JP3273578B2 - Method for producing salt of ornithine with acidic amino acids or keto acids - Google Patents
Method for producing salt of ornithine with acidic amino acids or keto acidsInfo
- Publication number
- JP3273578B2 JP3273578B2 JP23447293A JP23447293A JP3273578B2 JP 3273578 B2 JP3273578 B2 JP 3273578B2 JP 23447293 A JP23447293 A JP 23447293A JP 23447293 A JP23447293 A JP 23447293A JP 3273578 B2 JP3273578 B2 JP 3273578B2
- Authority
- JP
- Japan
- Prior art keywords
- ornithine
- acid
- keto
- acidic amino
- acids
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明はオルニチンと酸性アミノ
酸類又はケト酸類との塩の製造法に関する。The present invention relates to a process for producing a salt of ornithine with an acidic amino acid or a keto acid.
【０００２】[0002]
【従来の技術】オルニチンと酸性アミノ酸類又はケト酸
類との塩は、輸液、注射液、解毒剤又は栄養剤等の配合
成分として有用であり、これらは一般的に遊離型オルニ
チン又はオルニチン塩酸塩に酸性アミノ酸類又はケト酸
類を反応させることにより製造されている。しかし、こ
れらの方法のうち遊離型オルニチンを用いる方法は、遊
離型オルニチンが不安定な物質であり、一定品質を保つ
のは難しく、市販品入手が困難であるという欠点を有
し、一方、オルニチン塩酸塩を用いる方法は、反応後に
副生する塩化物を除去することができず、満足のいく品
質のものが得られないという欠点を有していた。2. Description of the Related Art Salts of ornithine and acidic amino acids or keto acids are useful as compounding components for infusions, injections, antidote or nutrients, and these are generally used as free ornithine or ornithine hydrochloride. It is produced by reacting acidic amino acids or keto acids. However, the method using free ornithine among these methods has a disadvantage that free ornithine is an unstable substance, it is difficult to maintain a constant quality, and it is difficult to obtain a commercial product. The method using a hydrochloride has a disadvantage that chloride produced as a by-product after the reaction cannot be removed, and a product of satisfactory quality cannot be obtained.
【０００３】そこで、オルニチンと酸性アミノ酸類との
塩の製造法としては、次のような方法が報告されてい
る。Therefore, the following methods have been reported as methods for producing salts of ornithine and acidic amino acids.
【０００４】（１）オルニチン塩酸塩を強酸性イオン交
換樹脂を用いて遊離型オルニチンとし、これに酸性アミ
ノ酸を加えて塩を生成させる方法〔イギリス特許第１０
６７７４２号〕。 （２）不水溶性の有機アミン塩酸塩又は硫酸塩を形成す
る有機アミンを用いる方法〔スペイン特許第３５５５０
７号〕。 （３）オルニチン塩酸塩とベンズアルデヒドによって得
られる、Ｎ−ベンジリジンオルニチンと酸性アミノ酸か
ら合成する方法〔スペイン特許第３８０３３０号〕。 （４）アルギニンをＬ−アルギナーゼ酵素の存在下に水
溶性の媒体中で酵素的に遊離型Ｌ−オルニチンに変換
し、次いで塩形成する方法〔ドイツ特許第４０２０９８
０号〕。(1) A method of converting ornithine hydrochloride into free ornithine using a strongly acidic ion exchange resin and adding an acidic amino acid thereto to form a salt [UK Patent No. 10
67742]. (2) A method using an organic amine which forms a water-insoluble organic amine hydrochloride or sulfate [Spanish Patent No. 35550]
No. 7]. (3) A method of synthesizing from N-benzylidine ornithine and an acidic amino acid obtained by ornithine hydrochloride and benzaldehyde [Spanish Patent No. 380330]. (4) A method of enzymatically converting arginine to free L-ornithine in an aqueous medium in the presence of an L-arginase enzyme followed by salt formation [DE 402098]
No. 0].
