JPH0680029B2 - Method for producing phenylpyruvic acid - Google Patents
Method for producing phenylpyruvic acidInfo
- Publication number
- JPH0680029B2 JPH0680029B2 JP60033193A JP3319385A JPH0680029B2 JP H0680029 B2 JPH0680029 B2 JP H0680029B2 JP 60033193 A JP60033193 A JP 60033193A JP 3319385 A JP3319385 A JP 3319385A JP H0680029 B2 JPH0680029 B2 JP H0680029B2
- Authority
- JP
- Japan
- Prior art keywords
- phenylpyruvic acid
- acid
- reaction
- water
- alkaline earth
- 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 - Lifetime
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、コバルトカルボニル化合物触媒の存在下、塩
化ベンジルと一酸化炭素及びアルカリ土類金属塩基とを
反応させる際に、溶媒として水と水に難溶性の溶媒を存
在させ反応させる事を特徴とするフェニルピルビン酸の
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to the use of water as a solvent when reacting benzyl chloride with carbon monoxide and an alkaline earth metal base in the presence of a cobalt carbonyl compound catalyst. The present invention relates to a method for producing phenylpyruvic acid, which comprises reacting a water-insoluble solvent in the presence thereof.
フェニルピルビン酸は、例えば甘味剤原料であるフェニ
ルアラニン等の製造原料として重要な出発物質である。Phenylpyruvic acid is an important starting material as a raw material for producing phenylalanine, which is a raw material for sweeteners, for example.
（ロ）従来の技術 塩化ベンジルと一酸化炭素との反応によるフェニルピル
ビン酸の製造方法は公知であり、例えば特公昭56−1858
7号公報等が挙げられる。(B) Prior Art A method for producing phenylpyruvic acid by the reaction of benzyl chloride and carbon monoxide is known, and for example, Japanese Patent Publication No. Sho 56-1858.
Publication No. 7 and the like can be mentioned.
特公昭56−18587号公報では、触媒として金属カルボニ
ル化合物、特にコバルトカルボニル化合物を使用して、
アルカリ土類金属塩基の存在下、塩化ベンジルと一酸化
炭素とを水／アルコール混合溶媒中で反応させフェニル
ピルビン酸を製造する方法が提案されている。In Japanese Examined Patent Publication No. 56-18587, a metal carbonyl compound, particularly a cobalt carbonyl compound is used as a catalyst,
A method has been proposed for producing phenylpyruvic acid by reacting benzyl chloride and carbon monoxide in a water / alcohol mixed solvent in the presence of an alkaline earth metal base.
（ハ）発明が解決しようとする問題点 しかし、上述の特公昭56−18587号公報をはじめとする
既存のフェニルピルビン酸製造方法では、フェニルピル
ビン酸は反応中に固体として析出するフェニルピルビン
酸のアルカリ金属塩又はアルカリ土類金属塩を濾過後酸
処理する事により簡単に得る事が出来るが、副生フェニ
ル酢酸のアルカリ金属塩又はアルカリ土類金属塩とコバ
ルトカルボニル触媒が反応濾液中に溶解しており、これ
ら副生フェニル酢酸アルカリ金属塩又はアルカリ土類金
属塩とコバルトカルボニル触媒の相互分離並びにコバル
トカルボニル触媒の再生には煩雑な工程を必要とする。(C) Problems to be Solved by the Invention However, in the existing methods for producing phenylpyruvic acid, including the above-mentioned Japanese Patent Publication No. 56-18587, phenylpyruvic acid is a solid of phenylpyruvic acid that precipitates during the reaction. It can be easily obtained by filtering the alkali metal salt or alkaline earth metal salt and then acid-treating, but the by-product phenylacetic acid alkali metal salt or alkaline earth metal salt and the cobalt carbonyl catalyst are dissolved in the reaction filtrate. Therefore, a complicated process is required for the mutual separation of the by-produced alkali metal salt of phenylacetic acid or alkaline earth metal salt and the cobalt carbonyl catalyst and the regeneration of the cobalt carbonyl catalyst.
