DE74912C - - Google Patents
Info
- Publication number
- DE74912C DE74912C DENDAT74912D DE74912DA DE74912C DE 74912 C DE74912 C DE 74912C DE NDAT74912 D DENDAT74912 D DE NDAT74912D DE 74912D A DE74912D A DE 74912DA DE 74912 C DE74912 C DE 74912C
- Authority
- DE
- Germany
- Prior art keywords
- phenyl
- base
- methylpyrazolone
- protected
- oxethyl
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-Chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000001476 alcoholic Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 229950009041 edaravone Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N Benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 229940091110 Antipyrine Drugs 0.000 description 2
- QELUYTUMUWHWMC-UHFFFAOYSA-N Edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 2
- VEQOALNAAJBPNY-UHFFFAOYSA-N Phenazone Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 210000004369 Blood Anatomy 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
- C07D231/26—1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Erhitzt man 1 - Phenyl - 3 - methylpyrazolon mit Aethylenchlorhydrin bei Gegenwart von Natronlauge oder Natriumäthylat, so entstehen neben einander zwei isomere Oxäthylderivate des ι - Phenyl - 3 - methylpyrazolons von basischem Charakter, welche sich durch ihre verschiedene Löslichkeit in Aether von einander trennen lassen.If 1 - phenyl - 3 - methylpyrazolone is heated with ethylene chlorohydrin in the presence of Caustic soda or sodium ethylate, two isomeric oxyethyl derivatives are formed alongside one another des ι - phenyl - 3 - methylpyrazolons of a basic character, which are distinguished by their different Let solubility in ether be separated from one another.
Die eine der beiden Basen besitzt die Formel:One of the two bases has the formula:
N-C6H, /\ CH2(OH) -CH2 -N CONC 6 H, / \ CH 2 (OH) -CH 2 -N CO
I II I
CH%-C=CHCH % -C = CH
(Base A)(Base A)
und ist als 1-Phenyl-2-oxäthyl-3-methylpyrazolon zu bezeichnen.and is as 1-phenyl-2-oxethyl-3-methylpyrazolone to call.
Die isomere Base, deren Gewinnung in dem Patent Nr. 66610 bereits geschützt ist, hat sich als ι - Phenyl - 3 - methyl - 5 - oxäthoxypyrazol der FormelThe isomeric base, the preparation of which is already protected in patent no. 66610, has become as ι - phenyl - 3 - methyl - 5 - oxäthoxypyrazol of the formula
N-C6H5 NC 6 H 5
JV_ C- O- CH2 ■ CH2 (OH) JV_ C- O- CH 2 ■ CH 2 (OH)
CH-C= CHCH-C = CH
(Base B)(Base B)
erwiesen.proven.
Es sollen in der folgenden Beschreibung die beiden isomeren Basen der Kürze wegen als Base A und Base B bezeichnet werden. Zur Darstellung und Trennung beider Basen verfährt man z. B. wie folgt:For the sake of brevity, the two isomeric bases should be used in the following description as Base A and Base B are designated. Proceed to display and separate the two bases one z. B. as follows:
23 Gewichtstheile Natrium werden in 300 Gewichtstheilen Alkohol gelöst und dazu i74Gewichtstheile 1-Phenyl- 3-methylpyrazolon und 81 Gewichtstheile Aethylenchlorhydrin hinzugefügt. Nach mehrstündigem Erwärmen der Lösung wird die Reaction neutral und es hat sich die berechnete Menge Kochsalz ausgeschieden. Nach dem Verdampfen des Alkohols bleibt ein rothbraunes OeI zurück, das mit Y2 1 Wasser und 1 1J2 1 Aether kräftig durchgeschüttelt wird.23 parts by weight of sodium are dissolved in 300 parts by weight of alcohol, and 14 parts by weight of 1-phenyl-3-methylpyrazolone and 81 parts by weight of ethylene chlorohydrin are added. After heating the solution for several hours, the reaction becomes neutral and the calculated amount of common salt has separated out. After evaporation of the alcohol, a reddish-brown oil remains, the 2 1 water and 1 1 J 2 1 of ether is shaken vigorously with Y.
Man erhält:You get:
ι. eine ätherische Schicht, welche circa 72 Gewichtstheile der Base B enthält;ι. an ethereal layer, which approx Contains 72 parts by weight of base B;
2. eine wässerige Schicht, welche Kochsalz und circa 122 Gewichtstheile der Base A gelöst enthält.2. an aqueous layer which dissolves table salt and about 122 parts by weight of base A. contains.
Man isolirt daraus die Base A in reinem Zustand durch folgendes Abscheidungsverfahren.The base A is isolated therefrom in the pure state by the following deposition process.
Die wässerige Lösung wird mit Salzsäure angesäuert und durch Zusatz von gelbem Blutlaugensalz die Base vollständig in Form ihres ferrocyanwasserstoffsauren Salzes ausgefällt. Das Salz wird durch Filtration isolirt und noch feucht durch Natronlauge 1 :3 zersetzt. Es scheidet sich dann Base A als OeI ab, das durch Ausschütteln mit Chloroform von der alkalischen Mutterlauge leicht getrennt werden kann.The aqueous solution is acidified with hydrochloric acid and by adding yellow blood liquor salt the base is completely precipitated in the form of its ferrocyanoic acid salt. That Salt is isolated by filtration and decomposed while still moist with sodium hydroxide solution 1: 3. It Then base A separates as OeI, which by shaking with chloroform from the alkaline mother liquor can be easily separated.