【０００５】しかしながら、これらのオルニチンと酸性
アミノ酸類との塩の製造方法は収率が低く、操作が煩雑
で、使用原料が高価である等の問題が多く、工業的な方
法とはいい難い。例えば、（１）の方法は、収率が低
く、しかも遊離型オルニチンは熱安定性が低く強酸性イ
オン交換樹脂、濃縮等の操作において環化してβ−アミ
ノ−α−ピペリドンに変成するため、取り扱いに困難を
来し、工業的に有利な方法とはいえない。また、
（２）、（３）及び（４）の方法では有機アミン、アル
デヒド、酵素等の高価な原料を使用し、かつ操作が煩雑
であり問題が多い。[0005] However, these methods for producing salts of ornithine and acidic amino acids have many problems such as low yield, complicated operations, and expensive raw materials, and are difficult to be regarded as industrial methods. For example, in the method (1), the yield is low, and free ornithine has low thermal stability and is cyclized in an operation such as a strongly acidic ion exchange resin or concentration to be transformed into β-amino-α-piperidone. It is difficult to handle and is not an industrially advantageous method. Also,
In the methods (2), (3) and (4), expensive raw materials such as organic amines, aldehydes and enzymes are used, and the operation is complicated and there are many problems.
【０００６】[0006]
【発明が解決しようとする課題】従って、安定かつ安価
な原料を用い、工業的に有利に、高品質のオルニチンと
酸性アミノ酸類又はケト酸類との塩を高収率で製造する
方法が求められていた。Accordingly, there is a need for a method for industrially and advantageously producing high-quality salts of ornithine and acidic amino acids or keto acids in high yields using stable and inexpensive raw materials. I was
【０００７】[0007]
【課題を解決するための手段】かかる実情において、本
発明者は酸解離指数が塩酸（−８）＜アスパラギン酸
（３．６５）＜グルタミン酸（４．２５）＜酢酸（４．
７５）の順であることを考慮し、かつオルニチン酢酸塩
が酸性アミノ酸と容易に塩を生成し酢酸を放出すること
に着目し、鋭意検討を行った結果、原料として安定なオ
ルニチン酢酸塩を用い、これと酸性アミノ酸類又はケト
酸類とを反応させる方法が上記課題を解決することを見
出し、本発明を完成した。Under such circumstances, the present inventors have found that the acid dissociation index of hydrochloric acid (-8) <aspartic acid (3.65) <glutamic acid (4.25) <acetic acid (4.
75) and taking into account that ornithine acetate easily forms a salt with an acidic amino acid and releases acetic acid. As a result of intensive studies, stable ornithine acetate was used as a raw material. The present inventors have found that a method for reacting this with an acidic amino acid or a keto acid solves the above-mentioned problems, and completed the present invention.
【０００８】すなわち、本発明はオルニチン酢酸塩に酸
性アミノ酸類又はケト酸類を反応させることを特徴とす
るオルニチンと酸性アミノ酸類又はケト酸類との塩の製
造法を提供するものである。That is, the present invention provides a method for producing a salt of ornithine with an acidic amino acid or a keto acid, which comprises reacting an ornithine acetate with an acidic amino acid or a keto acid.
【０００９】本発明に用いられるオルニチン酢酸塩は、
例えばオルニチン塩酸塩を選択的に塩素イオンを吸着除
去する酢酸型の強塩基性イオン交換樹脂で処理すること
により得ることができる。また、オルニチン酢酸塩は水
和物を使用することもできる。The ornithine acetate used in the present invention is
For example, it can be obtained by treating ornithine hydrochloride with an acetic acid type strongly basic ion exchange resin that selectively adsorbs and removes chloride ions. Ornithine acetate can also be used as a hydrate.
【００１０】酸性アミノ酸類としてはアスパラギン酸、
グルタミン酸等が挙げられ、ケト酸類としてはα−ケト
イソバレリアン酸、α−ケトイソカプロン酸、α−ケト
−β−メチルバレリアン酸等が挙げられる。As acidic amino acids, aspartic acid,
Glutamic acid and the like, and keto acids include α-ketoisovaleric acid, α-ketoisocaproic acid, α-keto-β-methylvaleric acid and the like.
