JPH03110464A - 液体クロマトグラフィー用充填剤 - Google Patents

液体クロマトグラフィー用充填剤

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Publication number
JPH03110464A
JPH03110464A JP1246444A JP24644489A JPH03110464A JP H03110464 A JPH03110464 A JP H03110464A JP 1246444 A JP1246444 A JP 1246444A JP 24644489 A JP24644489 A JP 24644489A JP H03110464 A JPH03110464 A JP H03110464A
Authority
JP
Japan
Prior art keywords
packing material
stationary phase
optically active
dicarboxylic acid
liquid chromatography
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
Application number
JP1246444A
Other languages
English (en)
Other versions
JP2841546B2 (ja
Inventor
Sotaro Miyano
壮太郎 宮野
Shuichi Oi
秀一 大井
Masayuki Shijo
雅之 四條
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
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Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to JP1246444A priority Critical patent/JP2841546B2/ja
Priority to EP90118330A priority patent/EP0420115B1/en
Priority to DE9090118330T priority patent/DE69000572T2/de
Priority to US07/587,942 priority patent/US5051176A/en
Publication of JPH03110464A publication Critical patent/JPH03110464A/ja
Application granted granted Critical
Publication of JP2841546B2 publication Critical patent/JP2841546B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は種々の化合物の分離、特に異性体、さらには従
来分離が困難であったラセミ体の光学分割、特に（ｄ　
ｌ）−アルコール修飾体の分割に有能な液体クロマトグ
ラフィー用充填剤である。
［産業上の技術］ 従来、種々の光学活性固定相によるラセミ体の直接分割
が知られている。例えば Ｙ、　　Ｏａｍｏ　　ｔ　　ｏ；　　ＣＨＥＭＴＥＣＨ
，１９８７゜１７６；Ｗ、　　Ｈ，Ｐｉｒｋｌｅ、　　
Ｔ、　　Ｃ。
Ｐｏｃｈａｐｓｋｙ、　　Ｇ、　　Ｓ、　　Ｍａｈｌｅ
ｒ、　　Ｄ。
Ｅ、　Ｃｏｒｅｙ、　　Ｄ、　　Ｓ、　　Ｒｅｎｏ、　
　ａｎｄ　　　Ｄ。
Ｍ、　Ａｌｅｓｓ　　ｔ、　　Ｊ、　　Ｏｒｇ、　　Ｃ
ｈｅｍ、　　、　　５１．４９９１　（１９８６）等に
詳しく記載されている。これまで、種々の光学活性化合
物を用いる固定相が知られている。例えば、（Ｌ）−ア
ミン酸、光学活性アミド、又は光学活性カルボン酸があ
る。具体的に化合物を示すと、（Ｌ）−バリン、（Ｌ）