本発明者らは、これらの欠点を改良すべく鋭意検討した
結果本発明を完成したものである。The present inventors have completed the present invention as a result of extensive studies to improve these drawbacks.
（ニ）問題点を解決するための手段 本発明は、コバルトカルボニル化合物触媒の存在下、塩
化ベンジルと一酸化炭素及びアルカリ土類金属塩基とを
反応させる際に、溶媒として水と水に難溶性の溶媒を存
在させ反応させる事を特徴とするフェニルピルビン酸の
製造方法に関するものである。(D) Means for Solving the Problems The present invention provides a method of reacting benzyl chloride with carbon monoxide and an alkaline earth metal base in the presence of a cobalt carbonyl compound catalyst, which is poorly soluble in water and water as a solvent. The present invention relates to a method for producing phenylpyruvic acid, which comprises reacting in the presence of the solvent.
本発明における水に難溶性の溶媒としては、ベンゼン、
トルエン等の芳香族炭化水素類、ヘキサン、ヘプタン等
の脂肪族炭化水素類、ジエチルエーテル、ジイソプロピ
ルエーテル、ジフェニルエーテル等の脂肪族及び芳香族
エーテル類、メチルイソブチルケトン、アセトフェノ
ン、ジイソプロピルケトン、メチルイソプロピルケト
ン、ジブチルケトン、ジイソブチルケトン、シクロペン
タノン等の脂肪族及び芳香族ケトン類が選ばれ、特にメ
チルイソブチルケトン、アセトフェノン等のケトン類が
好ましい。As the poorly water-soluble solvent in the present invention, benzene,
Aromatic hydrocarbons such as toluene, hexane, aliphatic hydrocarbons such as heptane, diethyl ether, diisopropyl ether, aliphatic and aromatic ethers such as diphenyl ether, methyl isobutyl ketone, acetophenone, diisopropyl ketone, methyl isopropyl ketone, Aliphatic and aromatic ketones such as dibutyl ketone, diisobutyl ketone and cyclopentanone are selected, and ketones such as methyl isobutyl ketone and acetophenone are particularly preferable.
反応溶媒中の塩化ベンジルの濃度は特に制限はないが、
水に難溶性の溶媒に対して一般に１〜50重量％使用され
る。The concentration of benzyl chloride in the reaction solvent is not particularly limited,
It is generally used in an amount of 1 to 50% by weight based on a water-insoluble solvent.
水の量は、一般に水に難溶性の溶媒に対し10〜200重量
％使用される。The amount of water is generally 10 to 200% by weight based on the solvent which is poorly soluble in water.
本発明で使用されるアルカリ土類金属塩基は、一般にア
ルカリ土類金属水酸化物、アルカリ土類金属酸化物及び
アルカリ土類金属炭酸塩から選ばれるが、特にアルカリ
土類金属水酸化物が使用され、なかでも水酸化カルシウ
ムが好ましい。The alkaline earth metal base used in the present invention is generally selected from alkaline earth metal hydroxides, alkaline earth metal oxides and alkaline earth metal carbonates, but particularly alkaline earth metal hydroxides are used. Among them, calcium hydroxide is preferable.
アルカリ土類金属塩基の使用量は、一般に塩化ベンジル
１モル当たり少なくとも１モル使用するする必要があ
り、塩化ベンジル１モル当たり少なくとも1.1〜2.0モル
の使用が好ましい。The amount of alkaline earth metal base used generally needs to be at least 1 mol per 1 mol of benzyl chloride, and is preferably 1.1 to 2.0 mol per 1 mol of benzyl chloride.
触媒としては、コバルトカルボニル化合物、特にジコバ
ルトオクタカルボニルが好ましい。As the catalyst, a cobalt carbonyl compound, especially dicobalt octacarbonyl is preferable.
触媒は、コバルトカルボニル化合物／塩化ベンジル（モ
ル比）として一般に1/1〜1/1000の範囲で使用される
が、1/30〜1/200の範囲が特に好ましい。The catalyst is generally used in the range of 1/1 to 1/1000 as cobalt carbonyl compound / benzyl chloride (molar ratio), but the range of 1/30 to 1/200 is particularly preferable.
