CH218517A - Process for the preparation of 1-methyl-4-phenyl-piperidyl-4-isopropyl-ketone. - Google Patents
Process for the preparation of 1-methyl-4-phenyl-piperidyl-4-isopropyl-ketone.Info
- Publication number
- CH218517A CH218517A CH218517DA CH218517A CH 218517 A CH218517 A CH 218517A CH 218517D A CH218517D A CH 218517DA CH 218517 A CH218517 A CH 218517A
- Authority
- CH
- Switzerland
- Prior art keywords
- piperidyl
- ketone
- isopropyl
- phenyl
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012230 colorless oil Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N N-Propyl bromide Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000000202 analgesic Effects 0.000 description 1
- 230000002921 anti-spasmodic Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000000812 cholinergic antagonist Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- -1 isopropylmagnesium halide Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Description
Verfahren zur Herstellung von 1-Hethyl-4-phenyl-piperidyl-4-isopi#opyl-keton. Es wurde gefunden, dass die nach dem deutschen Patent 679281 erhältlichen 4-Aryl- piperidin-4-carbonsäurenitriledurch "Umsetzung mit magnesiumorganischen Verbindungen und durch Zerlegung der so entstehenden Ketimid- zwischenprodukte mit verdünnten Säuren in vorzüglicher Ausbeute 4-Aryl-piperidyl-4- ketone liefern. Die Umsetzung vollzieht sich nach dem Schema:
EMI0001.0011
EMI0002.0001
(Hlg = Halogen R = Kohlenwasserstoffrest). Die neuen Verbindungen haben die bisher bei basisch substituierten Ketonen noch nicht beobachtete Eigenschaft, stark krampflösend und gut schmerzlindernd zu wirken und sind bei zugleich geringer Giftigkeit wertvolle Heil mittel.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 1-lllethyl- 4-plieny 1-pipei-idyl-4-isopi-opyl-keton, welches dadurch gekennzeichnet ist. dal') man auf 1-3Iethy 1-4-phenyl-pipei-idin-4-carbonsäure- nitril Isopropy lmagnesiumh@ilogenid einwirken lässt und das entstandene Ketimidzwischen- produkt mit verdünnter Säure zerlegt.
Das 1-3letliyl-4-plienyl-piperidyl-4-isopro- pylketon ist ein farbloses 01 vom Kp7 167-168'-'; das Phosphat ist ein farbloses Kristallpulver vom F. 199-202'. <I>Beispiel:
</I> Eine Isopropy#lniagnesiuinbromidlösung aus 61 Gewichtsteilen Propylbromid und 12 Ge wichtsteilen Magnesium in 300 Crewichtsteilen Alkohol bereitet, wird zu einer Lösung von 60 Gewichtsteilen 1--lIetliyl-4-lilienyl-piperidin- 4-carbonsäurenitril in 100 Gewichtsteilen To luol zugesetzt. Die auftretende Reaktions wärme ist nicht erheblich: nach ihrem Ab klingen wird das Gemisch auf dem Wasser bade am absteigenden Kühler erhitzt; der Äther destilliert ab, die Toluollösung wird drei Stunden bei Wasserbadtemperatur ge- halten.
Die Zerlegung erfolgt durch Aufgiessen auf Eis und Verrühren mit verdünnter Salz säure, von der soviel anzuwenden ist, dass kongosaure Reaktion auf die Dauer bestehen bleibt. Nach Abtrennung des Toluols fällt man die Base durch Übersättigen der wässe rigen Lösung mit Ammoniak als Öl aus, nimmt sie in Äther auf, trocknet über Kaliumcarbonat und destilliert. Kp<B>167--1680.</B> Die Base ist ein farbloses 01. Das aus der Lösung der Base in Aceton mit 1 141o1 85 G@iger Phosphorsäure sich abscheidende Phosphat ist ein farbloses Kristallpulver vom F. 199 - 202'.
In Wasser ist es ziemlich leicht löslich, die Lösung reagiert schwach lackmussauer.
Process for the preparation of 1-Hethyl-4-phenyl-piperidyl-4-isopi # opyl-ketone. It has been found that the 4-aryl-piperidine-4-carboxylic acid nitrile obtainable according to German patent 679281 is 4-aryl-piperidyl-4-ketones in excellent yield by "reaction with organomagnesium compounds and by decomposition of the ketimide intermediates thus formed with dilute acids The implementation takes place according to the scheme:
EMI0001.0011
EMI0002.0001
(Hlg = halogen R = hydrocarbon radical). The new compounds have the property, which has not yet been observed in basic substituted ketones, of being strong antispasmodic and good analgesic and, at the same time, they are valuable medicinal products with low toxicity.
The subject of the present patent is a process for the preparation of 1-lllethyl-4-plieny 1-pipei-idyl-4-isopi-opyl-ketone, which is characterized. that is, isopropylmagnesium halide is allowed to act on 1-3 ethyl 1-4-phenyl-pipei-idin-4-carboxylic acid nitrile and the resulting ketimide intermediate is decomposed with dilute acid.
The 1-3letliyl-4-plienyl-piperidyl-4-isopropyl ketone is a colorless oil of bp7 167-168'- '; the phosphate is a colorless crystal powder from F. 199-202 '. <I> example:
</I> An isopropylininagnesiuinbromide solution of 61 parts by weight of propyl bromide and 12 parts by weight of magnesium in 300 parts by weight of alcohol is added to a solution of 60 parts by weight of 1-ethyl-4-lilienyl-piperidine-4-carboxylic acid nitrile in 100 parts by weight of toluene . The heat of reaction that occurs is not significant: after it has subsided, the mixture is heated on the water bathing on the descending cooler; the ether distills off, the toluene solution is kept for three hours at water bath temperature.
It is broken down by pouring it onto ice and stirring it with dilute hydrochloric acid, of which enough must be used that the Congo acidic reaction persists in the long term. After the toluene has been separated off, the base is precipitated as an oil by supersaturating the aqueous solution with ammonia, it is taken up in ether, dried over potassium carbonate and distilled. Kp <B> 167--1680. </B> The base is a colorless 01. The phosphate which separates out of the solution of the base in acetone with 1 141o1 85% phosphoric acid is a colorless crystal powder of the range 199-202 ' .
It is fairly easily soluble in water, the solution reacts weakly to lackluster.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE218517X | 1939-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH218517A true CH218517A (en) | 1941-12-15 |
Family
ID=5831353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH218517D CH218517A (en) | 1939-03-30 | 1940-03-30 | Process for the preparation of 1-methyl-4-phenyl-piperidyl-4-isopropyl-ketone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH218517A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2486794A (en) * | 1943-06-25 | 1949-11-01 | Ciba Pharm Prod Inc | 1-alkyl-4-(meta-hydroxyphenyl)-piperidyl-(4)-alkylketones and their production |
| US2486796A (en) * | 1943-06-25 | 1949-11-01 | Ciba Pharm Prod Inc | Esters of 1-alkyl-4-hydroxyphenylpiperidyl-4-ketones |
-
1940
- 1940-03-30 CH CH218517D patent/CH218517A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2486794A (en) * | 1943-06-25 | 1949-11-01 | Ciba Pharm Prod Inc | 1-alkyl-4-(meta-hydroxyphenyl)-piperidyl-(4)-alkylketones and their production |
| US2486796A (en) * | 1943-06-25 | 1949-11-01 | Ciba Pharm Prod Inc | Esters of 1-alkyl-4-hydroxyphenylpiperidyl-4-ketones |
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