JP2003040927A - Optically active polymethacrylate derivative, and separating agent and separation method - Google Patents
Optically active polymethacrylate derivative, and separating agent and separation methodInfo
- Publication number
- JP2003040927A JP2003040927A JP2001229833A JP2001229833A JP2003040927A JP 2003040927 A JP2003040927 A JP 2003040927A JP 2001229833 A JP2001229833 A JP 2001229833A JP 2001229833 A JP2001229833 A JP 2001229833A JP 2003040927 A JP2003040927 A JP 2003040927A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- separating agent
- separating
- group
- polymethacrylate 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.)
- Pending
Links
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学活性ポリメタ
クリレート誘導体及びその誘導体からなる分離剤並びに
その分離剤を用いた分離方法に関する。TECHNICAL FIELD The present invention relates to an optically active polymethacrylate derivative, a separating agent comprising the derivative, and a separating method using the separating agent.
【０００２】[0002]
【従来の技術】光学分割用分離剤、液晶、非線形光学材
料などの機能材料として利用されている光学活性な合成
高分子物質は、従来から数多く知られている。例えば、
光学活性メタクリル酸トリフェニルメチル重合体（特開
昭56-106907号公報、特開昭56-142216号公報）、光学活
性アクリル酸アミド重合体（特開昭56-167708号公
報）、メタクリル酸ジフェニル-２-ピリジルメチル（特
開昭57-209908号公報）、シリカゲル表面に化学結合し
た側鎖に光学活性置換基を有するポリ（メタ）アクリル
アミド化合物（特開昭63-001446号公報）、光学活性な
合成高分子化合物を用いた液晶組成物（特開平01-07923
0号公報）、光学活性メタクリル酸エステル重合体（特
開平08-208749号公報、特開2001-114832号公報）等が知
られている。2. Description of the Related Art Many optically active synthetic polymer substances used as functional materials such as separating agents for optical resolution, liquid crystals and nonlinear optical materials have been known. For example,
Optically active triphenylmethyl methacrylate polymer (JP-A-56-106907, JP-A-56-142216), optically active acrylic acid amide polymer (JP-A-56-167708), diphenyl methacrylate -2-Pyridylmethyl (JP-A-57-209908), a poly (meth) acrylamide compound having an optically active substituent on the side chain chemically bonded to the surface of silica gel (JP-A-63-001446), and an optically active compound. Liquid crystal composition using various synthetic polymer compounds (Japanese Patent Application Laid-Open No. 01-07923)
No. 0), optically active methacrylic acid ester polymers (JP 08-208749 A, JP 2001-114832 A) and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】然しながら、これらの
光学活性高分子は、それぞれ特異な性質を有するが、得
意とする応用範囲が自ずと狭いものである。例えば、上
記の光学活性高分子を光学活性物質の分離剤とした場
合、分離可能なラセミ体化合物や使用可能な溶媒は限ら
れている。従って、このような応用範囲を広げるために
は、新規な光学活性高分子の種類を増やすことが必要で
ある。However, although each of these optically active polymers has unique properties, its application range is naturally narrow. For example, when the above-mentioned optically active polymer is used as a separating agent for an optically active substance, the separable racemic compound and usable solvent are limited. Therefore, in order to expand such application range, it is necessary to increase the kinds of novel optically active polymers.
【０００４】本発明は、上述した状況に鑑みなされたも
ので、優れた光学物性が期待できる、新規な光学活性高
分子及びそれからなる分離剤並びにその分離剤を用いた
光学活性物質の分離方法を提供することを目的とする。The present invention has been made in view of the above situation, and provides a novel optically active polymer, a separating agent comprising the same, and a method for separating an optically active substance using the separating agent, which are expected to have excellent optical properties. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】上記の目的を達成するた
め、本発明者は鋭意研究を重ねた結果、新規な光学活性
メタクリレート誘導体を見出し、更に、それが光学分割
剤としての優れた性能を発現することを見出し、本発明
を完成するに至ったものである。[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventor has conducted extensive studies, and as a result, found a novel optically active methacrylate derivative, which has an excellent performance as an optical resolving agent. The inventors have found that they are expressed and completed the present invention.
【０００６】即ち、本発明の光学活性ポリメタクリレー
ト誘導体は、下記一般式（１）で表される側鎖にウレア
結合を有する新規な光学活性ポリメタクリレート誘導体
であり、本発明の分離剤は、それからなる光学活性物質
の分離剤であり、本発明の分離方法は、その分離剤を用
いて光学活性物質を分離する方法である。That is, the optically active polymethacrylate derivative of the present invention is a novel optically active polymethacrylate derivative having a urea bond in the side chain represented by the following general formula (1), and the separating agent of the present invention is The separating method of the present invention is a method for separating an optically active substance using the separating agent.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】（式中、R1は、メチル基、又はアルコキシ
カルボニル基を、R2は、フェニル基、ナフチル基、又は
ベンジル基を表し、ｎは２〜5000の範囲の数、*印は光
学活性炭素を表す。）(In the formula, R 1 represents a methyl group or an alkoxycarbonyl group, R 2 represents a phenyl group, a naphthyl group, or a benzyl group, n is a number in the range of 2 to 5000, and * indicates optical. Represents activated carbon.)