一酸化炭素は、高純度である必要はなく水性ガス等も使
用出来る。一酸化炭素圧力は、一般に0.5〜200kg/cm2の
範囲が採用される。Carbon monoxide does not need to be highly pure, and water gas or the like can be used. The carbon monoxide pressure is generally in the range of 0.5 to 200 kg / cm 2 .
反応温度は、20〜150℃が好ましくは40〜100℃が良い。The reaction temperature is preferably 20 to 150 ° C, preferably 40 to 100 ° C.
一般に、反応は一酸化炭素の吸収が停止するまで行い、
反応溶液は目的物であるフェニルピルビン酸、副生物で
あるフェニル酢酸及びコバルトカルボニル触媒を回収す
る為に次のように処理される。Generally, the reaction is run until the absorption of carbon monoxide is stopped,
The reaction solution is treated as follows in order to recover the target product phenylpyruvic acid, the by-products phenylacetic acid and the cobalt carbonyl catalyst.
即ち、反応溶液は濾過する事により、反応中に固体とし
て析出したフェニルピルビン酸のアルカリ土類金属塩よ
りなる固体部分、フェニル酢酸のアルカリ土類金属塩を
含有する水層部分及びコバルトカルボニル触媒を含有す
る水に難溶性の溶媒層部分に分離する事が出来る。That is, by filtering the reaction solution, a solid portion consisting of an alkaline earth metal salt of phenylpyruvic acid precipitated as a solid during the reaction, an aqueous layer portion containing an alkaline earth metal salt of phenylacetic acid, and a cobalt carbonyl catalyst were obtained. It is possible to separate into a solvent layer portion which is hardly soluble in the contained water.
続いて、濾過操作により分取されたフェニルピルビン酸
のアルカリ土類金属塩は、鉱酸水溶液、例えば希塩酸水
溶液で酸性とし、得られた水溶液を適当な有機溶媒、例
えばジエチルエーテル等で抽出後、有機溶媒を除去する
事によりフェニルピルビン酸を得る事が出来る。Subsequently, the alkaline earth metal salt of phenylpyruvic acid collected by filtration is acidified with a mineral acid aqueous solution, for example, dilute hydrochloric acid aqueous solution, and the obtained aqueous solution is extracted with a suitable organic solvent, such as diethyl ether, Phenylpyruvic acid can be obtained by removing the organic solvent.
同様に、フェニル酢酸のアルカリ土類金属塩を有する水
層部分は、鉱酸水溶液、例えば希塩酸水溶液で酸性と
し、得られた水溶液を適当な有機溶媒、例えばジエチル
エーテル等で抽出後、有機溶媒を除去する事により副生
フェニル酢酸を回収する事が出来る。Similarly, the aqueous layer portion having an alkaline earth metal salt of phenylacetic acid is made acidic with a mineral acid aqueous solution, for example, dilute hydrochloric acid aqueous solution, and the obtained aqueous solution is extracted with a suitable organic solvent such as diethyl ether, and then the organic solvent is added. By removing it, the by-product phenylacetic acid can be recovered.
又、コバルトカルボニル触媒を含有する水に難溶性の溶
媒層部分は何等処理を行う事なくそのまま反応系にリサ
イクルし、再使用する事が可能である。Further, the solvent layer portion containing a cobalt carbonyl catalyst, which is poorly soluble in water, can be recycled and reused as it is in the reaction system without any treatment.
（ホ）発明の効果 本発明によれば、フェニルピルビン酸収率が高く、副性
フェニル酢酸のアルカリ土類金属塩とコバルトカルボニ
ル触媒の相互分離が容易で且つコバルトカルボニル触媒
はそのまま反応系にリサイクルして再使用する事が可能
であり、従って、経済的にフェニルピルビン酸を製造す
る事が出来る。(E) Effect of the Invention According to the present invention, the yield of phenylpyruvic acid is high, the secondary alkaline earth metal salt of phenylacetic acid and the cobalt carbonyl catalyst are easily separated from each other, and the cobalt carbonyl catalyst is recycled as it is to the reaction system. Phenylpyruvic acid can be economically produced.
