JP3230300B2 - Racemization of optically active diamines - Google Patents
Racemization of optically active diaminesInfo
- Publication number
- JP3230300B2 JP3230300B2 JP29189192A JP29189192A JP3230300B2 JP 3230300 B2 JP3230300 B2 JP 3230300B2 JP 29189192 A JP29189192 A JP 29189192A JP 29189192 A JP29189192 A JP 29189192A JP 3230300 B2 JP3230300 B2 JP 3230300B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- racemization
- reaction
- diamine
- dap
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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。The present invention relates to a pharmaceutical intermediate material,
The present invention also relates to a method for racemizing 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。2. Description of the Related Art 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 dibenzoyltartaric acid (JP-A-3-7
2446) or optically active N-benzenesulfonyl aspartic acid (Japanese Patent Application Laid-Open No. 4-18057) can be easily obtained by optical resolution. The optically active 1,2-diaminocyclohexane is (R
S) -1,2-Diaminocyclohexane was converted to optically active tartaric acid (Acta Chem. Scand. 26 (9) p3).
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。[0003] Diamines are industrially usually produced as racemates, and optically active diamines are produced by a method such as resolution. Here, the diamine having one asymmetric carbon atom has two R and S optical isomers.
Diamines having two asymmetric carbon atoms such as -diaminocyclohexane include trans- (S, S) and tran.
In addition to the s- (R, R) form, there are three optical isomers of the cis form, which is an optically inactive meso form. By optically resolving these racemates, one useful optically active substance is obtained. In this case, if the remaining optical enantiomer that becomes unnecessary 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。In general, as a method of racemizing an organic compound, a method of heating in the presence or absence of an acid or an alkali is known. For example, a method of racemizing an amine includes sodium, hydroxide, and the like. 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。If the racemization can proceed at 10 atm or less, the racemization reaction can be carried out in a simple pressure-resistant reactor with good operability and more safely, which 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 made intensive studies for the purpose of industrially advantageously racemizing 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、ラネー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 has been found that, for this purpose, the optically active diamine can be racemized by a heat reaction with a Raney 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 provides 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、ラネー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。Embedded image (In the formula, R1 represents a hydrogen atom, an alkyl group or an allyl group, R2 represents an alkyl group or an allyl group, or R1 and R2 represent an alkyl group having 2 to 6 carbon atoms which forms a ring by bonding. ) Represented by the optically active diamine,
This is a method for racemizing an optically active diamine, which comprises heating together with a Raney catalyst in the presence of hydrogen.
【００１０】以下、本発明の構成を詳細に説明する。Hereinafter, the configuration of the present invention will be described in detail.
【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), for example, 1,2-diaminopropane, 1,2-diaminocyclohexane, 1,2-diphenyl And ethylenediamine. The optically active diamine used in the present invention may be an R-form, an S-form, a meso-form, or a diamine containing at least one of the optical isomers.
【００１２】ラネー触媒としては、ラネーニッケル、ラ
ネーコバルト、ラネー鉄、ラネー銅などをそれぞれ単独
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。[0012] As the Raney catalyst, Raney nickel, Raney cobalt, Raney iron, either used alone respectively etc. Raney copper, or used as a mixture of two or more, in particular Raney nickel, Raney cobalt are preferable.
The use amount of these catalysts is preferably 0.01 to 0.5 part based on 1 part of the optically active diamine. The used catalyst can be recycled as many times 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 water is allowed to coexist, it is preferable to add ammonia. By the addition of ammonia, by-products such as alcohols derived from diamines can be suppressed. The amount of ammonia added depends on the water concentration, but is usually 0.1 to 0.1 mol per mol of optically active diamine.
5.0 mol is an appropriate amount. Of course, a solvent other than water may be added. Here, any solvent may be used as long as it does not deteriorate the optically active diamine and does not interfere with the racemization reaction.Aromatic solvents such as benzene and toluene, ethers such as ether and dioxane, hexane, and cyclohexane And other aliphatic hydrocarbon solvents.
【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 there is no particular restriction on the hydrogen pressure used. The reaction is usually carried out at normal pressure to 30 atm, but a pressure lower than 10 atm is sufficient. The reaction time can be appropriately selected depending on other conditions such as the reaction temperature, but 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 completion of the reaction, the desired racemized diamine can be easily isolated by a known method such as filtration of the catalyst and concentration or distillation of the filtrate as required.
【００１６】[0016]
【実施例】以下、実施例により本発明を説明するが、本
発明はこれらの実施例により限定されるものではない。EXAMPLES Hereinafter, the present invention will be described by examples, the present invention is not limited by 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 changes in optical purity due to the racemization in the Examples were as follows: diamine and 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylisothiothionate (GI
TC), and analyzed by high performance liquid chromatography (HPLC) under the following conditions. Also,
The racemization rate was calculated from the following equation.
