JPH06135906A - Method for racemizing optically active diamine - Google Patents
Method for racemizing optically active diamineInfo
- Publication number
- JPH06135906A JPH06135906A JP4291891A JP29189192A JPH06135906A JP H06135906 A JPH06135906 A JP H06135906A JP 4291891 A JP4291891 A JP 4291891A JP 29189192 A JP29189192 A JP 29189192A JP H06135906 A JPH06135906 A JP H06135906A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- racemization
- active diamine
- reaction
- diamine
- 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.)
- Granted
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医薬中間原料として、
また、塩基性光学分割剤として有用な光学活性ジアミン
のラセミ化方法に関する。BACKGROUND OF THE INVENTION The present invention is
It also relates to a racemization method of an optically active diamine useful as a basic optical resolving agent.
【０００２】[0002]
【従来の技術】光学活性１，２−ジアミノプロパンは
（ＲＳ）−１，２−ジアミノプロパンを光学活性酒石酸
（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．８１ ｐ２９０（１９
５８））、光学活性ジベンゾイル酒石酸（特開平３−７
２４４６号公報）または光学活性Ｎ−ベンゼンスルホニ
ルアスパラギン酸（特開平４−１８０５７号公報）を分
割剤として光学分割することにより容易に得られる。ま
た、光学活性１，２−ジアミノシクロヘキサンは（Ｒ
Ｓ）−１，２−ジアミノシクロヘキサンを光学活性酒石
酸（Ａｃｔａ Ｃｈｅｍ．Ｓｃａｎｄ．２６（９）ｐ３
６０５（１９７２））で光学分割することにより容易に
得ることができる。Optically active 1,2-diaminopropane is obtained by converting (RS) -1,2-diaminopropane into optically active tartaric acid (J. Am. Chem. Soc. 81 p290 (19).
58)), optically active dibenzoyl tartaric acid (JP-A-3-7)
2446) or optically active N-benzenesulfonylaspartic acid (JP-A-4-18057) as a resolving agent. Further, the optically active 1,2-diaminocyclohexane is (R
S) -1,2-diaminocyclohexane was converted into optically active tartaric acid (Acta Chem. Scand. 26 (9) p3).
It can be easily obtained by optical division at 605 (1972)).
【０００３】ジアミン類は工業的には通常ラセミ体とし
て製造され、分割などの方法により、光学活性ジアミン
類が生産される。ここで、不斉炭素原子１個のジアミン
にはＲ、Ｓ体の２つの光学異性体が存在するが、１，２
−ジアミノシクロヘキサンのように２個の不斉炭素原子
を持つジアミンにはｔｒａｎｓ−（Ｓ，Ｓ）、ｔｒａｎ
ｓ−（Ｒ，Ｒ）体の他に光学的に不活性なメソ体である
ｃｉｓ体の３種の光学異性体が存在する。これらのラセ
ミ体を光学分割することにより１つの有用な光学活性体
が得られる。この際、不要となる残りの光学対掌体をラ
セミ化して分割を繰返すことができれば工業的に有利な
光学活性体の製造法となる。したがって、ラセミ化は非
常に重要な技術となる。Diamines are usually industrially produced as a racemate, and optically active diamines are produced by a method such as resolution. Here, the diamine having one asymmetric carbon atom has two optical isomers of R and S isomers.
-For diamines having two asymmetric carbon atoms such as diaminocyclohexane, trans- (S, S), tran
In addition to the s- (R, R) isomer, there are three optical isomers of a cis isomer which is an optically inactive meso isomer. Optical resolution of these racemates gives one useful optically active substance. At this time, if the remaining unnecessary optical antipodes can be racemized and the division can be repeated, it is an industrially advantageous method for producing an optically active substance. Therefore, racemization is a very important technique.
