JPH0816078B2 - Process for producing optically active phenylacetic acid derivative - Google Patents
Process for producing optically active phenylacetic acid derivativeInfo
- Publication number
- JPH0816078B2 JPH0816078B2 JP62162690A JP16269087A JPH0816078B2 JP H0816078 B2 JPH0816078 B2 JP H0816078B2 JP 62162690 A JP62162690 A JP 62162690A JP 16269087 A JP16269087 A JP 16269087A JP H0816078 B2 JPH0816078 B2 JP H0816078B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- group
- phenylacetic acid
- acid derivative
- general formula
- 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
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
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、医・農薬等の中間体として有用な一般式
（Ｉ） （式中、R1およびR2は水素原子または低級アルキル基
を、R3およびR4は水素原子、ハロゲン原子、低級アルキ
ル基または低級アルコキシル基を示す） で示される光学活性フェニル酢酸誘導体の製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention provides a compound of the general formula (I) useful as an intermediate for medicines, agricultural chemicals and the like. (Wherein R 1 and R 2 represent a hydrogen atom or a lower alkyl group, and R 3 and R 4 represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group). Concerning the law.
＜従来の技術＞ 不斉水素還元法によって、光学活性フェニル酢酸を得
る方法において、その触媒として一般式（IV） （式中、Ｍはロジウム原子、ルテニウム原子またはイリ
ジウム原子を、Ｌはフェロセニルホスフィン、ピロリジ
ニルホスフィンの不斉配位子を示す。また、olefinは1,
5−ノルボルナルジエンまたは1,5−シクロオクタジエン
を、ＸはClO4,BF4またはPF6を示す） で示される触媒を用いる方法は米国特許第4,409,397号
明細書に示されている。<Prior Art> In the method of obtaining optically active phenylacetic acid by the asymmetric hydrogen reduction method, the catalyst of the general formula (IV) is used as the catalyst. (In the formula, M represents a rhodium atom, a ruthenium atom or an iridium atom, and L represents an asymmetric ligand of ferrocenylphosphine or pyrrolidinylphosphine.
A method of using a catalyst represented by 5-norbornaldiene or 1,5-cyclooctadiene, where X represents ClO 4 , BF 4 or PF 6 ) is shown in US Pat. No. 4,409,397.
＜発明が解決しようとする問題点＞ しかし、このようなフェロセニルホスフィンやピロリ
ジニルホスフィンを不斉配位子として有する触媒を用い
る方法では転化率や光学収率が必ずしも十分でなく、工
業的に十分に満足するものではなかった。<Problems to be Solved by the Invention> However, the conversion and the optical yield are not always sufficient in the method using a catalyst having such a ferrocenylphosphine or pyrrolidinylphosphine as an asymmetric ligand, I was not completely satisfied.
＜問題点を解決するための手段＞ このようなことから、本発明者らは上記問題点を解決
し、好転化率、好光学収率で光学活性フェニル酢酸誘導
体を製造すべく鋭意検討の結果、不斉配位子としての光
学活性ビナフチル誘導体で修飾したロジウム触媒を用い
ることにより、すぐれた転化率、光学収率で目的物が得
られ、さらには使用する不斉配位子の立体配置を選択す
ることにより所望の立体配置を有する光学活性フェニル
酢酸誘導体が得られることを見出し、本発明に至った。<Means for Solving Problems> From the above, the present inventors have earnestly studied to solve the above problems and produce an optically active phenylacetic acid derivative with good conversion and good optical yield. By using a rhodium catalyst modified with an optically active binaphthyl derivative as an asymmetric ligand, the desired product can be obtained with excellent conversion and optical yield, and the configuration of the asymmetric ligand used can be determined. It was found that an optically active phenylacetic acid derivative having a desired steric configuration can be obtained by selection, and the present invention has been completed.
すなわち本発明は、一般式（II） （式中、R1、R2、R3およびR4は前記と同じ意味を有す
る） で示されるオレフィン誘導体を、一般式（III） （式中、Ｒは低級アルキルフェニル基、低級アルコキシ
フェニル基またはC3〜C8のシクロアルキル基を示す） で示される光学活性ビナフチル誘導体で修飾したロジウ
ム触媒の存在下に不斉水素還元することを特徴とする前
記一般式（Ｉ）で示される光学活性フェニル酢酸誘導体
の製造法を提供するものである。That is, the present invention has the general formula (II) (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above), and the olefin derivative represented by the general formula (III) (Wherein R represents a lower alkylphenyl group, a lower alkoxyphenyl group or a C 3 to C 8 cycloalkyl group), and asymmetric hydrogen reduction is carried out in the presence of a rhodium catalyst modified with an optically active binaphthyl derivative. The present invention provides a method for producing an optically active phenylacetic acid derivative represented by the above general formula (I).
