JPH075528B2 - Method for producing carnitine hydrochloride - Google Patents
Method for producing carnitine hydrochlorideInfo
- Publication number
- JPH075528B2 JPH075528B2 JP63294595A JP29459588A JPH075528B2 JP H075528 B2 JPH075528 B2 JP H075528B2 JP 63294595 A JP63294595 A JP 63294595A JP 29459588 A JP29459588 A JP 29459588A JP H075528 B2 JPH075528 B2 JP H075528B2
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- water
- carnitine hydrochloride
- hydrochloric acid
- solvent
- reaction
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、3-メトキシカルボニル‐2-ヒドロキシ‐N,
N,N-トリメチル‐1-プロパナミウムクロライドを塩酸水
の下で加水分解させて、カルニチン（3-カルボキシ‐2-
ヒドロキシ‐N,N,N-トリメチル‐1-プロパナミウム）塩
酸塩を工業的に製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to 3-methoxycarbonyl-2-hydroxy-N,
N, N-trimethyl-1-propanium chloride was hydrolyzed under hydrochloric acid to give carnitine (3-carboxy-2-
It relates to a method for industrially producing hydroxy-N, N, N-trimethyl-1-propanamium) hydrochloride.
（従来の技術） カルニチンは、ビタミンBtとしても言われ、生体内で脂
肪酸の代謝に関係している重要な化合物である。特に、
近年心臓疾患治療剤（特開昭54-76830号参照）、過度脂
質血症治療剤（特開昭54-13409号参照）、静脈疾患治療
剤（特開昭58-88312号参照）などとして注目されてい
る。(Prior Art) Carnitine, which is also referred to as vitamin B t , is an important compound involved in the metabolism of fatty acids in vivo. In particular,
In recent years, it has attracted attention as a therapeutic agent for heart diseases (see JP-A-54-76830), an agent for treating hyperlipidemia (see JP-A-54-13409), an agent for treating venous diseases (see JP-A-58-88312), etc. Has been done.
従来カルニチン塩酸塩の製造法としては、例えば4-クロ
ロ‐3-ヒドロキシ酪酸アルキルエステルをメタノール、
エタノール等のアルコール系溶媒中でトリメチルアミン
を使用して４級アミノ化させて得られた下記構造式
（Ｉ）の3-アルコキシカルボニル‐2-ヒドロキシ‐N,N,
N-トリメチル‐1-プロパナミウムクロライドを塩酸水で
加水分解させる方法が一般的である。As a conventional method for producing carnitine hydrochloride, for example, 4-chloro-3-hydroxybutyric acid alkyl ester is methanol,
3-alkoxycarbonyl-2-hydroxy-N, N of the following structural formula (I) obtained by quaternary amination using trimethylamine in an alcohol solvent such as ethanol:
A general method is to hydrolyze N-trimethyl-1-propanium chloride with aqueous hydrochloric acid.
［（R1)3N+CH2‐CH（OH）‐CH2COOR2]C1- …（Ｉ） （式中、R1はメチル基、R2は低級アルキル基） 具体的に、この方法によってカルニチン塩酸塩を製造す
るには、上記構造式（Ｉ）のアルキルエステルに対して
５〜８倍量の塩酸水を加えて還流装置内で１〜2hr程度
沸騰させて加水分解反応を行なった後、塩酸水を蒸発乾
固し、更にエタノール−アセトン溶媒でカルニチン塩酸
塩を再結晶させたり、或いは上述のように加水分解反応
を行なわせた後、塩酸水を濃縮し、更にエタノール溶媒
で抽出し、エタノール溶媒を濃縮してからエタノール−
アセトン溶媒を加えてカルニチン塩酸塩を再結晶させる
方法が採られてきた（特開昭61-271261号、特開昭59-11
8093号等）。 [(R 1) 3 N + CH 2 -CH (OH) -CH 2 COOR 2] C1 - ... (I) ( wherein, R 1 is methyl, R 2 is a lower alkyl group) Specifically, the method In order to produce carnitine hydrochloride, a hydrolysis reaction was carried out by adding 5 to 8 times the amount of hydrochloric acid water to the alkyl ester of the above structural formula (I) and boiling in a reflux apparatus for about 1 to 2 hours. After that, the hydrochloric acid water is evaporated to dryness, and the carnitine hydrochloride is recrystallized with an ethanol-acetone solvent, or after the hydrolysis reaction is performed as described above, the hydrochloric acid water is concentrated and further extracted with an ethanol solvent. , Concentrate the ethanol solvent, and then
A method of recrystallizing carnitine hydrochloride by adding an acetone solvent has been adopted (JP-A-61-271261, JP-A-59-11).
