DE1223368B - Process for the preparation of 1-hydroxy-2-mercaptopropionic acid or its salts - Google Patents
Process for the preparation of 1-hydroxy-2-mercaptopropionic acid or its saltsInfo
- Publication number
- DE1223368B DE1223368B DEST21675A DEST021675A DE1223368B DE 1223368 B DE1223368 B DE 1223368B DE ST21675 A DEST21675 A DE ST21675A DE ST021675 A DEST021675 A DE ST021675A DE 1223368 B DE1223368 B DE 1223368B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- hydroxy
- preparation
- salts
- mercaptopropionic acid
- 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.)
- Pending
Links
- 150000003839 salts Chemical class 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- OTGHWLKHGCENJV-UHFFFAOYSA-N glycidic acid Chemical compound OC(=O)C1CO1 OTGHWLKHGCENJV-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZBOIDAGCMHDTSU-REOHCLBHSA-N (2r)-2-(hydroxyamino)-3-sulfanylpropanoic acid Chemical compound ON[C@@H](CS)C(O)=O ZBOIDAGCMHDTSU-REOHCLBHSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDVRLNCDFWRMLD-UHFFFAOYSA-M sodium oxirane-2-carboxylate Chemical compound [Na+].O1C(C1)C(=O)[O-] CDVRLNCDFWRMLD-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fodder In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. α.:Int. α .:
C07cC07c
Deutsche Kl.: 12 ο-23/03 German class: 12 ο -23/03
Nummer: 1223 368Number: 1223 368
Aktenzeichen: St 21675IV b/12 οFile number: St 21675IV b / 12 ο
Anmeldetag: 10. Februar 1964Filing date: February 10, 1964
Auslegetag: 25. August 1966Opening day: August 25, 1966
Die Erfindung betrifft ein Verfahren zur Herstellung von l-Hydroxy-2-mercaptopropionsäure (Hydroxycystein) oder von deren Salzen. Die Herstellung dieser Verbindung sowie deren Anwendung bei der Fütterung von Geflügel sind in der USA.-Patentschrift 2 828 208 beschrieben worden.The invention relates to a process for the production of l-hydroxy-2-mercaptopropionic acid (hydroxycysteine) or their salts. The production of this connection and its application in the Feeding of poultry has been described in U.S. Patent 2,828,208.
Gemäß dieser Patentschrift wird l-Hydroxy-2-mercaptopropionsäure durch Umsetzung von 1-Hydroxy-2-chlorpropionsäure mit einem Hydrosulfid bei einer Temperatur von 15 bis 12O0C in wäßriger Lösung hergestellt. Davon abgesehen, daß die erzielten Ausbeuten nicht beurteilt werden können, da darüber keine Angaben gemacht werden, ist die obige Herstellungsweise wirtschaftlich nicht interessant.According to this patent is l-hydroxy-2-mercaptopropionic acid by reacting 1-hydroxy-2-chloropropionic acid with a hydrosulfide at a temperature of 15 to 12O 0 C in an aqueous solution. Apart from the fact that the yields achieved cannot be assessed, since no information is given about this, the above method of preparation is of no economic interest.
Es ist außerdem bekannt, Epichlorhydrin und Schwefelwasserstoff bei 00C zu y-Chlor-ß-oxy-propylmercaptan (Thiochlorhydrin) umzusetzen (vgl. Ber. Chem. Ges., 74 [1941], S. 64). Allerdings verläuft diese Reaktion nur bei der erwähnten tiefen Temperatur einigermaßen zufriedenstellend und neigt zur Bildung unerwünschter Nebenprodukte unter Sulfidbrückenbildung, wobei die unerwünschte Nebenreaktion sogar ganz überwiegen kann.It is also known to react epichlorohydrin and hydrogen sulphide at 0 0 C to y-chloro-.beta.-oxy-propyl mercaptan (Thiochlorhydrin) (see. Ber. Chem. Ges., 74 [1941], p 64). However, this reaction proceeds to some extent satisfactorily only at the low temperature mentioned and tends to form undesirable by-products with formation of sulfide bridges, and the undesirable side reaction can even predominate.
Es wurde nun überraschenderweise gefunden, daß es möglich ist, l-Hydroxy-2-mercaptopropionsäure in technischem Maßstab durch Umsetzung von Epoxypropionsäure mit Schwefelwasserstoff bei Temperaturen von 90 bis 110° C herzustellen, wobei die Ausbeuten trotz der hohen Temperaturen, die angewandt werden, etwa 85°/0 betragen.It has now been found, surprisingly, that it is possible to produce l-hydroxy-2-mercaptopropionic acid on an industrial scale by reacting epoxypropionic acid with hydrogen sulfide at temperatures of 90 to 110 ° C., the yields, despite the high temperatures used, being about 85 ° / 0 .
