CH366289A - Process for the production of acetophenones - Google Patents
Process for the production of acetophenonesInfo
- Publication number
- CH366289A CH366289A CH5586858A CH5586858A CH366289A CH 366289 A CH366289 A CH 366289A CH 5586858 A CH5586858 A CH 5586858A CH 5586858 A CH5586858 A CH 5586858A CH 366289 A CH366289 A CH 366289A
- Authority
- CH
- Switzerland
- Prior art keywords
- isoquinoline
- methylene
- acyl
- dihydro
- methyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 150000008062 acetophenones Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- JZZLDIIDMFCOGF-UHFFFAOYSA-N 1-methyl-3,4-dihydroisoquinoline Chemical compound C1=CC=C2C(C)=NCCC2=C1 JZZLDIIDMFCOGF-UHFFFAOYSA-N 0.000 claims description 4
- VASUQTGZAPZKFK-UHFFFAOYSA-N 6,7-Dimethoxy-1-methyl-3,4-dihydroisoquinoline Chemical compound C1CN=C(C)C2=C1C=C(OC)C(OC)=C2 VASUQTGZAPZKFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- -1 methylenedioxy group Chemical group 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- JRMQVUQWPOMMAD-UHFFFAOYSA-N 1-(6,7-dimethoxy-1-methylidene-3,4-dihydroisoquinolin-2-yl)ethanone Chemical compound C1CN(C(C)=O)C(=C)C2=C1C=C(OC)C(OC)=C2 JRMQVUQWPOMMAD-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical class CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- SFUVLEGIZGPPNN-UHFFFAOYSA-N (2-pyridin-2-ylacetyl) 2-pyridin-2-ylacetate Chemical compound C=1C=CC=NC=1CC(=O)OC(=O)CC1=CC=CC=N1 SFUVLEGIZGPPNN-UHFFFAOYSA-N 0.000 description 1
- JESOYKLAQHJFSZ-UHFFFAOYSA-N 1-(5-methylidene-7,8-dihydro-[1,3]dioxolo[4,5-g]isoquinolin-6-yl)ethanone Chemical compound C=C1N(CCC2=CC3=C(C=C12)OCO3)C(C)=O JESOYKLAQHJFSZ-UHFFFAOYSA-N 0.000 description 1
- ADTRVJQAQKXLSP-UHFFFAOYSA-N 1-(6,7-dimethoxy-1-methylidene-3,4-dihydroisoquinolin-2-yl)propan-1-one Chemical compound C=C1N(CCC2=CC(=C(C=C12)OC)OC)C(CC)=O ADTRVJQAQKXLSP-UHFFFAOYSA-N 0.000 description 1
- GMLSKLPTUXTODA-UHFFFAOYSA-N 1-(6-methoxy-1-methylidene-3,4-dihydroisoquinolin-2-yl)ethanone Chemical compound C=C1N(CCC2=CC(=CC=C12)OC)C(C)=O GMLSKLPTUXTODA-UHFFFAOYSA-N 0.000 description 1
- KEWJUVKQFPXVHS-UHFFFAOYSA-N C=C1N(CCC2=CC(=C(C(=C12)OC)OC)OC)C(C)=O Chemical compound C=C1N(CCC2=CC(=C(C(=C12)OC)OC)OC)C(C)=O KEWJUVKQFPXVHS-UHFFFAOYSA-N 0.000 description 1
- 230000006181 N-acylation Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Description
Verfahren zur Herstellung von Acetophenonen
Die Erfindung betrifft ein Verfahren zur Herstellung von Acetophenonen der Formel :
EMI1.1
worin Rl, R2 und R3 Wasserstoff oder Alkoxygruppen, oder zwei dieser Reste zusammen eine Methylendioxygruppe, und R4 einen Acylrest bedeuten.
Das Verfahren besteht darin, dass man ein durch die Reste Rl, R2 und R3 entsprechend substituiertes 1-Methyl-3, 4-dihydro-isochinolin acyliert und das gebildete 1-Methylen-2-acyl-1, 2,3,4-tetrahydro-isochinolin mit verdünnter Mineralsäure behandelt.
Die Ausgangsmaterialien sind zum Teil bekannte Verbindungen. Sie können nach den Angaben von W. J. Gensler in R. C. Elderfield, Heterocyclic Compounds, Vol. IV, New York 1952, Seiten 347-353, hergestellt werden.