No. 8093).
（発明が解決しようとする課題） しかし、以上の方法においては構造式（Ｉ）で表わされ
るアルキルエステルに対して５〜８倍量の塩酸水を加え
て還流装置内で１〜2hr程度沸騰させて加水分解反応を
行なった後、塩酸水を釜内で濃縮乃至蒸発乾固させるも
のであるが、この方法を工業的に行なう場合、上述のよ
うな過剰量の塩酸水を釜内で濃縮乃至蒸発乾固すること
は極めて困難であり、一方アルキルエステルに対して加
える塩酸水の量を少量にすると加水分解反応が十分に進
行せず、未反応物が残留するという難点がある。(Problems to be Solved by the Invention) However, in the above method, 5 to 8 times the amount of hydrochloric acid water is added to the alkyl ester represented by the structural formula (I), and the mixture is boiled for about 1 to 2 hours in a reflux apparatus. After the hydrolysis reaction is carried out, the hydrochloric acid water is concentrated or evaporated to dryness in the kettle. When this method is industrially carried out, the excessive amount of hydrochloric acid water as described above is concentrated or evaporated in the kettle. It is extremely difficult to evaporate to dryness. On the other hand, if the amount of hydrochloric acid water added to the alkyl ester is small, the hydrolysis reaction does not proceed sufficiently, and unreacted substances remain.
そこで、この発明においては以上の課題を解消して工業
的にカルニチン塩酸塩を製造する方法を提供することを
目的とするものである。Therefore, it is an object of the present invention to provide a method for industrially producing carnitine hydrochloride by solving the above problems.
（課題を解決するための手段） このため、この発明では3-メトキシカルボニル‐2-ヒド
ロキシ‐N,N,N-トリメチル‐1-プロパナミウムクロライ
ドを塩酸水の下で加水分解させて、カルニチン酸塩酸塩
を製造するに際し、反応系内で生成するメタノールを含
む塩酸水を順次除去しながら加水分解反応を行なわせる
カルニチン塩酸塩の製造方法を提案するものである。(Means for Solving the Problems) Therefore, according to the present invention, carnitine is hydrolyzed with 3-methoxycarbonyl-2-hydroxy-N, N, N-trimethyl-1-propanium chloride under hydrochloric acid water. The present invention proposes a method for producing carnitine hydrochloride in which a hydrolysis reaction is carried out while sequentially removing hydrochloric acid water containing methanol produced in the reaction system when producing the hydrochloride.
即ち、この発明においては上述の加水分解反応によって
生成するメタノールを順次反応系外に除去しているた
め、少量の塩酸水の量で加水分解反応を進行させること
ができる。例えば従来の1/3以下の量で反応を進行させ
ることができる。That is, in the present invention, since the methanol produced by the above-mentioned hydrolysis reaction is sequentially removed from the reaction system, the hydrolysis reaction can proceed with a small amount of hydrochloric acid water. For example, the reaction can be carried out in an amount of 1/3 or less of the conventional amount.
また、この発明においては加水分解反応中にメタノール
とともに塩酸水を除去するため、反応終了後除去する塩
酸水の量が少量で済む。例えば従来の1/3程度で済むの
である。Further, in the present invention, since hydrochloric acid water is removed together with methanol during the hydrolysis reaction, the amount of hydrochloric acid water to be removed after completion of the reaction can be small. For example, it is about 1/3 of the conventional one.