本発明において、原料として用いられる一般式（II）
で示されるオレフィン誘導体としては、たとえば２−フ
ェニル−８−メチルクロトン酸、２−（４−クロロフェ
ニル）−３−メチルクロトン酸、２−（４−メトキシフ
ェニル）−３−メチルクロトン酸、２−フェニル−３−
エチルペンテン酸、２−（４−クロロフェニル）−３−
エチルペンテン酸などが例示され、これらは前記米国特
許明細書に記載の方法に準じて製造することができる。In the present invention, the general formula (II) used as a raw material
Examples of the olefin derivative represented by: 2-phenyl-8-methylcrotonic acid, 2- (4-chlorophenyl) -3-methylcrotonic acid, 2- (4-methoxyphenyl) -3-methylcrotonic acid, 2- Phenyl-3-
Ethylpentenoic acid, 2- (4-chlorophenyl) -3-
Ethyl pentenoic acid and the like are exemplified, and these can be produced according to the method described in the above-mentioned US Pat.
また、ロジウム触媒形成のための修飾剤である前記一
般式（III）で示される光学活性ビナフチル誘導体の置
換基Ｒにおいて、低級アルキルフェニル基としてはトリ
ル、エチルフェニル、ブチルフェニルなどが、低級アル
コキシフェニル基としてはメトキシフェニル、エトキシ
フェニル、プロポキシフェニル等が、シクロアルキル基
としはシクロプロピル、シクロヘキシル、シクロオクチ
ル等が例示され、これら低級アルキルフェニル基または
低級アルコキシフェニル基において、低級アルキル基ま
たは低級アルコキシル基の置換位置はｐ−位であること
が好ましい。Further, in the substituent R of the optically active binaphthyl derivative represented by the general formula (III), which is a modifier for forming a rhodium catalyst, the lower alkylphenyl group may be a lower alkoxyphenyl group such as tolyl, ethylphenyl or butylphenyl. Examples of the group include methoxyphenyl, ethoxyphenyl, propoxyphenyl, etc., and examples of the cycloalkyl group include cyclopropyl, cyclohexyl, cyclooctyl, etc., and in these lower alkylphenyl groups or lower alkoxyphenyl groups, lower alkyl groups or lower alkoxyl groups The substitution position of is preferably the p-position.
かかるロジウム触媒として、具体的には Rh〔Ｐ−CH3（BINAP）〕（NBD）BF4, Rh〔Ｐ−CH3O（BINAP）〕（NBD）BF4, Rh〔シクロヘキシル（BINAP）〕（NBD）BF4, Rh〔Ｐ−CH3（BINAP）〕2ClO4, Rh〔Ｐ−CH3（BINAP）〕（COD）BF4, 〔但し、上式においてＰ−CH3（BINAP）は2,2′−ビス
〔ジ−（ｐ−メチルフェニル）ホスフィノ〕−1,1′−
ビナフチルを、ｐ−CH3O（BINAP）は2,2′−ビス〔ジ
（ｐ−メトキシフェニル）ホスフィノ〕−1,1′−ビナ
フチルを、シクロヘキシル（BINAP）は2,2′−ビス（ジ
シクロヘキシルホスフィノ）−1,1′−ビナフチルを、C
ODは1,5−シクロオクタジエンを、NBDは2,5−ノルボル
ナジエンをそれぞれ示す。〕 などが例示され、これらロジウム触媒の製造はTetrahed
ron,40,1245（1984）,J.Chem.Soc.,Chem.Commum.,922
（1985）および特開昭60−61587号公報などに記載の方
法に準じて、たとえばRh〔Ｐ−CH3（BINAP）〕（NBD）B
F4を製造する場合には、Rh2（NBD）2Cl2をメタノール
中、AgBF4の存在下にＰ−CH3（BINAP）と反応させ、Ｐ
−CH3（BINAP）とNBDを配位交換することにより製造す
ることができる。As such a rhodium catalyst, in particular Rh [P-CH 3 (BINAP)] (NBD) BF 4, Rh [P-CH 3 O (BINAP)] (NBD) BF 4, Rh [cyclohexyl (BINAP)] ( NBD) BF 4 , Rh [P-CH 3 (BINAP)] 2 ClO 4 , Rh [P-CH 3 (BINAP)] (COD) BF 4 , [However, in the above formula, P-CH 3 (BINAP) is 2 , 2'-bis [di- (p-methylphenyl) phosphino] -1,1'-
Binaphthyl, a p-CH 3 O (BINAP) 2,2'-bis [di (p- methoxyphenyl) phosphino] -1,1'-binaphthyl, cyclohexyl (BINAP) 2,2'-bis (dicyclohexyl Phosphino) -1,1'-binaphthyl is replaced by C
OD represents 1,5-cyclooctadiene and NBD represents 2,5-norbornadiene. ] Are exemplified, and the production of these rhodium catalysts is performed by Tetrahed
ron, 40 , 1245 (1984), J.Chem.Soc., Chem.Commum., 922
(1985) and Japanese Patent Application Laid-Open No. 60-61587, for example, Rh [P-CH 3 (BINAP)] (NBD) B
In the case of producing F 4 , Rh 2 (NBD) 2 Cl 2 is reacted with P-CH 3 (BINAP) in methanol in the presence of AgBF 4 to produce P 4.