【０００９】[0009]
【発明の実施の形態】本発明の側鎖にウレア結合を有す
る光学活性ポリメタクリレート誘導体は、上記一般式
（１）で示される新規な化合物であり、その製造方法
は、特に本発明を限定するものではないが、例えば、下
記一般式（２）で表される光学活性メタクリレート誘導
体を、ラジカル開始剤（反応開始剤）存在下、ラジカル
重合することにより調製することができる。BEST MODE FOR CARRYING OUT THE INVENTION The optically active polymethacrylate derivative having a urea bond in the side chain of the present invention is a novel compound represented by the above general formula (1), and its production method particularly limits the present invention. Although not limited, for example, it can be prepared by radical polymerization of an optically active methacrylate derivative represented by the following general formula (2) in the presence of a radical initiator (reaction initiator).
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】（式中、R1は、メチル基、又はアルコキシ
カルボニル基を、R2は、フェニル基、ナフチル基、又は
ベンジル基を表し、*印は光学活性炭素を表す。）(In the formula, R 1 represents a methyl group or an alkoxycarbonyl group, R 2 represents a phenyl group, a naphthyl group or a benzyl group, and * represents an optically active carbon.)
【００１２】原料である上記一般式（２）で表される光
学活性メタクリレート誘導体としては、例えば、（Ｓ）
−メチルベンジルメタクリロイルオキシエチルウレア、
（Ｓ）-（メトキシカルボニルベンジル）メチルメタク
リロイルオキシエチルウレア等が挙げられる。Examples of the optically active methacrylate derivative represented by the above general formula (2), which is a raw material, include (S)
-Methylbenzyl methacryloyloxyethyl urea,
(S)-(methoxycarbonylbenzyl) methylmethacryloyloxyethylurea and the like can be mentioned.
【００１３】ラジカル開始剤としては、特に限定するも
のではないが、例えば、アゾビスイソブチロニトリル、
２, ２'-アゾビスイソブチレート、４, ４'-アゾビス
（４-シアノ吉草酸）等のアゾ化合物や、過酸化ベンゾ
イル、ジ-t-ブチルパーオキシド等の過酸化物が挙げら
れ、使用量としては、反応に供する原料の光学活性メタ
クリレート誘導体に対して0.01〜10モル％の範囲で使用
するのが好適である。The radical initiator is not particularly limited, but for example, azobisisobutyronitrile,
Examples include azo compounds such as 2,2′-azobisisobutyrate and 4,4′-azobis (4-cyanovaleric acid), and peroxides such as benzoyl peroxide and di-t-butyl peroxide. The amount used is preferably in the range of 0.01 to 10 mol% with respect to the optically active methacrylate derivative as a raw material to be used in the reaction.
【００１４】重合に用いる溶剤としては、反応に不活性
な溶剤であればあらゆる溶剤が使用可能であるが、通常
は、反応に用いる原料及び反応開始剤を充分に溶解させ
ることのできる溶剤を用いる。具体的には、テトラヒド
ロフラン（以下、THFと略す）、N, N-ジメチルホルムア
ミド（以下、DMFと略す）、ジクロロメタン、クロロホ
ルム、ベンゼン、トルエン、キシレン等が挙げられ、使
用量としては、反応に供する原料のメタクリレート誘導
体に対して重量で１〜100倍程度使用するのが好適であ
る。As the solvent used for the polymerization, any solvent can be used as long as it is an inert solvent for the reaction. Usually, a solvent that can sufficiently dissolve the raw materials and the reaction initiator used for the reaction is used. . Specific examples thereof include tetrahydrofuran (hereinafter abbreviated as THF), N, N-dimethylformamide (hereinafter abbreviated as DMF), dichloromethane, chloroform, benzene, toluene, xylene, and the like. It is preferable to use 1 to 100 times by weight of the raw material methacrylate derivative.
【００１５】反応温度は、反応に供する原料のメタクリ
レート誘導体や反応開始剤の種類により異なり、特に限
定するものではないが、通常50〜150℃の範囲が好適で
ある。The reaction temperature varies depending on the type of the methacrylate derivative or the reaction initiator used as the raw material to be subjected to the reaction and is not particularly limited, but usually in the range of 50 to 150 ° C.
【００１６】反応時間は、原料のメタクリレート誘導体
や反応開始剤の種類により異なり、特に限定するもので
はないが、通常、１時間〜240時間の範囲で反応は完結
する。The reaction time varies depending on the type of the raw material methacrylate derivative or the reaction initiator and is not particularly limited, but usually the reaction is completed within the range of 1 hour to 240 hours.
