DE89597C - - Google Patents
Info
- Publication number
- DE89597C DE89597C DENDAT89597D DE89597DA DE89597C DE 89597 C DE89597 C DE 89597C DE NDAT89597 D DENDAT89597 D DE NDAT89597D DE 89597D A DE89597D A DE 89597DA DE 89597 C DE89597 C DE 89597C
- Authority
- DE
- Germany
- Prior art keywords
- tropine
- tropinone
- ketone
- solution
- acid
- 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.)
- Active
Links
- QIZDQFOVGFDBKW-DHBOJHSNSA-N Pseudotropine Natural products OC1C[C@@H]2[N+](C)[C@H](C1)CC2 QIZDQFOVGFDBKW-DHBOJHSNSA-N 0.000 claims description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L Chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 8
- CYHOMWAPJJPNMW-JIGDXULJSA-N Tropine Chemical compound C1[C@@H](O)C[C@H]2CC[C@@H]1N2C CYHOMWAPJJPNMW-JIGDXULJSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 5
- QQXLDOJGLXJCSE-KNVOCYPGSA-N Tropinone Chemical compound C1C(=O)C[C@H]2CC[C@@H]1N2C QQXLDOJGLXJCSE-KNVOCYPGSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- 229960000583 Acetic Acid Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YYMCYJLIYNNOMK-UHFFFAOYSA-N 8-azabicyclo[3.2.1]octan-3-ol Chemical compound C1C(O)CC2CCC1N2 YYMCYJLIYNNOMK-UHFFFAOYSA-N 0.000 description 1
- MFSIEROJJKUHBQ-UHFFFAOYSA-N O.[Cl] Chemical compound O.[Cl] MFSIEROJJKUHBQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 tropine ketone Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
- C07D451/02—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof
- C07D451/04—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof with hetero atoms directly attached in position 3 of the 8-azabicyclo [3.2.1] octane or in position 7 of the 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring system
- C07D451/06—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMTPATENT OFFICE
Bisher war es nicht gelungen, ein Keton der Tropingruppe darzustellen. Das Tropin, welchem nach G. Merling (Berichte d. d. ehem. Ges. 24, 3108) folgende ConstitutionsformelSo far it had not been possible to produce a ketone from the troping group. The tropine, which according to G. Merling (reports of the former Ges. 24, 3108) the following constitutional formula
CHCH
H2CH 2 C
N CHN CH
CHOH CH2 CHOH CH 2
CH,CH,
H.H.
■t■ t
zuzuschreiben ist, lieferte bei gelinder Oxydation mit Kaliumpermanganat die entsprechende, am Stickstoff entmetlrylirte Base, das Tropigenin (Merling, Ann. d. Chem. 216, 340), hingegen bei der Oxydation mit Chromsäure unter Sprengung des den Tropinverbindungen eigenthümlichen Ringsystems eine zweicarboxylige Säure von der Zusammensetzung C6II15 NO1, die Tropinsäure (Merling, 1. c. 216, 348), und als Nebenproduct die sogenannte Ecgoninsä'ure, C7HnNO3 (C. Liebermann, Ber. d. d. chem. Ges. 23, 2518 und 24, 606).is to be ascribed to, on gentle oxidation with potassium permanganate produced the corresponding base, demetalated from the nitrogen, tropigenin (Merling, Ann. d. Chem. 216, 340), while oxidation with chromic acid gave a dicarboxylic acid of of the composition C 6 II 15 NO 1 , tropinic acid (Merling, 1. c. 216, 348), and as a by-product the so-called ecgonic acid, C 7 H n NO 3 (C. Liebermann, Ber. dd chem. Ges. 23, 2518 and 24, 606).
Dennoch hat es sich gezeigt, dafs sich aus Tropin das entsprechende Keton, welches Erfinder »Tropinon« nennt, in ausgezeichneter Ausbeute erhalten läfst, wenn man auf Tropin genau die theoretisch erforderliche Menge Chromsäure, d. i. 1 Mol. Cr O9 auf ι Y2 Mol. Tropin, am besten in Eisessiglösung oder schwefelsaurer Lösung langsam unter gelindem Erwärmen einwirken lä'fst.Nevertheless, it has been shown that the corresponding ketone, which the inventor calls "tropinone", can be obtained in excellent yield from tropine if one uses exactly the theoretically required amount of chromic acid, i.e. 1 mol. Cr O 9 to ι Y 2 mol . Tropine, preferably in glacial acetic acid solution or sulfuric acid solution, let it take effect slowly with gentle warming.