Die Acylierung der 1-Methyl-3, 4-dihydro-isochinoline wird am besten mit einem Säureanhydrid, wie z. B. Essigsäureanhydrid, Propionsäureanhydrid, Buttersäureanhydrid, Benzoesäureanhydrid, substituiertes Benzoesäureanhydrid, Phthalsäureanhydrid, substituiertes Phthalsäureanhydrid usw., und zwar vorzugsweise in der Wärme und in Gegenwart eines inerten wasserfreien Lösungsmittels, wie z. B. Pyridin, vorgenommen. Dabei entstehen unter N-Acylierung und Verschiebung der Doppelbindung l-Methylen-2- acyl-1, 2,3,4-tetrahydro-isochinoline.
Bei der Behandlung derselben mit verdünnten Mineralsäuren entstehen unter Ringöffnung die entsprechend substituierten 2--Acylaminoalkyl-acetophenone.
Die Isolierung der intermediär anfallenden 1-Me- thylen-2-acyl-1, 2,3,4-tetrahydro-isochinoline vor der Säurebehandlung ist nicht erforderlich ; man kann die Säuren auf das nach der Acylierung gebildete Reaktionsgemisch direkt einwirken lassen.
Die erfindungsgemäss erhaltenen Verbindungen sind wertvolle Zwischenprodukte zum Aufbau pharmakologisch interessanter Isochinolinderivate.
Beispiel 1
54 g 1-Methyl-6, 7-dimethoxy-3,4-dihydro-isochinolin werden in 270 ml einer Mischung von Pyridin-Acetanhydrid (1 : 1) gelöst und während 3 Stunden auf dem Wasserbad belassen. Dann wird im Wasserstrahlvakuum zur Trockne eingeengt. Der Rückstand liefert nach dem Aufkochen mit Essigester 51 g 1-Methylen-2-acetyl-6, 7-dimethoxy1,2,3,4-tetrahydro-isochinolin vom Schmelzpunkt 107 bis 108 C.
26 g 1-Methylen-2-acetyl-6, 7-dimethoxy-1, 2,3,4tetrahydro-isochinolin werden unter leichtem Erwär- men in 50 ml 3n Salzsäure gelöst. Die gelbe Lösung wird mit Eiswasser gekühlt und mit Kaliumcarbonat bis zur alkalischen Reaktion versetzt. Nach dem Filtrieren und Trocknen erhält man 26 g 2-4-Acet- aminoäthyl-4, 5-dimethoxy-acetophenon, das nach dem Umlösen aus Essigester bei 124 C schmilzt. Das W-Absorptionsspektrum in Alkohol zeigt Maxima bei 231,274 und 304 m, (e = 24,100 ; 8,750 und 5,500).
Beispiel 2
20 g 1-Methyl-6, 7-dimethoxy-3,4-dihydro-isochinolin werden in 40 ml Pyridin gelöst. Dann wird mit 20 ml Propionsäureanhydrid versetzt und wäh- rend 2 Stunden auf dem Wasserbad belassen. Nach dem Einengen im Vakuum wird wiederholt in Benzol gelöst und eingeengt. Der Rückstand kristallisiert aus EssigesterlPetroläther. Nach dem Umlösen aus Essig ester, lPetroläther erhält man 17 g 1-Methylen-2-propionyl-6,7-dimethoxy-1,2,3,4-tetrahydro-isochinolin vom Schmelzpunkt 99-100 C.
Zur tÇberführung der vorstehenden Verbindung in das 2-ss-Propionamidoäthyl-4, 5-dimethoxy-acetophenon löst man die Methylenverbindung in der lOfachen Menge In Salzsäure und neutralisiert anschliessend mit Kaliumcarbonat. Die Ausbeute ist quantitativ. Das Acetophenonderivat schmilzt nach dem Umlösen aus Essigester bei 125 C. Das UV Absorptionsspektrum in Athanol zeigt Maxima bei 230,274 und 303 mu (s = 22,400,8,320 und 5,100).