【００１７】反応終了後、ヘキサン、ヘプタン、メタノ
ール、エタノール等の、生成物の溶解度が低い溶剤に反
応液を滴下晶析させることにより、本発明の側鎖にウレ
ア結合を有する光学活性ポリメタクリレート誘導体を粉
末として取得できる。純度を向上させるために、THFやD
MF等の溶剤に溶解させ、再度メタノール等の溶剤に投入
し、再晶析を行っても良い。After completion of the reaction, the reaction solution is dropped and crystallized in a solvent having a low solubility of the product such as hexane, heptane, methanol and ethanol to give an optically active polymethacrylate derivative having a urea bond in the side chain of the present invention. Can be obtained as a powder. THF and D to improve purity
It is also possible to dissolve in a solvent such as MF and re-inject into a solvent such as methanol for recrystallization.
【００１８】本発明の側鎖にウレア結合を有する光学活
性ポリメタクリレート誘導体は、光学活性物質の分離剤
として使用することができる。The optically active polymethacrylate derivative having a urea bond in the side chain of the present invention can be used as a separating agent for an optically active substance.
【００１９】本発明の側鎖にウレア結合を有する光学活
性ポリメタクリレート誘導体を用いて光学活性物質を分
離する方法としては、特に限定するものではないが、例
えば、原料である上記一般式（２）で示される光学活性
メタクリレート誘導体を、表面にビニル基を有する多孔
質の担体存在下で重合することにより、本発明のウレア
結合を有する光学活性ポリメタクリレート誘導体を多孔
質の担体に化学的に結合させた分離剤を調製し、これを
充填したカラムを用い、高速液体クロマトグラフィーに
より光学活性物質を容易に分離することができる。The method of separating the optically active substance by using the optically active polymethacrylate derivative having a urea bond in the side chain of the present invention is not particularly limited, but, for example, the above-mentioned general formula (2) as a raw material is used. The optically active polymethacrylate derivative represented by is polymerized in the presence of a porous carrier having a vinyl group on the surface to chemically bond the optically active polymethacrylate derivative having a urea bond of the present invention to the porous carrier. It is possible to easily separate the optically active substance by high performance liquid chromatography using a column packed with the separating agent prepared as above.
【００２０】本発明のウレア結合を有する光学活性ポリ
メタクリレート誘導体を担持させる担体としては、特に
限定するものではないが、シリカゲル、アルミナ、架橋
スチレン、ポリシロキサン等が挙げられる。担体の粒子
としては１μm〜200μm、平均細孔径としては10Å〜300
Åのものが高速液体クロマトグラフィーにおける分離剤
としては好ましい。The carrier for supporting the optically active polymethacrylate derivative having a urea bond of the present invention is not particularly limited, and examples thereof include silica gel, alumina, crosslinked styrene, polysiloxane and the like. The carrier particles are 1 μm to 200 μm, and the average pore size is 10Å to 300
Those of Å are preferable as the separating agent in high performance liquid chromatography.
【００２１】表面にビニル基を有する多孔質の担体の調
製方法は、特に限定するものではないが、例えば、シリ
カゲルを３-アミノプロピルトリエトキシシランで表面
処理し、続いて２-メタクリロイルオキシエチルイソシ
アナートと反応させたものが挙げられる。The method for preparing the porous carrier having a vinyl group on the surface is not particularly limited. For example, silica gel is surface-treated with 3-aminopropyltriethoxysilane, and then 2-methacryloyloxyethylisocyanate is used. One that has been reacted with nato.
【００２２】担持方法としては、特に限定するものでは
ないが、本発明の光学活性ポリメタクリレート誘導体を
多孔質の担体に化学的に結合させてもよいし、光学活性
ポリメタクリレート誘導体を多孔質の担体と接触させ物
理的に担持させてもよい。The supporting method is not particularly limited, but the optically active polymethacrylate derivative of the present invention may be chemically bonded to the porous carrier, or the optically active polymethacrylate derivative may be chemically bonded to the porous carrier. It may be brought into contact with and physically supported.
【００２３】担体に対する本発明の側鎖にウレア結合を
有する光学活性ポリメタクリレート誘導体の担持量とし
ては、用いる担体の種類、物性により異なり、特に限定
するものではないが、通常、充填剤の重量に対して１〜
50重量％の範囲で担持可能である。The supported amount of the optically active polymethacrylate derivative having a urea bond in the side chain of the present invention with respect to the carrier varies depending on the type and physical properties of the carrier to be used and is not particularly limited, but usually it depends on the weight of the filler. 1 to
It can be supported in the range of 50% by weight.