なお、反応終了後残留する塩酸水を或る程度（例えば、
７割程度）除去したところで、例えばメチルイソブチル
ケトン（以下、MIKBと略記する。）、酢酸エチル、オク
タノール、ジブチルエーテル等の水と共沸する溶媒を加
え、水抜きを続行すればカルニチン塩酸塩の結晶を溶媒
中で析出させることができる。即ち、この方法によれば
残留する塩酸水の蒸発乾固という工業的に不可能な方法
を採用しなくても、カルニチン塩酸塩の結晶を得ること
ができる。It should be noted that the hydrochloric acid water remaining after the reaction is completed to some extent (for example,
After removal, about 70%), for example, methyl isobutyl ketone (hereinafter abbreviated as MIKB), ethyl acetate, octanol, dibutyl ether and other water-azeotropic solvents are added, and if water removal is continued, carnitine hydrochloride Crystals can be precipitated in the solvent. That is, according to this method, crystals of carnitine hydrochloride can be obtained without employing the industrially impossible method of evaporating the remaining hydrochloric acid water to dryness.
この発明において原料として使用する3-メトキシカルボ
ニル‐2-ヒドロキシ‐N,N,N-トリメチル‐1-プロパナミ
ウムクロライドは、光学活性を有する4-クロロ‐3-ヒド
ロキシ酪酸メチルエステルをトリメチルアミンを使用し
て４級アミノ化した反応生成物をそのまま使用すること
ができる。3-Methoxycarbonyl-2-hydroxy-N, N, N-trimethyl-1-propanamium chloride used as a raw material in this invention is an optically active 4-chloro-3-hydroxybutyric acid methyl ester using trimethylamine. The quaternary aminated reaction product can be used as it is.
しかし、光学的に純度の高いカルニチン塩酸塩を安価に
得るためには、上述のような４級アミノ化反応によって
得られた光学活性を有する反応生成物をイソプロピルア
ルコール等の溶媒を使用して再結晶した光学純度の高い
3-メトキシカルボニル‐2-ヒドロキシ‐N,N,N-トリメチ
ル‐1-プロパナミウムクロライドを使用する必要があ
る。However, in order to inexpensively obtain optically pure carnitine hydrochloride, the optically active reaction product obtained by the quaternary amination reaction as described above is regenerated using a solvent such as isopropyl alcohol. Crystallized high optical purity
It is necessary to use 3-methoxycarbonyl-2-hydroxy-N, N, N-trimethyl-1-propanium chloride.
これは、加水分解反応によって生成したカルニチン塩酸
塩を溶媒を用いて再結晶させると、ラセミ体の結晶が先
に析出して、光学的に純度の高いカルニチン塩酸塩を収
率良く得ることができず、また光学的に純度の高い4-ク
ロロ‐3-ヒドロキシ酪酸メチルエステルを製造する方法
も存在しないからである。This is because when the carnitine hydrochloride produced by the hydrolysis reaction is recrystallized using a solvent, the racemic crystals are precipitated first, and carnitine hydrochloride of high optical purity can be obtained in good yield. In addition, there is no method for producing optically pure 4-chloro-3-hydroxybutyric acid methyl ester.
（発明の効果） 以上要するに、この発明によれば加水分解反応中に生成
するメタノールを含む塩酸水を順次除去するため、反応
進行のために必要な塩酸水の量及び反応終了後に除去す
る塩酸水の量を従来に比べて極端に減少させることがで
きる。(Effects of the Invention) In summary, according to the present invention, since hydrochloric acid water containing methanol generated during the hydrolysis reaction is sequentially removed, the amount of hydrochloric acid water necessary for the progress of the reaction and the hydrochloric acid water removed after the reaction is completed. The amount of can be extremely reduced compared to the conventional one.
更に、この発明によれば加水分解反応終了後にMIBK等の
溶媒を加えて水抜きすれば、残存する塩酸水を蒸発乾固
しなくてもカルニチン塩酸塩の結晶を容易に析出させる
ことができる。Furthermore, according to the present invention, if a solvent such as MIBK is added after the completion of the hydrolysis reaction to remove water, carnitine hydrochloride crystals can be easily precipitated without evaporating the remaining hydrochloric acid water to dryness.
したがって、この発明では工業的に適したカルニチン塩
酸塩の製造方法が提供できる。Therefore, the present invention can provide an industrially suitable method for producing carnitine hydrochloride.