Es mußte außerdem überraschen, daß unter diesen Reaktionsbedingungen Epoxypropionsäure so erfolgreich als Ausgangsmaterial eingesetzt werden kann.It was also surprising that epoxypropionic acid was so successful under these reaction conditions can be used as starting material.
Das erfindungsgemäße Verfahren zur Herstellung von l-Hydroxy-2-mercaptopropionsäure oder ihren Salzen besteht darin, daß man Epoxypropionsäure und/oder ein Salz dieser Säure mit Schwefelwasserstoff unter Druck oder mit einem Alkali- oder Erdalkalihydrogensulfid bei einer Temperatur von 90 bis 110° C umsetzt und das Reaktionsprodukt in ein Salz bzw. in die Säure überführt.The process according to the invention for the preparation of l-hydroxy-2-mercaptopropionic acid or its Salting consists of epoxypropionic acid and / or a salt of this acid with hydrogen sulfide under pressure or with an alkali or alkaline earth hydrogen sulfide at a temperature of 90 to 110 ° C and the reaction product is converted into a salt or acid.
Die als Ausgangsprodukt verwendete Epoxypropionsäure kann nach einem nicht vorveröffentlichten eigenen Vorschlag bequem in industriellem Maßstab hergestellt werden.The epoxypropionic acid used as the starting product can after a not previously published own proposal can be easily produced on an industrial scale.
Das Verfahrensprodukt enthält keine nachweisbaren Mengen an l-Mercapto-2-hydroxypropionsäure, was mittels Infrarot- und Kernspinnresonanz-Analyse nachgewiesen wurde.The process product does not contain any detectable Amounts of l-mercapto-2-hydroxypropionic acid, as determined by infrared and nuclear magnetic resonance analysis has been proven.
Das erfindungsgemäße Verfahren wird zweckmäßig in der Weise durchgeführt, daß man ein Salz der
Epoxypropionsäure, z. B. das Natriumsalz, gegebenen-Verfahren zur Herstellung von
l-Hydroxy-2-mercaptopropionsäure
oder deren SalzenThe inventive method is advantageously carried out in such a way that a salt of epoxypropionic acid, for. B. the sodium salt, given process for the preparation of
l-hydroxy-2-mercaptopropionic acid
or their salts
Anmelder:Applicant:
Stamicarbon N. V., Heerlen (Niederlande)Stamicarbon N.V., Heerlen (Netherlands)
Vertreter:Representative:
Dr. F. Zumstein,Dr. F. Zumstein,
Dipl.-Chem. Dr. rer. nat. E. AssmannDipl.-Chem. Dr. rer. nat. E. Assmann
und Dipl.-Chem. Dr. R. Koenigsberger,and Dipl.-Chem. Dr. R. Koenigsberger,
Patentanwälte, München 2, Bräuhausstr. 4Patent Attorneys, Munich 2, Bräuhausstr. 4th
Als Erfinder benannt:Named as inventor:
Johannes Wilhelmus Gielkens, Sittard;Johannes Wilhelmus Gielkens, Sittard;
Franciscus Albertus Busschers, GeleenFranciscus Albertus Busschers, Geleen
(Niederlande)(Netherlands)
Beanspruchte Priorität:Claimed priority:
Niederlande vom 14. Februar 1963 (289 016)Netherlands of February 14, 1963 (289 016)
falls in wäßriger. Lösun'g, mit einem Überschuß an Schwefelwasserstoff in einem Autoklav während
mehrerer Stunden erhitzt.
Das folgende Beispiel erläutert die Erfindung.if in aqueous. Solution, heated with an excess of hydrogen sulfide in an autoclave for several hours.
The following example illustrates the invention.
g einer 5,5%igen wäßrigen Lösung von Natriumepoxypropional (Natriumglycidat) werden während 5 Stunden mit 160 g Schwefelwasserstoff in einem rotierenden Autoklav bei einer Temperatur von 1000C erhitzt.g of a 5.5% strength aqueous solution of sodium epoxypropional (sodium glycidate) are heated with 160 g of hydrogen sulfide in a rotating autoclave at a temperature of 100 ° C. for 5 hours.
