CH381663A - Process for the production of the higher-melting form of α-ethyl-crotonylurea - Google Patents
Process for the production of the higher-melting form of α-ethyl-crotonylureaInfo
- Publication number
- CH381663A CH381663A CH7810359A CH7810359A CH381663A CH 381663 A CH381663 A CH 381663A CH 7810359 A CH7810359 A CH 7810359A CH 7810359 A CH7810359 A CH 7810359A CH 381663 A CH381663 A CH 381663A
- Authority
- CH
- Switzerland
- Prior art keywords
- ethyl
- bromo
- butyrylurea
- crotonylurea
- urea
- Prior art date
Links
- 238000002844 melting Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 9
- QCUPYFTWJOZAOB-HWKANZROSA-N (e)-n-carbamoyl-2-ethylbut-2-enamide Chemical compound CC\C(=C/C)C(=O)NC(N)=O QCUPYFTWJOZAOB-HWKANZROSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- OPNPQXLQERQBBV-UHFFFAOYSA-N carbromal Chemical compound CCC(Br)(CC)C(=O)NC(N)=O OPNPQXLQERQBBV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000003204 tranquilizing agent Substances 0.000 claims description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung der höherschmelzenden Form des a-Äthyl-crotonylharnstoffes
Es ist bekannt, dass beim Erhitzen des a-Brom-a äthyl-butyrylharnstoffs mit Wasser oder Natronlauge ein Gemisch von zwei Isomeren des a-Äthylcrotonylharnstoffs entsteht, aus dem sich die höherschmelzende (F. 191-193 ), therapeutisch wertvollere Form isolieren lässt (Journ. Chem. Soc. [London], 295 [1925j).
Dieses Verfahren kommt aber für eine präparative Herstellung nicht in Frage, da die Ausbeuten sehr gering sind. Dies beruht darauf, dass die Ureidogruppe zur Amidogruppe bzw. bis zur Carboxylgruppe abgebaut wird.
Weiterhin ist bekannt, dass bei Verwendung von Pyridin als bromwasserstoffbindendes Mittel fast ausschliesslich die tieferschmelzende Form entsteht (Belg.
Patent Nr. 558088). Die höherschmelzende Form wird hingegen nach Belg. Patent Nr. 558088 durch Kochen des a-Brom-a-äthyl-butyrylharnstoffes in Isopropanol in Gegenwart von Silberoxyd erhalten.
Es wurde nun gefunden, dass man die höherschmelzende Form des a-Athyl-crotonylharnstoffs leicht erhält, wenn man a-Brom-a-äthyl-butyrylharnstoff längere Zeit in Wasser bei Gegenwart von Harnstoff kocht. Bei dieser vereinfachten Methode sind die Ausbeuten die gleichen wie bei Verwendung von Silberoxyd und Isopropylalkohol. Vorzugsweise werden äquivalente Mengen von a-Brom-a-äthylbutyrylharnstoff und Harnstoff verwendet.
Die Verwendung von Harnstoff an Stelle der üblichen bromwasserstoffbindenden Mittel, wie Natriumacetat, Calciumcarbonat und Natriumbicarbonat, erhöht die Ausbeuten wesentlich. Wie bekannt, wirkt die erfindungsgemäss hergestellte Verbindung als guter Tranquillizer.
Beispiel
237 g a-Brom-a-äthyl-butyrylharnstoff und 60 g Harnstoff werden in drei Liter Wasser 10-15 Stunden zum Sieden erhitzt. Nach dem Abkühlen wird das ausgefallene Rohprodukt abgesaugt und aus 20 Teilen Athanol umgelöst.
Ausbeute: 90-95 g a-Äthyl-crotonylharnstoff vom F. 190-193 (konz).
PATENTANSPRUCH
Verfahren zur Herstellung der höherschmelzenden Form des a-Sithyl-crotonylharnstoffs, dadurch gekennzeichnet, dass man a-Brom-a-äthyl-butyrylharnstoff längere Zeit in Wasser bei Gegenwart von Harnstoff kocht.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the production of the higher-melting form of α-ethyl-crotonylurea
It is known that when a-bromo-a-ethyl-butyrylurea is heated with water or sodium hydroxide solution, a mixture of two isomers of a-ethylcrotonylurea is formed, from which the higher-melting (F. 191-193), therapeutically more valuable form can be isolated ( Journ. Chem. Soc. [London], 295 [1925j).
However, this process is out of the question for preparative production, since the yields are very low. This is based on the fact that the ureido group is broken down into the amido group or down to the carboxyl group.
It is also known that when pyridine is used as a hydrogen bromide binding agent, the lower-melting form is almost exclusively the result (Belg.
Patent No. 558088). The higher melting form, however, is after Belg. Patent No. 558088 obtained by boiling the α-bromo-α-ethyl-butyrylurea in isopropanol in the presence of silver oxide.
It has now been found that the higher-melting form of α-ethyl-crotonylurea is easily obtained if α-bromo-α-ethyl-butyrylurea is boiled in water for a long time in the presence of urea. With this simplified method, the yields are the same as when using silver oxide and isopropyl alcohol. Equivalent amounts of α-bromo-α-ethylbutyrylurea and urea are preferably used.
The use of urea instead of the usual hydrogen bromide binding agents such as sodium acetate, calcium carbonate and sodium bicarbonate increases the yields significantly. As is known, the compound prepared according to the invention acts as a good tranquillizer.
example
237 g of a-bromo-a-ethyl-butyrylurea and 60 g of urea are heated to the boil in three liters of water for 10-15 hours. After cooling, the precipitated crude product is filtered off with suction and redissolved from 20 parts of ethanol.
Yield: 90-95 g of a-ethyl-crotonylurea with a melting point of 190-193 (conc).
PATENT CLAIM
Process for the preparation of the higher melting form of a-sithyl-crotonylurea, characterized in that a-bromo-a-ethyl-butyrylurea is boiled in water for a long time in the presence of urea.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0026719 | 1958-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH381663A true CH381663A (en) | 1964-09-15 |
Family
ID=7092132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH7810359A CH381663A (en) | 1958-10-03 | 1959-09-11 | Process for the production of the higher-melting form of α-ethyl-crotonylurea |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH381663A (en) |
-
1959
- 1959-09-11 CH CH7810359A patent/CH381663A/en unknown
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