【０００４】一般的に、有機化合物のラセミ化方法とし
ては、酸またはアルカリの存在下または不存在下で加熱
する方法が知られており、たとえば、アミンのラセミ化
方法としては、ナトリウム、水酸化ナトリウムなどの塩
基を用いる方法（特開昭５０−５０３１７号公報）が知
られている。[0004] Generally, as a method for racemizing an organic compound, a method of heating in the presence or absence of an acid or an alkali is known. For example, as a method for racemizing an amine, sodium or hydroxide is used. A method using a base such as sodium (JP-A-50-50317) is known.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、光学活
性ジアミンのラセミ化方法は知られていない。However, a method for racemizing an optically active diamine is not known.
【０００６】また、このラセミ化が１０気圧以下で進行
できれば、簡易な耐圧反応釜中で操作性よく、かつより
安全にラセミ化反応を行うことができ、工業的に有利で
ある。Further, if this racemization can proceed at 10 atm or less, the racemization reaction can be carried out safely in a simple pressure-resistant reaction vessel, and it is industrially advantageous.
【０００７】本発明者らは、特定の光学活性ジアミンを
工業的に有利にラセミ化することを目的として鋭意検討
した。The present inventors have conducted extensive studies for the purpose of industrially advantageous racemization of a specific optically active diamine.
【０００８】[0008]
【課題を解決するための手段】その結果、この目的は水
素存在下、接触還元触媒とともに加熱反応させることに
よって光学活性ジアミンをラセミ化できることが判っ
た。As a result, it was found that the purpose of this reaction is to racemize the optically active diamine by heating and reaction with a catalytic reduction catalyst in the presence of hydrogen.
【０００９】すなわち、本発明は次の一般式(I)That is, the present invention has the following general formula (I)
【化２】 （式中、Ｒ1 は水素原子、アルキル基あるいはアリル基
を示し、Ｒ2 はアルキル基あるいはアリル基を示し、ま
たはＲ1 、Ｒ2 は結合して環を形成する炭素数２〜６の
アルキル基を示す。）で表される光学活性ジアミンを、
水素存在下、接触還元触媒とともに加熱することを特徴
とする光学活性ジアミンのラセミ化方法である。[Chemical 2] (In the formula, R 1 represents a hydrogen atom, an alkyl group or an allyl group, R 2 represents an alkyl group or an allyl group, or R 1 and R 2 are alkyl having 2 to 6 carbon atoms to form a ring. Group), an optically active diamine represented by
A method for racemizing an optically active diamine, which comprises heating with a catalytic reduction catalyst in the presence of hydrogen.
【００１０】以下、本発明の構成を詳細に説明する。The structure of the present invention will be described in detail below.
【００１１】本発明で原料として使用される光学活性ジ
アミンは、前記式(I) で表される化合物であり、たとえ
ば、１，２−ジアミノプロパン、１，２−ジアミノシク
ロヘキサン、１，２−ジフェニルエチレンジアミンなど
が挙げられる。本発明で使用される光学活性ジアミン
は、Ｒ体、Ｓ体、メソ体あるいはこれらのうち１つの光
学異性体を等量以上含むものも使用することができる。The optically active diamine used as a raw material in the present invention is a compound represented by the above formula (I), and examples thereof include 1,2-diaminopropane, 1,2-diaminocyclohexane and 1,2-diphenyl. Examples thereof include ethylenediamine. As the optically active diamine used in the present invention, an R isomer, an S isomer, a meso isomer, or one containing one or more optical isomers in equal amounts or more can be used.
【００１２】接触還元触媒としてはパラジウム炭素など
の貴金属系触媒、ラネーニッケル、ラネーコバルト、ラ
ネー鉄、ラネー銅などのラネー触媒、還元ニッケル、漆
原ニッケル、ギ酸ニッケルなどのニッケル触媒をそれぞ
れ単独で使用するか、または２種以上の混合物として使
用するが、特にラネーニッケル、ラネーコバルトが好ま
しい。これらの触媒の使用量は光学活性ジアミン１部に
対して、０．０１〜０．５部がよい。また、使用した触
媒は活性のある限り何回でもリサイクル使用できる。As the catalytic reduction catalyst, are noble metal catalysts such as palladium carbon, Raney catalysts such as Raney nickel, Raney cobalt, Raney iron and Raney copper, nickel catalysts such as reduced nickel, lacquer nickel and nickel formate used alone? , Or a mixture of two or more thereof, and Raney nickel and Raney cobalt are particularly preferable. The amount of these catalysts used is preferably 0.01 to 0.5 part with respect to 1 part of the optically active diamine. Further, the catalyst used can be recycled and used as many times as long as it is active.
