JPH08208749A - Optically active methacrylic ester polymer and separating agent - Google Patents
Optically active methacrylic ester polymer and separating agentInfo
- Publication number
- JPH08208749A JPH08208749A JP2017595A JP2017595A JPH08208749A JP H08208749 A JPH08208749 A JP H08208749A JP 2017595 A JP2017595 A JP 2017595A JP 2017595 A JP2017595 A JP 2017595A JP H08208749 A JPH08208749 A JP H08208749A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- methacrylic acid
- acid ester
- ester polymer
- polymer
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な光学活性メタクリ
ル酸エステル重合体及びこの重合体からなる光学分割用
分離剤に関し、特に、耐久性に優れ、有用なラセミ体の
光学分割用分離剤となる光学活性メタクリル酸エステル
重合体、及びこの重合体からなる光学分割用分離剤に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel optically active methacrylic acid ester polymer and an optical resolution separating agent comprising the polymer, and particularly to a racemic optical resolution separating agent having excellent durability and usefulness. And an optically active methacrylic acid ester polymer, and a separating agent for optical resolution comprising the polymer.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】これま
でにメタクリル酸トリフェニルメチル（TrMA)(特開昭56
−142,216 号公報参照）やメタクリル酸ジフェニル−２
−ピリジルメチル（D2PyMA)(特開昭57−209,908 号公報
参照）、メタクリル酸シクロブチルジフェニルメチル
（CBDPMA）などの側鎖にかさ高いエステル基をもつメタ
クリル酸エステルを不斉なアニオン重合開始剤を用いて
重合すると左右どちらか一方巻きのらせん構造を有する
ポリマーが得られ、このポリマーは高度にイソタクチッ
クになることが知られている。このらせん構造を有する
ポリメタクリル酸トリフェニルメチル等は光学異性体分
離用充填剤として用いられるが、溶離液のメタノールに
より加溶媒分解されやすい欠点がある。PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION So far, triphenylmethyl methacrylate (TrMA) (JP-A-56
-142,216) and diphenyl methacrylate-2
-Pyridylmethyl (D2PyMA) (see JP-A-57-209,908), cyclobutyldiphenylmethylmethacrylate (CBDPMA), etc. It is known that when it is polymerized by using it, a polymer having a spiral structure of either left or right winding is obtained, and this polymer is highly isotactic. Polyphenylmethacrylate methacrylate having this helical structure is used as a filler for separating optical isomers, but it has a drawback that it is easily solvolyzed by methanol as an eluent.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、このよう
な欠点を克服すべく鋭意検討した結果、加溶媒分解に対
し安定な光学活性メタクリル酸エステル重合体を見いだ
し本発明を完成するに至った。即ち、本発明は、一般式
（Ｉ）で表される１−（２−ピリジル）ジベンゾシクロ
アルカンをアルコール部分とするメタクリル酸エステル
誘導体を重合させて得られる、新規な光学活性メタクリ
ル酸エステル重合体、及びこの光学活性メタクリル酸エ
ステル重合体からなることを特徴とする光学分割用分離
剤を提供するものである。Means for Solving the Problems As a result of intensive studies to overcome such drawbacks, the present inventors have found an optically active methacrylic acid ester polymer which is stable against solvolysis and completed the present invention. I arrived. That is, the present invention is a novel optically active methacrylic acid ester polymer obtained by polymerizing a methacrylic acid ester derivative having 1- (2-pyridyl) dibenzocycloalkane represented by the general formula (I) as an alcohol moiety. And a separating agent for optical resolution, characterized by comprising the optically active methacrylic acid ester polymer.