（実施例） 以下、この発明の実施例を示す。(Example) Hereinafter, the Example of this invention is shown.
実施例１ 3-メトキシカルボニル‐2-ヒドロキシ‐N,N,N-トリメチ
ル‐1-プロパナミウム211gに10％HC1水356gを仕込み、6
0℃にて1hr反応させる。Example 1 3-Methoxycarbonyl-2-hydroxy-N, N, N-trimethyl-1-propanamium 211 g was charged with 356 g of 10% HC1 water.
React at 0 ° C for 1 hr.
次に減圧下約70gのメタノールを含むHC1水を減圧下釜温
60℃にて除去する。その後、反応を行なう。上記反応操
作３〜４回を繰返すことにより反応を完了させた。Next, under reduced pressure, add HC1 water containing about 70 g of methanol to the kettle under reduced pressure.
Remove at 60 ° C. Then, the reaction is performed. The reaction was completed by repeating the above reaction procedure 3 to 4 times.
上記反応操作での脱水も含めてメタノールを含むHC1水
が釜温60℃で250gになる迄、濃縮し、更に反応装置に水
抜き装置を付け、MIBKを600ml加え、釜温60℃にて減圧
下水抜きを行なった結果、徐々にカルニチン塩酸塩の結
晶が析出した。そこで、水の生成が止ったら、MIBKの溶
液を０℃に冷却し、濾過してカルニチン塩酸塩の結晶18
2gを得た。HC1 water containing methanol, including dehydration in the above reaction procedure, was concentrated to 250 g at a kettle temperature of 60 ° C, a water removal device was attached to the reactor, 600 ml of MIBK was added, and decompression was performed at a kettle temperature of 60 ° C. As a result of drainage, carnitine hydrochloride crystals were gradually precipitated. Therefore, when water formation stopped, the MIBK solution was cooled to 0 ° C. and filtered to obtain carnitine hydrochloride crystals.
2g was obtained.
なお、使用したMIBKは精製することなく、次回の結晶析
出用の溶媒として使用した。The MIBK used was used as a solvent for the next crystal precipitation without purification.
実施例２ 実施例１のMIBKの代わりに、酢酸エチルを１加え、水
抜き装置を付けて常圧下で釜温70〜80℃で水抜きを行っ
た結果、徐々にカルニチン塩酸塩の結晶が析出した。そ
こで、水の生成が止ったら、酢酸エチルの溶液を０℃に
冷却し、濾過してカルニチン塩酸塩の結晶153gを得た。Example 2 In place of MIBK of Example 1, 1 ethyl acetate was added, and water was removed at a kettle temperature of 70 to 80 ° C. under a normal pressure by attaching a water removing device, and as a result, carnitine hydrochloride crystals were gradually precipitated. did. Then, when the production of water stopped, the solution of ethyl acetate was cooled to 0 ° C. and filtered to obtain 153 g of carnitine hydrochloride crystals.
実施例３ 実施例１のMIBKの代りに、１−オクタノール600mlを加
え、水抜き装置を付けずに釜温60℃減圧下で１−オクタ
ノールと水を蒸留した。この時、留出する１−オクタノ
ールと同量の１−オクタノールを滴下ロートを通して順
次反応装置に滴下した。水の留出量が600ml程度で、徐
々にカルニチン塩酸塩の結晶が析出した。そこで、水の
生成が止ったら、１−オクタノールの溶液を室温に冷却
し、濾過してカルニチン塩酸塩の結晶145gを得た。Example 3 600 ml of 1-octanol was added in place of the MIBK of Example 1, and 1-octanol and water were distilled under a reduced pressure at a kettle temperature of 60 ° C. without a water draining device. At this time, 1-octanol in the same amount as 1-octanol distilled out was sequentially added dropwise to the reactor through the dropping funnel. When the amount of water distilled off was about 600 ml, crystals of carnitine hydrochloride gradually precipitated. Then, when the production of water stopped, the 1-octanol solution was cooled to room temperature and filtered to obtain 145 g of a carnitine hydrochloride crystal.