−ロイシン、（Ｌ）−イソロイシン、（Ｌ）−フェニル
グリシン誘導体、（Ｓ）　−１−（１−ナフチル）エチ
ルアミン誘導体、（Ｓ）−又は（Ｒ）−１，１’−ビナ
フチル−’２．２’　−ジカルボン酸、又はキク酸など
である。それらの光学活性化合物を固定相とするために
、一般的には、シリカゲルなどの粒子表面にグラフトし
たアミノアルキル基と光学活性化合物のカルボキシル基
との間のイオン結合、又は共有結合を形成させ成立する
。又は、シリカゲルなどの粒子表面にグラフトしたカル
ボキシメチル基と光学活性アミノ化合物との間に先と同
様の結合様式により成立する。
これら光学活性固定相のラセミ体識別は一般に、に、ア
ミノ結合とラセミ体のアミド結合、エステル結合、水酸
基との間の水素結合およびπ−π相互作用などにより、
固定相にラセミ体が保持される際に、ｄ体１体間の保持
は立体的に微少な環境の差によって、保持能に差が生じ
ることによって、達成されるというものである。また、
その場合の溶離液としては、一般にヘキサン−アルコー
ル系が使用される。
［発明が解決しようとする課題］ 上述の作用′により、種々のラセミ体が分離されてきた
が、これまで、ｄｌ−アルコール修飾体の分離、特に脂
肪族（ｄ　ｌ）−アルコール修飾体の簡便な分割に有効
な固定相は見出されていなかった。
［課題を解決するための手段及び作用］本発明者らは、
前述したような、（ｄ　ｌ）−アルコール修飾体の光学
分割に広く使用出来る固定相を見°田すべく鋭意検討し
た結果。（Ｓ）−又は（Ｒ）−１，１’−ビアントリル
−２，２′　−ジカルボン酸を固定相とすることにより
優れた充填剤が得られることを見出し本発明を完成させ
た。
すなわち、本発明は、（Ｓ）−又は（Ｒ）−１゜１′−
とアントリル−２，２′−ジカルボン酸を固定相として
用いる液体クロマトグラフィー用充填剤を提供するもの
である。
［作用］ 以下更に本発明の詳細な説明する。
本発明の光学活性化合物（Ｓ）−又は（Ｒ）１．１′−
ビアシトリルー２，２′−ジカルボン酸は公知の方法つ
まり（ｄｉ）−１，１’　−ビアントリル−２，２′　
−ジカルボン酸をキニジンなどのアルカロイドを用い光
学分離することによって得ることが出来る。
即ち、（ｄ　１）−１，１’　　−とアントリル−２゜
２′−ジカルボン酸キニジン塩を加熱還流エタノールに
溶解させ冷時析出する結晶をろ別しさらにエタノールに
懸濁させ加熱還流により溶解させ放冷後、ろ別しくＲ）
−ジカルボン酸キニジン塩を得る。
ろ液を減圧留去し得られた粗結晶を同様の処理をするこ
とにより（Ｓ）−ジカルボン酸キニジン塩を得ることが
できる。
各々の塩を塩酸処理することにより光学活性（Ｓ）−又
は（Ｒ）−１，１’　　−とアントリル−／ ２．２′−ジカルボン酸をそれぞれ得ることが出来る。
本発明光学活性化合物を固定相とする充填剤を用いる場
合、その基材としては、シリカゲル、ガラスピーズ、ケ
イソウ土等の多孔性担体が用いられ、球状でも破砕状で
も良いが、好ましくは球状が良い。粒径は、０．１−１
０００μｍで細孔径が、１０〜１０００人のもの、好ま
しくは粒径１〜１００μｍ１細孔径５０〜５００人が良
い。該光学活性化合物を固定化する方法としては、基材
担体に、吸着させる方法、イオン結合により固定化する
方法、アミド結合などの共有結合により固定化する方法
などがあげられる。液体クロマトグラフィーとしての条
件を考慮すると、アミド結合又はイオン結合により固定
化するのが好ましい。
アミド結合又はイオン結合を形成させるには基材担体表
面にアミノ基含有のオイガノシラン処理剤を溶媒中で反
応させ、基材担体表面にアミノ基を導入する。このアミ
ノ基の導入料は、感想担体ペースで２．Ｏｍｅｑ、／ｇ
までが好ましい。このようにして得られたアミノ基含有
担体に、ペプチド合成時の縮合剤、例えば、ジシクロへ
キシルカルボジイミド、Ｎ−エトキシカルボニル−２−
エトキシ−１，３−ジヒドロキノリン、１−エチル−３
−（３−ジメチルアミノプロピル）−カルボジイミドな
