JPH11171860A - Production of optically active n-substituted azetidine-2-carboxylic acid - Google Patents
Production of optically active n-substituted azetidine-2-carboxylic acidInfo
- Publication number
- JPH11171860A JPH11171860A JP33540297A JP33540297A JPH11171860A JP H11171860 A JPH11171860 A JP H11171860A JP 33540297 A JP33540297 A JP 33540297A JP 33540297 A JP33540297 A JP 33540297A JP H11171860 A JPH11171860 A JP H11171860A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- optically active
- azetidine
- amine
- nitrobenzenesulfonyl
- 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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光学活性アゼチジン
−２−カルボン酸の製造方法に関する。The present invention relates to a method for producing optically active azetidine-2-carboxylic acid.
【０００２】[0002]
【従来の技術】光学活性アゼチジン−２−カルボン酸は
医薬品の原料として重要な化合物である。従来よりかか
る光学活性アゼチジン−２−カルボン酸の製造方法とし
ては、例えば光学活性Ｎ−トシル−アゼチジン−２−カ
ルボン酸をバーチ還元でトシル基を脱離する方法（特開
平４７−１４４５７号公報）が知られているが、この方
法では金属Naが必須であるため発火等、安全性の問題が
あり、また反応終了後生成する無機塩をイオン交換樹脂
等により除去し、精製する工程が必要であるため工業的
に有利な方法とは言い難かった。2. Description of the Related Art Optically active azetidine-2-carboxylic acid is an important compound as a raw material for pharmaceuticals. As a conventional method for producing such optically active azetidine-2-carboxylic acid, for example, a method in which an optically active N-tosyl-azetidine-2-carboxylic acid is eliminated from the tosyl group by Birch reduction (Japanese Patent Application Laid-Open No. 47-14457). However, in this method, there is a problem of safety such as ignition because metal Na is indispensable, and a step of removing inorganic salts generated after completion of the reaction with an ion exchange resin or the like and purifying is required. For this reason, it was difficult to say that this method was industrially advantageous.
【０００３】[0003]
【発明が解決しようとする課題】そこで本発明者らは、
より工業的に有利な光学活性アゼチジン−２−カルボン
酸の製造方法を鋭意検討した結果、特定の置換基を持つ
光学活性Ｎ置換アゼチジン−２−カルボン酸がアミンの
存在下で光学活性アゼチジン−２−カルボン酸に導かれ
得ることを見出し、本発明に至った。SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies on a method for producing an optically active azetidine-2-carboxylic acid which is more industrially advantageous, it has been found that an optically active N-substituted azetidine-2-carboxylic acid having a specific substituent can be obtained in the presence of an amine. -It has been found that carboxylic acid can be led to the present invention.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、一般
式（１） （式中、Ｎｓは２−ニトロベンゼンスルホニル基、４−
ニトロベンゼンスルホニル基または２，４−ジニトロベ
ンゼンスルホニル基を示し、＊は不斉炭素原子を示す）
で示される光学活性Ｎ置換アゼチジン−２−カルボン酸
とチオフェノールまたはフェノールとをアミンの存在下
で反応させることを特徴とする光学活性アゼチジン−２
−カルボン酸の製造方法を提供するものである。That is, the present invention provides a compound represented by the following general formula (1): (Wherein, Ns is a 2-nitrobenzenesulfonyl group,
Represents a nitrobenzenesulfonyl group or a 2,4-dinitrobenzenesulfonyl group, and * represents an asymmetric carbon atom)
Reacting an optically active N-substituted azetidine-2-carboxylic acid with thiophenol or phenol in the presence of an amine.
A method for producing a carboxylic acid.
