DE955061C - Process for the production of methionine hydantoin - Google Patents

Process for the production of methionine hydantoin

Info

Publication number
DE955061C
DE955061C DEB23472A DEB0023472A DE955061C DE 955061 C DE955061 C DE 955061C DE B23472 A DEB23472 A DE B23472A DE B0023472 A DEB0023472 A DE B0023472A DE 955061 C DE955061 C DE 955061C
Authority
DE
Germany
Prior art keywords
production
methionine hydantoin
ammonium
hydantoin
methionine
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
Application number
DEB23472A
Other languages
German (de)
Inventor
David Oliver Holland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beecham Research Laboratories Ltd
Original Assignee
Beecham Research Laboratories Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beecham Research Laboratories Ltd filed Critical Beecham Research Laboratories Ltd
Application granted granted Critical
Publication of DE955061C publication Critical patent/DE955061C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von Methionin-hydantoin Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Methionin-hydantoin (5-ß-Methylthioäthyl-hydantoin) aus ß-Methylthiopropionaldehyd.Process for the preparation of methionine hydantoin The invention relates to on a process for the production of methionine hydantoin (5-ß-methylthioethyl hydantoin) from ß-methylthiopropionaldehyde.

Bekanntlich lassen sich Hydantoine nach B u c h e r e r herstellen, d. h. derart, daß man die entsprechenden Aldehyde mit Ammoniumcarbonat (oder chemisch gleichwertigen Verbindungen, wie Ammoniumbicarbonat, Ammoniumcarbamat oder Ammoniak und Kohlendioxyd) und einem ionisierbaren anorganischen Cyanid, beispielsweise einem Alkali- oder Erdalkalicyanid, behandelt. Die Erfindung hat sich die Aufgabe gestellt, dieses Verfahren in Anwendung auf die Herstellung von Methionin-hydantoin, ,zu verbessern, so daß man mit kürzeren Reaktionszeiten bzw. niedrigeren Reaktionstemperaturen auskommt.It is well known that hydantoins can be produced according to B u c h e r e r, d. H. in such a way that the corresponding aldehydes are treated with ammonium carbonate (or chemically equivalent compounds such as ammonium bicarbonate, ammonium carbamate or ammonia and carbon dioxide) and an ionizable inorganic cyanide, for example one Alkali or alkaline earth cyanide treated. The invention has the task of this process in application to the production of methionine hydantoin, to improve, so that one manages with shorter reaction times or lower reaction temperatures.

Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß man das bekannte Verfahren durchführt in Gegenwart von r Mol Triäthylamin, je i Mol Aldehyd sowie in Gegenwart eines Lösungsmittels.According to the invention this object is achieved by the known The process is carried out in the presence of r moles of triethylamine and i moles of aldehyde as well in the presence of a solvent.

Das Verfahren nach der vorliegenden Erfindung kann bei normaler Raumtemperatur während eines Zeitraumes von wenigen Stunden durchgeführt werden, bei Anwendung von Wärme jedoch während eines bedeutend kürzeren Zeitraumes, beispielsweise beim Sieden am Rückflußkühler oder auf andere Weise während eines Zeitraumes von 15 bis 30 Minuten.The process according to the present invention can be carried out at normal room temperature for a period of a few hours, but with the application of heat for a significantly shorter period of time, for example when refluxing or otherwise for a period of 15 to 30 minutes.

Methionin-hydantoin kann in bekannter Weise zu Methionin hydrolisiert werden, welches wertvolle therapeutische Eigenschaften besitzt.Methionine hydantoin can be hydrolyzed to methionine in a known manner which has valuable therapeutic properties.