【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: UV 254 nm Retention time: GITC derivative of (S) -DAP
6 minutes, GITC derivatized product of (R) -DAP 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 conditions 2> (in the case of racemization of 1.2-diaminocyclohexane (hereinafter abbreviated as DACH)) Column: CAPCELL P
AK SG120 (Shiseido) 4.6mmφ × 150mm
Eluent: 0.05% phosphoric acid / acetonitrile = 40/6
0 Flow rate: 1.0 ml / min Detection: UV 254 nm Retention time: 14.0 minutes of GITC derivatized product of (1S, 2S) -DACH, 18.0 minutes of GITC derivatized product of cis-DACH, (1R, 2R) -DACH GITC derivatized product 21.5 minutes
【００２０】[0020]
【式１】 (Equation 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 was added to a 10 ml glass ampoule autoclave.
1.0 g (0.008 mol, optical purity 98% ee) of a 60% aqueous solution of P, 0.5 g (0.00%
8 mol), and Raney cobalt 0.13 g (wet) were charged and pressurized to a hydrogen pressure of 15 atm.
The reaction was performed for 8 hours. After completion of the reaction, the reaction solution was cooled and 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 was 78%.
Met. The optical purity is 0% and the racemization ratio 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 was added to a 10 ml glass ampoule autoclave.
1.0 g (0.013 mol, 98% ee of optical purity) of P and 0.13 g (wet) of Raney cobalt were charged, pressurized to 5 atm of hydrogen pressure, and reacted at a reaction temperature of 130 ° C. for 21 hours. After completion of the reaction, the reaction solution was cooled and 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 ratio 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.
10.0 g (0.081 mol, optical purity 98% ee) of a 60% aqueous solution of 2.5%
1 mol), and Raney cobalt 1.2 g (wet) were charged and hydrogen pressure was increased to 5 atm.
Reacted for hours. After completion of the reaction, the reaction solution was cooled and opened, and the reaction solution was filtered to remove the catalyst. 48% of the filtrate is distilled under normal pressure
8.9 g of a DAP aqueous solution was obtained. DAP recovery rate 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６５％で
あった。Example 4 A 10 ml glass ampoule autoclave (1R, 2
R) -DACH 0.7 g (0.006 mol, optical purity 9)
9% ee), 0.4 g of 28% ammonia water (0.007
Mol), 0.14 g (wet) of Raney cobalt, and pressurized to a hydrogen pressure of 5 atm.
Reacted for hours. After the reaction was completed, a part of the composition was examined by sampling to find that the composition ratio of DACH in the reaction filtrate was ci.
s / trans (1S, 2S) / trans (1R, 2
R) = 17/27/56, and the racemization ratio was 65 %.
【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９０％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 reaction solution was cooled and 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 /
A 38/46, racemization ratio was 90%.
【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, the optically active diamine can be racemized at a high racemization ratio. Therefore, by repeating the optical resolution after the racemization, it can be converted into a useful optically active substance in good yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０７Ｃ 211/27 Ｃ０７Ｃ 211/27 // Ｂ０１Ｊ 25/00 Ｂ０１Ｊ 25/00 Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 209/68 C07B 55/00 C07B 57/00 360 C07C 211/11 C07C 211/18 C07C 211/27 C07B 61/00 300 ────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C07C 211/27 C07C 211/27 // B01J 25/00 B01J 25/00 C07B 61/00 300 C07B 61/00 300 (58) Survey Field (Int.Cl. 7 , DB name) C07C 209/68 C07B 55/00 C07B 57/00 360 C07C 211/11 C07C 211/18 C07C 211/27 C07B 61/00 300
Claims (2)
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、ラネー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): (Wherein, R1 represents a hydrogen atom, an alkyl group or an allyl group, R2 represents an alkyl group or an allyl group, or R1 and R2 represent a group having 2 to 6 carbon atoms which form a ring by bonding.
Represents an alkyl group. A) racemization method for an optically active diamine, comprising heating the optically active diamine represented by the formula (1) together with a Raney catalyst in the presence of hydrogen.
特徴とする請求項１記載の光学活性ジアミンのラセミ化
方法。 2. Adding ammonia in the presence of water.
Racemization of the optically active diamine according to claim 1, characterized in that:
Method.
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 JPH06135906A (en) | 1994-05-17 |
| JP3230300B2 true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19905837A1 (en) * | 1999-02-12 | 2000-08-17 | Basf Ag | Process for the racemization of optically active amines |
| AU4034699A (en) * | 1998-11-13 | 2000-06-05 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06135906A (en) | 1994-05-17 |
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