JPS61167641A - Production of phenylpyruvic acid - Google Patents
Production of phenylpyruvic acidInfo
- Publication number
- JPS61167641A JPS61167641A JP60007432A JP743285A JPS61167641A JP S61167641 A JPS61167641 A JP S61167641A JP 60007432 A JP60007432 A JP 60007432A JP 743285 A JP743285 A JP 743285A JP S61167641 A JPS61167641 A JP S61167641A
- Authority
- JP
- Japan
- Prior art keywords
- phenylpyruvic acid
- benzylidenehydantoin
- reaction
- yield
- alkali
- 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.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
イ、産業上の利用分野
本発明は、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 a method for producing phenylpyruvic acid.
フェニルピルビン酸は医薬品、各種有用化合物の合成中
間体として、貴重な化合物である。特に、還元的アミン
化反応によシ医薬・食品として非常に有用なフェニルア
ラニンを得ることができる。Phenylpyruvic acid is a valuable compound as a synthetic intermediate for pharmaceuticals and various useful compounds. In particular, phenylalanine, which is very useful as a medicine and food, can be obtained by the reductive amination reaction.
口、従来の技術及び問題点
フェニルピルビン酸の従来の合成法としては、（１）
α−アセトアミノ桂皮醸または、α−ベンゾイル桂皮
酸を酸、またはアルカリ加水分解する方法。（Ｒ，Ｍ、
Ｈｅｒｂｓｔ ＆ Ｄ、Ｓｈｅｍｉｎ、Ｏｒｇ、Ｓｙｎ
、 １９（２）桂皮酸メチルをジブロム化し、次いでピ
ペリジノで置換させた後、酸で加水分解する方法。Conventional techniques and problems Conventional methods for synthesizing phenylpyruvic acid include (1)
A method of acid or alkali hydrolysis of α-acetamincinnamic acid or α-benzoylcinnamic acid. (R, M,
Herbst & D, Shemin, Org, Syn
, 19(2) A method in which methyl cinnamate is dibrominated, then substituted with piperidino, and then hydrolyzed with acid.
（Ｈｅｎｒｉ Ｍｏｕｒｅｕ、ＰａｕＬＣｈａｉｎ ｅ
ｔａｔＣｏｍｐｔ、ｒｅｎｄ。(Henri Moureu, Paul Chain e
tatCompt, rend.
２２１．４１０−１２（１９４５））
（３）５−ベンジリデンヒダントインをアルカリ加水分
解する方法。（Ｇ、Ｂｉｔｔｅｋ Ｍｏｎａｔｓｈ ９
２ 。221.410-12 (1945)) (3) A method for alkaline hydrolysis of 5-benzylidenehydantoin. (G, Bittek Monash 9
2.
等、種々の方法が知られている。Various methods are known.
しかし、一般的に収率が低く、特に高価な原料を使用す
る（１）や（２）の方法は工業的に不利な点が多−九。However, methods (1) and (2), which generally have low yields and use particularly expensive raw materials, have many industrial disadvantages.
本発明者らは、工業的に安価なヒダントインとへ／スア
ルデヒドから、容易に合成できる５−ベンジリデンヒダ
ントインを用いるフェニルピルビン酸合成に注目した。The present inventors focused on the synthesis of phenylpyruvic acid using 5-benzylidenehydantoin, which can be easily synthesized from industrially inexpensive hydantoin and he/saldehyde.
公知の方法としては、５−ベンジリデンヒダントインを
２０倍当量以上のカセイソーダを用い、沸点で加水分解
する方法が知られているが、低収率である。（Ｇ、Ｂｉ
Ｌｔｅｋ ； Ｍｏｎａｔｓｈ ９２ ｊ３３５−ハ１
問題点を解決するだめの手段
本発明者らは、鋭意研究の結果、５−ベンジリデン−ヒ
ダントインを、アルカリ濃度を低く抑え、即ち２．５〜
３．０倍当量のアルカリ金属もしくは、アルカリ土類金
属の水酸化物を用い、５〜１０ｗｔ％の初濃度にて、９
０〜１００℃で１．５〜２．５時間加水分解することに
よって、生成したフェニルピルビン酸の分解を効果的に
防止して、はぼ定量的に７エニルピルピン酸を合成でき
ることを見い出し、本発明を完成するに到った。As a known method, a method is known in which 5-benzylidenehydantoin is hydrolyzed at the boiling point using 20 times or more equivalent of caustic soda, but the yield is low. (G, Bi
Ltek ; Monatsh 92 j335-Ha1
Means to Solve the Problems As a result of intensive research, the present inventors have determined that 5-benzylidene-hydantoin has a low alkali concentration, that is, 2.5 to
Using 3.0 times equivalent of alkali metal or alkaline earth metal hydroxide, at an initial concentration of 5 to 10 wt%, 9
It has been discovered that by hydrolyzing at 0 to 100°C for 1.5 to 2.5 hours, it is possible to effectively prevent the decomposition of the generated phenylpyruvic acid and to synthesize 7-enylpyruvic acid almost quantitatively, and the present invention I have come to complete this.
