with suction and obtained I - hydroxymethyl - 1,2,3,4 - tetrahydrofluoranthene of melting point 83 to 85 ° C. (97% of theory).
10 Teile 1,2,3,4-Tetrahydrofluoranthen werden in 100 Teilen Dimethylsulfoxid gelöst. Man versetzt mit10 parts of 1,2,3,4-tetrahydrofluoranthene are dissolved in 100 parts of dimethyl sulfoxide. One adds
!,6Teilen Paraformaldeh>d und gibt nach Spülung mit Stickstoff 0,1 Teil 2-n äthanolische Kalilauge hinzu. Sobald die Kristallisation beendet ist, wird abgesaugt und aus 40 Teilen Petrolälher (Kp. 50 bis 75 C) umkristallisien. Man erhält ein Addukt von!, 6 parts Paraformaldeh> d and gives after rinsing 0.1 part of 2N ethanolic potassium hydroxide solution is added with nitrogen. As soon as the crystallization is over, will suctioned off and recrystallized from 40 parts of petroleum ether (boiling point 50 to 75 ° C.). An adduct of
ίο 1 - Hydroxymethyl - 1,2,3,4 - teirahydrofluoranthen mit einem Mol Kristall-Dimethylsulfoxid vom Schmelzpunkt 112 bis 113^C (70% der Theorie). Bei 95 C und 15 Torr wird das Addukt zerlegt; man erhält quantitativ 1 -Hydroxy methyl- 1,2,3,4-tetrahydroftuor-ίο 1 - hydroxymethyl - 1,2,3,4 - teirahydrofluoranthene with one mole of crystal dimethyl sulfoxide with a melting point of 112 to 113 ^ C (70% of theory). at The adduct is decomposed at 95 C and 15 Torr; you get quantitative 1 -hydroxy methyl 1,2,3,4-tetrahydroftuor-
!5 anthen vom Schmelzpunkt 85 C.! 5 anthers with a melting point of 85 C.
Claims (2)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691931946 DE1931946C3 (en) | 1969-06-24 | Process for the preparation of 1-hydroxymethyl-1.2.3.4-tetrahydrofluoranthene | |
| FR7018110A FR2052403A5 (en) | 1969-06-24 | 1970-05-19 | |
| GB1290586D GB1290586A (en) | 1969-06-24 | 1970-06-23 | |
| US298203A US3912781A (en) | 1969-06-24 | 1972-10-24 | 1-hydroxymethyl-1,2,3,4-tetrahydrofluoranthene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691931946 DE1931946C3 (en) | 1969-06-24 | Process for the preparation of 1-hydroxymethyl-1.2.3.4-tetrahydrofluoranthene |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1931946A1 DE1931946A1 (en) | 1971-01-07 |
| DE1931946B2 DE1931946B2 (en) | 1975-10-23 |
| DE1931946C3 true DE1931946C3 (en) | 1976-06-10 |
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