以下に本発明を実施例を挙げて詳細に説明するが、本発
明はこれらに限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
（ヘ）実施例 実施例１ 300mlのステンレス製オートクレーブに、メチルイソブ
チルメトン75ml、水75ml、水酸化カルシウム18.6g（0.2
51モル）、塩化ベンジル15.4g（0.122モル）、及びコバ
ルトオクタカルボニル1.2g（0.0035モル）を仕込んだ。(F) Example 1 In a 300 ml stainless steel autoclave, 75 ml of methyl isobutyl metone, 75 ml of water, 18.6 g of calcium hydroxide (0.2
51 mol), benzyl chloride 15.4 g (0.122 mol), and cobalt octacarbonyl 1.2 g (0.0035 mol) were charged.
オートクレーブ内を一酸化炭素で洗浄後、一酸化炭素圧
力50kg/cm2とし撹拌しながら昇温した。一酸化炭素圧力
50kg/cm2、温度70℃で一酸化炭素の吸収が停止するまで
６時間反応を行った。反応後、反応混合物は一酸化炭素
圧力を利用してオートクレーブから加圧濾過器を介して
固体と有機層及び水層に分離した。After washing the inside of the autoclave with carbon monoxide, the carbon monoxide pressure was set to 50 kg / cm 2 and the temperature was raised with stirring. Carbon monoxide pressure
The reaction was carried out at 50 kg / cm 2 and a temperature of 70 ° C. for 6 hours until the absorption of carbon monoxide stopped. After the reaction, the reaction mixture was separated into a solid, an organic layer and an aqueous layer from the autoclave using a pressure of carbon monoxide through a pressure filter.
得られた固体を500mlのフラスコに移し、10％塩酸水溶
液270mlとジエチルエーテル150mlを加え固体が完全に溶
解するまで撹拌した。ジエチルエーテル層を分離後、水
層を更にジエチルエーテル100mlで２回処理した。これ
らジエチルエーテル層を併せ、水洗後硫酸ナトリウムで
乾燥した。乾燥後ジエチルエーテルを留去するとフェニ
ルピルビン酸16.0gが得られ、収率は80.2％であった。The obtained solid was transferred to a 500 ml flask, 270 ml of 10% hydrochloric acid aqueous solution and 150 ml of diethyl ether were added, and the mixture was stirred until the solid was completely dissolved. After separating the diethyl ether layer, the aqueous layer was further treated twice with 100 ml of diethyl ether. These diethyl ether layers were combined, washed with water and dried over sodium sulfate. After drying, the diethyl ether was distilled off to obtain 16.0 g of phenylpyruvic acid, and the yield was 80.2%.
反応濾液の水層は、10％塩酸水溶液70mlで酸性としジエ
チルエーテル100mlで３回抽出した。これらジエチルエ
ーテル層を併せ、硫酸ナトリウム乾燥後、ジエチルエー
テルを留去するとフェニル酢酸のみが2.3g得られ、収率
は14.1％であった。The aqueous layer of the reaction filtrate was acidified with 70 ml of 10% aqueous hydrochloric acid and extracted 3 times with 100 ml of diethyl ether. These diethyl ether layers were combined, dried over sodium sulfate, and then the diethyl ether was distilled off to obtain only 2.3 g of phenylacetic acid, and the yield was 14.1%.
反応濾液の有機層には、コバルトカルボニル触媒の他に
少量のベンジルアルコールが存在していた。In the organic layer of the reaction filtrate, a small amount of benzyl alcohol was present in addition to the cobalt carbonyl catalyst.
実施例２ 水に難溶性の溶媒としてアセトフェノンを使用した他
は、実施例１と同様に反応及び処理を行った。フェニル
ピルビン酸の収率は72.5％、フェニル酢酸の収率は12.4
％であった。Example 2 The reaction and treatment were performed in the same manner as in Example 1 except that acetophenone was used as a poorly soluble solvent in water. The yield of phenylpyruvic acid is 72.5%, and the yield of phenylacetic acid is 12.4.