【０００５】[0005]
【発明の実施の形態】一般式（１）で示される光学活性
Ｎ置換アゼチジン−２−カルボン酸としては、（Ｓ）−
Ｎ−２−ニトロベンゼンスルホニルアゼチジン−２−カ
ルボン酸、（Ｓ）−Ｎ−４−ニトロベンゼンスルホニル
アゼチジン−２−カルボン酸、（Ｓ）−Ｎ−２，４−ジ
ニトロベンゼンスルホニルアゼチジン−２−カルボン
酸、（Ｒ）−Ｎ−２−ニトロベンゼンスルホニルアゼチ
ジン−２−カルボン酸、（Ｒ）−Ｎ−４−ニトロベンゼ
ンスルホニルアゼチジン−２−カルボン酸、（Ｒ）−Ｎ
−２，４−ジニトロベンゼンスルホニルアゼチジン−２
−カルボン酸が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION As the optically active N-substituted azetidine-2-carboxylic acid represented by the general formula (1), (S)-
N-2-nitrobenzenesulfonylacetidine-2-carboxylic acid, (S) -N-4-nitrobenzenesulfonylacetidine-2-carboxylic acid, (S) -N-2,4-dinitrobenzenesulfonylacetidine-2-carboxylic acid Carboxylic acid, (R) -N-2-nitrobenzenesulfonylacetidine-2-carboxylic acid, (R) -N-4-nitrobenzenesulfonylacetidine-2-carboxylic acid, (R) -N
-2,4-dinitrobenzenesulfonylacetidine-2
-Carboxylic acids.
【０００６】かかる光学活性Ｎ置換アゼチジン−２−カ
ルボン酸は、例えば一般式（２）、 （式中、Ｎｓ、＊は前記と同じ意味を表わし、Ｒは低級
アルキル基を、Ｘはハロゲン原子をそれぞれ表わす）で
示される光学活性Ｎ置換α−アミノ−γ−ハロゲノ酪酸
エステルを塩基の存在下に閉環させたのち、加水分解す
ることにより製造することができる。ここで、一般式
（２）において低級アルキル基としては炭素数１〜６の
直鎖または分岐状のアルキル基が、ハロゲン原子として
は塩素、臭素、ヨウ素原子等が挙げられる。また塩基と
しては例えば水素化ナトリウム、水素化リチウム等の水
素化アルカリ金属、ソジウムメチラート、ソジウムエチ
ラート等のアルカリ金属のアルコラート、水酸化ナトリ
ウム、水酸化カリウム等の水酸化アルカリ金属等が挙げ
られる。Such an optically active N-substituted azetidine-2-carboxylic acid has, for example, the general formula (2): (Wherein, Ns and * have the same meanings as described above, R represents a lower alkyl group, and X represents a halogen atom, respectively). It can be produced by hydrolyzing after ring closure below. Here, in the general formula (2), the lower alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, and the halogen atom includes chlorine, bromine, iodine atom and the like. Examples of the base include alkali metal hydrides such as sodium hydride and lithium hydride, alkali metal alcoholates such as sodium methylate and sodium ethylate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. No.
【０００７】上記光学活性Ｎ置換アゼチジンカルボン酸
とチオフェノールまたはフェノールとを、アミンの存在
下で反応させることにより、目的とする光学活性アゼチ
ジン−２−カルボン酸を製造することができる。The desired optically active azetidine-2-carboxylic acid can be produced by reacting the optically active N-substituted azetidine carboxylic acid with thiophenol or phenol in the presence of an amine.
【０００８】本発明において使用するアミンとしては、
脂肪族アミン、脂環式アミンまたは芳香族アミン等が挙
げられるが、中でも脂肪族アミンが好ましい。脂肪族ア
ミンとしては第１級アミン、第２級アミンおよび第３級
アミンいずれでもよくまた第２級および第３級アミンに
おいては各アルキル基が互いに同じであっても異なって
いてもよい。これら脂肪族アミンの中でもそのアルキル
基が全て炭素数１〜６の直鎖または分岐状の低級アルキ
ル基である低級アルキルアミンが、反応終了後、過剰の
アミンを除去する際、除去しやすいという観点から好ま
しい。The amine used in the present invention includes:
Examples thereof include aliphatic amines, alicyclic amines, and aromatic amines. Among them, aliphatic amines are preferable. The aliphatic amine may be any of a primary amine, a secondary amine and a tertiary amine. In the secondary and tertiary amines, each alkyl group may be the same or different. Among these aliphatic amines, lower alkylamines whose alkyl groups are all linear or branched lower alkyl groups having 1 to 6 carbon atoms are easily removed when excess amine is removed after the reaction. Is preferred.