実施例４ 実施例１のMIBKの代りに、ジブチルエーテル600mlを加
え、水抜き装置を付けて減圧下で釜温60℃で水抜きを行
った結果、徐々にカルニチン塩酸塩の結晶が析出した。
そこで、水の生成が止ったら、ジブチルエーテルの溶液
を室温に冷却し、濾過してカルニチン塩酸塩の結晶153g
を得た。Example 4 600 ml of dibutyl ether was added in place of MIBK of Example 1, and water was drained at a kettle temperature of 60 ° C. under reduced pressure with a water draining device. As a result, crystals of carnitine hydrochloride gradually precipitated.
Then, when the water production stopped, the solution of dibutyl ether was cooled to room temperature and filtered to obtain 153 g of carnitine hydrochloride crystals.
Got
なお、比較例として反応途中で水抜きを行なわずに加水
分解反応を行なった例（比較例１）、水と共沸を試みて
結晶化を企てたが、結晶化しなかった例（比較例２〜
４）を以下に示す。In addition, as a comparative example, an example in which a hydrolysis reaction was performed without draining water during the reaction (Comparative Example 1), an azeotropic reaction with water was attempted for crystallization, but an example in which crystallization was not performed (Comparative Example 2 to
4) is shown below.
なお、下記の液体クロマトグラフィーは次のような分析
条件で行った。The following liquid chromatography was performed under the following analytical conditions.
使用機種 （ポンプ）島津LC-5A （検出器）日本分光UV-IDEC-100-IV カラム NUCLEOSIL 5C18 4.6φ×250mm 溶離液 水（1000）にトリエチルアミン（10）を加え、
リン酸にてPH3.0とする。このリン酸溶液95volにメタノ
ール5volを加え溶離液とする。Model (pump) Shimadzu LC-5A (detector) JASCO UV-IDEC-100-IV column NUCLEOSIL 5C18 4.6φ x 250mm Eluent Add triethylamine (10) to water (1000),
Adjust to pH 3.0 with phosphoric acid. Add 5 vol of methanol to 95 vol of this phosphoric acid solution to make an eluent.
流速 0.5ml/min 温度 25℃ 検出波長 UV220nm 感度 0.08×AUF リテンションタイム カルニチン塩酸塩＝5.8分 カルニチンメチルエステルハライド＝6.7分 比較例１ 3-メトキシカルボニル‐2-ヒドロキシ‐N,N,N-トリメチ
ル‐1-プロパナミウム200gに10％HC1水400gを加え、60
℃にて加水分解させる。反応の進行状況を高速液体クロ
マトグラフィー（HPLC）にて分析すると、1.5〜2.0hrで
進行するが、その後は平衡状態となり、生成物70％未反
応物30％で反応は停止した。Flow rate 0.5ml / min Temperature 25 ℃ Detection wavelength UV220nm Sensitivity 0.08 × AUF Retention time Carnitine hydrochloride = 5.8 minutes Carnitine methyl ester halide = 6.7 minutes Comparative example 1 3-methoxycarbonyl-2-hydroxy-N, N, N-trimethyl- To 1-propanium 200g, add 10% HC1 water 400g, 60
Hydrolyze at ℃. When the progress of the reaction was analyzed by high performance liquid chromatography (HPLC), it proceeded in 1.5 to 2.0 hr, but after that, an equilibrium state was reached, and the reaction stopped at 70% product and 30% unreacted product.
比較例２ 実施例１のMIKBの代りに、トルエン600mlを加え、水抜
き装置を付けて水抜きを行った結果、反応生成物は装置
内でベタベタの団子状になり、結晶化しなかった。Comparative Example 2 600 ml of toluene was added in place of MIKB of Example 1, and water was removed by attaching a water draining device. As a result, the reaction product became a sticky dumpling inside the device and was not crystallized.
比較例３ 実施例１のMIKBの代りに、イソプロピルアルコール（IP
A）5lを加え、85℃で水抜き蒸留を行ったが、残存するI
PA中では結晶の析出が見られなかった。Comparative Example 3 Instead of MIKB in Example 1, isopropyl alcohol (IP
A) 5l was added and dehydration distillation was performed at 85 ° C.
No crystal precipitation was observed in PA.