Das nachstehende Ausführungsbeispiel dient zur Veranschaulichung der Erfindung: EineLösung von 2,7 g Natriumcyanid (0,055 M01) und io,6 Ammoniumcarbon@at (o, i i Mol) in 25 cm3 Wasser wird mit 25 cm3 Alkohol und o,o5 Mol Triäthylamin verdünnt. Man läßt bei gewöhnlicher Temperatur unter gelegentlichem Umscliütteln io Minuten lang stehen und fügt dann 5 cm3 ß-Methylthiopropionaldehyd (0,05 Mol) hinzu. Darauf läßt man die Mischung bei Raumtemperatur 24 Stunden stehen oder bringt sie 15 Minuten lang am RückfluBkühler heftig zum Sieden. Die Mischung wird dann unter reduziertem Druck auf ein kleines Volumen eingeengt und mit konzentrierter Salzsäure stark angesäuert. Nachdem das Reaktionsgemisch einige Stunden im Kühlschrank gestanden hat, kann man einen hellen Niederschlag von Methionin-hydantoin abtrennen und mit wenig kaltem Wasser waschen. Das Filtrat wird eingeengt und ergibt eine zweite Ausbeute. Die Gesamtausbeute beträgt go bis 95 °/o.The following exemplary embodiment serves to illustrate the Invention: A solution of 2.7 g of sodium cyanide (0.055 M01) and io.6 ammonium carbon @ at (0.11 mol) in 25 cm3 of water is mixed with 25 cm3 of alcohol and 0.05 mol of triethylamine diluted. It is left at ordinary temperature with occasional shaking Stand for 10 minutes and then add 5 cm3 of ß-methylthiopropionaldehyde (0.05 mol) added. The mixture is then left to stand or brought to room temperature for 24 hours boil it violently for 15 minutes on the reflux condenser. The mixture is then concentrated to a small volume under reduced pressure and concentrated with Hydrochloric acid strongly acidified. After the reaction mixture has been in the refrigerator for a few hours has stood, you can separate a light precipitate of methionine hydantoin and wash with a little cold water. The filtrate is concentrated and gives a second crop. The total yield is up to 95%.

Das neue Verfahren eignet sich auch für eine kontinuierliche Durchführung, indem die Dämpfe kontinuierlich abgeführt werden, um unmittelbar ein konzentriertes Reaktionsprodukt zu ergeben.The new process is also suitable for continuous implementation, by continuously evacuating the vapors to immediately produce a concentrated To give reaction product.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Methioninhydantoin durch Umsetzung von 2-Methylthiopropaldehyd mit Ammoniumcarbonat, Ammoniumbicarbonat, Ammoniumcarbamat oder mit Ammoniak und Kohlendioxyd sowie einem ionisierbaren anorganischen Cyanid, dadurch gekennzeichnet, daB -die Reaktion in Gegenwart von. einem Mol Triäthylamin pro Mol Aldehyd in einem Lösungsmittel, wie .z. B. wäBrigem Alkohol, ohne Anwendung von, Wärme oder unter nur kurzzeitiger Erwärmung durchgeführt wird. In Betracht gezogene Druckschriften: USA.-Patentschriff Nr. 2 557 9i3. PATENT CLAIM: Process for the production of methionine hydantoin by reacting 2-methylthiopropaldehyde with ammonium carbonate, ammonium bicarbonate, ammonium carbamate or with ammonia and carbon dioxide and an ionizable inorganic cyanide, characterized in that the reaction in the presence of. one mole of triethylamine per mole of aldehyde in a solvent such as .z. B. aqueous alcohol is carried out without the application of heat or with only brief heating. References considered: U.S. Patent No. 2,557,913.
DEB23472A 1951-12-21 1952-12-23 Process for the production of methionine hydantoin Expired DE955061C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB955061X 1951-12-21

Publications (1)

Publication Number Publication Date
DE955061C true DE955061C (en) 1956-12-27

Family

ID=10786422

Family Applications (1)

Application Number Title Priority Date Filing Date
DEB23472A Expired DE955061C (en) 1951-12-21 1952-12-23 Process for the production of methionine hydantoin

Country Status (1)

Country Link
DE (1) DE955061C (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2557913A (en) * 1946-11-07 1951-06-19 Dow Chemical Co Production of methionine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2557913A (en) * 1946-11-07 1951-06-19 Dow Chemical Co Production of methionine

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