CH277202A - Process for the preparation of a methionine derivative. - Google Patents
Process for the preparation of a methionine derivative.Info
- Publication number
- CH277202A CH277202A CH277202DA CH277202A CH 277202 A CH277202 A CH 277202A CH 277202D A CH277202D A CH 277202DA CH 277202 A CH277202 A CH 277202A
- Authority
- CH
- Switzerland
- Prior art keywords
- methionine
- ester
- formic acid
- ammonia
- ethyl acetate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- 150000002741 methionine derivatives Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 229930182817 methionine Natural products 0.000 claims description 8
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- -1 methionine ester Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- GSYTVXOARWSQSV-BYPYZUCNSA-N L-methioninamide Chemical compound CSCC[C@H](N)C(N)=O GSYTVXOARWSQSV-BYPYZUCNSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ARJXIGOIOGJAKR-LURJTMIESA-N ethyl L-methioninate Chemical compound CCOC(=O)[C@@H](N)CCSC ARJXIGOIOGJAKR-LURJTMIESA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical class CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 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
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- 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
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
- C07C323/59—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton with acylated amino groups bound to the carbon skeleton
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 eines Methioninderivates. Das Hauptpatent betrifft ein Verfahren zur Herstellung eines Methioninderivates, nach welchem aus hlethioninestern durch Einwir kung von Ammoniak das a-Amino-y-methyl- mereapto-buttersäureamid hergestellt wird.
Man gelangt nun zu einem neuen Derivat des AAIethionins, wenn man erfindungsgemäss, ausgehend von einem Methioninester, einer seits Ammoniak und anderseits Ameisensäure zur Einwirkung bringt. Hierbei entsteht das a-Formylamino-y-metliylmereapto-buttersäure- amid, eine leicht in Wasser lösliche Verbin dung, die, aus Essigester umkristallisiert, farb lose Kristalle bildet, welche bei etwa 1200 C schmelzen.
Durch Einwirkung verseifender Mittel entsteht daraus Methionin. Vorzugs weise verwendet man als Ausgangsmaterial für das neue Verfahren Ester des Methionins mit niederen aliphatischen Alkoholen, insbe sondere den Methyl- oder den Äthylester.
Für die Behandlung mit Ammoniak eignen sich wässrige oder alkoholische Ammoniak lösungen besonders gut. Zur Behandlung mit Ameisensäure wird das betreffende Produkt vorzugsweise mit wasserfreier Ameisensäure einige Stunden erwärmt. Das nach der Erfindung hergestellte a Formylamino-y-methylmercapto-buttersäure amid soll als Arzneimittel mit den Indika tionen des Methionins benutzt werden. Es hat dem Methionin gegenüber den Vorteil einer grösseren Wasserlöslichkeit.
Das a-Formylamino-y-methylmercapto-but- tersäureamid hat die Formel
EMI0001.0023
Es ist eine in Wasser leicht lösliche Ver bindung, die aus Essigester in farblosen, der ben Kristallen auskristallisiert. Eine wässrige Lösung der Konzentration 10 weist ein pn von 5,5 auf.
<I>Beispiele:</I> 1. d,1-Methionin wird zur Überführung in das Methylesterchlorhydrat mit 3 Volum- teilen Methylalkohol, in dem 1,5 Mol Chlor wasserstoff gelöst sind, 2 Stunden am Rück fluss gekocht. Der Rückstand der im Vakuum eingedampften Lösung wird in 5 Volumteilen Chloroform aufgenommen, und diese Lösung unter Kühlung so lange mit Ammoniakgas be handelt, als noch Ammoniumchlorid aus der Lösung ausfällt. Das Ammonchlorid wird ab gesaugt und mit Chloroform ausgewaschen. Filtrat und Waschlösungsmittel werden ver einigt und im Vakuum eingedampft.
