DE830049C - Process for the preparation of d, 1-valine - Google Patents

Process for the preparation of d, 1-valine

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Publication number
DE830049C
DE830049C DEM119A DEM0000119A DE830049C DE 830049 C DE830049 C DE 830049C DE M119 A DEM119 A DE M119A DE M0000119 A DEM0000119 A DE M0000119A DE 830049 C DE830049 C DE 830049C
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DE
Germany
Prior art keywords
valine
nitro
preparation
ester
acid ester
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
DEM119A
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German (de)
Inventor
Dr Oskar Sues
Werner Schaefer
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.)
Kalle GmbH and Co KG
Original Assignee
Kalle GmbH and Co KG
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 Kalle GmbH and Co KG filed Critical Kalle GmbH and Co KG
Priority to DEM119A priority Critical patent/DE830049C/en
Application granted granted Critical
Publication of DE830049C publication Critical patent/DE830049C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/50—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/04—Alpha- or beta- amino acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von d,1-Valin Nach den bisher bekannten Verfahren wird Valiti (x-.lminois@@@aleriansät»-ej aus x-tironiisovaleriaiisäure durch Umsetzung mit Ammoniak oder aus Iso>1>utyraldelivd nach der Streckerschen Aminosäuresynthese oder aus Isopropylbromid und Acetaminomalonester dargestellt. Diese Verfahren sind zum Teil umständlich und gehen von verhältnismäßig schwierig herzustellenden Ausgangsstoffen aus.Process for the preparation of d, 1-valine According to the previously known Process becomes Valiti (x-.lminois @@@ aleriansät »-ej from x-tironiisovaleriaiicäure by reaction with ammonia or from Iso> 1> utyraldelivd according to the Strecker Amino acid synthesis or from isopropyl bromide and acetaminomalone ester. Some of these procedures are cumbersome and relatively difficult raw materials to be produced.

Es ist nun gefunden worden, daß d, 1-Valin in guter Ausbeute dadurch hergestellt wird, daß man a-Nitro-ß, ß-diniethylacrylsäureester mit alkoholischem Kali in die ß-Form des Nitroesters überführt und diese in wäßriger Lösung in Gegenwart von hochwirksamen Nickelkatalysatoren mit Wasserstoff unter Druck behandelt.It has now been found that d, 1-valine in good yield thereby is prepared that one a-nitro-ß, ß-diniethylacryläureester with alcoholic Potash converted into the ß-form of the nitroester and this in aqueous solution in the presence treated with hydrogen under pressure by highly effective nickel catalysts.

Die Reduktion der ß-Form des a-Nitroesters, die nach den Angaben von Bo u ve au 1 t und W ahl in Blt. soc. chim 35 (3) Seite Bot aus a-Nitro-ß, ß-dimethylacrylsäureester hergestellt werden kann, geht bei Verwendung eines Hochleistungsnickelkontakts, z. B. Raneynickel, bereits bei Zimmertemperatur vonstatten. Man muß diesen Umweg über die ß-Form des a-Nitroesters wählen, weil die direkte Reduktion des a-Nitro-ß, ß-dimethylacrylsäureesters mit Raneynickel nur zum a-Amino-ß, ß-dimethylacrylsäureester führt. Die weitere Hydrierung der Doppelbindung dieses ungesättigten a-Aminoesters zum Valinester gelingt nicht, in L"hereinstimmung mit der bekannten Tatsache, daß an Äthylene mit der Gruppierung Wasserstoffanlagerung nur äußerst schwer erfolgt (S c hr ö t e r : Methoden der präp. organ. Chemie, Seite 93; Verl. Chemie, Berlin). Durch überführung des a-Nitro-ß, ß-dimethylacrylsäureesters in seine ß-Form mittels alkoholischem Kali wird eine Verlagerung der Doppelbindung in die ß-y-Stellung erzielt, die sich unter den genannten Bedingungen leicht hydrieren läßt. Man erhält das Kaliumsalz des a-Nitroisobutylencarbonsäureesters, das sich dann durch Behandlung mit Wasserstoff unter den Bedingungen nach der vorliegenden Erfindung bei .gleichzeitiger Verseifung der Estergruppe durch das während der Reduktion frei werdende Alkali in etwa 5o%iger Ausbeute in d, 1-Valin überführen läßt.The reduction of the ß-form of the a-nitroester, which according to the information from Bo u ve au 1 t and W ahl in Blt. soc. chim 35 (3) side bot can be produced from α-nitro-ß, ß-dimethylacrylic acid ester, is possible when using a high-performance nickel contact, e.g. B. Raneynickel, already at room temperature. You have to choose this detour via the ß-form of the a-nitro ester, because the direct reduction of the a-nitro-ß, ß-dimethylacrylic acid ester with Raney nickel only leads to the a-amino-ß, ß-dimethylacrylic acid ester. The further hydrogenation of the double bond of this unsaturated α-amino ester to the valine ester does not succeed, in agreement with the known fact that there are ethylene with the group Hydrogen addition is extremely difficult (S chröter: Methods of preparative organic chemistry, page 93; Verl. Chemie, Berlin). By converting the a-nitro-ß, ß-dimethylacrylic acid ester into its ß-form by means of alcoholic potash, a shift of the double bond into the ß-y position is achieved, which can easily be hydrogenated under the conditions mentioned. The potassium salt of the a-nitroisobutylenecarboxylic acid ester is obtained, which is then converted into d, 1-valine in about 50% yield by treatment with hydrogen under the conditions according to the present invention with simultaneous saponification of the ester group by the alkali liberated during the reduction leaves.