比較例４ 実施例１のMIKBの代りに、ベンゼン600mlを加え、水抜
き装置を付けて水抜きを行った結果、反応生成物は装置
内でベタベタの団子状固形物になり、結晶化しなかっ
た。Comparative Example 4 600 ml of benzene was added in place of MIKB of Example 1, and water was removed by attaching a water draining device. As a result, the reaction product became a sticky solid dumpling solid in the device and was not crystallized. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 雲林 秀徳 神奈川県茅ケ崎市中海岸１―４―39 (72)発明者 長島 弘幸 神奈川県横浜市戸塚区鳥が丘17―５ (56)参考文献 特開 昭53−63123（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hidenori Unbayashi 1-4-39 Nakakaigan, Chigasaki City, Kanagawa Prefecture (72) Inventor Hiroyuki Nagashima 17-5 Torigaoka, Totsuka-ku, Yokohama City, Kanagawa Prefecture (56) References Sho 53-63123 (JP, A)
Claims (3)
N,N-トリメチル‐1-プロパナミウムクロライドを塩酸水
の下で加水分解させて、カルニチン塩酸塩を製造するに
際し、反応系内で生成するメタノールを含む塩酸水を順
次除去しながら加水分解を行わせ、加水分解終了後、塩
酸水をカルニチン塩酸塩の結晶が析出しない程度に濃縮
し、水と共沸する溶媒を加え、更に水抜きを続行し、カ
ルニチン塩酸塩の結晶を溶媒中で析出させることを特徴
とするカルニチン塩酸塩の製造方法。1. A 3-methoxycarbonyl-2-hydroxy-N,
When N, N-trimethyl-1-propanium chloride is hydrolyzed under hydrochloric acid water to produce carnitine hydrochloride, hydrolysis is performed while sequentially removing hydrochloric acid water containing methanol generated in the reaction system. After the completion of hydrolysis, the hydrochloric acid water is concentrated to the extent that carnitine hydrochloride crystals do not precipitate, a solvent that azeotropes with water is added, and water removal is further continued to precipitate carnitine hydrochloride crystals in the solvent. A method for producing carnitine hydrochloride, which comprises:
ン、酢酸エチル、オクタノール、ジブチルエーテルより
選ばれた１種以上である特許請求の範囲第１項記載のカ
ルニチン塩酸塩の製造方法。2. The method for producing carnitine hydrochloride according to claim 1, wherein the solvent azeotropic with water is at least one selected from methyl isobutyl ketone, ethyl acetate, octanol and dibutyl ether.
ルをトリメチルアミンを４級アミノ化した反応生成物を
再結晶して得られる光学的純度の高い3-メトキシカルボ
ニル‐2-ヒドロキシ‐N,N,N-トリメチル‐1-プロパナミ
ニウムクロライドを原料とする範囲第１項記載の特許請
求の範囲第１項記載のカルニチン塩酸塩の製造方法。3. 3-Methoxycarbonyl-2-hydroxy-N, N with high optical purity obtained by recrystallizing a reaction product obtained by quaternary amination of trimethylamine with 4-chloro-3-hydroxybutyric acid methyl ester. A method for producing carnitine hydrochloride according to claim 1, wherein N, N-trimethyl-1-propanaminium chloride is used as a raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63294595A JPH075528B2 (en) | 1988-11-24 | 1988-11-24 | Method for producing carnitine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63294595A JPH075528B2 (en) | 1988-11-24 | 1988-11-24 | Method for producing carnitine hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02142759A JPH02142759A (en) | 1990-05-31 |
| JPH075528B2 true JPH075528B2 (en) | 1995-01-25 |
Family
ID=17809798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63294595A Expired - Fee Related JPH075528B2 (en) | 1988-11-24 | 1988-11-24 | Method for producing carnitine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075528B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3119430B2 (en) * | 1995-07-25 | 2000-12-18 | 大鵬薬品工業株式会社 | Hydroxyl radical scavenger |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR205840A1 (en) * | 1974-09-25 | 1976-06-07 | Lonza Ag | PROCEDURE FOR THE PREPARATION OF CARNITINE |
-
1988
- 1988-11-24 JP JP63294595A patent/JPH075528B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02142759A (en) | 1990-05-31 |
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