JPS6360954A - Optically active beta-amino acid derivative - Google Patents
Optically active beta-amino acid derivativeInfo
- Publication number
- JPS6360954A JPS6360954A JP20518286A JP20518286A JPS6360954A JP S6360954 A JPS6360954 A JP S6360954A JP 20518286 A JP20518286 A JP 20518286A JP 20518286 A JP20518286 A JP 20518286A JP S6360954 A JPS6360954 A JP S6360954A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- amino acid
- optically active
- acid derivative
- 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
- 150000001576 beta-amino acids Chemical class 0.000 title claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 abstract description 4
- -1 amino acid ester Chemical class 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 abstract 2
- 102000004190 Enzymes Human genes 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001540 azides Chemical class 0.000 description 4
- 108010059892 Cellulase Proteins 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229940106157 cellulase Drugs 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 108090000604 Hydrolases Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- OJQNRNQELNLWHH-UHFFFAOYSA-N alpha-Fluoro-beta-alanine Chemical compound NCC(F)C(O)=O OJQNRNQELNLWHH-UHFFFAOYSA-N 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- DLWIEHPLFDUIGE-LURJTMIESA-N ethyl (2s)-2-fluoro-3-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)[C@@](C)(F)CO DLWIEHPLFDUIGE-LURJTMIESA-N 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229950003188 isovaleryl diethylamide Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- XYWJNTOURDMTPI-UHFFFAOYSA-N procodazole Chemical compound C1=CC=C2NC(CCC(=O)O)=NC2=C1 XYWJNTOURDMTPI-UHFFFAOYSA-N 0.000 description 1
- 229950000989 procodazole Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 235000020138 yakult Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は一般式
（式中、Ｒは水素原子又はアルキルノ１（である。）で
表わされるβ−アミノＭｍＭ導体に関する。The present invention relates to a β-amino MmM conductor represented by the general formula (wherein R is a hydrogen atom or an alkyl group).
本発明は前記一般式（１）で表わされるβ−アミノ酸誘
導体は、セルラーゼの存在下、組合させることにより、
撥水撥油性イｊ゛する含フツ素ポリマーに導くことがで
きる。又、本発明の前記一般式（１）で表わされるβ−
アミノ酸誘導体は、酸素阻害剤として使用できる可能性
なイｊしている。The present invention provides that the β-amino acid derivative represented by the general formula (1) can be combined in the presence of cellulase to
This can lead to fluorine-containing polymers that are water and oil repellent. Further, β- represented by the general formula (1) of the present invention
Amino acid derivatives have the potential to be used as oxygen inhibitors.
しかしながら、従来の含フツ素ポリマーは主鎖が含フツ
素アルキル又は含フツイ；アルキルエーテルから成るも
のく例えばナフィオン）、或はパーフルオロアルキル基
を１ｌｉ１７鎖に持つアクリル酸ポリマーであり、機能
性高分子としての官能基はカルボン酸或はスルホン酸及
びそのエステルに限られていた。そのため特定の用途以
外には使用範囲が限られていた。However, conventional fluorine-containing polymers are those whose main chain is composed of a fluorine-containing alkyl or alkyl ether (for example, Nafion), or acrylic acid polymers having perfluoroalkyl groups in 1li17 chains, and have high functionality. The molecular functional groups were limited to carboxylic acids or sulfonic acids and their esters. Therefore, the scope of use was limited except for specific purposes.
本発明者は、従来の欠点を克服すべく検討した結果、各
１ｎの官能」、（を含む高性能高分子誘導できるβ−ア
ミノ酸１；Ａ導体を見出し、本発明を完成した。更に、
本発明によれば従来導入が困ｖ１ｔであった不斉因子を
ポリマーの主鎖に導入することが可能となった。As a result of studies to overcome the conventional drawbacks, the present inventors discovered a β-amino acid 1;A conductor that can be derived from high-performance polymers containing each 1n functionality, and completed the present invention.Furthermore,
According to the present invention, it has become possible to introduce an asymmetric factor into the main chain of a polymer, which has been difficult to introduce in the past.