%Met.
実施例３ 一酸化炭素圧力を10kg/cm2とした他は、実施例１と同様
に反応及び処理を行った。フェニルピルビン酸の収率は
73.5％、フェニル酢酸の収率は15.0％であった。Example 3 The reaction and treatment were carried out in the same manner as in Example 1 except that the carbon monoxide pressure was 10 kg / cm 2 . The yield of phenylpyruvic acid is
73.5%, and the yield of phenylacetic acid was 15.0%.
参考例１ 水25ml、水酸化カルシウム6.2g、塩化ベンジル5.1g及び
実施例３で得られたコバルトカルボニル触媒を含有する
メチルイソブチルケトン溶液25mlを135mlのステンレス
製オートクレーブに仕込み、実施例３と同様に反応及び
処理を行った。フェニルピルビン酸の収率は73.0％、フ
ェニル酢酸の収率は15.2％であった。Reference Example 1 25 ml of water, 6.2 g of calcium hydroxide, 5.1 g of benzyl chloride and 25 ml of the methyl isobutyl ketone solution containing the cobalt carbonyl catalyst obtained in Example 3 were charged into a 135 ml stainless steel autoclave, and the same as in Example 3. The reaction and treatment were carried out. The yield of phenylpyruvic acid was 73.0% and the yield of phenylacetic acid was 15.2%.
実施例４ 500mlのガラス製オートクレーブに、メチルイソブチル
ケトン100ml、水50ml、水酸化カルシウム9.3g（0.126モ
ル）、塩化ベンジル7.7g（0.061モル）、及びジコバル
トオクタカルボニル1.2g（0.0035モル）を仕込んだ。Example 4 A 500 ml glass autoclave was charged with 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 7.7 g (0.061 mol) of benzyl chloride and 1.2 g (0.0035 mol) of dicobalt octacarbonyl. It is.
オートクレーブ内を一酸化炭素で洗浄し、一酸化炭素加
圧下で撹拌しながら昇温後、一酸化炭素圧力1kg/cm2、
温度55℃で一酸化炭素の吸収が停止するまで10時間反応
を行った。The inside of the autoclave was washed with carbon monoxide, the temperature was raised while stirring under pressure of carbon monoxide, and the carbon monoxide pressure was 1 kg / cm 2 ,
The reaction was carried out at a temperature of 55 ° C for 10 hours until the absorption of carbon monoxide stopped.
反応後、実施例１と同様に処理したところフェニルピル
ビン酸の収率は、72.1％、フェニル酢酸の収率は17.9％
であった。After the reaction, when treated in the same manner as in Example 1, the yield of phenylpyruvic acid was 72.1% and the yield of phenylacetic acid was 17.9%.
Met.
実施例５ 水に難溶性の溶媒としてアセトフェノンを使用した他
は、実施例４と同様に反応及び処理を行った。フェニル
ピルビン酸の収率は75.0％、フェニル酢酸の収率は15.5
％であった。Example 5 The reaction and treatment were carried out in the same manner as in Example 4 except that acetophenone was used as a poorly soluble solvent in water. The yield of phenylpyruvic acid is 75.0%, and the yield of phenylacetic acid is 15.5.
%Met.
実施例６ 常圧下一酸化炭素を吸込みながら、反応温度を50℃、反
応時間を20時間とした他は、実施例１と同様に反応及び
処理を行った。フェニルピルビン酸の収率は71.0％、フ
ェニル酢酸の収率は22.2％であった。Example 6 The reaction and treatment were carried out in the same manner as in Example 1 except that the reaction temperature was 50 ° C. and the reaction time was 20 hours while sucking carbon monoxide under normal pressure. The yield of phenylpyruvic acid was 71.0% and the yield of phenylacetic acid was 22.2%.