【０００４】[0004]
【化２】 Embedded image
【０００５】は炭素数６〜14からなる２価の芳香族環を
示し、ｎはメチレン鎖の数を示す０〜５の整数であ
る。） これまでに得られているメタクリル酸トリフェニルメチ
ル（TrMA）やメタクリル酸ジフェニル−２−ピリジルメ
チル（D2PyMA）は、アルコール部分が加溶媒分解により
安定な３級カチオンを生じやすいために溶離液のメタノ
ールにより加溶媒分解されやすい。そこで、カチオンを
不安定化して加溶媒分解性を抑制するために、カチオン
になる炭素に立体的、電子的な検討を加え、耐加溶媒分
解性に優れた前記一般式（Ｉ）で表される１−(2−ピリ
ジル）ジベンゾシクロアルカンをアルコール部分とする
メタクリル酸エステル誘導体を重合させて得られる重合
体を見いだしたのである。Is a divalent aromatic ring having 6 to 14 carbon atoms, and n is an integer of 0 to 5 showing the number of methylene chains. ) The triphenylmethylmethacrylate (TrMA) and diphenyl-2-pyridylmethylmethacrylate (D2PyMA) obtained up to now have a tendency to generate stable tertiary cations due to the solvolysis of the alcohol moiety, so It is easily subjected to solvolysis by methanol. Therefore, in order to destabilize the cation and suppress the solvolysis, the carbon that becomes the cation is sterically and electronically examined, and is represented by the general formula (I) having excellent solvolysis resistance. They have found a polymer obtained by polymerizing a methacrylic acid ester derivative having 1- (2-pyridyl) dibenzocycloalkane as an alcohol moiety.
【０００６】前記一般式（Ｉ）で表されるメタクリル酸
エステル誘導体中のIn the methacrylic acid ester derivative represented by the general formula (I),
【０００７】[0007]
【化３】 Embedded image
【０００８】は炭素数６〜14からなる２価の芳香族環を
示し、具体的にはフェニレン基やナフチレン基が例示さ
れ、好ましくはフェニレン基である。また、シクロアル
カン部の大きさを示すｎは０〜５の整数であるが、好ま
しくは１〜２であり、さらに好ましくは２である。Is a divalent aromatic ring having 6 to 14 carbon atoms, and specific examples thereof include a phenylene group and a naphthylene group, and a phenylene group is preferable. Further, n showing the size of the cycloalkane part is an integer of 0 to 5, preferably 1 to 2, and more preferably 2.
【０００９】上記一般式（Ｉ）で表されるメタクリル酸
エステル誘導体は、下記一般式（II）で表される３級ア
ルコールのナトリウムアルコキシドに、メタクリル酸ク
ロリドを反応させることにより容易に得ることが出来
る。The methacrylic acid ester derivative represented by the above general formula (I) can be easily obtained by reacting methacrylic acid chloride with a sodium alkoxide of a tertiary alcohol represented by the following general formula (II). I can.
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】また、上記一般式（II）で表される３級ア
ルコールは、下記反応式に示すように常法に従って、一
般式(III) で表されるジベンゾシクロアルカノンに、一
般式(IV) で表される芳香族有機金属を作用させること
により得ることができる。The tertiary alcohol represented by the general formula (II) can be obtained by converting the tertiary alcohol represented by the general formula (IV) into the dibenzocycloalkanone represented by the general formula (III) according to a conventional method as shown in the following reaction formula. ) It can be obtained by reacting an aromatic organic metal represented by
【００１２】[0012]
【化５】 Embedded image
【００１３】及びｎは前記の意味を示し、M は金属ハロ
ゲナイドを示す。） 本発明の光学活性メタクリル酸エステル重合体は、上記
一般式（Ｉ）で表されるメタクリル酸エステル誘導体
を、既に知られている光学活性な配位子有機金属との組
み合わせを開始剤として用いて低温でアニオン不斉重合
することによって容易に合成できる。ここで用いられる
光学活性な配位子有機金属との組み合わせからなる開始
剤としては、下記式（Ｖ）で表されるN,N'−ジフェニル
エチレンジアミンのモノリチウムアミドと、下記式 (V
I) で表される（−）−スパルティン（Sp）、下記式(VI
I) で表される（＋）−2,3 −ジメトキシ−1,4 −ビス
（ジメチルアミノ）ブタン（DDB)、下記式(VIII)で表さ
れる（＋）−１−（２−ピロリジニルメチル）ピロリジ
ン（PMP)等の不斉配位子との錯体が挙げられる。And n have the above-mentioned meanings, and M represents a metal halogenide. ) The optically active methacrylic acid ester polymer of the present invention uses, as an initiator, a methacrylic acid ester derivative represented by the above general formula (I) in combination with an already known optically active ligand organometal. It can be easily synthesized by anionic asymmetric polymerization at low temperature. As an initiator composed of a combination with an optically active ligand organometallic used here, monolithium amide of N, N′-diphenylethylenediamine represented by the following formula (V) and the following formula (V
(-)-Spartine (Sp) represented by I)
(+)-2,3-dimethoxy-1,4-bis (dimethylamino) butane (DDB) represented by I), and (+)-1- (2-pyrrolidini represented by the following formula (VIII): Examples thereof include complexes with asymmetric ligands such as rumethyl) pyrrolidine (PMP).