【００１３】ラセミ化反応は無溶媒でも、水が共存して
も実施できる。水を共存させるときは、アンモニアを添
加することが好ましい。アンモニアの添加によってジア
ミンから誘導されるアルコールなどの副生を抑制するこ
とができる。アンモニアの添加量は水濃度にも関係する
が、通常、光学活性ジアミン１モルに対して０．１〜
５．０モルが適量である。もちろん、水以外の溶媒を添
加してもよい。ここで、使用する溶媒としては光学活性
ジアミンを変質せしめることなく、かつラセミ化反応を
妨害しないものであれば何でもよく、ベンゼン、トルエ
ンなど芳香族系、エーテル、ジオキサンなどのエーテル
系、ヘキサン、シクロヘキサンなどの脂肪族炭化水素系
溶媒を用いることができる。The racemization reaction can be carried out without solvent or in the presence of water. When coexisting with water, it is preferable to add ammonia. By-products such as alcohol derived from diamine can be suppressed by adding ammonia. Although the addition amount of ammonia depends on the water concentration, it is usually 0.1 to 0.1 mol per 1 mol of the optically active diamine.
A suitable amount is 5.0 moles. Of course, a solvent other than water may be added. Here, the solvent to be used may be any as long as it does not deteriorate the optically active diamine and does not interfere with the racemization reaction, benzene, aromatic compounds such as toluene, ethers, ethers such as dioxane, hexane, cyclohexane. Aliphatic hydrocarbon solvents such as can be used.
【００１４】ラセミ化反応は加熱下に行われ、通常温度
５０〜２００℃、好ましくは９０〜１７０℃で行われ
る。反応は水素存在下で行われ、使用水素圧は特に規制
はなく、通常常圧から３０気圧で行われるが、１０気圧
より低圧下でも十分である。反応時間は反応温度などそ
の他の条件により適宜選択することができるが、一般的
には１〜３０時間で終了する。The racemization reaction is carried out under heating, usually at a temperature of 50 to 200 ° C, preferably 90 to 170 ° C. The reaction is carried out in the presence of hydrogen, and the hydrogen pressure used is not particularly limited and is usually carried out at atmospheric pressure to 30 atm, but a pressure lower than 10 atm is also sufficient. The reaction time can be appropriately selected depending on other conditions such as reaction temperature, but it is generally completed in 1 to 30 hours.
【００１５】目的とするラセミ化されたジアミンは反応
終了後、触媒を濾過し、濾液を濃縮あるいは必要に応じ
て蒸留するなどして公知の方法によって容易に単離する
ことができる。After the completion of the reaction, the desired racemized diamine can be easily isolated by a known method by filtering the catalyst and concentrating the filtrate or distilling it if necessary.
【００１６】[0016]
【実施例】以下、実施例により本発明を説明するが、本
発明はこれれの実施例により限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例のラセミ化に伴う光学純度の変化
は、ジアミンと２，３，４，６−テトラ−Ｏ−アセチル
−β−Ｄ−グルコピラノシルイソチオシオナート（ＧＩ
ＴＣ）とを反応させたのち、高速液体クロマトグラフィ
ー（ＨＰＬＣ）により次の条件で分析を行った。また、
ラセミ化率は次式より算出した。The change in optical purity due to racemization in the examples was as follows. Diamine and 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate (GI
After reacting with TC), analysis was performed by high performance liquid chromatography (HPLC) under the following conditions. Also,
The racemization rate was calculated from the following formula.