【００２４】本発明の側鎖にウレア結合を有する光学活
性ポリメタクリレート誘導体を多孔質の担体に担持させ
た分離剤は、水素結合やπ−π相互作用作用等が可能な
光学活性物質の分離に適用可能である。例えば、高速液
体クロマトグラフィー用のカラムの充填剤として使用す
る場合、溶離液としてヘキサン-イソプロパノール等を
用いる順相系、アルコール-水等を用いる逆相系のいず
れにおいても幅広く応用可能である。The separating agent of the present invention in which an optically active polymethacrylate derivative having a urea bond in the side chain is supported on a porous carrier is used for separating an optically active substance capable of hydrogen bonding, π-π interaction and the like. Applicable. For example, when it is used as a packing material for a column for high performance liquid chromatography, it can be widely applied to both a normal phase system using hexane-isopropanol or the like as an eluent and a reverse phase system using alcohol-water or the like.
【００２５】以上、詳細に説明した実施の形態により、
本発明は、優れた光学物性が期待できる、新規な光学活
性高分子及びそれからなる分離剤並びにその分離剤を用
いた光学活性物質の分離方法を提供するものであると共
に、（１）ラジカル重合で調製できるため製造が簡便で
ある、（２）担体と化学結合又は物理結合の両方が可能
である、（３）化学結合型分離剤とした場合、溶離液に
制限がなく、順相系、逆相系共に使用できる、などの効
果を有するものである。According to the embodiment described in detail above,
INDUSTRIAL APPLICABILITY The present invention provides a novel optically active polymer, a separating agent comprising the same, and a method for separating an optically active substance using the separating agent, which are expected to have excellent optical properties. Since it can be prepared, it is easy to manufacture. (2) Both the chemical bond and the physical bond are possible with the carrier. (3) When the chemical bond type separating agent is used, the eluent is not limited, and the normal phase system and the reverse phase system can be used. It has an effect that it can be used in both phase systems.
【００２６】[0026]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明がこれらの実施例に限定されるものではな
いことは言うまでもない。EXAMPLES The present invention will be specifically described below with reference to examples, but it goes without saying that the present invention is not limited to these examples.
【００２７】以下の実施例において、平均分子量は、ゲ
ルパーミエーションクロマトグラフィー（島津製SPD-10
A）によりポリスチレン換算で算出し、旋光度はJASCO製
DIP-140、赤外分光スペクトルは島津製FT IR-8100Aによ
り測定したものである。 なお、調製した光学活性ポリ
メタクリレート誘導体の分離能の測定には、島津製液体
クロマトグラフィーLC-10AT、紫外可視検出器SPD-10A、
クロマトパックC-R8Aを用いた。In the following examples, the average molecular weight is determined by gel permeation chromatography (SPD-10 manufactured by Shimadzu Corporation).
Calculated in terms of polystyrene according to A) and the optical rotation is made by JASCO
DIP-140 and infrared spectrum were measured by FT IR-8100A manufactured by Shimadzu. Incidentally, the measurement of the separation ability of the prepared optically active polymethacrylate derivative, liquid chromatography LC-10AT manufactured by Shimadzu, UV-visible detector SPD-10A,
Chromatopack C-R8A was used.
【００２８】実施例１：光学活性ポリメタクリレート誘
導体の調製（その例１）
重合管に（Ｓ）-メチルベンジルメタクリロイルオキシ
エチルウレア（以下MBMOUと略す）500ｍｇ、アゾビスイ
ソブチロニトリル（以下AIBNと略す）10ｍｇ及びTHF２
ｍＬを仕込み、窒素雰囲気下、60℃で振とうさせながら
24時間重合を行った。Example 1 Preparation of Optically Active Polymethacrylate Derivative (Example 1) 500 mg of (S) -methylbenzylmethacryloyloxyethylurea (hereinafter abbreviated as MBMOU), azobisisobutyronitrile (hereinafter referred to as AIBN) were placed in a polymerization tube. Abbreviated) 10 mg and THF2
Charge mL and shake at 60 ° C under a nitrogen atmosphere.
Polymerization was carried out for 24 hours.
【００２９】重合終了後、反応液を100ｍＬのメタノー
ルに投入し、次いで上澄み液をデカンテーションにより
除去し、析出物を室温、減圧下で乾燥させた。乾燥後、
析出物をDMF２ｍＬに溶解させ、再度100ｍＬのメタノー
ルに投入し再晶析を行った。さらに、同様な方法により
もう一度再晶析を行った後、室温、減圧下で乾燥するこ
とにより目的物のポリ（MBMOU）350ｍｇを得た（収率70
％）。After completion of the polymerization, the reaction solution was poured into 100 mL of methanol, the supernatant was removed by decantation, and the precipitate was dried at room temperature under reduced pressure. After drying
The precipitate was dissolved in DMF (2 mL) and re-crystallized by adding it again to 100 mL of methanol. Further, recrystallization was performed again by the same method and then dried at room temperature under reduced pressure to obtain 350 mg of the target poly (MBMOU) (yield 70
%).