【００１４】[0014]
【化６】 [Chemical 6]
【００１５】また、本発明の光学活性メタクリル酸エス
テル重合体は、ラジカル重合によっても得ることができ
る。この場合の開始剤としては（ｉ−PrOCOO)2、または
アゾイソブチロニトリル(AIBN)が挙げられる。The optically active methacrylic acid ester polymer of the present invention can also be obtained by radical polymerization. Examples of the initiator in this case include (i-PrOCOO) 2 or azoisobutyronitrile (AIBN).
【００１６】このようにして得られる本発明の光学活性
メタクリル酸エステル重合体の重合度は10〜1000の範囲
である。なお、重合度はゲル・パーミエーション・クロ
マトグラフ法（GPC 法）で測定するが、不溶性重合体に
ついては、試重合体を加水分解し、ポリメタクリル酸と
し、これをさらにメチルエステル化してポリメタクリル
酸メチルに変換して測定する。The degree of polymerization of the optically active methacrylic acid ester polymer of the present invention thus obtained is in the range of 10 to 1,000. The degree of polymerization is measured by gel permeation chromatography (GPC method). For insoluble polymers, the test polymer is hydrolyzed to polymethacrylic acid, which is further methyl esterified to form polymethacrylic acid. Convert to methyl acid and measure.
【００１７】本発明の光学活性メタクリル酸エステル重
合体は、種々のラセミ体を光学分割することが出来、光
学分割用分離剤として有用である。本発明の光学活性メ
タクリル酸エステル重合体からなる分離剤を用いた光学
分割法としては、本発明の光学活性メタクリル酸エステ
ル重合体を光学異性体分離用充填剤として用い、カラム
に充填し、このカラムを用いていわゆる液体クロマトグ
ラフィー（HPLC）法で光学分割する方法等が挙げられ
る。具体的には、例えば、本発明の光学活性メタクリル
酸エステル重合体をHPLC用担体（例えば、シリカゲル）
などに担持させてカラムに充填する既知の方法がある。The optically active methacrylic acid ester polymer of the present invention can optically resolve various racemates and is useful as a separating agent for optical resolution. As an optical resolution method using a separating agent composed of the optically active methacrylic acid ester polymer of the present invention, the optically active methacrylic acid ester polymer of the present invention is used as a packing material for separating optical isomers, and packed in a column. Examples include a method of performing optical resolution by a so-called liquid chromatography (HPLC) method using a column. Specifically, for example, the optically active methacrylic acid ester polymer of the present invention is used as a carrier for HPLC (for example, silica gel).
There is a known method in which a column is supported and packed in a column.
【００１８】[0018]
【発明の効果】本発明で得られた光学活性メタクリル酸
エステル重合体は、耐加溶媒分解性に優れ、光学分割用
分離剤として最適である。The optically active methacrylic acid ester polymer obtained in the present invention is excellent in solvolysis resistance and is most suitable as a separating agent for optical resolution.