-CH 3 (BINAP) and NBD can be manufactured by coordinate exchange.
本発明の方法において、ロジウム触媒の使用量は原料
オレフィン誘導体に対して0.001〜10モル％、好ましく
は0.1〜１モル％である。In the method of the present invention, the amount of the rhodium catalyst used is 0.001 to 10 mol%, preferably 0.1 to 1 mol% based on the raw material olefin derivative.
反応は通常溶媒中で行われ、その溶媒としてはたとえ
ばメタノール、エタノール、イソプロパノール、ブタノ
ール、酢酸メチル、ベンゼン、トルエン、キシレン、テ
トラヒドロフランなどの有機溶媒または水あるいはこれ
らの混合物が挙げられるが、メタノール、エタノールが
好ましく使用される。The reaction is usually carried out in a solvent, and examples of the solvent include organic solvents such as methanol, ethanol, isopropanol, butanol, methyl acetate, benzene, toluene, xylene, and tetrahydrofuran, or water or a mixture thereof, such as methanol and ethanol. Is preferably used.
かかる溶媒の使用量は原料オレフィン誘導体に対して
通常１〜500重量倍、好ましくは10〜200重量倍である。The amount of such a solvent used is usually 1 to 500 times by weight, preferably 10 to 200 times by weight, based on the raw material olefin derivative.
反応に際しての水素圧力は、一般的には常圧〜500Kg/
cm2での範囲であるが、好ましくは30〜150kg/cm2であ
る。The hydrogen pressure during the reaction is generally from atmospheric pressure to 500 Kg /
The range is cm 2 , but preferably 30 to 150 kg / cm 2 .
反応温度は０〜150℃、好ましくは50〜100℃である。 The reaction temperature is 0 to 150 ° C, preferably 50 to 100 ° C.
反応時間は特に制限されないが、一般的には１〜20時
間である。The reaction time is not particularly limited, but is generally 1 to 20 hours.
尚、反応に際して反応系に三級アミンたとえばトリエ
チルアミン、トリ−ｎ−プロピルアミンなどを添加する
ことは反応をより円滑に進めるうえで好ましい。Incidentally, it is preferable to add a tertiary amine such as triethylamine or tri-n-propylamine to the reaction system during the reaction in order to promote the reaction more smoothly.
三級アミンを使用する場合、その使用量はロジウム触
媒に対して0.1〜100倍モル、好ましくは１〜20倍モルで
ある。When a tertiary amine is used, the amount thereof used is 0.1 to 100 times mol, preferably 1 to 20 times mol, of the rhodium catalyst.
＜発明の効果＞ かくして、本発明の方法によれば前記一般式（Ｉ）で
示される光学活性フェニル酢酸誘導体を好転化率、好光
学収率で得ることができ、また用いるロジウム触媒の立
体配位を変えることにより、生成する光学活性フェニル
酢酸誘導体の立体配置を制御することができる。<Effects of the Invention> Thus, according to the method of the present invention, the optically active phenylacetic acid derivative represented by the general formula (I) can be obtained with a good conversion and a good optical yield, and the configuration of the rhodium catalyst used is By changing the position, the configuration of the resulting optically active phenylacetic acid derivative can be controlled.
＜実施例＞ 以下、実施例により本発明を説明する。<Example> Hereinafter, the present invention will be described with reference to Examples.