【００３０】旋光度 [α]435 25＝-１２．９゜（Ｃ＝
１．０ｇ／ｄＬ，DMF）
分子量 Ｍｎ＝７２００００Optical rotation [α] 435 25 = -12.9 ° (C =
1.0 g / dL, DMF) Molecular weight Mn = 720,000
【００３１】実施例２：光学活性ポリメタクリレート誘
導体の調製（その例２）
実施例１と同じ装置を用い、（Ｓ）-（メトキシカルボ
ニルベンジル）メチルメタクリロイルオキシエチルウレ
ア（以下MCMOUと略す）500ｍｇ、AIBN10ｍｇ及びTHF２
ｍＬを仕込み、60℃で振とうさせながら24時間重合を行
い、実施例１と同じ後処理操作の後、目的物のポリ（MC
MOU）325ｍｇを得た（収率65％）。Example 2 Preparation of Optically Active Polymethacrylate Derivative (Example 2) Using the same apparatus as in Example 1, (S)-(methoxycarbonylbenzyl) methylmethacryloyloxyethylurea (hereinafter abbreviated as MCMOU) 500 mg, AIBN 10mg and THF2
After adding mL, polymerization was carried out for 24 hours while shaking at 60 ° C., and after the same post-treatment operation as in Example 1, the target poly (MC
325 mg of MOU was obtained (yield 65%).
【００３２】旋光度 [α]435 25＝＋３１．５゜（Ｃ＝
１．０ｇ／ｄＬ，DMF）
分子量 Ｍｎ＝３２００００Optical rotation [α] 435 25 = + 31.5 ° (C =
1.0 g / dL, DMF) Molecular weight Mn = 320,000
【００３３】参考例１：表面にビニル基を有するシリカ
ゲルの調製
還流コンデンサーを備えた100ｍＬのナスフラスコにシ
リカゲル（東ソー社製TSK-GEL SI100、平均粒径５μ
ｍ、平均細孔径100Å）10ｇ、３-アミノプロピルトリエ
トキシシラン14ｍＬ及びトルエン80ｍＬを仕込み、24時
間還流を行った。反応物を冷却後、ろ過、次いでトルエ
ン、アセトン、メタノールの順で洗浄、乾燥することに
より、３-アミノプロピルトリエトキシシラン処理シリ
カゲルを得た。Reference Example 1: Preparation of silica gel having vinyl group on the surface Silica gel (TSK-GEL SI100 manufactured by Tosoh Corporation, average particle size 5 μm) was placed in a 100 mL eggplant flask equipped with a reflux condenser.
m, average pore size 100 Å) 10 g, 3-aminopropyltriethoxysilane 14 mL and toluene 80 mL were charged and refluxed for 24 hours. The reaction product was cooled, filtered, washed with toluene, acetone, and methanol in this order, and dried to obtain 3-aminopropyltriethoxysilane-treated silica gel.
【００３４】続いて、100ｍＬのナスフラスコに３-アミ
ノプロピルトリエトキシシラン処理シリカゲル８ｇ、２
-メタクリロイルオキシエチルイソシアナート16ｍＬ及
びジクロロメタン80ｍＬを仕込み、35℃で36時間反応さ
せた。反応終了後、ろ過、次いでジクロロメタン、アセ
トン、メタノールの順で洗浄、乾燥することにより、表
面にビニル基を有するシリカゲルを得た。Then, in a 100 mL eggplant-shaped flask, 8 g of 3-aminopropyltriethoxysilane-treated silica gel, 2 g
-Methacryloyloxyethyl isocyanate 16mL and dichloromethane 80mL were prepared and reacted at 35 ° C for 36 hours. After completion of the reaction, the silica gel having a vinyl group on the surface was obtained by filtering, then washing with dichloromethane, acetone, and methanol in this order and drying.
【００３５】実施例３：ポリ（MBMOU）を化学的に結合
させたシリカゲル及びその充填カラムの調製
50ｍＬのシュレンク管に、参考例１で調製した表面にビ
ニル基を有するシリカゲル１ｇ、MBMOU0.5ｇ、AIBN10ｍ
ｇ及びTHF５ｍＬを仕込み、窒素雰囲気下、60℃で48時
間振とうさせながら反応を行った。反応終了後、反応物
をろ過、次いでTHF、アセトン、メタノールの順で洗
浄、乾燥した。このようにして、目的物のポリ（MBMO
U）を化学的に結合させたシリカゲルを得た。Example 3: Preparation of silica gel chemically bound to poly (MBMOU) and packed column thereof 1 g of silica gel having vinyl group on the surface prepared in Reference Example 1 and 0.5 g of MBMOU in a 50 mL Schlenk tube. AIBN10m
g and 5 mL of THF were charged, and the reaction was carried out while shaking at 60 ° C. for 48 hours in a nitrogen atmosphere. After completion of the reaction, the reaction product was filtered, washed with THF, acetone, and methanol in this order and dried. In this way, the target poly (MBMO
U) was chemically bound to obtain silica gel.
