DE79385C - Process for the preparation of p-Amidoj'-phenylquinoline and p-Amido-7-phenylchh> aldin - Google Patents
Process for the preparation of p-Amidoj'-phenylquinoline and p-Amido-7-phenylchh> aldinInfo
- Publication number
- DE79385C DE79385C DENDAT79385D DE79385DA DE79385C DE 79385 C DE79385 C DE 79385C DE NDAT79385 D DENDAT79385 D DE NDAT79385D DE 79385D A DE79385D A DE 79385DA DE 79385 C DE79385 C DE 79385C
- Authority
- DE
- Germany
- Prior art keywords
- phenylquinoline
- amido
- alcohol
- preparation
- base
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims 2
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- 150000004005 nitrosamines Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 acetyl compound Chemical class 0.000 description 2
- 230000001476 alcoholic Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- OQYGEKFQPSZLHP-UHFFFAOYSA-N 2-cyclohex-2-en-1-ylquinoline Chemical compound C1CCC=CC1C1=CC=C(C=CC=C2)C2=N1 OQYGEKFQPSZLHP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000003057 platinum Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/08—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms with acylated ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/58—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems with hetero atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Quinoline Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Es hat sich gezeigt, dafs man aus y-Phenylchinolin das bisher unbekannte ρ - Amido- γ - phenylchinolin und ebenso aus y - Phenylchinaldin das p-Amido-y-phenylchinaldin herstellen kann. Es wird dies auf folgende Weise erreicht:It has been shown that the hitherto unknown ρ-amido- γ-phenylquinoline can be prepared from γ- phenylquinoline, and p-amido-γ-phenylquinaldine can also be prepared from γ-phenylquinaldine. It does this in the following ways:
γ - Phenylchinolin bezw. γ - Phenylchinaldin werden reducirt, die entstehenden secundären Basen Tetrahydro-y-phenylchinolin und Tetrahydro -y-phenylchinaldin werden in Nitrosamine übergeführt, diese sodann durch Salzsäure in sogenannte ρ - Nitrosoverbindungen und die letzteren weiter in p-Amido-y-phenylchinolin bezw. -chinaldin umgelagert. γ - phenylquinoline respectively. γ- phenylquinaldine are reduced, the secondary bases tetrahydro-γ-phenylquinoline and tetrahydro-γ-phenylquinoline are converted into nitrosamines, these are then converted by hydrochloric acid into so-called ρ-nitroso compounds and the latter further into p-amido-γ-phenylquinoline and p-amido-γ-phenylquinoline. -chinaldin rearranged.
Das Verfahren ist bei der Verarbeitung des y-Phenylchinaldins dasselbe, wie bei derjenigen des y-Phenylchinolins; im Folgenden wird daher nur ein Beispiel des Verfahrens für das y-Phenylchinolin angegeben.The procedure for processing the γ-phenylquinaldine is the same as that for that des γ-phenylquinoline; The following is therefore only one example of the procedure for the γ-phenylquinoline specified.
Reduction des y-Phenylchinolins. 50 g y-Phenylchinolin, 100 g Zinn, 1400 ecm cone. Salzsäure (spec. 1 · 19), 600 g Alkohol und 600 g Wasser werden bis zur vollständigen Lösung unter Rückflufskühlung gekocht. Die Lösung wird concentrirt und das abgeschiedene schwer lösliche Zinndoppelsalz des Tetrahydrophenylchinolins filtrirt. Das Zinndoppelsalz wird durch Alkali zerlegt, die neue Base in Aether aufgenommen und durch Vermittlung ihres leicht krystallisirenden Sulfats gereinigt. Die Base krystallisirt aus Alkohol in Blättchen, deren Schmelzpunkt bei 74 ° liegt. Das Sulfat und Hydrochlorid der Base sind in Wasser schwer löslich. Die Acetyl-Verbindung schmilzt bei 120°, die Benzoyl-Verbindung bei 147 °.Reduction of y-phenylquinoline. 50 g γ-phenylquinoline, 100 g tin, 1400 ecm cone. Hydrochloric acid (spec. 1 · 19), 600 g alcohol and 600 g of water are refluxed until completely dissolved. the The solution is concentrated, and the sparingly soluble tin double salt of tetrahydrophenylquinoline separated out filtered. The tin double salt is decomposed by alkali, the new base in Aether taken up and purified by the mediation of its easily crystallizing sulphate. The base crystallizes from alcohol into leaflets, the melting point of which is 74 °. The sulfate and the hydrochloride of the base are sparingly soluble in water. The acetyl compound melts at 120 °, the benzoyl compound at 147 °.
Die Reduction kann auch leicht in der üblichen Weise durch Natrium in alkoholischen Lösungen erzielt werden.The reduction can also easily be done in the usual way by sodium in alcoholic Solutions are achieved.
Darstellung des Nitrosamins.
y-Phenyltetrahydrochinolin wird in saurer Lösung mit Natriumnitrit behandelt und das
entstehende Nitrosamin in Aether aufgenommen. Die. ätherische Lösung wird abdestillirt und
hinterläfst das Nitrosamin als Pulver, das durch !Crystallisation aus Alkohol in gelben Nadeln
vom Schmelzpunkt 72 ° erhalten wird.Presentation of nitrosamine.
γ-Phenyltetrahydroquinoline is treated with sodium nitrite in an acidic solution and the nitrosamine formed is taken up in ether. The. The ethereal solution is distilled off, leaving behind the nitrosamine as a powder, which is obtained by crystallization from alcohol in yellow needles with a melting point of 72 °.
Umlagerung des Nitrosamins.