a-Aminoisovaleriansäure (Valin) hat praktische Bedeutung für die Heilmittelsynthese. Seine Herstellung nach dem Verfahren der vorliegenden Erfindung ist als wertvolle Bereicherung der Technik anzusehen. Beispiel 5o g Kalium-a-Nitroisobutylencarbonsäureäthylester mit der Formel werden in Zoo ccm Wasser gelöst und mit 25 g Raneynickel in einem 5oo-ml-Rührautoklaven bei einem Wasserstoffdruck von 5o bis 8o Atmosphären bei Zimmertemperatur reduziert. Nach etwa 2o Stunden kommt die Wasserstoffaufnahme zum Stillstand. Nach Absaugen des Kontaktes wird das Filtrat mit konzentrierter Salzsäure kongosauer gestellt und die Lösung im Vakuum bei etwa 5o bis 6o° bis zur Trockne eingedampft. Der Rückstand wird mit absolutem Alkohol warm digeriert und der alkoholische Auszug nach der Filtration mit Pyridin alkalisch gestellt. Nach kurzem Reiben kristallisiert das freie d, 1-Valin aus. Das Rohprodukt wird durch Lösen in wenig Wasser und Fällen mit Alkohol umkristallisiert. Ausbeute: 13 g entsprechend 47 % der Theorie. Fp. = 296°.α-Aminoisovaleric acid (valine) is of practical importance for the synthesis of medicinal products. Its preparation by the process of the present invention is to be regarded as a valuable addition to the art. Example 50 g of ethyl potassium a-nitroisobutylenecarboxylate with the formula are dissolved in zoo cc of water and reduced with 25 g of Raney nickel in a 500 ml stirred autoclave at a hydrogen pressure of 50 to 80 atmospheres at room temperature. After about 20 hours the uptake of hydrogen comes to a standstill. After the contact has been suctioned off, the filtrate is rendered Congo acidic with concentrated hydrochloric acid and the solution is evaporated to dryness in vacuo at about 50 to 60 °. The residue is digested warm with absolute alcohol and the alcoholic extract is made alkaline with pyridine after filtration. After brief rubbing, the free d, 1-valine crystallizes out. The crude product is recrystallized by dissolving it in a little water and precipitating it with alcohol. Yield: 13 g corresponding to 47% of theory. Mp = 296 °.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von d, 1-Valin, dadurch gekennzeichnet, daß man a-Nitro-ß, ß-dimethylacrylsäureestermit alkoholischemKali in die ß-Form des Nitroesters überführt und diese in wäßriger Lösung in Gegenwart von hochwirksamen N ickelkatalysatoren.mit Wasserstoff unter Druck behandelt. PATENT CLAIM: A process for the production of d, 1-valine, characterized in that a-nitro-ß, ß-dimethylacrylic acid ester is converted into the ß-form of the nitroester with alcoholic potassium and this in an aqueous solution in the presence of highly effective nickel catalysts with hydrogen Pressure treated.
DEM119A 1949-10-18 1949-10-18 Process for the preparation of d, 1-valine Expired DE830049C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEM119A DE830049C (en) 1949-10-18 1949-10-18 Process for the preparation of d, 1-valine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM119A DE830049C (en) 1949-10-18 1949-10-18 Process for the preparation of d, 1-valine

Publications (1)

Publication Number Publication Date
DE830049C true DE830049C (en) 1952-01-31

Family

ID=7290558

Family Applications (1)

Application Number Title Priority Date Filing Date
DEM119A Expired DE830049C (en) 1949-10-18 1949-10-18 Process for the preparation of d, 1-valine

Country Status (1)

Country Link
DE (1) DE830049C (en)

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