本発明で使用されるアルカリとじ【は、ナトリウム、カ
リウム等のアルカリ金属、もしくはカルシウム、バリウ
ム等のアルカリ土類金属の水酸化物を挙げることができ
る。The alkali metal used in the present invention includes hydroxides of alkali metals such as sodium and potassium, or alkaline earth metals such as calcium and barium.
アルカリ量は２．５〜３．０倍当量がよく、少ない場合
は、反応が遅く、しかも収率・選択率の低下を招き、反
対に多いとアルカリ濃度が上がシ、生成したフェニルピ
ルビン酸が分解するので好ましくない。The amount of alkali should preferably be 2.5 to 3.0 times equivalent; if it is too small, the reaction will be slow and the yield and selectivity will be reduced.On the other hand, if it is too large, the alkali concentration will increase and the generated phenylpyruvic acid is undesirable because it decomposes.
５−ベンジリデンヒダントインの濃度は、２〜ｌ Ｑ
ｗｔ％、好ましくは５〜８ ｗｔ％である。濃度が低い
と反応が遅く実用的でなく、高いと生成したフェニルピ
ルビン酸が分解するので好ましくない。The concentration of 5-benzylidenehydantoin is 2 to 1 Q
wt%, preferably 5 to 8 wt%. If the concentration is low, the reaction will be slow and impractical; if the concentration is high, the generated phenylpyruvic acid will be decomposed, which is not preferable.
反応温度は８０〜１００℃、好ましくは９０〜１００℃
である。温度が低いと十分な反応速度が得られず、しか
も長時間に渡るとフェニルピルビン酸の分解を招くので
好ましくな（・。Reaction temperature is 80-100°C, preferably 90-100°C
It is. If the temperature is low, a sufficient reaction rate cannot be obtained, and furthermore, if it continues for a long time, it will lead to decomposition of phenylpyruvic acid, so it is not preferable (・.
反応時間は１〜４時間、好ましくは２〜３時間である。The reaction time is 1 to 4 hours, preferably 2 to 3 hours.
それ以上加水分解すると、生成したフェニルピルビン酸
が分解するので好ましくない。Further hydrolysis is not preferable because the generated phenylpyruvic acid will be decomposed.
二、実施例
以下、実施例において本発明の方法について更に具体的
に説明する。但し、これらは単なる例示にすぎず、本発
明はこれらの例に何ら制限されることはない。2. Examples The method of the present invention will be explained in more detail in the following examples. However, these are merely examples, and the present invention is not limited to these examples in any way.
実施例１
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセットした。Example 1 A 200-3-hole flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４ｇ （０，０３
００ｍｏｔ）、カセイソーダ３．６０９ （０，０９０
０ｅｑ）、及び水９０ｇを仕込み、昇温した。１００℃
にて２時間反応させたところ、フェニルピルビン酸が４
．８５ｇ（０，０２９６ｍｏＬ）生成していた。５−ベ
ンジリデンヒダントイン基準の収率９８．６％であった
０
実施例２
還流冷却器、攪はん機、温度計を備えた２０〇−３つ目
フラスコを恒温槽中にセットした。5-Benzylidenehydantoin 5.64g (0,03
00mot), caustic soda 3.609 (0,090
0 eq) and 90 g of water were charged, and the temperature was raised. 100℃
When the reaction was carried out for 2 hours, phenylpyruvic acid was
．． 85g (0,0296mol) was produced. The yield was 98.6% based on 5-benzylidenehydantoin.Example 2 A third flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４９ （０，０３
００ｍｏＬ ） 、水酸化カリウム４．２０９ （０，
０７５０ｅｑ）、及び水７０ｇを仕込み、昇温した。１
００℃にて２時間反応させたところ、フェニルピルビン
酸が４．７８ｇ（０，０２９１ｍｏＬ）生成していた。5-Benzylidenehydantoin 5.649 (0,03
00mol), potassium hydroxide 4.209 (0,
0750 eq) and 70 g of water were charged, and the temperature was raised. 1
When the reaction was carried out at 00° C. for 2 hours, 4.78 g (0,0291 mol) of phenylpyruvic acid was produced.