【０００９】かかる低級アルキルアミンとしては、第１
級アミンとしてメチルアミン、エチルアミン、ｎ−プロ
ピルアミン、イソプロピルアミン、ブチルアミン、イソ
ブチルアミン、ｔｅｒｔ−ブチルアミン、ｎ−ペンチル
アミン、ｓｅｃ−ペンチルアミン等が例示でき、第２級
アミンとしてはジメチルアミン、ジエチルアミン、ジ−
ｎ−プロピルアミン、ジ−ｎ−ブチルアミン、ジ−ｎ−
ペンチルアミン、メチルエチルアミン、メチルプロピル
アミン等が例示でき、また第３級アミンとしてはトリメ
チルアミン、トリエチルアミン、トリ−ｎ−プロピルア
ミン、トリ−ｎ−ブチルアミン、メチルジエチルアミン
等が例示できる。As such lower alkylamines, there are
Examples of the secondary amine include methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, isobutylamine, tert-butylamine, n-pentylamine, and sec-pentylamine. Examples of the secondary amine include dimethylamine, diethylamine, Jee
n-propylamine, di-n-butylamine, di-n-
Examples of pentylamine, methylethylamine, methylpropylamine and the like, and examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, methyldiethylamine and the like.
【００１０】上記低級アルキルアミンの中でも、室温付
近以上の沸点を有する低級アルキルアミンが取り扱いの
観点からより好ましく、また本発明において溶媒を使用
する場合は、使用する溶媒の沸点付近より低い沸点を有
する低級アルキルアミンが使用した溶媒から過剰のアミ
ンを分離しやすいという観点からより好ましい。例えば
本発明において後述するような溶媒を使用する場合、低
級アルキルアミンの中でもｎ−プロピルアミン、ｎ−ブ
チルアミン、ｎ−ペンチルアミン、ジエチルアミン、ジ
−ｎ−プロピルアミン、トリエチルアミン、トリ−ｎ−
プロピルアミン等が特に好ましい。[0010] Of the above-mentioned lower alkylamines, lower alkylamines having a boiling point of about room temperature or higher are more preferable from the viewpoint of handling, and when a solvent is used in the present invention, it has a boiling point lower than the boiling point of the solvent used. Lower alkylamines are more preferable from the viewpoint that excess amine can be easily separated from the solvent used. For example, when a solvent as described later in the present invention is used, among lower alkylamines, n-propylamine, n-butylamine, n-pentylamine, diethylamine, di-n-propylamine, triethylamine, tri-n-
Propylamine and the like are particularly preferred.
【００１１】本発明において、上記アミンを単独で使用
しても２種以上を併用してもよく、２種以上を併用する
場合はその使用順序等には特に制限はない。またアミン
の使用量は光学活性Ｎ置換アゼチジン−２−カルボン酸
に対して通常１〜５０モル倍程度の範囲であり、２種以
上を併用する場合はその合計量が該範囲内であればよ
い。In the present invention, the above-mentioned amines may be used alone or in combination of two or more. When two or more are used in combination, there is no particular limitation on the order of use. The amount of the amine to be used is generally in the range of about 1 to 50 moles per mol of the optically active N-substituted azetidine-2-carboxylic acid, and when two or more kinds are used in combination, the total amount may be within the above range. .
【００１２】本発明において、チオフェノールまたはフ
ェノールの使用量は光学活性Ｎ置換アゼチジン−２−カ
ルボン酸の使用量以上であればよく、その上限値は経済
効率の観点から光学活性Ｎ置換アゼチジン−２−カルボ
ン酸に対して１０モル倍程度であればよい。反応効率の
観点から、チオフェノールまたはフェノールの使用量は
光学活性Ｎ置換アゼチジン−２−カルボン酸より過剰量
であることが好ましく、より好ましくは１．１〜２モル
倍程度の範囲である。反応速度の観点からチオフェノー
ルがより好ましい。In the present invention, the amount of thiophenol or phenol used may be at least the amount of the optically active N-substituted azetidine-2-carboxylic acid, and the upper limit thereof is from the viewpoint of economic efficiency. -It may be about 10 mole times the carboxylic acid. From the viewpoint of reaction efficiency, the amount of thiophenol or phenol used is preferably in excess of the optically active N-substituted azetidine-2-carboxylic acid, and more preferably in the range of about 1.1 to 2 moles. Thiophenol is more preferred from the viewpoint of the reaction rate.
