CH126529A - Process for the preparation of 1-p-tolyl-3,4-trimethylene pyrazolone. - Google Patents
Process for the preparation of 1-p-tolyl-3,4-trimethylene pyrazolone.Info
- Publication number
- CH126529A CH126529A CH126529DA CH126529A CH 126529 A CH126529 A CH 126529A CH 126529D A CH126529D A CH 126529DA CH 126529 A CH126529 A CH 126529A
- Authority
- CH
- Switzerland
- Prior art keywords
- tolyl
- pyrazolone
- trimethylene
- preparation
- alcohol
- 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 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 claims description 3
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 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
- 239000000155 melt Substances 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- -1 carbonic acid ethyl ester tolyl hydrazone Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von 1-p-Tolyl-3.4-trimethylenpyrazolon. Es ist bekannt, dass die Reaktions produkte des ss-Ketopentamethylencarbon- säureäthylesters mit Hydrazin sehr leicht unter Ringschluss Alkohol abspalten, wobei sich ein System von zwei kondensierten Fünfringen bildet. Im Gegensatz hierzu und auch in Abweichung von den Erfahrungen in der Hexamethylenreihe konnte Dieckmann bei aromatischer Substituierung des Hydra zins den Ringschluss nicht erreichen (Lie bigs Annalen der Chemie, 317, 1901, S. 60).
Wie gefunden wurde, gelingt es, bei An wendung von alkalischen Kondensations mitteln, den Ringschluss' leicht herbeizu führen.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Darstellung von 1- p-Tolyl-3.4-trimethylenpyrazolon, welches dadurch gelzennzeichnet ist, dass man ein Reaktionsprodukt aus einem Ester der ss- Ketopentainethylencarbonsäure und p-Tolyl- hydrazin mit einem alkalischen Kondensa tionsmittel behandelt. Dabei kann man ent weder von gereinigtem Plienylhy drazon oder auch vom Rohprodukt, ausgehen. Das 1-p-Tolyl-3.4-trimethylenpyrazolon bildet schwach gefärbte, sauer reagierende Kristalle und schmilzt bei 202 .
Es ist in Wasser unlöslich. Lösungsmittel sind Äthyl- alkohol, Methylalkohol und Ätzalkalien. Die neue Verbindung soll als Ausgangsprodukt für die Herstellung von Farbstoffen und Arzneimitteln Verwendung finden.
Beispiel: 260 Teile ss-Isetopentamethylencarbon- säureäthylestertolylliydrazon, welches durch Einwirkung von p-Tolylhydrazin auf ss- Iietopentaniethylenearbonsäureäthylester er halten wird und bei 84' schmelzende Kri stalle bildet, werden mit<B>136</B> Teilen gut ge trocknetem Natriumätliylat gemischt und die Mischung im Wasserstoffstrom auf 110 und hernach auf<B>160'</B> erwärmt.
Wenn kein Äthylalkohol mehr abdestilliert, wird das Reaktionsprodukt in Wasser gelöst, die Lö sung ausgeäthert, hernach mit Säure ver setzt und dem Niederschlag aus Alkohol um kristallisiert.
Process for the preparation of 1-p-tolyl-3,4-trimethylene pyrazolone. It is known that the reaction products of ethyl β-ketopentamethylene carbonate with hydrazine very easily split off alcohol with ring closure, a system of two condensed five-membered rings being formed. In contrast to this and also in deviation from the experience with the hexamethylene series, Dieckmann was unable to achieve ring closure with aromatic substitution of the hydrazine (Lie bigs Annalen der Chemie, 317, 1901, p. 60).
As has been found, it is possible to use alkaline condensation agents to easily bring about the ring closure.
The present invention relates to a process for the preparation of 1- p-tolyl-3,4-trimethylene pyrazolone, which is characterized in that a reaction product of an ester of β-ketopentainethylene carboxylic acid and p-tolylhydrazine is treated with an alkaline condensation agent. You can either start from purified Plienylhy drazon or from the crude product. The 1-p-tolyl-3,4-trimethylene pyrazolone forms weakly colored, acidic crystals and melts at 202.