【００１９】[0019]
【実施例】以下、本発明を合成例、実施例及び応用例に
よって詳細に説明するが、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 synthesis examples, examples and application examples, but the present invention is not limited to these examples.
【００２０】合成例１：１−（２−ピリジル）ジベンゾ
スベロールの合成 ２−ブロモピリジン75ｇ（0.475mol）にエチルエーテル
325ml を加え−78℃に保ち、ｎ−ブチルリチウム（ヘキ
サン溶液） 309ml（0.485mol）を滴下した。ジベンゾス
ベロン82.3ml（0.457mol）をエチルエーテル193ml に溶
かした溶液を系に滴下し、系の温度を−35℃に上げた。
しばらく攪拌した後、塩化アンモニウム飽和水溶液を加
えて反応を停止した。水層部に析出したやや褐色の白色
結晶を濾過し、下記式 (IX) で表される構造を有する目
的生成物を得た。 収量：88.94 ｇ 収率：67.7％（ジベンゾスベロンに対して） 元素分析値： C ；実測値 82.39％, 計算値 83.59％ H ；実測値 6.00％, 計算値 5.96％ N ；実測値 4.73％, 計算値 4.87％ 融点：205 −206 ℃Synthesis Example 1: Synthesis of 1- (2-pyridyl) dibenzosuberol 75 g (0.475 mol) of 2-bromopyridine in ethyl ether
325 ml was added and kept at -78 ° C, and 309 ml (0.485 mol) of n-butyllithium (hexane solution) was added dropwise. A solution of 82.3 ml (0.457 mol) of dibenzosuberone in 193 ml of ethyl ether was added dropwise to the system, and the temperature of the system was raised to -35 ° C.
After stirring for a while, a saturated aqueous solution of ammonium chloride was added to stop the reaction. The slightly brown white crystals precipitated in the aqueous layer were filtered to obtain the desired product having a structure represented by the following formula (IX). Yield: 88.94 g Yield: 67.7% (relative to dibenzosuberone) Elemental analysis: C; found 82.39%, calculated 83.59% H; found 6.00%, calculated 5.96% N; found 4.73%, Calculated value 4.87% Melting point: 205-206 ℃
【００２１】[0021]
【化７】 [Chemical 7]
【００２２】合成例２：メタクリル酸 １−（２−ピリ
ジル）ジベンゾスベリルの合成 水素化ナトリウム29.2ｇ（0.730mol) 及びテトラヒドロ
フラン(THF)40ml に、合成例１で合成した１−（２−ピ
リジル）ジベンゾスベロール41.2ｇ（0.143mol) をTHF
640ml に溶かした溶液を滴下し、水素の発生の完了確認
後、系を０℃に冷却した。メタクリル酸クロリド20.0ml
（0.205mol）をTHF 40mlに溶かした溶液を滴下し、しば
らく攪拌した後、系の温度を70℃まで昇温し、水−エチ
ルエーテル、及び水−ベンゼンで抽出した。有機層を乾
燥後、減圧蒸留して黄色結晶を得た。 粗収量：47.59 ｇ 粗収率：93.6％（１−（２−ピリジル）ジベンゾスベロ
ールに対して） 得られた粗結晶を、溶離液としてベンゼン／エチルエー
テル＝20／１(ｖ／ｖ)を用いオープンカラムで目的生成
物及び不純物（主に未反応アルコール）とに分離後、再
結晶を行い、下記式（Ｘ）で表される目的化合物を得
た。 収量：18.46 ｇ 収率：36.3％（１−（２−ピリジル）ジベンゾスベーロ
ルに対して） 元素分析値： C ；実測値 81.60％, 計算値 81.09％ H ；実測値 5.85％, 計算値 5.96％ N ；実測値 3.92％, 計算値 3.94％ 融点：168 −169 ℃Synthesis Example 2: Synthesis of 1- (2-pyridyl) dibenzosuberyl methacrylate Methacrylate 1- (2-pyridyl) synthesized in Synthesis Example 1 was added to 29.2 g (0.730 mol) of sodium hydride and 40 ml of tetrahydrofuran (THF). ) Dibenzosuberol 41.2 g (0.143 mol) in THF
The solution dissolved in 640 ml was added dropwise, and after confirming the completion of hydrogen generation, the system was cooled to 0 ° C. Methacrylic acid chloride 20.0 ml