Die Base wird nach dem Abtreiben des Chloroforms als bald erstarrendes OeI erhalten und kann durch Fällung aus der alkoholischen Lösung mit Aether oder durch UmkrystallisirenAfter the chloroform has been stripped off, the base is obtained as an oil which soon solidifies and can by precipitation from the alcoholic solution with ether or by recrystallization
1U1U
aus Toluol in schönen Krystallen vom Schmelzpunkt 143° erhalten werden.can be obtained from toluene in beautiful crystals with a melting point of 143 °.
Das ι -Phenyl- 2 - oxäthyl- 3 -methylpyrazolon (sogen. Base A) ist in seinen physikalischen und chemischen Eigenschaften dem Antipyrin ähnlich. Es ist aufserordentlich leicht löslich in Wasser, Alkohol und Chloroform, schwer löslich in Aether, Ligroin und kaltem Toluol. Durch starke Alkalien wird es1 aus der wässerigen Lösung gefällt.The ι -Phenyl- 2 - oxäthyl- 3 -methylpyrazolon (so-called. Base A) is similar in its physical and chemical properties to the antipyrine. It is extremely easily soluble in water, alcohol, and chloroform, and sparingly soluble in ether, ligroin, and cold toluene. By strong alkalis it is one precipitated from the aqueous solution.
Das ferrocyanwasserstoffsaure Salz, das, wie oben angegeben, zur Reinigung der Base Verwendung finden kann, hat die Zusammensetzung The ferrocyanwasserstoffsaure salt, which, as stated above, to purify the Base can be used has the composition
(C12H11N2 O2), H, Fe (C N)6.(C 12 H 11 N 2 O 2 ), H, Fe (CN) 6 .
Das Chloroplatinat krystallisirt aus verdünnter Salzsäure in orangerothen Nadeln, welche unscharf bei 1760 schmelzen. Das Pikrat stellt gelbe Nädeichen vom Schmelzpunkt 114 bis 11 50 (unscharf) dar.The chloroplatinate crystallizes from dilute hydrochloric acid in orange red needles that melt at 176 blurred 0th The picrate represents yellow oaks with a melting point of 114 to 11 5 0 (out of focus).
Mit salpetriger Säure liefert das i-Phenyl-2 -oxäthyl - 3 - methylpyrazolon ebenso wie Antipyrin eine Nitrosoverbindung vom Zersetzungspunkt 173 °, deren Lösungen grüne Farbe besitzen.With nitrous acid it gives i-phenyl-2 -oxäthyl - 3 - methylpyrazolon as well as antipyrine a nitroso compound from the decomposition point 173 °, the solutions of which are green in color.
Der Alkoholcharakter des 1-Phenyl-2-oxäthyl -3 -methylpyrazolons tritt deutlich bei der Behandlung mit Essigsäureanhydrid und Benzoylchlorid hervor.The alcohol character of 1-phenyl-2-oxäthyl -3 -methylpyrazolons occurs significantly on treatment with acetic anhydride and benzoyl chloride emerged.
Kocht man die Base z. B. mit der doppelten Menge Essigsäureanhydrid kurze Zeit, versetzt die Lösung mit Wasser und dampft zur Trockne ein, so hinterbleibt das Acetyl derivat von der Formel:If you boil the base z. B. with twice the amount of acetic anhydride for a short time the solution with water and evaporated to dryness, leaving behind the acetyl derivative of the Formula:
N-C6H5 NC 6 H 5
/\ CHCO- O- CHn- CH,-N CO/ \ CHCO- O- CH n - CH, -N CO
I II I
CHS- C = CH.CH S - C = CH.
Es schmilzt bei 114 bis ii6°, ist leicht löslich in Wasser und Alkohol, schwer löslich in Aether und kann gut aus Toluol umkrystallisirt werden.It melts at 114 to 116 ° and is easily soluble in water and alcohol, sparingly soluble in ether, and can easily be recrystallized from toluene will.
Das entsprechende Benzoylderivat der FormelThe corresponding benzoyl derivative of the formula
N-C6H5 C6H5COOCH2-CH2. N CONC 6 H 5 C 6 H 5 COOCH 2 -CH 2 . N CO
CH3-C=CHCH 3 -C = CH
gewinnt man leicht z. B. in der Weise, dafs man die Base mit der gleichen Menge Benzoylchlorids bis nahe zum Siedepunkt des Benzoylchlorids erhitzt. Auf Zusatz von Natronlauge und etwas Aether erstarrt die Reactionsmasse und kann nach dem Auswaschen mit Wasser aus heifsem Toluol umkrystallisirt werden. Das Benzoylderivat schmilzt bei 1620, ist leicht löslich in Alkohol, schwer in Aether, unlöslich in Wasser und zeigt ebenso wie die Acetylverbindung die Salpetrigsäurereaction der Mutterlauge.one wins easily z. B. in such a way that the base is heated with the same amount of benzoyl chloride to near the boiling point of the benzoyl chloride. On the addition of caustic soda and a little ether, the reaction mass solidifies and can be recrystallized from hot toluene after washing with water. The benzoyl derivative melts at 162 0, is easily soluble in alcohol, heavy in ether, insoluble in water, and also shows how the acetyl the Salpetrigsäurereaction the mother liquor.
Die Körper sollen zu medicinischen Zwecken Verwendung finden.The bodies should be used for medical purposes.
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE74912C true DE74912C (en) |
Family
ID=347918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT74912D Active DE74912C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE74912C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515944A (en) * | 1981-08-20 | 1985-05-07 | Kali-Chemie Pharma Gmbh | 1,5-Diphenyl-2-haloalkylpyrazolin-3-one intermediates |
-
0
- DE DENDAT74912D patent/DE74912C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515944A (en) * | 1981-08-20 | 1985-05-07 | Kali-Chemie Pharma Gmbh | 1,5-Diphenyl-2-haloalkylpyrazolin-3-one intermediates |
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