【００１３】反応は上述したアミン中で行なってもよい
が、通常は溶媒中で行われ、かかる溶媒としては、例え
ばテトラヒドロフラン、エチルエーテル、イソプロピル
エーテル、ｔｅｒｔ−ブチルエーテル、ジオキサン、ジ
メトキシエタンなどのエーテル系溶媒、ジメチルホルム
アミド等のアミド系溶媒、ジクロロメタン、ジクロロエ
タン、クロロホルム等のハロゲン系溶媒、トルエン等の
芳香族炭化水素系溶媒、ジメチルスルホキシドなどの非
プロトン性極性溶媒等が例示できる。これらの溶媒はそ
れぞれ単独もしくは２種以上が用いられ、その使用量は
反応速度および経済効率の観点から、光学活性Ｎ置換ア
ゼチジン−２−カルボン酸に対して通常２〜５０重量倍
程度の範囲である。The reaction may be carried out in the above-mentioned amine, but is usually carried out in a solvent. Examples of such a solvent include ethers such as tetrahydrofuran, ethyl ether, isopropyl ether, tert-butyl ether, dioxane and dimethoxyethane. Solvents, amide solvents such as dimethylformamide, halogen solvents such as dichloromethane, dichloroethane and chloroform, aromatic hydrocarbon solvents such as toluene, and aprotic polar solvents such as dimethyl sulfoxide can be exemplified. Each of these solvents may be used alone or in combination of two or more. The amount of the solvent used is usually about 2 to 50 times by weight based on the optically active N-substituted azetidine-2-carboxylic acid from the viewpoint of reaction rate and economic efficiency. is there.
【００１４】反応温度は通常０℃以上であればよく、そ
の上限値は特に制限はないが１００℃程度であればよ
く、好ましくは２５℃〜６０℃の範囲である。反応終点
は通常行われる分析方法等により適宜決定すればよい。The reaction temperature may be generally 0 ° C. or higher, and the upper limit thereof is not particularly limited, but may be about 100 ° C., preferably in the range of 25 ° C. to 60 ° C. The end point of the reaction may be appropriately determined by a commonly used analysis method or the like.
【００１５】かくして光学活性アゼチジン−２−カルボ
ン酸を得ることができるが、得られた光学活性アゼチジ
ン−２−カルボン酸は分離回収してもよいし、得られた
光学活性アゼチジン−２−カルボン酸から他の化合物を
製造する場合は、反応液をそのまま別工程に用いてもよ
い。また分離回収した光学活性アゼチジン−２−カルボ
ン酸をさらにカラムクロマトグラフィー法や再結晶法等
の通常行われる方法により精製してもよい。Thus, the optically active azetidine-2-carboxylic acid can be obtained. The obtained optically active azetidine-2-carboxylic acid may be separated and recovered, or the obtained optically active azetidine-2-carboxylic acid can be obtained. When producing another compound from the above, the reaction solution may be used in another step as it is. The separated and recovered optically active azetidine-2-carboxylic acid may be further purified by a commonly used method such as column chromatography or recrystallization.
【００１６】分離回収の方法としては例えば、反応中析
出してきた沈殿物を濾過し再結晶する方法や、反応終了
後溶媒を留去した残さに酢酸エチルなどの疎水性の有機
溶媒と水を加えて分液し、水層から再結晶する方法等が
例示できる。Examples of the method for separation and recovery include a method of filtering a precipitate deposited during the reaction and recrystallization, and a method of adding a hydrophobic organic solvent such as ethyl acetate and water to the residue after distilling off the solvent after completion of the reaction. And recrystallization from the aqueous layer.
【００１７】[0017]
【発明の効果】本発明の方法により、工業的に有利な方
法で光学活性アゼチジン−２−カルボン酸を得ることが
できる。According to the method of the present invention, optically active azetidine-2-carboxylic acid can be obtained by an industrially advantageous method.