どの存在下、前述した光学活性１゜１′−ビアシトリル
ー２．２′−ジカルボン酸を作用させ固定化する。又は
縮合剤を添加せずイオン結合により固定化することもで
きる。もちろん両結合が存在することも可能である。
本発明充填剤のカラムへの充填方法は公知の常法により
行なうことが出来る。
［実施例］ 以下、本発明を実施例によりさらに説明するが、本発明
はこれに限定されるものではない。
実施例１ （１）（アミノアルキルグラフトシリカゲルの調製） シリカゲル（１５０℃、ｌＸｌ０−’ｔｔｏｒで約６時
間乾燥したもの）５０．２４ｇの無水トルエン３００　
ｍｌの懸濁液に３−アミノプロピルトリエトキシシラン
１００ｇ　（０，４５ｍｏ　ｌ）を加え、Ｎ２下、穏や
かに４０時間加熱還流する。反応懸濁液を冷却後Ｇ４の
ガラスフィルターでシリカをろ別し、トルエン、Ｍ　ｅ
　ＯＨｓアセトン、エーテルで順次洗浄した後、乾燥し
アミノプロピル基グラフトシリカゲルを得た。
収量　５９．６６ｇ、元素分析値＝Ｃ％。
８．１０；Ｈ％、２．０７．Ｎ％、１．４２゜７ミノ基
導入量：　１．０１ｍｍｏ　１／ｇ　（Ｎ−元素分析値
より） （２）（ｄｉ−１，１’　　−ビアントリル−２゜２′
−ジカルボン酸の光学分割） ｄｉ−１，１’−ビアシトリルー２．２′−ジカル°ボ
ン酸２．６ｇ　（５，６５ｍｍｏ　ｌ）をエタノール１
２５　ｍｌに懸濁後、加熱還流溶解させキニジン４．２
５ｇ　（１３，８４ｍｍｏ　１）を溶解後再び３０分加
熱還流した後放冷し析出する結晶をろ別後、結晶をエタ
ノール５０ｍ１で再結晶を行い（Ｒ）−１，１’−ビア
ントリル−２，２′　−ジカルボン酸のキニジン塩２．
４７ｇを得る。
塩は２Ｎ−ＨＣｌ中で拡販後、酢酸エチルで抽出しくＲ
）−１，１’−ビアシトリルー２．２′−ジカルボン酸
−２，２′−ジカルボン酸０．９３ｇ　（収率７４．４
％）を得る。
得られた光学活性体の光学純度はジアゾメタンでメチル
エステルとしＰｉｒｋｌｅ型の光学分割用カラムの分析
により光学純度１００％であることを確認した。
ろ液を減圧留去後同様の再結晶を繰り返し、得られた塩
を同様に塩酸処理することにより（Ｓ）一体を得る事が
できた。
（３）（Ｒ）−１，１’　−とアントリル−２゜２′−
ジカルボン酸による光学活性固定相担体の合成 （Ｒ）−１，１’　　−ビアントリル−２，２′ジカル
ボン酸０．９２ｇ　（２，０８ｍｍｏ　ｌ）とＮ−エト
キシカルボニル−２−エトキシ−１，３−ジヒドロキノ
ン１．０３ｇ　（４，０６ｍｍｏ　ｌ）のＤＨＦ溶液に
（１）で合成したアミノプロピル基結合シリカ３．ＯＯ
ｇを懸濁させ、Ｎ２下で超音波を８時間照射する。次に
反応懸濁液を６４のガラスフィルターを用いてシリカ１
２５℃の恒温浴中をろ別し、そのシリカをＴＨＦ、メタ
ノール。
アセトン、エーテルで順次洗浄後減圧乾燥した。
秋涼は３．４４ｇであった。
［応用例］ 実施例で得られた光学活性液体クロマトグラフィー用充
填剤をスラリー法によりカラムへ充填し、下記のハ１定
条件でラセミ体試料の分離を行い、保持係数（Ｋ’　）
、分離係数（α）を求めた。得られた結果を表１に示し
た。また、比較として、（Ｓ）−１，１’−ビナフチル
−２，２’−ジカルボン酸を固定相として測定した得ら
れた結果を表１に示した。
測定条件二カラム　４．６ｍｍ１．Ｄ。
Ｘ２５．ＯｃｍＬ、ステンレ スカラム ＵＶ−８０１０（東ソー製） ＣＣＰＯ（〃　　） ２５℃ １．０ｍｌ／ｍ　Ｌ　ｎ。
ヘキサン−アルコール系（割 合は表１に示す） 検出器 ポンプ 温　　度 流　　速 移動相 ［発明の効果コ 以上、説明したように、本発明光学活性化合物固定相は
、これまで分割が困難であったｄｉ−アルコール類の分
割に非常に有効であり、その合成も容易であり、極めて
優れた充填剤である。
【図面の簡単な説明】
第１図は、本発明充填剤を用いた（ｄｉ）−２−Ｂｕｔ
ｙｌ−３，５−ｄｉｎｉｔｏｒｏｐｈｒｎｙｌ−ｃａｒ
ｂａｍａｔｅ分割のり０７トを示す図である。