Das gleiche Verhalten wie Tropin zeigt das Pseudotropin oder ψ -Tropin, eine von C.Liebermann (Ber. d. d. chem. Ges. 24, 2336) entdeckte, mit Tropin isomere Base. Das aus Pseudotropin gewonnene Keton zeigte mit dem aus Tropin erhaltenen Tropinon vollkommene Uebereinstimmung.The same behavior as tropine shows the pseudotropin or ψ-tropin, one of C.Liebermann (Ber. D. D. Chem. Ges. 24, 2336) discovered, base isomeric with tropine. The ketone obtained from pseudotropin showed with the Tropinone obtained from tropine is in perfect agreement.
Dem Tropinketon oder Tropinon(CSH1BNOJ
kommt folgende Constitution zu
CH The tropine ketone or tropinone (C S H 1B NOJ has the following constitution
CH
H2CH 2 C
CO CH2 N CH, CHCO CH 2 N CH, CH
Es vereinigt die Eigenschaften einer Base sowie eines Ketons. Das Tropinon schmilzt bei 41 bis 420 und siedet bei 224 bis 225° (corr.). Das Chlorhydrat ist in Wasser sehr leicht, in kaltem Alkohol schwer löslich; Schmelzpunkt 189° unter Zersetzung. Schmelzpunkt des Pikrats 220°, Schmelzpunkt des Platindoppelsalzes 191 bis 192° unter Zersetzung, Schmelzpunkt des Oxims 111 bis 112 °, des Jodmethylats 263 bis 265° unter Zersetzung.It combines the properties of a base and a ketone. The tropinone melts at 41 to 42 0 and boils at 224 to 225 ° (corr.). The chlorine hydrate is very easily soluble in water and sparingly soluble in cold alcohol; Melting point 189 ° with decomposition. Melting point of the picrate 220 °, melting point of the platinum double salt 191 to 192 ° with decomposition, melting point of the oxime 111 to 112 °, of the iodine methylate 263 to 265 ° with decomposition.
Zur Erläuterung der Darstellung diene folgendes Beispiel:The following example serves to explain the illustration:
Zu einer Lösung von 100 g Tropin in 2 kg Eisessig, welche andauernd auf 60 bis 70° erwärmt wird, läfst man die Lösung von 48 g Chromsäure in 50 g Wasser und 250 g Eisessig unter beständigem Rühren mittels Turbine eintropfen. Nach dem Eintragen des Oxydationsmittels wird die Lösung kurze Zeit auf ioo° erwärmt und dann mit einem Ueberschufs von Aetznatron in concentrirter wässeriger Lösung versetzt. Aus der alkalischen Flüssigkeit läfstTo a solution of 100 g tropine in 2 kg Glacial acetic acid, which is continuously heated to 60 to 70 °, is used to make the solution of 48 g Chromic acid in 50 g water and 250 g glacial acetic acid Drip in with constant stirring using the turbine. After applying the oxidizing agent the solution is warmed to 100 ° for a short time and then with an excess of Caustic soda added to a concentrated aqueous solution. Runs out of the alkaline liquid
sich das entstandene Tropinon mit Wasserdampf abdestilliren oder besser durch wiederholtes Ausschütteln mit Aether extrahiren. Das durch Eindunsten der ätherischen Lösung gewonnene Rohproduct wird durch wiederholte Destillation leicht in chemisch reinem Zustand erhalten. Die Ausbeute beträgt über 80 pCt; der berechneten Menge.distill the resulting tropinone with steam or, better, by repeating it Shake out with ether. That obtained by evaporation of the ethereal solution Through repeated distillation, raw product easily becomes chemically pure obtain. The yield is over 80 pCt; the calculated amount.
Das Tropinon soll zu pharmaceutischen Zwecken Verwendung finden.The tropinone is said to be used for pharmaceutical purposes.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE89597C true DE89597C (en) |
Family
ID=361403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT89597D Active DE89597C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE89597C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2552607A1 (en) * | 1975-11-24 | 1977-06-02 | Rothenberger Gmbh Co | HAND TOOL FOR EXPANSION OF PIPE ENDS |
-
0
- DE DENDAT89597D patent/DE89597C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2552607A1 (en) * | 1975-11-24 | 1977-06-02 | Rothenberger Gmbh Co | HAND TOOL FOR EXPANSION OF PIPE ENDS |
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