【００１８】[0018]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
【００１９】実施例１ 窒素気流下に、（Ｓ）−Ｎ−２−ニトロベンゼンスルホ
ニル−アゼチジン−２−カルボン酸１．０ｇ（３．５ｍ
ｍｏｌ）をジメトキシエタン５ｍｌに溶解し、３０℃に
てｎ−プロピルアミン４ｍｌ（４９ｍｍｏｌ）を加えた
後、チオフェノール０．３８ｇ（３．５ｍｍｏｌ）を徐
々に滴下し室温で１２時間撹拌した。次いで、反応液中
沈殿物を濾過し、酢酸エチル２０ｍｌで洗浄し淡黄色結
晶１．２３ｇを得た。この結晶０．５ｇをエタノール
８．５ｍｌで再結晶することで（Ｓ）−アゼチジン−２
−カルボン酸０．２３ｇ（白色結晶、収率７０％）を得
た。Example 1 1.0 g of (S) -N-2-nitrobenzenesulfonyl-azetidine-2-carboxylic acid (3.5 m
mol) was dissolved in 5 ml of dimethoxyethane, 4 ml (49 mmol) of n-propylamine was added at 30 ° C., and then 0.38 g (3.5 mmol) of thiophenol was gradually added dropwise, followed by stirring at room temperature for 12 hours. Next, the precipitate in the reaction solution was filtered and washed with 20 ml of ethyl acetate to obtain 1.23 g of pale yellow crystals. By recrystallizing 0.5 g of the crystal with 8.5 ml of ethanol, (S) -azetidine-2 was obtained.
-0.23 g of carboxylic acid (white crystals, yield 70%) was obtained.
【００２０】実施例２ 窒素気流下に、（Ｓ）−Ｎ−２−ニトロベンゼンスルホ
ニル−アゼチジン−２−カルボン酸１．０ｇ（３．５ｍ
ｍｏｌ）をジメチルホルムアミド１０ｍｌに溶解し、３
０℃にてトリエチルアミン１５ｍｌ（１０８ｍｍｏｌ）
を加えた後、チオフェノール１．６５ｇ（１５ｍｍｏ
ｌ）を徐々に滴下し室温で２日間撹拌した。次いで、反
応液をエバポレーターにより濃縮し得られた残さ２．９
ｇに、酢酸エチル４０ｍｌ、水４０ｍｌを加え分液し、
得られた水層を約１．５ｍｌになるまで濃縮した後、エ
タノール８．５ｍｌ加え再結晶することで、（Ｓ）−ア
ゼチジン−２−カルボン酸０．１９ｇ（白色結晶、収率
５３％、光学純度９９％ｅｅ以上）を得た。Example 2 1.0 g of (S) -N-2-nitrobenzenesulfonyl-azetidine-2-carboxylic acid (3.5 m
mol) was dissolved in 10 ml of dimethylformamide, and 3
15 ml (108 mmol) of triethylamine at 0 ° C
After addition of 1.65 g of thiophenol (15 mmol
l) was gradually added dropwise, and the mixture was stirred at room temperature for 2 days. Next, the reaction solution was concentrated by an evaporator, and the obtained residue was 2.9.
g, 40 ml of ethyl acetate and 40 ml of water were added and the mixture was separated.
After concentrating the obtained aqueous layer to about 1.5 ml, adding 8.5 ml of ethanol and recrystallizing, 0.19 g of (S) -azetidine-2-carboxylic acid (white crystals, yield 53%, Optical purity of 99% ee or more) was obtained.
【００２１】実施例３ 窒素気流下に、（Ｓ）−Ｎ−２−ニトロベンゼンスルホ
ニル−アゼチジン−２−カルボン酸１．０ｇ（３．５ｍ
ｍｏｌ）、ｎ−プロピルアミン２０ｍｌ、トリエチルア
ミン１．７７ｇ（１７．５ｍｍｏｌ）を加えた液に、３
０℃にてチオフェノール０．４６ｇ（４．２ｍｍｏｌ）
を徐々に滴下し室温で３時間撹拌した。次いで、反応液
をエバポレーターにより濃縮し得られた残さ１．８５ｇ
に、酢酸エチル４０ｍｌ、水４０ｍｌを加え分液し、得
られた水層を約１．５ｍｌになるまで濃縮した後、エタ
ノール９．５ｍｌ加え再結晶することで、（Ｓ）−アゼ
チジン−２−カルボン酸０．１５ｇ（白色結晶、収率４
３％、光学純度９９％ｅｅ以上）を得た。Example 3 1.0 g of (S) -N-2-nitrobenzenesulfonyl-azetidine-2-carboxylic acid (3.5 m
mol), 20 ml of n-propylamine and 1.77 g (17.5 mmol) of triethylamine were added to the solution.
0.46 g (4.2 mmol) of thiophenol at 0 ° C.
Was slowly added dropwise and stirred at room temperature for 3 hours. Then, the reaction solution was concentrated by an evaporator to obtain 1.85 g of a residue.