A solution obtained by dissolving (0.205 mol) in 40 ml of THF was added dropwise and stirred for a while, then the temperature of the system was raised to 70 ° C. and extracted with water-ethyl ether and water-benzene. The organic layer was dried and then distilled under reduced pressure to obtain yellow crystals. Crude yield: 47.59 g Crude yield: 93.6% (relative to 1- (2-pyridyl) dibenzosuberol) The obtained crude crystals were eluted with benzene / ethyl ether = 20/1 (v / v). The target product and impurities (mainly unreacted alcohol) were separated using an open column and recrystallized to obtain the target compound represented by the following formula (X). Yield: 18.46 g Yield: 36.3% (relative to 1- (2-pyridyl) dibenzosuberol) Elemental analysis: C; found 81.60%, calculated 81.09% H; found 5.85%, calculated 5.96 % N ； Measured value 3.92%, Calculated value 3.94% Melting point: 168 −169 ℃
【００２３】[0023]
【化８】 Embedded image
【００２４】実施例１：ラジカル重合 トルエン８ml中に、合成例２で合成したメタクリル酸
１−（２−ピリジル）ジベンゾスベリルを0.494ｇ(1.39
mmol)、開始剤としてAIBNを0.048ｇ(0.292mol)用い、60
℃に昇温することで重合を開始した。24時間60℃に保っ
た後、冷却して重合を停止した。これをメタノール160m
l に滴下し不溶部をポリマーとして回収した。Example 1 Radical Polymerization Methacrylic acid synthesized in Synthesis Example 2 in 8 ml of toluene
0.494 g (1.39) of 1- (2-pyridyl) dibenzosuberyl
mmol), using 0.048 g (0.292 mol) of AIBN as an initiator, 60
Polymerization was initiated by raising the temperature to ° C. After keeping at 60 ° C. for 24 hours, the polymerization was stopped by cooling. 160m of this methanol
The mixture was added dropwise to l and the insoluble portion was recovered as a polymer.
【００２５】実施例２：アニオン重合 乾燥窒素下、トルエン40mlに、合成例２で合成したメタ
クリル酸 １−（２−ピリジル）ジベンゾスベリル2.00
ｇを溶かし−78℃に冷却した。開始剤として、N,N'−ジ
フェニルエチレンジアミンモノリチウムアミド (DPEDA-
Li) と、（S)−（＋）−１−（２−ピロリジニルメチ
ル）ピロリジン(PMP) からなる不斉配位子との錯体を用
いた。開始剤比がリチウムイオンでモノマーに対し１／
20になるように調製し、これをモノマー溶液に加えるこ
とで重合を開始した。重合中は系を−78℃に保ち、48時
間重合を行った。メタノールを少量加えることで重合を
停止し、系の内容物をメタノール800ml に滴下し不溶部
をポリマーとして回収した。Example 2: Anionic Polymerization 1- (2-Pyridyl) dibenzosuberyl methacrylic acid synthesized in Synthesis Example 2 in 40 ml of toluene under dry nitrogen.
g was melted and cooled to -78 ° C. As an initiator, N, N'-diphenylethylenediamine monolithium amide (DPEDA-
A complex of Li) with an asymmetric ligand consisting of (S)-(+)-1- (2-pyrrolidinylmethyl) pyrrolidine (PMP) was used. Initiator ratio is 1 / to monomer for lithium ion
It was adjusted to 20 and the polymerization was initiated by adding it to the monomer solution. During the polymerization, the system was kept at -78 ° C and the polymerization was carried out for 48 hours. Polymerization was stopped by adding a small amount of methanol, and the contents of the system were dropped into 800 ml of methanol to recover the insoluble portion as a polymer.