Beispiel 3
10 g 1-Methyl-6, 7-dimethoxy-3, 4-dihydro-isochinolin und 14 g Benzoesäureanhydrid werden in 50 ml Pyridin gelöst und während 1 Stunde auf dem Wasserbad erwärmt. Nach dem Einengen löst man unter leichtem Erwärmen in der lOfachen Menge In Salzsäure und neutralisiert anschliessend mit Kaliumcarbonat. Man erhält 8 g 2-ss-Benzamidoäthyl- 4,5-dimethoxy-acetophenon, das nach dem Umlösen aus Alkohol/Wasser bei 143 C schmilzt. Das UV Absorptionsspektrum in Athanol zeigt Maxima bei 230,272 und 303 m, (e = 28,900 ; 8,800 und 5,100).
Beispiel 4
Gemäss den Angaben im Beispiel 1 werden aus entsprechenden 1-Methyl-3, 4-dihydro-isochinolinen noch folgende Zwischen-und Endprodukte erhalten :
1-Methylen-2-acetyl-6-methoxy-1, 2,3,4-tetra hydro-isochinolin, Schmelzpunkt 98 C ; 1-Methylen-2-acetyl-6, 7-methylendioxy-1, 2,3,4 tetrahydro-isochinolin, Schmelzpunkt 128 C ;
1-Methylen-2-acetyl-6,7,8-trimethoxy-1,2,3,4 tetrahydro-isochinolin, Schmelzpunkt 85 C.
2--Acylaminoalkyl-acetophenone : 2-ss-Acetaminoäthyl-4-methoxy-acetophenon,
Schmelzpunkt 87 C ; UV-Absorptionsmaxima in Athanol bei 221 und 269 m, (e = 14,700 und 13,600) ; 2-, B-Acetaminoäthyl-4, 5-methylendioxy-aceto phenon, Schmelzpunkt 122 C ; W-Absorp- tionsmaxima in Athanol bei 230,273 und
307 m, u (e = 36,500 ; 5,200 und 5,460) ; 2-ss-Acetaminoäthyl-4, 5,6-trimethoxy-aceto phenon, Schmelzpunkt 58 C ; UV-Absorp tionsmaxima in Athanol bei 222 und 263 m, u (e = 14, 700 und 16,250).
Process for the production of acetophenones
The invention relates to a process for the preparation of acetophenones of the formula:
EMI1.1
wherein Rl, R2 and R3 are hydrogen or alkoxy groups, or two of these radicals together represent a methylenedioxy group and R4 is an acyl radical.
The process consists in acylating a 1-methyl-3, 4-dihydro-isoquinoline correspondingly substituted by the radicals R1, R2 and R3 and the 1-methylene-2-acyl-1,2,3,4-tetrahydro formed -isoquinoline treated with dilute mineral acid.
Some of the starting materials are known compounds. They can be prepared as described by W. J. Gensler in R. C. Elderfield, Heterocyclic Compounds, Vol. IV, New York 1952, pages 347-353.
The acylation of the 1-methyl-3, 4-dihydro-isoquinolines is best done with an acid anhydride, such as. B. acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, substituted benzoic anhydride, phthalic anhydride, substituted phthalic anhydride, etc., preferably in the heat and in the presence of an inert anhydrous solvent, such as. B. pyridine made. With N-acylation and displacement of the double bond, l-methylene-2-acyl-1,2,3,4-tetrahydroisoquinolines are formed.
When these are treated with dilute mineral acids, the correspondingly substituted 2-acylaminoalkyl-acetophenones are formed with ring opening.
It is not necessary to isolate the intermediate 1-methylene-2-acyl-1,2,3,4-tetrahydroisoquinolines prior to the acid treatment; the acids can be allowed to act directly on the reaction mixture formed after the acylation.
The compounds obtained according to the invention are valuable intermediates for the construction of pharmacologically interesting isoquinoline derivatives.
example 1
54 g of 1-methyl-6,7-dimethoxy-3,4-dihydro-isoquinoline are dissolved in 270 ml of a mixture of pyridine-acetic anhydride (1: 1) and left on the water bath for 3 hours. It is then concentrated to dryness in a water jet vacuum. After boiling with ethyl acetate, the residue yields 51 g of 1-methylene-2-acetyl-6, 7-dimethoxy1,2,3,4-tetrahydroisoquinoline with a melting point of 107 to 108 C.