５−ベンジリデンヒダントイン基準の収率９７．１％で
あった。The yield was 97.1% based on 5-benzylidenehydantoin.
実施例３
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセットした。Example 3 A 200-3-hole flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４９ （０，０３
００ｍｏＬ ） 、水酸化カルシウム３．３１９（０，
０９００ｅｑ）、及び水１２０ｇを仕込み、昇温した。5-Benzylidenehydantoin 5.649 (0,03
00mol), calcium hydroxide 3.319(0,
0900 eq) and 120 g of water were charged, and the temperature was raised.
９５℃にて３時間反応させたところ、フェニルピルビン
酸が４．８０ｇ（０，０２９３ｍｏｔ）生成□していた
。When the reaction was carried out at 95° C. for 3 hours, 4.80 g (0,0293 mot) of phenylpyruvic acid was produced.
５−ベンジリデンヒダントイン基準の収率９７．６−で
あった。The yield was 97.6 based on 5-benzylidenehydantoin.
比較例１
還流冷却器、攪はん機、温度計を備えた２０〇−３つロ
フラスコを恒温槽中にセットした。Comparative Example 1 A 200° flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４ 、！７ （０
，０３００ｍｏＬ ） 、カセイソーダ７．２０９ （
０，１８００ｅｑ）、及び水９０９を仕込み、昇温した
。１００℃にて２時間反応させたところ、フェニルピル
ビン酸力３．８９９ （０，０２３７ｍｏｔ）生成して
いた。５−ペンジリデンヒダントイン基準の収率７９．
１％であったＯ
比較例２
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセントした。5-Benzylidenehydantoin 5.64,! 7 (0
,0300mol), caustic soda 7.209 (
0,1800 eq) and water 909 were charged, and the temperature was raised. When the reaction was carried out at 100° C. for 2 hours, phenylpyruvic acid power of 3.899 (0,0237 mot) was produced. Yield based on 5-penzylidenehydantoin: 79.
Comparative Example 2 A 200-3 flask equipped with a reflux condenser, stirrer, and thermometer was placed in a constant temperature bath.
５−ベンジリデンヒダントイン５．６１ （０，０３０
０ｍｏｂ ）、カセイソーダ１．８０９ （０，０４５
０ｅｑ）、及び水９０ｇを仕込み、昇温した。１００℃
にて３時間反応させたところ、フェニルピルビン酸が３
、２５９ （０，０１９８ｍａｔ ）生成していた。５
−ベンジリデンヒダントイン基準の収率６６．１％であ
った。5-Benzylidenehydantoin 5.61 (0,030
0 mob ), caustic soda 1.809 (0,045
0 eq) and 90 g of water were charged, and the temperature was raised. 100℃
When the reaction was carried out for 3 hours, phenylpyruvic acid was
, 259 (0,0198mat) were generated. 5
- The yield was 66.1% based on benzylidenehydantoin.
比較例３
還流冷却器、攪はん機、温度計を備えた２００ｆｆ１７
！３つロフラスコを恒温槽中にセットした。Comparative Example 3 200ff17 equipped with reflux condenser, stirrer, and thermometer
! Three flasks were placed in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４９ （０，０３
００ｍｏｔ） 、カセイソーダ３．６０ＩＩ（０，０９
００ｅｑ）、及び水３０．９を仕込み、昇温した。１０
０℃にて２時間反応させたところ、フェニルピルビン酸
力３、５３９ （０，０２１５ｍｏＡ ）生成していた
。５−ベンジリデンヒダントイン基準の収率７１．７％
であった。5-Benzylidenehydantoin 5.649 (0,03
00mot), caustic soda 3.60II (0,09
00 eq) and 30.9 g of water were charged, and the temperature was raised. 10
When the reaction was carried out at 0°C for 2 hours, 3,539 phenylpyruvic acid (0,0215 moA) was produced. Yield 71.7% based on 5-benzylidenehydantoin
Met.
比較例４
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセットした。Comparative Example 4 A 200-meter flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
・ ５−ベンジリデンヒダントイン１．８８９ （０，
０１００ｍｏｌ ） 、カセイソーダ１．２０９ （０
，０３００ｅｑ）、及び水１００ｇを仕込み、昇温した
。１００℃にて４時間反応させたところ、フェニルピル
ビン酸が１．２０９ （０，００７３ｍｏｂ ）生成し
ていた。５−ベンジリデンヒダントイン基準の収率７２
．５％であった。・5-Benzylidenehydantoin 1.889 (0,
0100 mol), caustic soda 1.209 (0
, 0300 eq) and 100 g of water were charged, and the temperature was raised. When the reaction was carried out at 100°C for 4 hours, 1.209 (0,0073 mob) of phenylpyruvic acid was produced. Yield based on 5-benzylidenehydantoin 72
．． It was 5%.