【００２６】実施例３：アニオン重合 開始剤として（−）−スパルティン(Sp)−ジフェニルエ
チレンジアミンのモノリチウムアミド(DPEDA-Li)錯体を
用い、反応時間を97時間とした以外は実施例２と同様に
してポリマーを得た。Example 3: Anionic Polymerization Same as Example 2 except that a monolithium amide (DPEDA-Li) complex of (-)-spartine (Sp) -diphenylethylenediamine was used as an initiator and the reaction time was 97 hours. To obtain a polymer.
【００２７】実施例４：アニオン重合 開始剤として（＋）−2,3 −ジメトキシ−1,4 −ビス
（ジメチルアミノ）ブタン(DDB) −ジフェニルエチレン
ジアミンのモノリチウムアミド(DPEDA-Li)錯体を用いた
以外は実施例２と同様にしてポリマーを得た。Example 4 Anionic Polymerization A monolithium amide (DPEDA-Li) complex of (+)-2,3-dimethoxy-1,4-bis (dimethylamino) butane (DDB) -diphenylethylenediamine was used as an initiator. A polymer was obtained in the same manner as in Example 2 except that it was present.
【００２８】実施例１〜４で得られたポリマーをポリメ
タクリル酸メチル（PMMA）へと誘導し、1H−NMR 、GPC
を測定した。得られたPMMAの1H−NMR からタクチシチー
を、GPC から重合度及び分子量分布を測定した。また、
旋光度をクロロホルム中で測定した。結果は表１に示し
た。The polymers obtained in Examples 1 to 4 were derivatized into polymethylmethacrylate (PMMA) and subjected to 1 H-NMR and GPC.
Was measured. The tacticity was measured from 1 H-NMR of the obtained PMMA, and the polymerization degree and the molecular weight distribution were measured from GPC. Also,
The optical rotation was measured in chloroform. The results are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１から明らかなように、メタクリル酸
１−（２−ピリジル）ジベンゾスベリルは、不斉配位子
を用いたアニオン重合でも、ラジカル重合でも、非常に
高いタクチシチーをもつポリマーを与えた。特に、ラジ
カル重合では、先行技術である特開平６−87929 号公報
に記載のメタクリル酸 １−フェニルジベンゾスベリル
を用いた場合よりもさらにイソタクチシチーに富むポリ
マーが得られた。As is clear from Table 1, methacrylic acid
1- (2-pyridyl) dibenzosuberyl gave polymers with very high tacticity, both in anionic and radical polymerizations using asymmetric ligands. In particular, in radical polymerization, a polymer further rich in isotacticity was obtained as compared with the case of using 1-phenyldibenzosuberyl methacrylate described in JP-A-6-87929 which is a prior art.
【００３１】応用例１〜４：不斉識別能 粒径７μm 、孔径100nm のシリカゲルを乾燥後、ベンゼ
ン、ピリジン、及び３−アミノプロピルトリエトキシシ
ランと共に攪拌、還流し、さらにメタノールに再沈し、
これを乾燥することによりシリカゲルの表面処理を行っ
た。実施例２で得られた光学活性ポリマー0.75ｇをクロ
ロホルムに溶解させ、この溶液を表面処理したシリカゲ
ル 3.0ｇに物理的に担持し、高速液体クロマトグラフィ
ー（HPLC）用キラル固定相とした。この固定相を用い、
HPLCに検出器としてＵＶ及び旋光計を装着し、流速0.5
ml／min., 溶離液としてメタノールを用いて、表２に示
した各種ラセミ体を光学分割した結果、これらのラセミ
体に対し不斉識別能を有していることがわかった。分離
できたラセミ体の容量比（k1')及び分離係数（α）の値
を表２にまとめて示した。尚、容量比（k1')及び分離係
数（α）の定義は次の通りである。Application Examples 1 to 4: Asymmetric Discrimination Ability Silica gel having a particle size of 7 μm and a pore size of 100 nm is dried, then stirred and refluxed with benzene, pyridine and 3-aminopropyltriethoxysilane, and reprecipitated in methanol.