実施例１ Rh2（NBD）2Cl22.3mg（0.005mmol）,S（−）−2,2′
−ビス（ジシクロヘキスルホスフィノ）−1,1′−ビナ
フチル8.1mg（0.0125mmol）、AgBF4 1.9mg（0.01mmo
l）、トリエチルアミン5.1mg（0.05mmol）およびメタノ
ール15mlを35ml容のオートクレーブに仕込み、溶解す
る。これに２−（４−クロロフェニル）−３−メチルク
ロトン酸0.42g（2mmol）を仕込み、溶解させた。Example 1 Rh 2 (NBD) 2 Cl 2 2.3 mg (0.005 mmol), S (−)-2,2 ′
-Bis (dicyclohexulfosphino) -1,1'-binaphthyl 8.1 mg (0.0125 mmol), AgBF 4 1.9 mg (0.01 mmo
l), 5.1 mg (0.05 mmol) of triethylamine and 15 ml of methanol are charged into a 35 ml autoclave and dissolved. To this, 0.42 g (2 mmol) of 2- (4-chlorophenyl) -3-methylcrotonic acid was charged and dissolved.
オートクレーブ内を水素ガスで置換後、水素圧50Kg/c
m2に加圧し、室温で24時間撹拌した。After replacing the inside of the autoclave with hydrogen gas, hydrogen pressure is 50 Kg / c
The pressure was increased to m 2 , and the mixture was stirred at room temperature for 24 hours.
反応終了後、水素を除圧後、メタノールを留去し、更
にアルカリ抽出、酸析、エーテル抽出および濃縮を行う
ことにより（Ｓ）−２−（４−クロロフェニル）−３−
メチル酪酸0.42gを得た。After completion of the reaction, hydrogen is depressurized, then methanol is distilled off, and then alkali extraction, acid precipitation, ether extraction and concentration are carried out to obtain (S) -2- (4-chlorophenyl) -3-.
0.42 g of methyl butyric acid was obtained.
転化率 100％ 選択率 ＞98％ 光学収率 76.5％（＋）体 実施例２ Rh2（NBD）2Cl2 2.3mg（0.005mmol）,R（＋）−2,
2′−ビス〔ジ（ｐ−トリル）ホスフィノ〕−1,1′−ビ
ナフチル8.5mg（0.0125mmol）、AgBF4 1.9mg（0.01mmo
l）、トリエチルアミン5.1mg（0.05mmol）およびメタノ
ール15mgを35ml容のオートクレーブに仕込み、溶解す
る。これに２−（４−クロロフェニル）−３−メチルク
ロトン酸0.42g（2mmol）を仕込み、溶解させた。100% conversion selectivity of> 98% optical yields 76.5 percent (+) isomer Example 2 Rh 2 (NBD) 2 Cl 2 2.3mg (0.005mmol), R (+) - 2,
2′-bis [di (p-tolyl) phosphino] -1,1′-binaphthyl 8.5 mg (0.0125 mmol), AgBF 4 1.9 mg (0.01 mmo
l), 5.1 mg (0.05 mmol) of triethylamine and 15 mg of methanol are charged into a 35 ml autoclave and dissolved. To this, 0.42 g (2 mmol) of 2- (4-chlorophenyl) -3-methylcrotonic acid was charged and dissolved.
オートクレーブ内を水素ガスで置換後、水素圧50Kg/c
m2に加圧し、80℃４時間撹拌した。After replacing the inside of the autoclave with hydrogen gas, hydrogen pressure is 50 Kg / c
The pressure was increased to m 2 , and the mixture was stirred at 80 ° C. for 4 hours.
反応終了後、水素を除圧後、メタノールを留去し、更
にアルカリ抽出、酸析、エーテル抽出および濃縮を行う
ことにより（Ｓ）−２−（４−クロロフェニル）−３−
メチル酪酸0.42gを得た。After completion of the reaction, hydrogen is depressurized, then methanol is distilled off, and then alkali extraction, acid precipitation, ether extraction and concentration are carried out to obtain (S) -2- (4-chlorophenyl) -3-.
0.42 g of methyl butyric acid was obtained.