【００１８】＜ＨＰＬＣ条件１＞ （１，２−ジアミノプロパン（以下、ＤＡＰと略す）の
ラセミ化の場合） カラム：μ−Ｂｏｎｄａｓｐｈｅｒｅ（Ｗａｔｅｒｓ）
３．９ｍｍφ×１５０ｍｍ 溶離液：０．０５％リン酸／アセトニトリル＝６５／３
５ 流速：１．０ml／min 検出：ＵＶ２５４nm 保持時間：（Ｓ）−ＤＡＰのＧＩＴＣ誘導体化物１９．
６分、（Ｒ）−ＤＡＰのＧＩＴＣ誘導体化物２３．４分<HPLC condition 1> (In the case of racemization of 1,2-diaminopropane (hereinafter abbreviated as DAP)) Column: μ-Bondasphere (Waters)
3.9 mmφ × 150 mm Eluent: 0.05% phosphoric acid / acetonitrile = 65/3
5. Flow rate: 1.0 ml / min Detection: UV254 nm Retention time: GITC derivative of (S) -DAP 19.
6 minutes, (R) -DAP GITC derivative 23.4 minutes
【００１９】＜ＨＰＬＣ条件２＞ （１．２−ジアミノシクロヘキサン（以下、ＤＡＣＨと
略す）のラセミ化の場合）カラム：ＣＡＰＣＥＬＬ Ｐ
ＡＫ ＳＧ１２０（資生堂）４．６ｍｍφ×１５０ｍｍ
溶離液：０．０５％リン酸／アセトニトリル＝４０／６
０ 流速：１．０ml／min 検出：ＵＶ２５４nm 保持時間：（１Ｓ、２Ｓ）−ＤＡＣＨのＧＩＴＣ誘導体
化物１４．０分、ｃｉｓ−ＤＡＣＨのＧＩＴＣ誘導体化
物１８．０分、（１Ｒ、２Ｒ）−ＤＡＣＨのＧＩＴＣ誘
導体化物２１．５分<HPLC condition 2> (In the case of racemization of 1.2-diaminocyclohexane (hereinafter abbreviated as DACH)) Column: CAPCELL P
AK SG120 (Shiseido) 4.6mmφ x 150mm
Eluent: 0.05% phosphoric acid / acetonitrile = 40/6
0 Flow rate: 1.0 ml / min Detection: UV254 nm Retention time: (1S, 2S) -DACCH GITC derivative 14.0 minutes, cis-DACH GITC derivative 18.0 minutes, (1R, 2R) -DACH GITC derivative 21.5 minutes
【００２０】[0020]
【式１】 [Formula 1]
【００２１】実施例１ １０mlガラス製アンプルオートクレーブに（Ｓ）−ＤＡ
Ｐの６０％水溶液１．０ｇ（０．００８モル、光学純度
９８％ｅｅ）、２８％アンモニア水０．５ｇ（０．００
８モル）、ラネーコバルト０．１３ｇ（ｗｅｔ）を仕込
み、水素圧１５気圧に加圧して、反応温度１３０℃で１
８時間反応した。反応終了後、冷却したのち開封し、反
応液を濾過して触媒を除いた。反応濾液中のＤＡＰ濃度
をＨＰＬＣで分析したところ、ＤＡＰの回収率は７８％
であった。光学純度は０％であり、ラセミ化率は１００
％であった。Example 1 (S) -DA in a 10 ml glass ampoule autoclave.
1.0% of 60% aqueous solution of P (0.008 mol, optical purity 98% ee), 0.5% of 28% ammonia water (0.00
8 mol) and Raney cobalt 0.13 g (wet) were charged, the hydrogen pressure was increased to 15 atm, and the reaction temperature was 130 ° C.
Reacted for 8 hours. After completion of the reaction, the mixture was cooled and then opened, and the reaction solution was filtered to remove the catalyst. When the DAP concentration in the reaction filtrate was analyzed by HPLC, the DAP recovery rate was 78%.
Met. Optical purity is 0%, racemization rate is 100
%Met.