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 production of dyes and drugs.
Example: 260 parts of ß-isetopentamethylene carbonic acid ethyl ester tolyl hydrazone, which is obtained by the action of p-tolyl hydrazine on ß-Iietopentaniethylenearbonsäureäthylester and forms melting crystals at 84 ', are mixed with 136 parts of well-dried sodium ethylate and the mixture is heated in a stream of hydrogen to 110 and then to <B> 160 '</B>.
When no more ethyl alcohol distills off, the reaction product is dissolved in water, the solution is etherified, then ver with acid and the precipitate is crystallized from alcohol.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE126529X | 1925-10-27 | ||
| CH123733T | 1926-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH126529A true CH126529A (en) | 1928-06-16 |
Family
ID=25710138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH126529D CH126529A (en) | 1925-10-27 | 1926-09-30 | Process for the preparation of 1-p-tolyl-3,4-trimethylene pyrazolone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH126529A (en) |
-
1926
- 1926-09-30 CH CH126529D patent/CH126529A/en unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CH126529A (en) | Process for the preparation of 1-p-tolyl-3,4-trimethylene pyrazolone. | |
| DE442038C (en) | Process for the preparation of oxyalkylamides of o-oxybenzoic acids | |
| CH126528A (en) | Process for the preparation of 1-p-bromophenyl-3,4-trimethylene pyrazolone. | |
| DE206638C (en) | ||
| CH123733A (en) | Process for the preparation of 1-phenyl-3,4-trimethylene pyrazolone. | |
| DE668628C (en) | Process for the preparation of alkyl and aralkyl compounds of 3,4-cyclotetramethylene-1-aryl-5-pyrazolones | |
| AT109413B (en) | Process for the preparation of 1-aryl derivatives of 3,4-trimethylene-5-pyrazolone. | |
| DE464482C (en) | Process for the preparation of dicyclic pentamethylene derivatives of the pyrazolone series | |
| DE611003C (en) | Process for the preparation of 5-pyrazolone compounds | |
| DE351464C (en) | Process for the preparation of derivatives of a hydrogenated 2-phenylquinoline-4-carboxylic acid | |
| AT117475B (en) | Process for the preparation of substitution products of ß-iodopyridine. | |
| AT88635B (en) | Process for the preparation of arsenic compounds of the pyrazolone series. | |
| DE454697C (en) | Process for the preparation of compounds of the 1-aryl-2-alkyl- and 1-aryl-2-aralkyl-3, 4-cyclotrimethylene-5-pyrazolones with dialkyl and arylalkyl barbituric acids | |
| AT152837B (en) | Process for the preparation of 2.4-dioxo-3.3-dialkyl-1.2.3.4-tatrahydropyridines. | |
| CH106086A (en) | Process for the production of a new intermediate product. | |
| CH138229A (en) | Process for the production of a new azo dye. | |
| CH175885A (en) | Process for the preparation of a substantive copper-containing azo dye. | |
| CH160945A (en) | Process for the preparation of N-acetyl-2-ethoxy-3-nitrocarbazole. | |
| CH181733A (en) | Process for the preparation of a compound of 1-phenyl-2,3-dimethyl-4-isopropyl-5-pyrazolone with B-bromoallyl-isopropylbarbituric acid. | |
| CH211775A (en) | Process for the preparation of 5-methyl-4-nitro-2-chlorophenyl-1-trifluoromethylsulfone. | |
| CH104472A (en) | Process for the preparation of a new pyrazolone derivative. | |
| CH89636A (en) | Process for the preparation of the Bromdiäthylacetylurethans of p-acetylaminophenol. | |
| CH183066A (en) | Method for preparing a salicylic acid compound. | |
| CH90884A (en) | Process for the preparation of p-arseno-di- (1-phenyl-2,3-dimethyl-4-amino-5-pyrazolone) -monomethylene sulfoxylic acid. | |
| CH143236A (en) | Process for the preparation of a compound with a hydrogenated ring system. |