• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for producing α-alanine or methionine, which are used in veterinary medicine and medicine. The goal is to increase the service life of the catalyst. The production of the target products is carried out by catalytic hydration of the corresponding α-aminonitrile in an aqueous-ammonia medium in the presence of an alkali metal hydroxide (at a concentration of hydroxidion of 0.15 M) and a catalyst, a poly-N-acylpiperidine resin, obtained by polymerization of acryloylpiperidone and its subsequent crosslinking N, N - bisacryloyl piperazine at a molar ratio of 80:20 and having a capacity of 2.5 meq / g. The ammonia-water solution of α-aminonitrile is pre-diluted with a cooled α-amino acid solution that is recycled from the hydrolysis stage to a 0.1 M concentration of α-aminoamide at the hydration stage. The hydrolysis of the resulting α-aminoamide is carried out in the presence of an alkali metal hydroxide at an equimolar concentration of hydroxide ions with respect to the concentration of α-aminoamide.
    公开号:SU1500154A3
    申请号:SU853912653
    申请日:1985-06-04
    公开日:1989-08-07
    发明作者:Коммейрас Огюст；Тэллад Жак；Брюжиду Жан；Мион Луи；Сола Режин；Паскаль Робер；Ласперас Моник；Руссе Ален
    申请人:Сантр Насьональ Де Ля Решерш Сьянтифик (Снрс) (Фирма)；
    IPC主号:
    专利说明:

    O1
    Yu
    The invention relates to an improved method for producing i-amino acids, specifically ib-alanine and methionine, which are widely used in veterinary medicine as a feed additive, in medicine, as well as in the manufacture of cosmetic preparations.
    The purpose of the invention is to simplify the process by increasing the service life of the catalyst.
    Example 1. Getting l-alanine.
    A. Stage hydration (catalysis). A column (height 250 mm, diameter 6 mm) is used, which is thermostated at and containing 1.5 g of N-acyl-piperidone resin, which corresponds to 5.5 g of wetted resin. The resin is obtained by polymerization of acrmloylpiperidone and a sieve with M, K-bis-ac110ylpiparazine at a molar ratio of 80:20. The capacity of the resin is 2.5 meq / g. In it continuously pd t with speed O, 1 c. 1 / -aminopropionitrile in 5,
    ate


    s
    3,150
    solution. At the entrance to the column, this solution is diluted with an alkaline solution of "J-aminopropionic acid in the form of sodium salt, coming from the hydrolysis stage at a rate of 0.9 and containing 0.88 mol / l of amino acid, 0.166 mol / l ions) and. 5.4 mmol / l amhak. The temperature of the column is maintained at 29-30 ° C. The hydration of o-aminonitrile to noamide is controlled by NMR analysis.
    When the pH of the hydration medium is 7.6, the signal of the methyl group of the c6-aminonitrile and the signal (x.-aminoamide are quite clearly separated.
    At the exit of the column, pacTSop ui-aminopropion 1da with a concentration of 0.1 mol / l is obtained, leaving at a rate of 1. B. Stage hydrolysis. The solution with α-aminopropioamide, obtained at the hydration stage, is continuously introduced at a flow rate of 1 cm / min into the 150 cm3 hydrolysis reactor.
    To conduct hydrolysis, a solution of sodium hydroxide with a concentration of 10.9 mol / s is continuously fed at a rate of 0.01. The temperature of the reactor is maintained at 80 C.
    As a result of hydrolysis, an alanine solution is obtained containing: 0.88 M alanine (in the form of sodium salt), 0.166 M sodium hydroxide; 5.4 M ammonia.
    A portion of the resulting solution was recycled at a rate of hydration (catalysis) at a rate of 0.9 cm / min, and the rest was withdrawn from a hydrolysis reactor at a rate of 0 cm / min, the reaction mixture was treated with hydrochloric acid to create an isoelectric state of the system and the precipitated the alanine is precipitated by filtration. The yield of alanine is 96%.
    The purity of alanine is determined by thin layer chromatography on SiO, eluent propanol 2 / ammonium hydroxide and 34% (70:30): Rf 0.30.
    Example 2. Preparation of methionine.
    The procedure is the same as in the case of the preparation of alanine (Example 1). However, it is derived from 1 M ci-amino
    d
    five
    0 5
    0
    g
    0
    five
    five
    tylmercaptobronitrile, which is injected at a rate of 0.06 cm / min into a catalysis column thermostatted at 37 ° C and containing 2 g of piperidonic resin (emulsion capacity 2.4 meq / g).