【００２２】実施例２ １０mlガラス製アンプルオートクレーブに（Ｓ）−ＤＡ
Ｐ１．０ｇ（０．０１３モル、光学純度９８％ｅｅ）と
ラネーコバルト０．１３ｇ（ｗｅｔ）を仕込み、水素圧
５気圧に加圧して、反応温度１３０℃で２１時間反応し
た。反応終了後、冷却したのち開封し、反応液を濾過し
て触媒を除いた。反応濾液中のＤＡＰ濃度をＨＰＬＣで
分析したところ、ＤＡＰの回収率は５７％であった。光
学純度は０％であり、ラセミ化率は１００％であった。Example 2 (S) -DA in a 10 ml glass ampoule autoclave.
P1.0 g (0.013 mol, optical purity 98% ee) and Raney cobalt 0.13 g (wet) were charged, the hydrogen pressure was increased to 5 atm, and the reaction was carried out at a reaction temperature of 130 ° C. for 21 hours. After completion of the reaction, the mixture was cooled and then opened, and the reaction solution was filtered to remove the catalyst. When the DAP concentration in the reaction filtrate was analyzed by HPLC, the DAP recovery rate was 57%. The optical purity was 0% and the racemization rate was 100%.
【００２３】実施例３ １００mlステンレス製オートクレーブに（Ｓ）−ＤＡＰ
の６０％水溶液１０．０ｇ（０．０８１モル、光学純度
９８％ｅｅ）、２８％アンモニア水２．５ｇ（０．０４
１モル）、ラネーコバルト１．２ｇ（ｗｅｔ）を仕込
み、水素圧５気圧に加圧して、反応温度１２５℃で１８
時間反応した。反応終了後、冷却したのち開封し、反応
液を濾過して触媒を除いた。濾液を常圧蒸留して４８％
のＤＡＰ水溶液８．９ｇを得た。ＤＡＰの回収率は７１
％であり、ラセミ化率は１００％であった。Example 3 (S) -DAP was added to a 100 ml stainless steel autoclave.
60% aqueous solution of 10.0 g (0.081 mol, optical purity 98% ee), 28% ammonia water 2.5 g (0.04
1 mol) and Raney cobalt 1.2 g (wet) were charged, the hydrogen pressure was increased to 5 atm, and the reaction temperature was 125 ° C. for 18 minutes.
Reacted for hours. After completion of the reaction, the mixture was cooled and then opened, and the reaction solution was filtered to remove the catalyst. The filtrate is distilled at atmospheric pressure to 48%
8.9 g of an aqueous DAP solution was obtained. Recovery rate of DAP is 71
%, And the racemization rate was 100%.
【００２４】実施例４ １０mlガラス製アンプルオートクレーブに（１Ｒ、２
Ｒ）−ＤＡＣＨ０．７ｇ（０．００６モル、光学純度９
９％ｅｅ）、２８％アンモニア水０．４ｇ（０．００７
モル）、ラネーコバルト０．１４ｇ（ｗｅｔ）を仕込
み、水素圧５気圧に加圧して、反応温度１３０℃で２１
時間反応した。反応終了後、一部サンプリングして組成
を調べたところ、反応濾液中のＤＡＣＨの組成比はｃｉ
ｓ／ｔｒａｎｓ（１Ｓ、２Ｓ）／ｔｒａｎｓ（１Ｒ、２
Ｒ）＝１７／２７／５６であり、ラセミ化率は７１％で
あった。Example 4 Into a 10 ml glass ampoule autoclave (1R, 2
R) -DACH 0.7 g (0.006 mol, optical purity 9
9% ee), 28% ammonia water 0.4 g (0.007)
Mol) and Raney cobalt 0.14 g (wet) were charged, the hydrogen pressure was increased to 5 atm, and the reaction temperature was 130 ° C. for 21 minutes.
Reacted for hours. After completion of the reaction, part of the composition was sampled and the composition was investigated.
s / trans (1S, 2S) / trans (1R, 2
R) = 17/27/56, and the racemization rate was 71%.