Der Rückstand wird in 5 Volumteilen Methanol gelöst und diese Lösung unter Kühlung mit gasförmigem Ammoniak gesättigt. Nach ein tägigem Stehen wird die Lösung im Vakuum eingedampft. Es hinterbleibt d,1-Methionin- amid, das nach dem Umkristallisieren aus Benzol bei<B>520</B> schmilzt. Zur Weiterverarbei tung kann auch das Rohprodukt verwendet werden. 15 g des so hergestellten Methioninamids werden mit 45g wasserfreier Ameisensäure 3 Stunden auf dem Dampfbad erwärmt. Der Rückstand der im Vakuum eingedampften Lösung wird nochmals mit 30 g wasserfreier Ameisensäure 3 Stunden erwärmt.
Schliesslich wird im Vakuum eingedampft und der Rück stand aus Essigester umkristallisiert, wobei das a-Formylamino-y-methylmercapto-butter- säureamid in farblosen, derben Kristallen vom Schmelzpunkt 1200 erhalten wird.
2. Durch Übergiessen von Methioninäthyl- ester-chlorhydrat mit 25 o/oigem wässrigem Ammoniak scheidet man den freien Äthylester des d,1-ll-Tethionins als farbloses Öl vom Siede punkt<B>860</B> C bei 0,6 mm Quecksilberdruck ab. Er wird durch 3 Tage lang fortgesetztes Be handeln mit 25 o/oigem wässrigem Ammoniak in Methioninamid übergeführt.
Das freie Methioninamid bildet farblose Kristalle, die bei<B>520</B> C schmelzen und die sich sehr leicht mit alkalischer Reaktion in Wasser auflösen. Durch Versetzen mit 1 Mol Eisessig in metha- nolischer Lösung stellt. man daraus das, Acetat her, das aus Essigester umkristallisiert werden kann. Es bildet farblose Blättchen, die bei <B>1570</B> C schmelzen.
10 g des so hergestellten Methioninamid- acetats oder des analog mit Ameisensäure her gestellten Methioninamid-formiats werden mit 100 g wasserfreier Ameisensäure 2 Stunden am Rüekfluss gekocht. Die Lösung wird im Vakuum eingedampft. Der zum überwiegen den Teil kristallisierte Rückstand wird abge saugt und aus Essigester umkristallisiert. Das resultierende a-Formylamino-y-methylmer- capto-buttersäureamid hat. die in Beispiel 1 angegebenen. Eigenschaften.
3. 142g Methioninäthylester werden mit 220 cms wasserfreier Ameisensäure 3 Stun den auf dem Dampfbad erwärmt. Die Lösung wird im Vakuum eingedampft und der Rüek- stand mit 142 cm3 wasserfreier Ameisensäure weitere 3 Stunden auf dem Dampfbad er wärmt. Sehliesslich wird im Vakuum einge dampft, der Rückstand in 1 Liter Methanol aufgenommen und unter Kühlung mit Eis wasser mit gasförmigem Ammoniak gesättigt. Nach 24 Stunden wird im Vakuum einge dampft und der Rückstand, ein braunes Öl, in 250 em3 heissem Essigester gelöst.
Nach dem Erkalten wird das Kristallisat isoliert und durch Umkristallisieren aus Essigester gerei nigt. Man erhält a-Formy iamino-r-methylmer- capto-buttersäureamid mit den in Beispiel 1 angegebenen Eigenschaften.
Process for the preparation of a methionine derivative. The main patent relates to a process for the production of a methionine derivative, according to which the α-amino-γ-methyl-mereapto-butyric acid amide is produced from halethionine esters by the action of ammonia.
A new derivative of ethionine is now obtained if, according to the invention, starting from a methionine ester, ammonia on the one hand and formic acid on the other hand are brought into action. This produces the α-formylamino-y-methylmereapto-butyric acid amide, a compound which is easily soluble in water and which, when recrystallized from ethyl acetate, forms colorless crystals which melt at around 1200 ° C.
Methionine is formed from it through the action of saponifying agents. Preference is used as the starting material for the new process esters of methionine with lower aliphatic alcohols, in particular the special methyl or ethyl ester.