【００３６】シリカゲルに化学的に結合したポリ（MBMO
U）の重量は、以下のような操作により算出した。Poly (MBMO chemically bonded to silica gel
The weight of U) was calculated by the following operation.
【００３７】実施例１で調製したポリ（MBMOU）と参考
例１で調製した表面にビニル基を有するシリカゲルを適
当な重量比で混合し、赤外分光スペクトル測定を行い、
700ｃｍ-1のポリ（MBMOU）中のフェニル基に起因する吸
収と、800ｃｍ-1のシリカゲルに起因する吸収の吸光強
度比より検量線を作成し、次いでポリ（MBMOU）を化学
的に結合させたシリカゲルの赤外分光スペクトル測定を
行うことにより、ポリ（MBMOU）が32ｗｔ％でシリカゲ
ルに化学的に結合していることが確認された。The poly (MBMOU) prepared in Example 1 and the silica gel having vinyl groups on the surface prepared in Reference Example 1 were mixed in an appropriate weight ratio, and infrared spectroscopic measurement was carried out.
A calibration curve was prepared from the absorption intensity ratio of the absorption due to the phenyl group in poly (MBMOU) at 700 cm -1 and the absorption due to silica gel at 800 cm -1 , and then poly (MBMOU) was chemically bound. By performing infrared spectroscopy measurement on silica gel, it was confirmed that poly (MBMOU) was chemically bonded to silica gel at 32 wt%.
【００３８】調製したポリ（MBMOU）を化学的に結合さ
せたシリカゲルをメタノールに分散させた後、ステンレ
ス製の２ｍｍ（ID）×150ｍｍ（L）のカラムに高圧ポン
プを用い、流量1.4ｍＬ／ｍｉｎ、最高圧力295ｋｇ／ｃ
ｍ2で充填した。得られたカラムの理論段数は274段であ
った。After dispersing the prepared silica gel chemically bound to poly (MBMOU) in methanol, a stainless steel column of 2 mm (ID) × 150 mm (L) was used with a high-pressure pump and a flow rate of 1.4 mL / min. , Maximum pressure 295kg / c
filled with m 2 . The theoretical plate number of the obtained column was 274 plates.
【００３９】理論段数の測定は、溶離液にメタノールを
用い、トルエンの溶出により測定した。なお、理論段数
は下式により算出した。The theoretical plate number was measured by eluting toluene with methanol as the eluent. The theoretical plate number was calculated by the following formula.
【００４０】理論段数（Ｎ）＝５．５４×［Ｔｒ／（Ｗ
1/2）］2
Ｔｒ＝保持時間（ｓｅｃ）
Ｗ1/2＝半値幅（ｍｍ）Theoretical plate number (N) = 5.54 × [Tr / (W
1/2 )] 2 Tr = holding time (sec) W 1/2 = full width at half maximum (mm)
【００４１】実施例４：ポリ（MCMOU）を化学的に結合
させたシリカゲル及びその充填カラムの調製
実施例３と同様な操作で、参考例１で調製した表面にビ
ニル基を有するシリカゲル１ｇ、MCMOU0.5ｇ、AIBN10ｍ
ｇ及びTHF５ｍＬより、目的物のポリ（MCMOU）を化学的
に結合させたシリカゲルを得た。Example 4: Preparation of silica gel chemically bound to poly (MCMOU) and packed column thereof By the same operation as in Example 1, 1 g of silica gel having a vinyl group on the surface prepared in Reference Example 1, MCMOU0 .5g, AIBN10m
From g and 5 mL of THF, silica gel to which poly (MCMOU) of the target substance was chemically bound was obtained.
【００４２】実施例３と同様に、シリカゲルに化学的に
結合したポリ（MCMOU）の量を測定した結果、17ｗｔ％
であった。As in Example 3, the amount of poly (MCMOU) chemically bonded to silica gel was measured, and the result was 17 wt%.
Met.
【００４３】実施例３と同様に、テンレス製の２ｍｍ
（ID）×150ｍｍ（L）のカラムにポリ（MCMOU）を化学
的に結合させたシリカゲルを充填し、理論段数を測定し
た結果、346段であった。As in Example 3, 2 mm made of Tenres
A column of (ID) × 150 mm (L) was packed with silica gel in which poly (MCMOU) was chemically bound, and the theoretical plate number was measured, resulting in 346 plates.
【００４４】実施例５〜９
実施例３及び実施例４で調製したカラムを用い、表１中
に示した条件下で各種ラセミ体の分離を行った。結果
を、表１中に併せて示す。Examples 5 to 9 Using the columns prepared in Examples 3 and 4, various racemates were separated under the conditions shown in Table 1. The results are also shown in Table 1.