100 g Nitrosamin werden in gleicher Menge Eisessig gelöst und alkoholische Salzsäure unter
Vermeidung von starker Erwärmung zugegeben. Die vorher gelb gefärbte Lösung wird bald
rothbraun und scheidet das salzsaure Salz des y-Phenyl-p-nitrosotetrahydrochinolins in gelbrothen
Nadeln ab. Die durch Ammoniak freigemachte Nitrosobase krystallisirt aus Alkohol
in grünen Blättchen, die bei 199 ° schmelzen. Das Sulfat und Hydrochlorid der Nitrosobase
sind in Wasser schwer, in Alkohol dagegen leicht löslich. - · ■ .Rearrangement of the nitrosamine.
100 g of nitrosamine are dissolved in the same amount of glacial acetic acid and alcoholic hydrochloric acid is added while avoiding excessive heating. The solution, which was previously yellow in color, soon turns red-brown and separates the hydrochloric acid salt of γ-phenyl-p-nitrosotetrahydroquinoline in yellow-red needles. The nitroso base, freed by ammonia, crystallizes from alcohol in green leaves, which melt at 199 °. The sulfate and hydrochloride of the nitroso base are difficult in water, but easily soluble in alcohol. - · ■.
Umwandlung der Nitrosobase in Amidophenyl-Conversion of the nitroso base into amidophenyl
chinolin.quinoline.
20 g der Nitrosobase werden mit ioproc. Salzsäure mehrere Stunden gekocht, sodann Ammoniak zugesetzt und der entstehende Niederschlag mit Aether extrahirt. Nach Entfernung des Aethers wird die Base in Alkohol gelöst und durch Schwefelsäure das in Alkohol schwer lösliche Sulfat des ρ - Amidophenylchinolins20 g of the nitroso base are mixed with ioproc. Hydrochloric acid boiled for several hours, then added ammonia and the resulting precipitate extracted with ether. After removing the ether, the base is dissolved in alcohol and through sulfuric acid the sulphate of ρ - amidophenylquinoline, which is sparingly soluble in alcohol
ausgefällt. Auch durch das schwer lösliche und in gelben Nadeln aus Alkohol krystallisirende Pikrat läfst sich die neue Base reinigen. Sie krystallisirt aus Benzol oder Chloroform in gelblichen Nadeln vom Schmelzpunkt 205°; die ätherische Lösung der Base fluorescirt blau. Das Platinsalz der Base enthält 1 Molecül Wasser, das bei 1500 entweicht.failed. The new base can also be purified by the sparingly soluble picrate, which crystallizes from alcohol in yellow needles. It crystallizes from benzene or chloroform in yellowish needles with a melting point of 205 °; the ethereal solution of the base fluoresces blue. The platinum salt of the base containing 1 molecule of water which escapes at 150 0th
Die Eigenschaften der auf ganz analogem Wege gewonnenen Derivate des γ - Phenylchinaldins sind die folgenden: The properties of the γ- phenylquinaldine derivatives obtained in a completely analogous way are as follows:
y-Phenyltetrahydrochinaldin ist leicht löslich in Alkohol, Aether oder Benzol; es schmilzt bei 67 bis 68°; das salzsaure Salz scheidet sich aus concentrirter Lösung als OeI aus.y-phenyltetrahydroquinaldine is easily soluble in alcohol, ether or benzene; it melts at 67 to 68 °; the hydrochloric acid separates from concentrated solution as OeI.
Das Nitrosamin der Tetrahydrobase ist unlöslich in Wasser, verdünnten Säuren oder Alkalien, leicht löslich in Alkohol oder Aether; es schmilzt bei 97 bis 98 °.The nitrosamine of the tetrahydrobase is insoluble in water, dilute acids or Alkalis, easily soluble in alcohol or ether; it melts at 97 to 98 °.
Das ρ - Nitroso - y - phenyltetrahydrochinaldin bildet grüne Blättchen, die sich bei 164 ° zersetzen; es ist in verdünnten Säuren und in heifsem Alkohol leicht löslich. Das Chlorhydrat der Nitrosobase ist in Wasser wenig löslich und bildet krystallisirt braune Nädelchen.The ρ - nitroso - y - phenyltetrahydrochinaldin forms green leaflets which decompose at 164 °; it is easily soluble in dilute acids and in hot alcohol. The hydrochloride the nitroso base is sparingly soluble in water and forms crystallized brown needles.
Das p-Amido-y-phenylchinaldin ist unlöslich in Wasser, leicht löslich in verdünnten Säuren, Alkohol, Chloroform etc.; es krystallisirt aus Alkohol in gelblichen Nadeln vom Schmelzpunkt 1830.The p-amido-y-phenylquinaldine is insoluble in water, easily soluble in dilute acids, alcohol, chloroform etc .; it crystallizes from alcohol in yellowish needles with a melting point of 183 ° .
ρ - Amido -γ- phenylchinolin und p-Amidoy-phenylchinaldin sollen selbst und in weiteren Umwandlungsproducten als Heilmittel Verwendung finden.ρ - Amido- γ- phenylquinoline and p-amido-phenylchinaldine are said to be used as remedies themselves and in other conversion products.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE79385C true DE79385C (en) |
Family
ID=352027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT79385D Expired - Lifetime DE79385C (en) | Process for the preparation of p-Amidoj'-phenylquinoline and p-Amido-7-phenylchh> aldin |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE79385C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454947A (en) * | 1981-12-07 | 1984-06-19 | Olin Corporation | Product inspection and ejection system |
-
0
- DE DENDAT79385D patent/DE79385C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454947A (en) * | 1981-12-07 | 1984-06-19 | Olin Corporation | Product inspection and ejection system |
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