【００１１】本発明方法を実施するにはオルニチン酢酸
塩に、相当する酸性アミノ酸類又はケト酸類を加え、溶
解した後、減圧濃縮を行って、塩交換により生成する酢
酸を除去する。この際、オルニチンの環化物質であるβ
−アミノ−α−ピペリドンの副生を抑制するために減圧
濃縮は３０〜８０℃、好ましくは４０〜５０℃に加熱し
ながら行う。次いで、メタノール、エタノール、イソプ
ロピルアルコール等のアルコール系溶剤を加えて析出し
た結晶を濾過、減圧乾燥することにより、残留酢酸が１
００ppm以下のオルニチンと酸性アミノ酸類又はケト酸
類との塩を得ることができる。In order to carry out the method of the present invention, the corresponding acidic amino acids or keto acids are added to ornithine acetate, dissolved and concentrated under reduced pressure to remove acetic acid generated by salt exchange. At this time, β which is a cyclized substance of ornithine
The concentration under reduced pressure is carried out while heating to 30 to 80 ° C, preferably 40 to 50 ° C, in order to suppress the by-product of -amino-α-piperidone. Next, an alcohol-based solvent such as methanol, ethanol, or isopropyl alcohol was added, and the precipitated crystals were filtered and dried under reduced pressure to remove residual acetic acid.
It is possible to obtain a salt of not more than 00 ppm of ornithine with acidic amino acids or keto acids.
【００１２】[0012]
【実施例】以下に実施例を挙げて本発明を更に詳細に説
明するが、本発明はこれらによって何ら限定されるもの
ではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.
【００１３】実施例１ Ｌ−オルニチン塩酸塩３．４ｇ（２０mmol）を純水１７
mlに溶解し、強塩基性イオン交換樹脂ダイヤイオンＳＡ
１１Ａ（酢酸型）５８ml（２．５当量）で処理しＬ−オ
ルニチン酢酸塩溶液を収率９８．１％で回収した。次
に、樹脂処理溶液にＬ−アスパラギン酸２．５ｇ（０．
９５当量）を加え溶解し、４０〜５０℃で減圧濃縮し
た。残渣にイソプロピルアルコール２０mlを加え、室温
で撹拌晶析を行った。析出した結晶を濾過、減圧乾燥し
Ｌ−オルニチン・Ｌ−アスパラギン酸４．０ｇ（収率７
５．２％）を得た。Example 1 3.4 g (20 mmol) of L-ornithine hydrochloride was added to pure water 17
dissolved in water, and the strong basic ion exchange resin Diaion SA
The mixture was treated with 58 ml (2.5 equivalents) of 11A (acetic acid type) to recover an L-ornithine acetate solution with a yield of 98.1%. Next, 2.5 g of L-aspartic acid (0.
95 eq.) And dissolved, and concentrated under reduced pressure at 40-50 ° C. 20 ml of isopropyl alcohol was added to the residue, and crystallization with stirring was performed at room temperature. The precipitated crystals were filtered and dried under reduced pressure to obtain 4.0 g of L-ornithine / L-aspartic acid (yield 7).
5.2%).
【００１４】実施例２ Ｌ−オルニチン酢酸塩一水和物４．２ｇ（２０mmol）を
純水２００mlに溶解する。次に、Ｌ−アスパラギン酸
２．７ｇ（１．０当量）を加え溶解し、４０〜５０℃で
減圧濃縮を行った。残渣を活性炭処理し、イソプロピル
アルコール２０mlを加え、室温で撹拌晶析を行った。晶
析した結晶を濾過、減圧乾燥しＬ−オルニチン・Ｌ−ア
スパラギン酸５．１ｇ（収率９６．７％）を得た。Example 2 4.2 g (20 mmol) of L-ornithine acetate monohydrate are dissolved in 200 ml of pure water. Next, 2.7 g (1.0 equivalent) of L-aspartic acid was added and dissolved, and the mixture was concentrated under reduced pressure at 40 to 50 ° C. The residue was treated with activated carbon, isopropyl alcohol (20 ml) was added, and the mixture was stirred and crystallized at room temperature. The crystallized crystals were filtered and dried under reduced pressure to obtain 5.1 g (yield 96.7%) of L-ornithine / L-aspartic acid.