Nach Entfernung des Überschusses an Schwefelwasserstoff wird die Reaktionsflüssigkeit angesäuert und mit Äther extrahiert.After removing the excess of hydrogen sulfide, the reaction liquid is acidified and extracted with ether.
Aus der ätherischen Lösung fällt nach Trocknung und Eindampfen l-Hydroxy-2-mercaptopropionsäure in einer Ausbeute von 85% an. Der Schmelzpunkt beträgt 62 bis 630C.After drying and evaporation of the ethereal solution, l-hydroxy-2-mercaptopropionic acid is obtained in a yield of 85%. The melting point is 62 to 63 0 C.
Die so erhaltene Säure läßt sich mit Hilfe einer Suspension von Calciumcarbonat quantitativ in das Calciumsalz überführen.The acid obtained in this way can be quantitatively converted into the with the aid of a suspension of calcium carbonate Transfer calcium salt.
609 657/419609 657/419
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL289016 | 1963-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1223368B true DE1223368B (en) | 1966-08-25 |
Family
ID=19754422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST21675A Pending DE1223368B (en) | 1963-02-14 | 1964-02-10 | Process for the preparation of 1-hydroxy-2-mercaptopropionic acid or its salts |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE643752A (en) |
| CH (1) | CH446306A (en) |
| DE (1) | DE1223368B (en) |
| GB (1) | GB1035382A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6601300A (en) * | 1966-02-01 | 1967-08-02 | Stamicarbon |
-
1964
- 1964-02-10 GB GB553264A patent/GB1035382A/en not_active Expired
- 1964-02-10 DE DEST21675A patent/DE1223368B/en active Pending
- 1964-02-11 CH CH159864A patent/CH446306A/en unknown
- 1964-02-13 BE BE643752D patent/BE643752A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1035382A (en) | 1966-07-06 |
| BE643752A (en) | 1964-08-13 |
| CH446306A (en) | 1967-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1795808C2 (en) | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine | |
| DE3703389A1 (en) | METHOD FOR PRODUCING N-ALKYL-N'-METHYL-ALKYLENE-UREAS, IN PARTICULAR N, N'-DIMETHYL-ALKYLENE-URINS | |
| DE69302848T2 (en) | Process for the preparation of guanidine derivatives | |
| DE1223368B (en) | Process for the preparation of 1-hydroxy-2-mercaptopropionic acid or its salts | |
| DE1174312B (en) | Process for the preparation of ª ‰ -hydroxyalkylsulfonium salts | |
| DE2105473A1 (en) | ||
| DE3538746C2 (en) | ||
| DE2558507C3 (en) | Process for the resolution of dJ-1-phenyl-2-amino-1-propanol | |
| EP0304685B1 (en) | Process for the preparation of n-alkylocaprolactams | |
| EP0171046B1 (en) | Process for the preparation of pantolactone | |
| DE2118493C3 (en) | Process for the preparation of aminostilbenes | |
| DE2454277A1 (en) | METHOD FOR PRODUCING MERCAPTOBENZTHIAZOLE | |
| DE1273529B (en) | Process for the preparation of diorganotin S, O-mercapto-acylates | |
| DE749643C (en) | Process for the production of unsaturated carboxamides | |
| DE3225605A1 (en) | METHOD FOR PRODUCING CYCLOPROPAN DERIVATIVES | |
| DE3833972A1 (en) | DERIVATIVES OF 2-PYRROLIDONE-5-CARBONIC ACID AND METHOD FOR THEIR PRODUCTION | |
| DE944790C (en) | Process for the preparation of thioether dicarboxylic acids or their salts | |
| DE2720911B2 (en) | Process for the production of n-hexyl carborane | |
| EP0127121A1 (en) | Process for the preparation of tetrahydro-thiophen-3-one | |
| EP0320727A2 (en) | Process for the preparation of cysteamine acid addition salts | |
| DE3546858C2 (en) | N-Methyl-1-alkylthio-2-nitro:ethenamine cpds. prepn. | |
| DE886600C (en) | Process for the preparation of aryl sulfone derivatives of thiourea | |
| DE1235940B (en) | Process for the preparation of 4-methyl mercaptophenols | |
| DE2127898B2 (en) | PROCESS FOR THE PREPARATION OF INERT-SUBSTITUTED O- AND P-AMINOTHIOPHENOLS, IF NECESSARY | |
| DE2041941A1 (en) | Sulphaguanidine prodn - from acetylsulphanilchloride and free guanidine-medicinal and intermediates |