実施例７ 水に難溶性の溶媒としてアセトフェノンを使用した他
は、実施例６と同様に反応及び処理を行った。フェニル
ピルビン酸の収率は71.2％、フェニル酢酸の収率は21.7
％であった。Example 7 The reaction and treatment were performed in the same manner as in Example 6 except that acetophenone was used as a poorly soluble solvent in water. The yield of phenylpyruvic acid is 71.2%, and the yield of phenylacetic acid is 21.7.
%Met.
比較例１ 水に難溶性の溶媒としてメチルイソブチルケトンを使用
し、水酸化カルシウム及び水の代わりに24重量％の苛性
ソーダ水溶液75mlを４時間かけて添加した他は、実施例
３と同様に反応及び処理を行った。固体からはフェニル
ピルビン酸は検出されず、水層からフェニルピルビン酸
及びフェニル酢酸を得た。フェニルピルビン酸の収率は
19.8％、フェニル酢酸の収率は7.1％であった。Comparative Example 1 Reaction was carried out in the same manner as in Example 3 except that methylisobutylketone was used as a poorly soluble solvent in water and 75 ml of a 24 wt% caustic soda aqueous solution was added over 4 hours instead of calcium hydroxide and water. Processed. Phenylpyruvic acid was not detected from the solid, and phenylpyruvic acid and phenylacetic acid were obtained from the aqueous layer. The yield of phenylpyruvic acid is
The yield of phenylacetic acid was 19.8% and 7.1%.
Claims (4)
塩化ベンジルと一酸化炭素及びアルカリ土類金属塩基と
を反応させる際に、溶媒として水と水に対して難溶性の
ケトン類を用い反応させる事を特徴とするフェニルピル
ビン酸の製造方法。1. In the presence of a cobalt carbonyl compound catalyst,
A method for producing phenylpyruvic acid, which comprises reacting benzyl chloride with carbon monoxide and an alkaline earth metal base using water and a sparingly water-soluble ketone as a solvent.
ン又はアセトフェノンである特許請求の範囲第１項記載
のフェニルピルビン酸の製造方法。2. The method for producing phenylpyruvic acid according to claim 1, wherein the hardly soluble ketone is methyl isobutyl ketone or acetophenone.
である特許請求の範囲第１項記載のフェニルピルビン酸
の製造方法。3. The method for producing phenylpyruvic acid according to claim 1, wherein the alkaline earth metal base is calcium hydroxide.
クタカルボニルである特許請求の範囲第１項記載のフェ
ニルピルビン酸の製造方法。4. The method for producing phenylpyruvic acid according to claim 1, wherein the cobalt carbonyl compound is dicobalt octacarbonyl.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60033193A JPH0680029B2 (en) | 1985-02-21 | 1985-02-21 | Method for producing phenylpyruvic acid |
| US06/831,312 US4689431A (en) | 1985-02-21 | 1986-02-20 | Method for the preparation of phenyl pyruvic acid |
| DE8686301269T DE3674027D1 (en) | 1985-02-21 | 1986-02-21 | METHOD FOR THE PRODUCTION OF PHENYL PYRIC ACID. |
| EP86301269A EP0195530B1 (en) | 1985-02-21 | 1986-02-21 | Process for the preparation of phenyl pyruvic acid |
| CA000502471A CA1264766A (en) | 1985-02-21 | 1986-02-21 | Method for the preparation of phenyl pyruvic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60033193A JPH0680029B2 (en) | 1985-02-21 | 1985-02-21 | Method for producing phenylpyruvic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61191650A JPS61191650A (en) | 1986-08-26 |
| JPH0680029B2 true JPH0680029B2 (en) | 1994-10-12 |
Family
ID=12379645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60033193A Expired - Lifetime JPH0680029B2 (en) | 1985-02-21 | 1985-02-21 | Method for producing phenylpyruvic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680029B2 (en) |
-
1985
- 1985-02-21 JP JP60033193A patent/JPH0680029B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61191650A (en) | 1986-08-26 |
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|---|---|---|---|
| EXPY | Cancellation because of completion of term |