CH123733A - Process for the preparation of 1-phenyl-3,4-trimethylene pyrazolone. - Google Patents
Process for the preparation of 1-phenyl-3,4-trimethylene pyrazolone.Info
- Publication number
- CH123733A CH123733A CH123733DA CH123733A CH 123733 A CH123733 A CH 123733A CH 123733D A CH123733D A CH 123733DA CH 123733 A CH123733 A CH 123733A
- Authority
- CH
- Switzerland
- Prior art keywords
- phenyl
- pyrazolone
- trimethylene
- parts
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Description
Verfahren zur Darstellung von 1-Phenyl-3.4-trimethylenpyrazolon. Es ist bekannt, dass die Reaktionsprodukte des ss - Ketopentamethylenkarbonsäureäthyl- esters mit Hydrazin sehr leicht unter Ring schluss Alkohol abspalten, wobei sich ein<B>Sy-</B> stem von zwei kondensierten Fünfringen bildet.
Im Gegensatz hierzu und auch in AbvJeichung von den Erfahrungen in der Hexamethylen- reihe konnte Dieckmann bei aromatischer Substituierung des Hydrazins den Ring schluss nicht erreichen (Liebigs Annalen der Chemie, 317, 1901, Seite 60).
Wie gefunden wurde, gelingt es, bei An wendung von alkalischen Kondensationsmit teln den Ringschluss leicht herbeizuführen.
Gegenstand der vorliegenden Erfindung isst ein Verfahren zur Darstellung von 1- Phenyl - 3. 4 - trimethylenpyra.zolon, welches dadurch gekennzeichnet ist, @dass man ein Re aktionsprodukt aus einem Ester der ss-Keto- pentamethylenkarbonsäure und Phenylhydra- zin mit einem alkalischen Kondensationsmit tel behandelt. Dabei kann man entweder von gereinigtem Phenylhydra.zon oder auch vom Rohprodukt ausgehen.
Das 1 - Phenyl-3. 4-trim-ethylenpyrazolon bildet schwach gefärbte Kristalle, welches bei 183 bis 184' schmelzen.. Es ist in Wasser un löslich. Lösungsmittel sind Äthylalkohol, Methylalkohol und Ätzalkalien. Die neue Verbindung soll als Ausgangsprodukt für die Herstellung von Farbstoffen und Arzneimit teln Verwendung finden.
<I>Beispiel</I> r: Man mischt zu 246 Teilen des aus<B>156</B> Teilen ss-Ketopentamethylenka,rbonsäureäthyl- ester und 108 Teilen Phenylhydra.zin erhal tenen Hydrazons 136 Teile getrocknetes Na- triumäthylat und erhitzt die Mischung lang sam auf 160 , zweckmässig in einer Wasser stoffatmosphäre. Dabei färbt sich die Reak tionsmasse leicht bräunlich. Während der Reaktion destilliert Alkohol ab. Der Ring schluss ist beendigt, wenn die Menge des ab ,destillierten Alkohols 90 Teile erreicht hat.
Das Reaktionsprodukt wird in Wasser gelöst und die wässerige Lösung durch Ausschüt teln mit Äther von Verunreinigungen befreit. Aus der Lösung erhält man !das entstandene Kondensationsprodukt durch Ausfällen finit Schwefelsäure. Zur- vollständigen Reinigung kristallisiert man dasselbe aus der 1.5-fachen Menge Äthylalkohol 94% um.
<I>Beispiel 2:</I> <B>1</B> an mischt 14,2 Teile ss-Kcl:opexit_i.- methy lenkarbonsäuremethylester mit 108 Tei len PhenylhydTa.zin und erwärmt das Ge misch, bis kein Wasser mehr abgegeben wird. Hierauf gibt man 108 Teile Natriummethylat zu und erhitzt langsam auf etwa. 160 . Es destilliert Methylalkohol ab.
Die Aufarbei tung des entstandenen Kondensationsproduk tes erfolgt, nachdem sich kein Methylalkohol mehr entwickelt; sie geschieht in gleicher Weise wie in Beispiel 1.
<I>Beispiel, 3:</I> In eine Lösung von 246 Teilen ss-Ke- topentamethylenkarbonsä,ureäthylesterpheny 1- hydrazon in 750 Teilen Toluol werden 28 Teile Natrium eingetragen und die Mischung zwei Stunden im Kochsalzbad e erhitzt. Das Natrium verschwindet allmählich, und es bil det sich ein dicker, gelber Brei, indem sich das Natriumsalz des Pyrazolonkörpers aus scheidet.
Durch vorsichtigen Zusatz von Was ser bringt man Natriumreste in Lösung, gibt dann soviel Wasser hinzu, dass das ausge schiedene Natriumsalz sich löst und trennt die Toluolschicht ab. Aus der wässerigen Lösung fällt man sodann durch Zusatz von Säure das 1-Phenyl-3.4-trimethylenpyrazo- lon aus.