【００２５】実施例５ 実施例４で得られた反応液をさらに水素圧５気圧に加圧
して、反応温度１４０℃で２１時間反応した。反応終了
後、冷却したのち開封し、反応液を濾過して触媒を除い
た。反応濾液中のＤＡＣＨの組成比はｃｉｓ／ｔｒａｎ
ｓ（１Ｓ、２Ｓ）／ｔｒａｎｓ（１Ｒ、２Ｒ）＝１７／
３８／４６であり、ラセミ化率は９２％であった。Example 5 The reaction solution obtained in Example 4 was further pressurized to a hydrogen pressure of 5 atm and reacted at a reaction temperature of 140 ° C. for 21 hours. After completion of the reaction, the mixture was cooled and then opened, and the reaction solution was filtered to remove the catalyst. The composition ratio of DACH in the reaction filtrate is cis / tran
s (1S, 2S) / trans (1R, 2R) = 17 /
It was 38/46 and the racemization rate was 92%.
【００２６】[0026]
【発明の効果】本発明によれば、光学活性ジアミンを高
ラセミ化率でラセミ化できる。したがって、ラセミ化後
さらに光学分割を繰返すことにより、収率よく有用な光
学活性体に転換できる。According to the present invention, an optically active diamine can be racemized at a high racemization rate. Therefore, by repeating optical resolution after racemization, a useful optically active substance can be converted in good yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 211/27 9280−4Ｈ // Ｂ０１Ｊ 25/00 Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C07C 211/27 9280-4H // B01J 25/00 C07B 61/00 300
Claims (1)
を表し、Ｒ2 はアルキル基あるいはアリル基を表し、ま
たは、Ｒ1 、Ｒ2 は結合して環を形成する炭素数２〜６
のアルキル基を表す。）で表される光学活性ジアミン
を、水素存在下、接触還元触媒とともに加熱することを
特徴とする光学活性ジアミンのラセミ化方法。1. The following general formula (I): (In the formula, R 1 represents a hydrogen atom, an alkyl group or an allyl group, R 2 represents an alkyl group or an allyl group, or R 1 and R 2 are bonded to each other to form a ring.
Represents an alkyl group. ) The optically active diamine represented by the formula (1) is heated with a catalytic reduction catalyst in the presence of hydrogen, to provide a racemization method for the optically active diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29189192A JP3230300B2 (en) | 1992-10-30 | 1992-10-30 | Racemization of optically active diamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29189192A JP3230300B2 (en) | 1992-10-30 | 1992-10-30 | Racemization of optically active diamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06135906A true JPH06135906A (en) | 1994-05-17 |
| JP3230300B2 JP3230300B2 (en) | 2001-11-19 |
Family
ID=17774793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29189192A Expired - Lifetime JP3230300B2 (en) | 1992-10-30 | 1992-10-30 | Racemization of optically active diamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3230300B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6049007A (en) * | 1999-02-12 | 2000-04-11 | Basf Aktiengesellschaft | Racemization of optically active amines |
| WO2000029357A1 (en) * | 1998-11-13 | 2000-05-25 | Basf Aktiengesellschaft | Method for racemization of optically active amines |
| WO2001096301A1 (en) * | 2000-06-14 | 2001-12-20 | Toray Industries, Inc. | Processes for producing racemic piperidine derivative and for producing optically active piperidine derivative |
-
1992
- 1992-10-30 JP JP29189192A patent/JP3230300B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153797A (en) * | 1998-02-12 | 2000-11-28 | Basf Aktiengesellschaft | Racemizing of optically active amines |
| WO2000029357A1 (en) * | 1998-11-13 | 2000-05-25 | Basf Aktiengesellschaft | Method for racemization of optically active amines |
| US6160178A (en) * | 1998-11-13 | 2000-12-12 | Basf Aktiengesellschaft | Racemization of optically active amines |
| US6049007A (en) * | 1999-02-12 | 2000-04-11 | Basf Aktiengesellschaft | Racemization of optically active amines |
| WO2001096301A1 (en) * | 2000-06-14 | 2001-12-20 | Toray Industries, Inc. | Processes for producing racemic piperidine derivative and for producing optically active piperidine derivative |
| US6962998B2 (en) | 2000-06-14 | 2005-11-08 | Toray Industries, Inc. | Processes for producing racemic piperidine derivative and for producing optically active piperidine derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3230300B2 (en) | 2001-11-19 |
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