転化率 95％ 選択率 ＞98％ 光学収率 63.0％（＋）体 実施例３ Ｒ（＋）−2,2′−ビス〔ジ（ｐ−トリル）ホスフィ
ノ〕−1,1′−ビナフチルに代えてＲ（＋）−2,2′−ビ
ス〔ジ（ｐ−メトキシフェニル）ホスフィノ〕−1,1′
−ビナフチル9.3mg（0.0125mmol）を使用する以外は実
施例２と同様に反応、後処理を行って（Ｓ）−２−（４
−クロロフェニル）−３−メチル酪酸を得た。Conversion 95% Selectivity> 98% Optical yield 63.0% (+) form Example 3 R (+)-2,2'-bis [di (p-tolyl) phosphino] -1,1'-binaphthyl was used instead. R (+)-2,2'-bis [di (p-methoxyphenyl) phosphino] -1,1 '
-The reaction and post-treatment were carried out in the same manner as in Example 2 except that 9.3 mg (0.0125 mmol) of binaphthyl was used, and (S) -2- (4
-Chlorophenyl) -3-methylbutyric acid was obtained.
転化率 95％ 選択率 ＞98％ 光学収率 57.9％（＋）体 実施例４〜７ ２−（４−クロロフェニル）−３−メチルクロトン酸
に代えて表−１に記載の基質を用いる以外は実施例１と
同様に反応、後処理して表−１に示す結果を得た。Conversion rate 95% Selectivity> 98% Optical yield 57.9% (+) form Examples 4 to 7 2- (4-chlorophenyl) -3-methylcrotonic acid was replaced with the substrates shown in Table-1. Reaction and post-treatment were carried out in the same manner as in Example 1 to obtain the results shown in Table 1.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｂ 53/00 Ｂ 7419−4Ｈ 61/00 ３００ Ｃ０７Ｍ 7:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C07B 53/00 B 7419-4H 61/00 300 C07M 7:00
Claims (1)
を、R3およびR4は水素原子、ハロゲン原子、低級アルキ
ル基または低級アルコキシル基を示す） で示されるオレフィン誘導体を、一般式（III） （式中、Ｒは低級アルキルフェニル基、低級アルコキシ
フェニル基またはC3〜C8のシクロアルキル基を示す） で示される光学活性ビナフチル誘導体で修飾したロジウ
ム触媒の存在下に不斉水素還元することを特徴とする一
般式（Ｉ） （式中、R1、R2、R3、R4は前記したと同じ意味を有す
る） で示される光学活性フェニル酢酸誘導体の製造法。1. General formula (II) (In the formula, R 1 and R 2 represent a hydrogen atom or a lower alkyl group, and R 3 and R 4 represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group). III) (Wherein R represents a lower alkylphenyl group, a lower alkoxyphenyl group or a C 3 to C 8 cycloalkyl group), and asymmetric hydrogen reduction is carried out in the presence of a rhodium catalyst modified with an optically active binaphthyl derivative. General formula (I) characterized by (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62162690A JPH0816078B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing optically active phenylacetic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62162690A JPH0816078B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing optically active phenylacetic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS649952A JPS649952A (en) | 1989-01-13 |
| JPH0816078B2 true JPH0816078B2 (en) | 1996-02-21 |
Family
ID=15759448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62162690A Expired - Lifetime JPH0816078B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing optically active phenylacetic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816078B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730104B2 (en) * | 1987-09-08 | 1995-04-05 | 高砂香料工業株式会社 | Ruthenium-phosphine complex |
| EP0420623B1 (en) * | 1989-09-28 | 1995-11-22 | Canon Kabushiki Kaisha | Communication apparatus and method |
| JP2681057B2 (en) * | 1990-10-01 | 1997-11-19 | 高砂香料工業株式会社 | 2,2'-bis (diphenylphosphino) -5,5 ', 6,6', 7,7 ', 8,8'-octahydro-1,1'-binaphthyl and transition metal having this as a ligand Complex |
| JP3020128B2 (en) * | 1994-03-08 | 2000-03-15 | 高砂香料工業株式会社 | Method for producing optically active carboxylic acid |
| US5910606A (en) * | 1996-01-31 | 1999-06-08 | Hoffmann-La Roche Inc. | Process for making α,β-unsaturated carboxylic acids |
| JP4714864B2 (en) * | 2005-06-14 | 2011-06-29 | 株式会社デュプロ | Bookbinding equipment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63239245A (en) * | 1986-11-14 | 1988-10-05 | Takasago Corp | Production of optically active carboxylic acid |
-
1987
- 1987-06-29 JP JP62162690A patent/JPH0816078B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63239245A (en) * | 1986-11-14 | 1988-10-05 | Takasago Corp | Production of optically active carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS649952A (en) | 1989-01-13 |
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