【００１５】実施例３ Ｌ−オルニチン酢酸塩一水和物１０．５ｇ（５０mmol）
を純水８５mlに溶解する。次に、α−ケトイソカプロン
酸６．５ｇ（１．０当量）を加え溶解、活性炭処理し、
４０〜５０℃で減圧濃縮乾固した。濃縮残渣にメタノー
ル１０mlを加え６０℃で溶解し、撹拌晶析を行った。晶
析した結晶を濾過し、メタノール１０mlで懸濁、洗浄を
行い、減圧乾燥しＬ−オルニチン・α−ケトイソカプロ
ン酸２．９ｇ（収率５６．２％）を得た。Example 3 10.5 g (50 mmol) of L-ornithine acetate monohydrate
Is dissolved in 85 ml of pure water. Next, 6.5 g (1.0 equivalent) of α-ketoisocaproic acid was added, dissolved and treated with activated carbon.
The solution was concentrated under reduced pressure at 40 to 50 ° C to dryness. 10 ml of methanol was added to the concentrated residue and dissolved at 60 ° C., followed by crystallization with stirring. The crystallized crystals were filtered, suspended and washed with 10 ml of methanol, and dried under reduced pressure to obtain 2.9 g of L-ornithine.α-ketoisocaproic acid (yield: 56.2%).
【００１６】実施例４ Ｌ−オルニチン酢酸塩一水和物７．４ｇ（３５mmol）を
純水６０mlに溶解する。次に、α−ケト−β−メチルバ
レリアン酸４．６ｇ（１．０当量）を加え溶解、活性炭
処理し、４０〜５０℃で減圧濃縮乾固した。濃縮残渣に
メタノール３０mlを加え６０℃で溶解し、撹拌晶析を行
った。晶析した結晶を濾過、減圧乾燥しＬ−オルニチン
・α−ケト−β−メチルバレリアン酸５．４ｇ（収率５
８．８％）を得た。Example 4 7.4 g (35 mmol) of L-ornithine acetate monohydrate are dissolved in 60 ml of pure water. Next, 4.6 g (1.0 equivalent) of α-keto-β-methylvaleric acid was added and dissolved, treated with activated carbon, and concentrated to dryness at 40 to 50 ° C. under reduced pressure. 30 ml of methanol was added to the concentrated residue and dissolved at 60 ° C., followed by crystallization with stirring. The crystallized crystals were filtered and dried under reduced pressure, and 5.4 g of L-ornithine / α-keto-β-methylvaleric acid was obtained (yield: 5).
8.8%).
【００１７】実施例５ Ｌ−オルニチン酢酸塩一水和物１０．５ｇ（５０mmol）
を純水８５mlに溶解する。次に、α−ケトイソバレリア
ン酸５．８ｇ（１．０当量）を加え溶解、活性炭処理
し、４０〜５０℃で減圧濃縮乾固した。濃縮残渣にメタ
ノール３７mlを加え６０℃で加温溶解し、その後撹拌晶
析を行った。晶析した結晶を減圧乾燥しＬ−オルニチン
・α−ケトイソバレリアン酸７．８ｇ（収率６２．７
％）を得た。Example 5 10.5 g (50 mmol) of L-ornithine acetate monohydrate
Is dissolved in 85 ml of pure water. Next, 5.8 g (1.0 equivalent) of α-ketoisovaleric acid was added and dissolved, treated with activated carbon, and concentrated to dryness under reduced pressure at 40 to 50 ° C. 37 ml of methanol was added to the concentrated residue and dissolved by heating at 60 ° C., followed by stirring crystallization. The crystallized crystals were dried under reduced pressure, and 7.8 g of L-ornithine / α-ketoisovaleric acid was obtained (yield: 62.7).
%).
【００１８】[0018]
【発明の効果】本発明の製造法によれば、安定かつ安価
な原料を用い、工業的に有利に、高品質のオルニチンと
酸性アミノ酸類又はケト酸類との塩を高収率で得ること
ができる。According to the production method of the present invention, it is possible to industrially and advantageously obtain a high-quality salt of ornithine and an acidic amino acid or a keto acid in a high yield by using a stable and inexpensive raw material. it can.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭46−3194（ＪＰ，Ａ) 特公 昭40−18288（ＪＰ，Ｂ１) 特公 昭40−24793（ＪＰ，Ｂ１) 特公 昭38−24890（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 229/26 C07C 227/18 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-46-3194 (JP, A) JP-B-40-18288 (JP, B1) JP-B-40-24793 (JP, B1) JP-B Showa 38- 24890 (JP, B1) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 229/26 C07C 227/18 CA (STN) REGISTRY (STN)
Claims (3)
ケト酸類を反応させることを特徴とするオルニチンと酸
性アミノ酸類又はケト酸類との塩の製造法。1. A method for producing a salt of ornithine with an acidic amino acid or keto acids, which comprises reacting ornithine acetate with an acidic amino acid or keto acids.