The surface of silica gel was treated by drying this. 0.75 g of the optically active polymer obtained in Example 2 was dissolved in chloroform, and this solution was physically supported on 3.0 g of surface-treated silica gel to prepare a chiral stationary phase for high performance liquid chromatography (HPLC). With this stationary phase,
The HPLC is equipped with UV and polarimeter as detectors, and the flow rate is 0.5.
As a result of optical resolution of various racemates shown in Table 2 using ml / min. and methanol as an eluent, it was found that these racemates have an asymmetric discrimination ability. The values of the volume ratio (k 1 ') and the separation coefficient (α) of the separated racemates are summarized in Table 2. The definitions of the capacity ratio (k 1 ') and the separation coefficient (α) are as follows.
【００３２】[0032]
【数１】 [Equation 1]
【００３３】[0033]
【表２】 [Table 2]
Claims (3)
ジル）ジベンゾシクロアルカンをアルコール部分とする
メタクリル酸エステル誘導体を重合させて得られる、新
規な光学活性メタクリル酸エステル重合体。 【化１】 は炭素数６〜14からなる２価の芳香族環を示し、ｎはメ
チレン鎖の数を示す０〜５の整数である。）1. A novel optically active methacrylic acid ester polymer obtained by polymerizing a methacrylic acid ester derivative having 1- (2-pyridyl) dibenzocycloalkane represented by the general formula (I) as an alcohol moiety. Embedded image Represents a divalent aromatic ring having 6 to 14 carbon atoms, and n is an integer of 0 to 5 representing the number of methylene chains. )
光学活性メタクリル酸エステル重合体。2. The optically active methacrylic acid ester polymer according to claim 1, which has a degree of polymerization of 10 to 1000.
ル酸エステル重合体からなることを特徴とする光学分割
用分離剤。3. A separating agent for optical resolution, comprising the optically active methacrylic acid ester polymer according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017595A JPH08208749A (en) | 1995-02-08 | 1995-02-08 | Optically active methacrylic ester polymer and separating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017595A JPH08208749A (en) | 1995-02-08 | 1995-02-08 | Optically active methacrylic ester polymer and separating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08208749A true JPH08208749A (en) | 1996-08-13 |
Family
ID=12019850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017595A Pending JPH08208749A (en) | 1995-02-08 | 1995-02-08 | Optically active methacrylic ester polymer and separating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08208749A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006109560A1 (en) * | 2005-04-07 | 2006-10-19 | Nara Institute Of Science And Technology | Optically active copolymer, process for producing the same, and packing for chromatography comprising the copolymer |
| WO2007034962A1 (en) * | 2005-09-26 | 2007-03-29 | Japan Science And Technology Agency | Composition with asymmetric structure and process for producing the same |
-
1995
- 1995-02-08 JP JP2017595A patent/JPH08208749A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006109560A1 (en) * | 2005-04-07 | 2006-10-19 | Nara Institute Of Science And Technology | Optically active copolymer, process for producing the same, and packing for chromatography comprising the copolymer |
| WO2007034962A1 (en) * | 2005-09-26 | 2007-03-29 | Japan Science And Technology Agency | Composition with asymmetric structure and process for producing the same |
| JPWO2007034962A1 (en) * | 2005-09-26 | 2009-04-02 | 国立大学法人 奈良先端科学技術大学院大学 | Composition having asymmetric structure and process for producing the same |
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