<I>Beispiel</I> In eine kalte Lösung von 246 Teilen ss-Ke topentamethylenliarbonsä.ureäthylesterphenyl- hydrazon in 800 Teilen Toluol trägt man 78 Teile fein gepulvertes Natriuma.mid ein. Die Reaktion setzt bald unter beträchtlicher Wärmeentwicklung ein. Man lä,sst über Nacht stehen und versetzt sodann den ent standenen gelben Kristallbrei mit soviel Was ser, dass das ausgeschiedene Natriumsalz ge löst wird.
Man trennt die Toluolschicht ab tznd fällt aus der wässerigen Lösung das 1 Phenyl-3.4-trimet.hylenpyrazolon aus. Es jvird durch Umkristallisieren aus Alkohol ge reinigt.
Process for the preparation of 1-phenyl-3,4-trimethylene pyrazolone. It is known that the reaction products of the ß-ketopentamethylene carboxylic acid ethyl ester with hydrazine very easily split off alcohol with a ring closure, forming a system of two condensed five-membered rings.
In contrast to this and also in deviation from the experience with the hexamethylene series, Dieckmann was unable to achieve the ring closure with aromatic substitution of the hydrazine (Liebigs Annalen der Chemie, 317, 1901, page 60).
As has been found, it is possible to easily bring about ring closure when using alkaline condensation agents.
The subject of the present invention is a process for the preparation of 1-phenyl-3, 4-trimethylenepyra.zolon, which is characterized in that a reaction product of an ester of ß-ketopentamethylene carboxylic acid and phenylhydrazine with an alkaline condensation agent tel treated. You can either start from purified Phenylhydra.zon or from the crude product.
The 1 - phenyl-3. 4-trim-ethylene pyrazolone forms pale colored crystals which melt at 183 to 184 '. It is insoluble in water. Solvents are ethyl alcohol, methyl alcohol and caustic alkalis. The new compound is to be used as a starting product for the manufacture of dyes and drugs.
<I> Example </I> r: 136 parts of dried sodium ethylate are mixed with 246 parts of the hydrazone obtained from 156 parts of β-ketopentamethylene ka, ethyl ester and 108 parts of phenylhydrazine and heated the mixture slowly sam to 160, conveniently in a hydrogen atmosphere. The reac tion mass turns slightly brownish. Alcohol distills off during the reaction. The ring closure is complete when the amount of distilled alcohol has reached 90 parts.
The reaction product is dissolved in water and the aqueous solution is freed from impurities by shaking out with ether. The condensation product formed is obtained from the solution by precipitation of finite sulfuric acid. For complete purification, the same is recrystallized from 1.5 times the amount of ethyl alcohol 94%.
<I> Example 2: </I> <B> 1 </B> mixes 14.2 parts of ss-Kcl: opexit_i.- methy lenkarbonsäuremethylester with 108 parts of PhenylhydTa.zin and heats the mixture until no more water is delivered. Then 108 parts of sodium methylate are added and the mixture is slowly heated to about. 160. Methyl alcohol is distilled off.
The resulting condensation product is worked up after no more methyl alcohol develops; it happens in the same way as in example 1.
<I> Example, 3: </I> 28 parts of sodium are introduced into a solution of 246 parts of ß-ketopentamethylene carboxylic acid, ureäthylesterpheny 1-hydrazone in 750 parts of toluene and the mixture is heated in the salt bath for two hours. The sodium gradually disappears and a thick, yellow pulp forms as the sodium salt of the pyrazolone body precipitates.
By carefully adding water, residual sodium is dissolved, then enough water is added to dissolve the precipitated sodium salt and the toluene layer is separated off. The 1-phenyl-3,4-trimethylene pyrazolone is then precipitated from the aqueous solution by adding acid.
<I> Example </I> 78 parts of finely powdered sodium amide are introduced into a cold solution of 246 parts of ss-ke topentamethylenliarbonsä.ureäthylesterphenylhydrazone in 800 parts of toluene. The reaction soon sets in with considerable evolution of heat. It is left to stand overnight and the resulting yellow crystal paste is then mixed with enough water to dissolve the sodium salt which has separated out.
The toluene layer is separated off and the 1-phenyl-3,4-trimet.hylenpyrazolone precipitates out of the aqueous solution. It is purified by recrystallization from alcohol.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE123733X | 1925-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH123733A true CH123733A (en) | 1927-12-16 |
Family
ID=5657917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH123733D CH123733A (en) | 1925-10-27 | 1926-09-30 | Process for the preparation of 1-phenyl-3,4-trimethylene pyrazolone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH123733A (en) |
-
1926
- 1926-09-30 CH CH123733D patent/CH123733A/en unknown
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