【発明の（１°へ成］
本発明の前記一般式（１）で表わされるβ−アミノ酸誘
導体は、以下の反応式に従い製造することができる。
□ （ｌ ）
【ａ工（？］
イ： Ｔ Ｔ’−は前記一般式（１１）で表わされる光
学活性なマロン酸モノエステル、；７４；、７体をオキ
サリルクロライドで処理し、Ｎ ａ １１ ＋１４で１
ワ元することにより、１）ＸＪ記一般式（Ｉｌｌ ”）
で表わされるヒドロキシ誘導体を１１）ろものである。
本工程の原料である前記一般式（１１）で表わされるマ
ロン酸モノエステルは、Ｊ、Ｏｒ ｇ、Ｃｈｅｍ、＋
Ｆ’ｉ １＋ １００ｔ３（１９８６）に記桟の方法
により容易に１”）ることかできる化合物である。
【ｂ工程】
本工程は前記ａ工程で得られた前記一般式（Ｉｌｌ ）
で表わされるヒドロキシ酸誘導体をＴｓＣｌと反応させ
前記一般式（ＩＶ ’）で表わされる化合物を製造する
ものである。
反応を行うにあたっては病媒を用いることが好ましく、
例えばピリジン、ピペラジン′５７￥を好適に使用する
ことができる。
反応は一１０〜５０°Ｃで円滑に進行する。[(1° helical formation) of the invention] The β-amino acid derivative represented by the general formula (1) of the present invention can be produced according to the following reaction formula. T T'- is an optically active malonic acid monoester represented by the general formula (11);
1) General formula XJ (Ill ”)
The hydroxy derivative represented by 11) is The malonic acid monoester represented by the general formula (11), which is the raw material for this step, is J, Or g, Chem, +
F'i 1+ 100t3 (1986) is a compound that can be easily determined by the method of Kisan (1"). [Step b] This step is a compound of the general formula (Ill) obtained in step a.
The hydroxy acid derivative represented by the formula (IV') is reacted with TsCl to produce the compound represented by the general formula (IV'). In carrying out the reaction, it is preferable to use a disease medium,
For example, pyridine and piperazine can be preferably used. The reaction proceeds smoothly at -10 to 50°C.
本工程は前記す工程で得られた前記一般式（１ｖ）で表
わされる化合物ぞアジ（ヒナトリウムと反応させること
により前記一般式（■）で表わされるアジドな製造する
ものである。
通常、反応は、イソプロピルアルコール中で行うことが
できるが、その他エタノール、ブクノール等の！：”＞
媒を用いてもさしつかいない。
反応は溶媒の還流温度即ち６０〜８０℃の範囲を選択す
ることにより円滑に反応が進行する。In this step, the azide represented by the general formula (■) is produced by reacting the compound represented by the general formula (1v) obtained in the above step with azide (hysodium). Usually, the reaction can be carried out in isopropyl alcohol, but other methods such as ethanol, buknol, etc.
It is okay to use a medium. The reaction proceeds smoothly by selecting the reflux temperature of the solvent, that is, in the range of 60 to 80°C.
本工程は前記Ｃ工程で１１）られだ前記一般式（Ｖ）で
表わされるアジドを還元し、前記一般式（Ｖｌ）で表わ
されるアミノ酸エステルを製造するものである。
還元するにあたっては、例えば、水酸ｆヒホウ素ナトリ
ウム、ジイソブチルアルミニウムハイドライドなどの還
元剤を使用することができろ。
還元剤の種類によってもｌｌ、ｊなるが反１．しはエタ
ンール、イソプロパツール、プロパツール等などの溶媒
中で行うことができる。
反応は５０〜８０℃で円：イ１に進行する。In this step, the azide represented by the general formula (V) obtained in step C (11) is reduced to produce an amino acid ester represented by the general formula (Vl). For the reduction, reducing agents such as sodium hydroborate and diisobutylaluminum hydride can be used. It depends on the type of reducing agent, but the difference is 1. The reaction can be carried out in a solvent such as ethanol, isopropanol, propazol, etc. The reaction proceeds at a temperature of 50 to 80°C.