Then, 40 ml of ethyl acetate and 40 ml of water were added to the mixture, and the mixture was separated. The obtained aqueous layer was concentrated to about 1.5 ml, and then 9.5 ml of ethanol was added thereto for recrystallization, whereby (S) -azetidine-2- was obtained. 0.15 g of carboxylic acid (white crystals, yield 4
3% and an optical purity of 99% ee or more).
Claims (5)
ニトロベンゼンスルホニル基または２，４−ジニトロベ
ンゼンスルホニル基を示し、＊は不斉炭素原子を示す）
で示される光学活性Ｎ置換アゼチジン−２−カルボン酸
とチオフェノールまたはフェノールとをアミンの存在下
で反応させることを特徴とする光学活性アゼチジン−２
−カルボン酸の製造方法。1. The general formula (1) (Wherein, Ns is a 2-nitrobenzenesulfonyl group,
Represents a nitrobenzenesulfonyl group or a 2,4-dinitrobenzenesulfonyl group, and * represents an asymmetric carbon atom)
Reacting an optically active N-substituted azetidine-2-carboxylic acid with thiophenol or phenol in the presence of an amine.
-A process for producing carboxylic acids.
の製造方法。2. The method according to claim 1, wherein the amine is an aliphatic amine.
請求項２記載の製造方法。3. The method according to claim 2, wherein the aliphatic amine is a lower alkylamine.
ン、ｎ−ブチルアミン、ｎ−ペンチルアミン、ジエチル
アミン、ジ−ｎ−プロピルアミン、トリエチルアミン、
トリ−ｎ−プロピルアミンの少なくとも１種である請求
項３記載の製造方法。4. The lower alkylamine is n-propylamine, n-butylamine, n-pentylamine, diethylamine, di-n-propylamine, triethylamine,
The production method according to claim 3, wherein the production method is at least one of tri-n-propylamine.
が光学活性Ｎ置換アゼチジン−２−カルボン酸の１．１
〜２モル倍であることを特徴とする請求項１記載の製造
方法。5. The amount of thiophenol or phenol used is 1.1 of optically active N-substituted azetidine-2-carboxylic acid.
2. The method according to claim 1, wherein the molar ratio is up to 2 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33540297A JP3551735B2 (en) | 1997-12-05 | 1997-12-05 | Method for producing optically active azetidine-2-carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33540297A JP3551735B2 (en) | 1997-12-05 | 1997-12-05 | Method for producing optically active azetidine-2-carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11171860A true JPH11171860A (en) | 1999-06-29 |
| JP3551735B2 JP3551735B2 (en) | 2004-08-11 |
Family
ID=18288148
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33540297A Expired - Fee Related JP3551735B2 (en) | 1997-12-05 | 1997-12-05 | Method for producing optically active azetidine-2-carboxylic acid |
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| Country | Link |
|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001055104A1 (en) * | 2000-01-25 | 2001-08-02 | Kaneka Corporation | Process for preparation of optically active n-substituted azetidine-2-carboxylic acids |
| WO2001060795A1 (en) * | 2000-02-17 | 2001-08-23 | Kaneka Corporation | Processes for preparing optically active amino acid derivatives |
| WO2002022549A1 (en) * | 2000-09-14 | 2002-03-21 | Kaneka Corporation | Process for the removal of nitrobenzenesulfonyl |
-
1997
- 1997-12-05 JP JP33540297A patent/JP3551735B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001055104A1 (en) * | 2000-01-25 | 2001-08-02 | Kaneka Corporation | Process for preparation of optically active n-substituted azetidine-2-carboxylic acids |
| WO2001060795A1 (en) * | 2000-02-17 | 2001-08-23 | Kaneka Corporation | Processes for preparing optically active amino acid derivatives |
| US6720449B2 (en) | 2000-02-17 | 2004-04-13 | Kaneka Corporation | Process for preparing optically active amino acid derivatives |
| US7109352B2 (en) | 2000-02-17 | 2006-09-19 | Kaneka Corporation | Process for producing optically active amino acid derivatives |
| WO2002022549A1 (en) * | 2000-09-14 | 2002-03-21 | Kaneka Corporation | Process for the removal of nitrobenzenesulfonyl |
| US6515179B2 (en) | 2000-09-14 | 2003-02-04 | Kaneka Corporation | Process for the removal of nitrobenzenesulfonyl |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3551735B2 (en) | 2004-08-11 |
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