【００４５】[0045]
【表１】
備考１ ラセミ体（１）：マンデル酸エチルエステル
ラセミ体（２）：マンデル酸
ラセミ体（３）：ケトプロフェン
ラセミ体（４）：Ｎ-アセチル-１-フェニルエチルアミ
ン
備考２ 移動相：メタノール／水（ｖｏｌ／ｖｏｌ）[Table 1] Remarks 1 Racemic compound (1): Mandelic acid ethyl ester racemic compound (2): Mandelic acid racemic compound (3): Ketoprofen racemic compound (4): N-acetyl-1-phenylethylamine Remarks 2 Mobile phase: Methanol / water ( vol / vol)
【００４６】なお、実測したクロマトグラムの例とし
て、実施例８で得られたクロマトグラムを図１に示し
た。図１は、本発明の側鎖にウレア結合を有する光学活
性ポリメタクリレート誘導体が、高い不斉認識能を持つ
ことを示している。As an example of the actually measured chromatogram, the chromatogram obtained in Example 8 is shown in FIG. FIG. 1 shows that the optically active polymethacrylate derivative having a urea bond in the side chain of the present invention has a high asymmetric recognition ability.
【００４７】[0047]
【発明の効果】本発明は、優れた光学物性を有する新規
な光学活性高分子及びそれからなる分離剤並びにその分
離剤を用いた光学活性物質の分離方法を提供するもので
あると共に、ラジカル重合で調製できるため製造が簡便
である、担体と化学結合又は物理結合の両方が可能であ
る、化学結合型分離剤とした場合、溶離液に制限がな
く、順相系、逆相系共に使用できる、などの効果を有す
る。INDUSTRIAL APPLICABILITY The present invention provides a novel optically active polymer having excellent optical physical properties, a separating agent comprising the same, and a method for separating an optically active substance using the separating agent, and by radical polymerization. Since it can be prepared, the production is simple, both the chemical bond and the physical bond with the carrier are possible, and when the chemical bond type separating agent is used, the eluent is not limited, and both normal phase system and reverse phase system can be used. And so on.
【００４８】[0048]
【図１】本発明の側鎖にウレア結合を有する光学活性ポ
リメタクリレート誘導体を、表面にビニル基を有するシ
リカゲルに化学結合させた分離剤を用いて、ケトプロフ
ェンを分離したクロマトグラムの例を示す概念図であ
る。FIG. 1 is a concept showing an example of a chromatogram obtained by separating ketoprofen using a separating agent in which an optically active polymethacrylate derivative having a urea bond in a side chain of the present invention is chemically bonded to silica gel having a vinyl group on the surface. It is a figure.
フロントページの続き Ｆターム(参考） 4D017 BA03 CA13 CA14 CB01 DA03 EA05 4J100 AL08P BA20P BA37P BC43P BC49P BD11P CA01 DA01 DA61 JA15 JA17 Continued front page F-term (reference) 4D017 BA03 CA13 CA14 CB01 DA03 EA05 4J100 AL08P BA20P BA37P BC43P BC49P BD11P CA01 DA01 DA61 JA15 JA17
Claims (6)
ア結合を有する光学活性ポリメタクリレート誘導体。 【化１】 （式中、R1は、メチル基、又はアルコキシカルボニル基
を、R2は、フェニル基、ナフチル基、又はベンジル基を
表し、ｎは２〜5000の範囲の数、*印は光学活性炭素を
表す。）1. An optically active polymethacrylate derivative having a urea bond in a side chain represented by the following general formula (1). [Chemical 1] (In the formula, R 1 represents a methyl group or an alkoxycarbonyl group, R 2 represents a phenyl group, a naphthyl group, or a benzyl group, n is a number in the range of 2 to 5000, and * indicates an optically active carbon. Represents.)
ート誘導体からなる分離剤。2. A separating agent comprising the optically active polymethacrylate derivative according to claim 1.
ート誘導体を担体に担持してなる分離剤。3. A separating agent obtained by supporting the optically active polymethacrylate derivative according to claim 1 on a carrier.
い光学活性物質を分離する方法。4. A method for separating an optically active substance using the separating agent according to claim 2 or 3.
填した高速液体クロマトグラフィーカラム。5. A high performance liquid chromatography column packed with the separating agent according to claim 2 or 3.