本工程は前記ｄ工程で得られた＋’ｆｉｊ記一般式（Ｖ
ｌ）で表わされるアミノ酸エステルを加水分解酵素の存
在下、に反応させ、１）１ｊ記一般式（１）で表わされ
るβ−アミノ酸誘導体を製、造するものである。
本工程で用いる加水分’ｒ’ｒ’Ｉ’ ｈ’ｆ 累とし
ては、例えばリーバーゼー〜１′Ｆ、セルラーゼ、など
が使用できる。
反応を行うにあたっては、緩ｉφ１１容液中で行うのが
好ましく、例えば、Ｋ１１２１１０４−Ｎａ２１！ＰＯ
４緩衝溶液を好１図に使用できる。
反応温度は、：３０〜４５℃の範囲が目的物が効率良く
得られる点で好ましい。
以下実施例により本発明を更に詳３（１１に１１ｊ２明
する。
参考例 Ｉ
Ｄｔ４Ｆ（３，４ｍ１）をＣ１１２ＣＩ ２ （４０ｍ
ｌ ）に溶かし、更ニｔ キサリルクロライド（８ｍ
ｌ）を注入した。Ｏ”Ｃ１時間撹拌後、減圧下に溶媒を
留去し、系内な窒素置換した。得られた白色の固体にＣ
ＩＩ：３ ＣＮ （３０ｍ ｌ ） 、Ｔ ＨＦ （１
００）））を加えて、−３０℃まで冷却した。これに（
Ｓ）−（−）−２−メチル−２−フルオロマロン酸モノ
エチル（４０ｍｍｏｌ）を加え、１時間撹拌した。
次に反応液を一７８℃まで冷却したのち、ＮａＢＩＩ４
（３，５３，９３ｍｍｏｌ）のＤＭＦ溶４（２０ｍｌ）
をゆっくり注入した。−２０℃に保ち４時間撹拌したの
ち、３Ｎ−）ＨＣｌ（５０ｍｌ）を加えて反応を終了し
た。酢酸エチルで抽出を行ない、ｌＮ−ＨＣｌ水溶？伎
％ ｊ％Ｎ ａ ＨＣ０３水溶液、水、飽和食塩水で順
次洗浄しＭ ｇ Ｓ ０４で乾燥した。蒸留にて（Ｓ）
−（−）−３−ヒドロキシ−２−フルオロ−２−メチル
プロパン酸エチルを得た。収率６９％［ａｌＤ／Ｍｅ０
１１−８．９７（ｃ １．８１） ｂｐ、 ８４−８５
℃／８ｍｍ１１ｇ。
参考例 ２
同様に反応を行ない（Ｒ）−（−）−〜ｌｅ体、（Ｒ）
−（十）−１ｒ体を得た。その結果を参考例１の結果と
あわせ、表１に示した。
参考例 ３
（Ｓ）−（−）−３−ヒドロキシ−２−フルオロホフホ
メチルブロバン酸エチル（２，０ｇ、 １３＋ｒ＋＋ｎ
ｏ ｌ ）をピリジン（２０ｍｌ）に溶がし、Ｔ ｓ
ＣＩ （３，０ｇ、１６ｍｍｏｌ）を加えて、室温で３
時間撹拌した。単雛は、カラムクロマトグラフィーにて
ヘキサン−ジエチルエーテル（５：１）を用いて行った
。収率９５％、［α］。
／１４ｅＯＨ−１，９７（ｃ １．３４） ＞９９
％ｅｅ参考例 １１
同４美に反応を行ない（ＩＮ） （） Ｍｅ体、（
Ｉｔ）−（＋）−１１体を得た。その結果を参４例３の
結果とあわせ、表２に示した。
参考例 ５
（Ｓ）−（−）−３−ヒドロキシ−２−フルオロ−２−
メチルプロパン酸エチルのトシレート体（２０ｍｒｎｏ
Ｉ ） 、ＮａＮ３（５５ｍｍｏｌ ）をイソプロパ
ツール（１００ｍｌ）に溶かし、１５時間還流したのち
、反応液に水を加え、生じた油試物を塩化メチレンで抽
出した。
溶媒を留去したのち目的物を得た。同様に反応を行ない
（Ｒ）−Ｍｅ体、（Ｉｔ）−０体を得た。その結果を表
３に示した。
実躾例 １
参考例５で一７ｉ’７られたアジド（１０ｍｍｏ ＋
）、ＮａＢＨ４（３］ｍｍ。
１）をエタノール（３０ｍ ｌ ）に溶かし５時間還流
したのち、飽和塩化アンモニウム溶液を加え、生じた油
状物をジエチルエーテルで抽出した。溶媒を留去したの
ち得られたβ−アミノ酸誘導体をカラムクロマトグラフ
ィーにてヘキサン−ジエチルエーテル（１０：１）溶液
を用いて単離した。その結果を表４に示した。
参考例 ６
セルラーゼ（５Ｐｂヤクルト社製）をＫＩＩ２Ｐ０４−
Ｎａ ＩＩＰＯ４１９ｊ ：容、Ｉ（ｐｉｔ ８．０，
１００ｍ１）に懸）蜀させ、４０−・１１℃で１５分間
撹拌した。この液にα−フルオロ−β−アラニン（２０
ｍｍｏｌ）を加え、４０−４１℃で５日間撹拌しながら
重合反応したのち、重合生成物を酢酸エチルで抽出した
。精製はカラムクロマトグラフィーにて行った。その結
果を表５に示した。This step is performed using the +'fij general formula (V