を選択的に塩素イオンを吸着除去する酢酸型の強塩基性
イオン交換樹脂により塩交換して得られるものである、
請求項１記載のオルニチンと酸性アミノ酸類又はケト酸
類との塩の製造法。2. The ornithine acetate is obtained by salt-exchanging ornithine hydrochloride with an acetic acid type strong basic ion exchange resin that selectively adsorbs and removes chloride ions.
A method for producing a salt of ornithine according to claim 1 with an acidic amino acid or a keto acid.
ギン酸、グルタミン酸、α−ケトイソバレリアン酸、α
−ケトイソカプロン酸又はα−ケト−β−メチルバレリ
アン酸である、請求項１記載のオルニチンと酸性アミノ
酸類又はケト酸類との塩の製造法。3. The method according to claim 1, wherein the acidic amino acids or keto acids are aspartic acid, glutamic acid, α-ketoisovaleric acid, α
The method for producing a salt of ornithine and an acidic amino acid or a keto acid according to claim 1, which is -keto isocaproic acid or α-keto-β-methyl valeric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23447293A JP3273578B2 (en) | 1993-09-21 | 1993-09-21 | Method for producing salt of ornithine with acidic amino acids or keto acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23447293A JP3273578B2 (en) | 1993-09-21 | 1993-09-21 | Method for producing salt of ornithine with acidic amino acids or keto acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0789914A JPH0789914A (en) | 1995-04-04 |
| JP3273578B2 true JP3273578B2 (en) | 2002-04-08 |
Family
ID=16971553
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| US10173964B2 (en) | 2009-04-03 | 2019-01-08 | Ocera Therapeutics, Inc. | L-ornithine phenyl acetate and methods of making thereof |
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| US11066352B2 (en) | 2017-05-11 | 2021-07-20 | Ocera Therapeutics, Inc. | Processes of making L-ornithine phenylacetate |
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| CN101880240B (en) * | 2010-06-13 | 2013-05-29 | 王明 | Ornithine and aspartate compound and novel method thereof |
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-
1993
- 1993-09-21 JP JP23447293A patent/JP3273578B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10610506B2 (en) | 2004-11-26 | 2020-04-07 | Ucl Business Ltd | Compositions comprising ornithine and phenylacetate or phenylbutyrate for treating hepatic encephalopathy |
| US10173964B2 (en) | 2009-04-03 | 2019-01-08 | Ocera Therapeutics, Inc. | L-ornithine phenyl acetate and methods of making thereof |
| US10550069B2 (en) | 2009-04-03 | 2020-02-04 | Ocera Therapeutics, Inc. | L-ornithine phenyl acetate and methods of making thereof |
| US11266620B2 (en) | 2009-06-08 | 2022-03-08 | Ucl Business Ltd | Treatment of portal hypertension and restoration of liver function using L-ornithine phenylacetate |
| KR20140053807A (en) * | 2010-10-06 | 2014-05-08 | 오세라 테라퓨틱스, 아이엔씨. | Methods of making l-ornithine phenyl acetate |
| KR101888215B1 (en) * | 2010-10-06 | 2018-09-20 | 오세라 테라퓨틱스, 아이엔씨. | Methods of making l-ornithine phenylacetate |
| US10835506B2 (en) | 2015-08-18 | 2020-11-17 | Ocera Therapeutics, Inc. | Treatment and prevention of muscle loss using L-ornithine in combination with at least one of phenylacetate and phenylbutyrate |
| US11066352B2 (en) | 2017-05-11 | 2021-07-20 | Ocera Therapeutics, Inc. | Processes of making L-ornithine phenylacetate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0789914A (en) | 1995-04-04 |
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