    The ji-aminomethylmercaptobutyronitrile at the inlet to the catalysis column is diluted with III of the basic solution of α-amino acid and 0.15 N, sodium hydroxide solution recycled with a 0.92 cm / min. The hydrolysis reactor is maintained at.
    The yield determined by quantitative analysis of the carboxyl group of the amino acid is 95%.
    The hydration reaction is monitored by NMR, For the pH at which the signal is operated, the methyl signal of the () -aminonitrile group and the α-α-amide signal are quite clearly separated, which allows monitoring the hydration reaction, the release of methionine from the reaction the medium is carried out by precipitation with hydrochloric acid and subsequent filtration.The purity of methionine is determined by chromatography in a thin layer on SiO., Eluent: 2-propanol / / ammonium hydroxide 34% (70/30), Rf - methionine 0.45.
    Methionine is separated from the reaction medium by adding HCl acid, and the precipitated methionine is separated by filtration.
    The proposed method eliminates the disadvantage of the known method, which consists in reducing the catalytic activity of the resin due to poisoning of the terminal carbonyl groups. The method is continuous, eliminates the poisoning of the catalyst and thereby increases its service life.
    权利要求:
    Claims (1)
    [1]
    Formula isobteni
    The method of producing "-alanine or methionine by catalytic hydration of the corresponding c-amino-nitrile in an aqueous ammonia medium in the presence of an alkali metal hydroxide at a concentration of hydroxidions of 0.15M and a catalyst is a poly-N-acylpiperidine resin obtained by polymerizing acryloylpiperidone and subsequent its N, N-5 n & 3K-riloylpiperazine at a molar ratio of 80:20 and having a capacity of 2.5 meq / g followed by hydrolysis
    51500154. .6
    obtained in -aminoamide in primer, ammonia-water solution of a-amino acid of alkali mononitrile hydroxide is pre-diluted with thall at an equimolar concentration recirculated from the stage of hydrolysis of hydroxydione with respect to con-cooled u j-amino acid oi-o aminoamide, about tl i-thief to ensure 0.1 M is condensed by the fact that, with the aim of lradiation of amino-amide at the stage of hydro- expansion of the service life of the catalyst.
    类似技术:
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    同族专利:
    公开号 | 公开日
    DE3560510D1|1987-10-01|
    FR2565225B1|1986-10-17|
    CA1242451A|1988-09-27|
    US4677224A|1987-06-30|
    EP0168282B1|1987-08-26|
    FR2565225A1|1985-12-06|
    AT29130T|1987-09-15|
    BR8502656A|1986-02-12|
    JPS617240A|1986-01-13|
    EP0168282A1|1986-01-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2372797B1|1976-12-03|1979-03-30|Anvar|
    EP0067499B1|1981-03-26|1985-10-23|Mitsubishi Gas Chemical Company, Inc.|Process for producing alpha-amino acids|
    FR2519973B1|1982-01-15|1985-04-26|Centre Nat Rech Scient|FR2590896B1|1985-12-03|1988-07-22|Aec Chim Organ Biolog|PROCESS FOR THE PREPARATION OF AN AQUEOUS SOLUTION OF AN ALKALINE SALT OF METHIONINE|
    FR2633295B1|1988-06-27|1992-03-13|Centre Nat Rech Scient|PROCESS FOR THE PREPARATION OF SOLID PHASE POLYPEPTIDES|
    DE4235295A1|1992-10-20|1994-04-21|Degussa|Continuously feasible process for the preparation of methionine or methionine derivatives|
    US5856567A|1995-06-07|1999-01-05|Novus International, Inc.|Continuous hydrolysis process for preparing 2-hydroxy-4-methylthiobutanioc acid or salts thereof|
    JPH11508876A|1995-06-07|1999-08-03|ノーバスインターナショナルインコーポレイテッド|Continuous hydrolysis method for producing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof|
    FR2785609B1|1998-11-06|2000-12-15|Rhone Poulenc Nutrition Animal|PROCESS FOR THE PREPARATION OF METHIONINE|
    GB0413090D0|2004-06-11|2004-07-14|Degussa|Process for preparing amino acids using the amidocarbonylation reaction |
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8408762A|FR2565225B1|1984-06-05|1984-06-05|PROCESS FOR THE CONTINUOUS SYNTHESIS OF AN A-AMINO ACID BY CHEMICAL CATALYTIC HYDROLYSIS AND DEVICE FOR CARRYING OUT THE METHOD|
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