1) The β-amino acid derivative represented by general formula (1) in 1j is produced by reacting the amino acid ester represented by 1) in the presence of a hydrolase. As the hydrolyzed water 'r'r'I'h'f used in this step, for example, Liebersee-1'F, cellulase, etc. can be used. When carrying out the reaction, it is preferable to carry out the reaction in a solution with a slow iφ11 volume, for example, K1121104-Na21! P.O.
4 buffer solutions can be used in a preferred manner. The reaction temperature is preferably in the range of 30 to 45°C since the desired product can be obtained efficiently. The present invention will be explained in further detail with reference to Examples below. Reference Example I Dt4F (3,4m1) was converted into C112CI2 (40m
Dissolve in xalyl chloride (8m
l) was injected. After stirring for 1 hour, the solvent was distilled off under reduced pressure and the system was replaced with nitrogen.
II: 3CN (30ml), THF (1
00))) was added and cooled to -30°C. to this(
Monoethyl S)-(-)-2-methyl-2-fluoromalonate (40 mmol) was added and stirred for 1 hour. Next, after cooling the reaction solution to -78°C, NaBII4
(3,53,93mmol) in DMF solution 4 (20ml)
was injected slowly. After stirring at −20° C. for 4 hours, 3N-)HCl (50 ml) was added to terminate the reaction. Extract with ethyl acetate and dilute with 1N-HCl aqueous solution.伎%j%N a It was washed successively with an aqueous HC03 solution, water, and saturated saline, and dried with MgS04. By distillation (S)
Ethyl -(-)-3-hydroxy-2-fluoro-2-methylpropanoate was obtained. Yield 69% [alD/Me0
11-8.97 (c 1.81) bp, 84-85
°C/8mm 11g. Reference Example 2 Reaction was carried out in the same manner to form (R)-(-)-~le form, (R)
-(10)-1r form was obtained. The results are shown in Table 1 together with the results of Reference Example 1. Reference Example 3 Ethyl (S)-(-)-3-hydroxy-2-fluorophofophomethylbrobanate (2.0 g, 13+r++n
o l ) in pyridine (20 ml) and T s
Add CI (3.0 g, 16 mmol) and stir at room temperature.