Aqueous or alcoholic ammonia solutions are particularly suitable for treatment with ammonia. For treatment with formic acid, the product in question is preferably heated for a few hours with anhydrous formic acid. The a formylamino-y-methylmercapto-butyric acid amide produced according to the invention is to be used as a medicament with the indica functions of methionine. Compared to methionine, it has the advantage of greater water solubility.
The α-formylamino-γ-methylmercapto-but- tersäureamid has the formula
EMI0001.0023
It is a compound that is easily soluble in water and crystallizes from ethyl acetate to form colorless crystals. An aqueous solution of concentration 10 has a pn of 5.5.
<I> Examples: </I> 1. d, 1-methionine is refluxed for 2 hours with 3 parts by volume of methyl alcohol in which 1.5 mol of hydrogen chloride are dissolved to convert it into the methyl ester chlorohydrate. The residue of the solution evaporated in vacuo is taken up in 5 parts by volume of chloroform, and this solution is treated with ammonia gas with cooling as long as ammonium chloride still precipitates from the solution. The ammonium chloride is sucked off and washed out with chloroform. The filtrate and washing solvent are combined and evaporated in vacuo.
The residue is dissolved in 5 parts by volume of methanol and this solution is saturated with gaseous ammonia while cooling. After standing for a day, the solution is evaporated in vacuo. What remains is d, 1-methionine amide which, after recrystallization from benzene, melts at <B> 520 </B>. The raw product can also be used for further processing. 15 g of the methionine amide thus produced are heated with 45 g of anhydrous formic acid on the steam bath for 3 hours. The residue of the solution evaporated in vacuo is heated again for 3 hours with 30 g of anhydrous formic acid.
Finally, it is evaporated in vacuo and the residue is recrystallized from ethyl acetate, the α-formylamino-γ-methylmercapto-butyric acid amide in colorless, coarse crystals with a melting point of 1200 being obtained.
2. By pouring methionine ethyl ester chlorohydrate with 25% aqueous ammonia, the free ethyl ester of d, 1-ll-tethionine is separated as a colorless oil with a boiling point <B> 860 </B> C at 0.6 mm Mercury pressure. It is converted into methionine amide by treatment with 25% aqueous ammonia for 3 days.
The free methionine amide forms colorless crystals which melt at <B> 520 </B> C and which dissolve very easily in water with an alkaline reaction. By adding 1 mol of glacial acetic acid in methanol solution. from it the acetate, which can be recrystallized from ethyl acetate. It forms colorless leaflets that melt at <B> 1570 </B> C.
10 g of the methionine amide acetate prepared in this way or of the methionine amide formate prepared analogously with formic acid are refluxed with 100 g of anhydrous formic acid for 2 hours. The solution is evaporated in vacuo. The predominantly crystallized residue is filtered off with suction and recrystallized from ethyl acetate. The resulting a-formylamino-y-methylmer-capto-butyric acid amide has. those given in Example 1. Characteristics.
3. 142 g of methionine ethyl ester are heated on the steam bath for 3 hours with 220 cms of anhydrous formic acid. The solution is evaporated in vacuo and the residue is warmed for a further 3 hours on the steam bath with 142 cm3 of anhydrous formic acid. Sehliesslich is evaporated in a vacuum, the residue is taken up in 1 liter of methanol and saturated with ice water with gaseous ammonia while cooling with ice. After 24 hours, it is evaporated in vacuo and the residue, a brown oil, is dissolved in 250 cubic meters of hot ethyl acetate.
After cooling, the crystals are isolated and cleaned by recrystallization from ethyl acetate. A-Formy iamino-r-methylmer-capto-butyric acid amide with the properties given in Example 1 is obtained.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH273549 | 1949-02-14 | ||
| CH277202T | 1949-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH277202A true CH277202A (en) | 1951-08-15 |
Family
ID=25691279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH277202D CH277202A (en) | 1949-02-14 | 1949-02-14 | Process for the preparation of a methionine derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH277202A (en) |
-
1949
- 1949-02-14 CH CH277202D patent/CH277202A/en unknown
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