Claims (1)

    【特許請求の範囲】
  1. （Ｓ）−又は（Ｒ）−１，１′−ビアントリル−２，２
    ′−ジカルボン酸を固定相として用いることを特徴とす
    る液体クロマトグラフィー用充填剤。
JP1246444A 1989-09-25 1989-09-25 液体クロマトグラフィー用充填剤 Expired - Fee Related JP2841546B2 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP1246444A JP2841546B2 (ja) 1989-09-25 1989-09-25 液体クロマトグラフィー用充填剤
EP90118330A EP0420115B1 (en) 1989-09-25 1990-09-24 Packing material for liquid chromatography
DE9090118330T DE69000572T2 (de) 1989-09-25 1990-09-24 Packungsmaterial fuer fluessigkeitschromatographie.
US07/587,942 US5051176A (en) 1989-09-25 1990-09-25 Packing material for liquid chromatography

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1246444A JP2841546B2 (ja) 1989-09-25 1989-09-25 液体クロマトグラフィー用充填剤

Publications (2)

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JPH03110464A true JPH03110464A (ja) 1991-05-10
JP2841546B2 JP2841546B2 (ja) 1998-12-24

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US5338529A (en) * 1992-04-27 1994-08-16 Research Corporation Technologies, Inc. Recognition and separation of carbon clusters
US5290440A (en) * 1992-06-23 1994-03-01 Research Corporation Technologies, Inc. High performance chiral selector
JPH07260762A (ja) * 1994-03-17 1995-10-13 Daicel Chem Ind Ltd 高速液体クロマトグラフィー用充填剤及びその製造法
AU2002364803A1 (en) * 2002-11-29 2004-06-23 Pascal Aznar Pre-filled columns for flash chromatography and for solid-phase extraction with higher separating efficiency
US8137548B2 (en) * 2003-10-17 2012-03-20 Zirchrom Separations, Inc. Chelator-modified inorganic oxide particles
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JPS58202043A (ja) * 1982-05-19 1983-11-25 Sumitomo Chem Co Ltd グラフトしたクロマトグラフ充填剤およびそれを用いる鏡像体混合物の分析法
CA1204720A (en) * 1982-09-30 1986-05-20 Hajimu Kitahara Packing materials for chromatographic use and a method for analysis of an enantiomer mixture using the same
JPS59166502A (ja) * 1983-03-10 1984-09-19 Daicel Chem Ind Ltd 分離剤
JPS60161928A (ja) * 1984-01-31 1985-08-23 Daicel Chem Ind Ltd セルロースの硝酸エステルを含有する分離剤
JPS60226829A (ja) * 1984-03-29 1985-11-12 Daicel Chem Ind Ltd 多糖誘導体より成る分離剤
JPS60226830A (ja) * 1984-03-30 1985-11-12 Daicel Chem Ind Ltd １，３−グルカンより成る分離剤
JPS60226832A (ja) * 1984-04-02 1985-11-12 Daicel Chem Ind Ltd 多糖の脂肪族エステルを含む分離剤
JPS60226833A (ja) * 1984-04-05 1985-11-12 Daicel Chem Ind Ltd 多糖の芳香族エステル誘導体より成る分離剤
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EP0420115A1 (en) 1991-04-03
JP2841546B2 (ja) 1998-12-24
DE69000572D1 (de) 1993-01-21
US5051176A (en) 1991-09-24
EP0420115B1 (en) 1992-12-09
DE69000572T2 (de) 1993-04-15

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