Stir for hours. Single chicks were subjected to column chromatography using hexane-diethyl ether (5:1). Yield 95%, [α]. /14eOH-1,97 (c 1.34) >99
%ee reference example 11 React to the same 4 beauty (IN) () Me body, (
It)-(+)-11 bodies were obtained. The results are shown in Table 2 together with the results of Example 3. Reference example 5 (S)-(-)-3-hydroxy-2-fluoro-2-
Tosylate form of ethyl methylpropanoate (20mrno
I), NaN3 (55 mmol) was dissolved in isopropanol (100 ml), and after refluxing for 15 hours, water was added to the reaction solution, and the resulting oil sample was extracted with methylene chloride. After distilling off the solvent, the desired product was obtained. A similar reaction was carried out to obtain (R)-Me form and (It)-0 form. The results are shown in Table 3. Practical example 1 Azide (10mmo +
), NaBH4 (3] mm. 1) was dissolved in ethanol (30 ml) and refluxed for 5 hours, then saturated ammonium chloride solution was added and the resulting oil was extracted with diethyl ether. After distilling off the solvent, the resulting β-amino acid derivative was isolated by column chromatography using a hexane-diethyl ether (10:1) solution. The results are shown in Table 4. Reference example 6 Cellulase (manufactured by 5Pb Yakult) was used as KII2P04-
Na IIPO419j: Yong, I (pit 8.0,
The mixture was suspended in 100 ml of water and stirred at 40-11°C for 15 minutes. Add α-fluoro-β-alanine (20
mmol) was added, and the polymerization reaction was carried out at 40-41°C for 5 days with stirring, and then the polymerization product was extracted with ethyl acetate. Purification was performed by column chromatography. The results are shown in Table 5.
Claims (1)
、表等があります▼ で表わされる光学活性なβ−アミノ酸誘導体（式中、Ｒ
は水素原子又はアルキル基である。）。(1) Optically active β-amino acid derivatives (in the formula, R
is a hydrogen atom or an alkyl group. ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20518286A JPH0796536B2 (en) | 1986-09-02 | 1986-09-02 | Optically active β-amino acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20518286A JPH0796536B2 (en) | 1986-09-02 | 1986-09-02 | Optically active β-amino acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6360954A true JPS6360954A (en) | 1988-03-17 |
| JPH0796536B2 JPH0796536B2 (en) | 1995-10-18 |
Family
ID=16502772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20518286A Expired - Lifetime JPH0796536B2 (en) | 1986-09-02 | 1986-09-02 | Optically active β-amino acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796536B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH021447A (en) * | 1988-01-22 | 1990-01-05 | W R Grace & Co | Preparation of amino acid derivative |
| WO2000069817A1 (en) * | 1999-05-14 | 2000-11-23 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acids |
| WO2003089402A1 (en) * | 2002-04-19 | 2003-10-30 | Daikin Industries, Ltd. | PROCESS FOR PRODUCING α-FLUORO-β-ALANINE COMPOUND AND PRODUCING INTERMEDIATE THEREFOR |
-
1986
- 1986-09-02 JP JP20518286A patent/JPH0796536B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH021447A (en) * | 1988-01-22 | 1990-01-05 | W R Grace & Co | Preparation of amino acid derivative |
| WO2000069817A1 (en) * | 1999-05-14 | 2000-11-23 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acids |
| US6838567B1 (en) | 1999-05-14 | 2005-01-04 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acids |
| US7262308B2 (en) | 1999-05-14 | 2007-08-28 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acids |
| WO2003089402A1 (en) * | 2002-04-19 | 2003-10-30 | Daikin Industries, Ltd. | PROCESS FOR PRODUCING α-FLUORO-β-ALANINE COMPOUND AND PRODUCING INTERMEDIATE THEREFOR |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0796536B2 (en) | 1995-10-18 |
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