26 g of 1-methylene-2-acetyl-6, 7-dimethoxy-1, 2,3,4-tetrahydroisoquinoline are dissolved in 50 ml of 3N hydrochloric acid with gentle warming. The yellow solution is cooled with ice water and treated with potassium carbonate until an alkaline reaction is achieved. After filtering and drying, 26 g of 2-4-acetaminoethyl-4,5-dimethoxy-acetophenone are obtained, which melts at 124 ° C. after being dissolved from ethyl acetate. The UV absorption spectrum in alcohol shows maxima at 231.274 and 304 m, (e = 24.100; 8.750 and 5.500).
Example 2
20 g of 1-methyl-6, 7-dimethoxy-3,4-dihydro-isoquinoline are dissolved in 40 ml of pyridine. Then 20 ml of propionic anhydride are added and the mixture is left on the water bath for 2 hours. After concentration in vacuo, it is repeatedly dissolved in benzene and concentrated. The residue crystallizes from ethyl acetate / petroleum ether. After dissolving from ethyl acetate, petroleum ether, 17 g of 1-methylene-2-propionyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline with a melting point of 99-100 ° C. are obtained.
To convert the above compound into 2-ß-propionamidoethyl-4,5-dimethoxyacetophenone, ten times the amount of the methylene compound is dissolved in hydrochloric acid and then neutralized with potassium carbonate. The yield is quantitative. The acetophenone derivative melts after dissolving from ethyl acetate at 125 ° C. The UV absorption spectrum in ethanol shows maxima at 230.274 and 303 μm (s = 22,400, 8,320 and 5,100).
Example 3
10 g of 1-methyl-6, 7-dimethoxy-3, 4-dihydro-isoquinoline and 14 g of benzoic anhydride are dissolved in 50 ml of pyridine and heated on a water bath for 1 hour. After concentration, dissolve 10 times the amount in hydrochloric acid with gentle warming and then neutralize with potassium carbonate. 8 g of 2-β-benzamidoethyl-4,5-dimethoxy-acetophenone, which melts at 143 ° C. after being redissolved from alcohol / water, are obtained. The UV absorption spectrum in ethanol shows maxima at 230.272 and 303 m, (e = 28.900; 8.800 and 5.100).
Example 4
According to the information in Example 1, the following intermediate and end products are also obtained from corresponding 1-methyl-3, 4-dihydro-isoquinolines:
1-methylene-2-acetyl-6-methoxy-1, 2,3,4-tetra hydro-isoquinoline, melting point 98 C; 1-methylene-2-acetyl-6, 7-methylenedioxy-1, 2,3,4 tetrahydroisoquinoline, melting point 128 C;
1-methylene-2-acetyl-6,7,8-trimethoxy-1,2,3,4 tetrahydroisoquinoline, melting point 85 C.
2 - acylaminoalkyl-acetophenone: 2-ss-acetaminoethyl-4-methoxy-acetophenone,
Melting point 87 C; UV absorption maxima in ethanol at 221 and 269 m, (e = 14.700 and 13.600); 2-, B-acetaminoethyl-4, 5-methylenedioxy-aceto phenone, melting point 122 ° C; W absorption maxima in ethanol at 230, 273 and
307 m, u (e = 36,500; 5,200 and 5,460); 2-ß-acetaminoethyl-4, 5,6-trimethoxy-aceto phenone, melting point 58 C; UV absorption maxima in ethanol at 222 and 263 m, u (e = 14, 700 and 16.250).
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5586858A CH366289A (en) | 1958-02-14 | 1958-02-14 | Process for the production of acetophenones |
| BE575322A BE575322A (en) | 1958-02-14 | 1959-02-02 | Acetophenone derivatives and process for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5586858A CH366289A (en) | 1958-02-14 | 1958-02-14 | Process for the production of acetophenones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH366289A true CH366289A (en) | 1962-12-31 |
Family
ID=4520143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH5586858A CH366289A (en) | 1958-02-14 | 1958-02-14 | Process for the production of acetophenones |
Country Status (2)
| Country | Link |
|---|---|
| BE (1) | BE575322A (en) |
| CH (1) | CH366289A (en) |
-
1958
- 1958-02-14 CH CH5586858A patent/CH366289A/en unknown
-
1959
- 1959-02-02 BE BE575322A patent/BE575322A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE575322A (en) | 1959-08-03 |
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