ィーカラムを用い高速液体クロマトグラフィーにより光
学活性物質を分離する方法。6. A method for separating an optically active substance by high performance liquid chromatography using the high performance liquid chromatography column according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001229833A JP2003040927A (en) | 2001-07-30 | 2001-07-30 | Optically active polymethacrylate derivative, and separating agent and separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001229833A JP2003040927A (en) | 2001-07-30 | 2001-07-30 | Optically active polymethacrylate derivative, and separating agent and separation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003040927A true JP2003040927A (en) | 2003-02-13 |
Family
ID=19062130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001229833A Pending JP2003040927A (en) | 2001-07-30 | 2001-07-30 | Optically active polymethacrylate derivative, and separating agent and separation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003040927A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016352A (en) * | 2004-07-02 | 2006-01-19 | Chiba Univ | Columnar liquid crystal compound exhibiting ferroelectricity |
| WO2006035915A1 (en) * | 2004-09-29 | 2006-04-06 | Kansai Paint Co., Ltd. | Monomer compound, process for producing the same, polymer thereof, and water-based curable composition |
| WO2007034551A1 (en) * | 2005-09-22 | 2007-03-29 | Taiyo Nippon Sanso Corporation | Spheroidizig system and its operating method |
| WO2012176631A1 (en) * | 2011-06-24 | 2012-12-27 | 昭和電工株式会社 | Method for producing isocyanate compound containing ethylenically unsaturated group |
-
2001
- 2001-07-30 JP JP2001229833A patent/JP2003040927A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016352A (en) * | 2004-07-02 | 2006-01-19 | Chiba Univ | Columnar liquid crystal compound exhibiting ferroelectricity |
| JP4599552B2 (en) * | 2004-07-02 | 2010-12-15 | 国立大学法人 千葉大学 | Columnar liquid crystal compounds exhibiting ferroelectricity |
| WO2006035915A1 (en) * | 2004-09-29 | 2006-04-06 | Kansai Paint Co., Ltd. | Monomer compound, process for producing the same, polymer thereof, and water-based curable composition |
| WO2007034551A1 (en) * | 2005-09-22 | 2007-03-29 | Taiyo Nippon Sanso Corporation | Spheroidizig system and its operating method |
| WO2012176631A1 (en) * | 2011-06-24 | 2012-12-27 | 昭和電工株式会社 | Method for producing isocyanate compound containing ethylenically unsaturated group |
| JP5165815B2 (en) * | 2011-06-24 | 2013-03-21 | 昭和電工株式会社 | Process for producing ethylenically unsaturated group-containing isocyanate compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107430100B (en) | Stationary phase for supercritical fluid chromatography | |
| EP1591462A2 (en) | Temperature-responsive polymer compound and process for producing the same | |
| JP2812765B2 (en) | Optically active (meth) acrylic acid derivatives, their production, polymerization to give their optically active polymers, and their use | |
| JPS631446A (en) | Optically active adsorbent | |
| JP6940410B2 (en) | Method of addition manufacturing using photoregulated radical polymerization | |
| JP2003040927A (en) | Optically active polymethacrylate derivative, and separating agent and separation method | |
| US11040330B2 (en) | Chromatography stationary phase | |
| JPH09176243A (en) | Novel polymer of acetylene derivative | |
| JP2965752B2 (en) | Optically active N-α-fluoroacryloylamino acid derivatives, their production, optically active polymers produced therefrom and their use for resolving racemates | |
| JP2003128727A (en) | Optically active polymethacrylate derivative having urethane bond on side chain, separating agent and method for separation | |
| JP4876346B2 (en) | Optically active maleimide derivative, optically active polymaleimide derivative, production method thereof, separating agent comprising optically active polymaleimide derivative, and separation method of optically active compound using the same | |
| JP2003040932A (en) | Optically active polyacrylamide macromonomer and polymer thereof, and separating agent and separation method | |
| US7381742B2 (en) | Optically active polymaleimide derivatives and process for their production | |
| JP4422540B2 (en) | Temperature responsive surface and its use | |
| JP5263478B2 (en) | Optically active block copolymer, process for producing the same, and chromatographic filler using the block copolymer | |
| JP2003073401A (en) | Cellulose derivative having vinyl group, separating agent and separating method | |
| JP4534329B2 (en) | Separation agent comprising optically active polymaleimide derivative and method for separating optically active compound using the same | |
| JP2001106729A (en) | Optically active polymaleimide derivative, method for producing the same, optical resolution agent consisting of the same and method for resolution of optically active compound using the same | |
| JP6095129B2 (en) | Separating agent for optical isomers | |
| JP2008019351A (en) | Method for separating optically active n-substituted homophenylalanine | |
| JP2000128910A (en) | Synthesis of optically active crosslinked gel | |
| JP4380367B2 (en) | Optically active maleimide derivative, optically active polymaleimide derivative, production method thereof, separating agent comprising optically active polymaleimide derivative, and separation method of optically active compound using the same | |
| JPWO2003102039A1 (en) | Optically active polymer compound | |
| JP2005344040A (en) | Optically active polymaleimide derivative, and optical isomer-separating agent comprising the same and method for separating optically active compound with the separating agent | |
| JP4306296B2 (en) | Optically active maleimide derivative, optically active polymaleimide derivative, production method thereof, separating agent comprising optically active polymaleimide derivative, and separation method of optically active compound using the same |