比較例５
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセットした。Comparative Example 5 A 200-3 flask equipped with a reflux condenser, a stirrer, and a thermometer was set in a constant temperature bath.
５−ベンジリデンヒダントイン５．６０＋（０，０３０
０ｍｏＬ）、カセイソーダ３．６０ 、！ｉｌ ＣＯ，
０９００ｅｑ）、及び水９０．９を仕込み、昇温した。5-Benzylidenehydantoin 5.60+(0,030
0mol), caustic soda 3.60,! il CO,
0900 eq) and 90.9 g of water were charged, and the temperature was raised.
７０℃にて２時間反応させたところ、フェニルピルビン
酸が／ジリデンヒダントイン基準の収率８０．３％であ
った０
比較例６
還流冷却器、攪はん機、温度計を備えた２００−３つロ
フラスコを恒温槽中にセットした。When the reaction was carried out at 70°C for 2 hours, the yield of phenylpyruvic acid/dylidenehydantoin was 80.3%.Comparative Example 6 200- Three flasks were placed in a constant temperature bath.
５−ベンジリデンヒダントイン５．６４ ｇ （０，０
３００ｍｏｔ） 、カセイソーダ３．６０．ｌｉ’ （
０，０９００ｅｑ）、及び水９０１１を仕込み、昇温し
た。１００℃にて６時間反応させたところ、フェニルピ
ルビン酸が３、８１ ｇ（０，０２３３ｍｏｔ）生成し
ていた。５−ペンジリデンヒダントイン基準の収率７７
．５％であった０5-Benzylidenehydantoin 5.64 g (0,0
300mot), caustic soda 3.60. li' (
0,0900 eq) and 9011 of water were charged, and the temperature was raised. When the reaction was carried out at 100° C. for 6 hours, 3.81 g (0.0233 mot) of phenylpyruvic acid was produced. Yield based on 5-penzylidenehydantoin: 77
．． 5% was 0
Claims (1)
で２．５〜３．０倍当量のアルカリ金属もしくは、アル
カリ土類金属の水酸化物を用い、９０〜１００℃で加水
分解することを特徴とするフェニルピルビン酸の製造方
法。It is characterized by hydrolyzing 5-benzylidenehydantoin at a concentration of 5 to 10 wt% using 2.5 to 3.0 times equivalent of alkali metal or alkaline earth metal hydroxide at 90 to 100°C. Method for producing phenylpyruvic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60007432A JPS61167641A (en) | 1985-01-21 | 1985-01-21 | Production of phenylpyruvic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60007432A JPS61167641A (en) | 1985-01-21 | 1985-01-21 | Production of phenylpyruvic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61167641A true JPS61167641A (en) | 1986-07-29 |
Family
ID=11665701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60007432A Pending JPS61167641A (en) | 1985-01-21 | 1985-01-21 | Production of phenylpyruvic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61167641A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014057A1 (en) * | 2001-08-08 | 2003-02-20 | Tanabe Seiyaku Co., Ltd. | Processes for producing halogenophenylpyruvic acid and optically active halogenophenylalanine |
| JP2003104932A (en) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Method for producing 4-hydroxyphenylpyruvic acid |
| CN100412047C (en) * | 2005-12-15 | 2008-08-20 | 南京工业大学 | Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6122042A (en) * | 1984-07-10 | 1986-01-30 | Mitsui Toatsu Chem Inc | Production of alpha-keto acid |
| JPS6143136A (en) * | 1984-08-07 | 1986-03-01 | Mitsui Toatsu Chem Inc | Production of alkali metal salt of alpha-keto acid |
-
1985
- 1985-01-21 JP JP60007432A patent/JPS61167641A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6122042A (en) * | 1984-07-10 | 1986-01-30 | Mitsui Toatsu Chem Inc | Production of alpha-keto acid |
| JPS6143136A (en) * | 1984-08-07 | 1986-03-01 | Mitsui Toatsu Chem Inc | Production of alkali metal salt of alpha-keto acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014057A1 (en) * | 2001-08-08 | 2003-02-20 | Tanabe Seiyaku Co., Ltd. | Processes for producing halogenophenylpyruvic acid and optically active halogenophenylalanine |
| JP2003104932A (en) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Method for producing 4-hydroxyphenylpyruvic acid |
| CN100412047C (en) * | 2005-12-15 | 2008-08-20 | 南京工业大学 | Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives |
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