JPH07118172A - Polymer of optically active norbornene derivative and optical resolution agent - Google Patents
Polymer of optically active norbornene derivative and optical resolution agentInfo
- Publication number
- JPH07118172A JPH07118172A JP26061993A JP26061993A JPH07118172A JP H07118172 A JPH07118172 A JP H07118172A JP 26061993 A JP26061993 A JP 26061993A JP 26061993 A JP26061993 A JP 26061993A JP H07118172 A JPH07118172 A JP H07118172A
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- Prior art keywords
- polymer
- optically active
- norbornene derivative
- optical
- formula
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な光学活性なノル
ボルネン誘導体の重合体、及びこの重合体からなる光学
分割剤に関するものである。この光学活性なノルボルネ
ン誘導体の重合体は、旋光度を有し、光学異性体や幾何
異性体の分割剤として有効な物質であり、また、合成反
応中に存在させることにより、不斉の場の形成に利用す
ることも可能である。TECHNICAL FIELD The present invention relates to a novel polymer of an optically active norbornene derivative and an optical resolving agent comprising the polymer. This polymer of an optically active norbornene derivative has optical rotation and is an effective substance as a resolving agent for optical isomers and geometric isomers. Also, when it is present in a synthetic reaction, it is possible to produce an asymmetric field. It can also be used for forming.
【０００２】[0002]
【従来技術及び発明が解決しようとする課題】よく知ら
れているように、化学的には同じ化合物であっても、そ
の光学異性体は、通常、生体に対する作用を異にする。
従って、医薬、農薬、生化学関連産業等の分野におい
て、単位当たりの薬効の向上や、副作用・薬害の防止の
ために、光学的に純粋な化合物を調製することが極めて
重要になってきている。2. Description of the Related Art As is well known, the optical isomers of the same chemical compound have different effects on the living body.
Therefore, in the fields of medicine, agricultural chemicals, biochemical related industries, etc., it has become extremely important to prepare an optically pure compound in order to improve the drug efficacy per unit and to prevent side effects and phytotoxicity. .
【０００３】現在までに、光学異性体の混合物を分離、
即ち光学分割するために、数多くの光学分割剤が研究さ
れてきている。例えば、光学活性な（メタ）アクリルア
ミド重合体を利用したもの（特開昭63−1,446 号公報
等）、光学活性なメタクリル酸トリフェニルメチルエス
テル重合体を利用したもの（特公昭63−56,208号公報
等）、多糖誘導体を利用したもの（特公昭63−12,850号
公報、特公平４−30,376号公報、特公平４−30,377号公
報等）、光学活性なクラウン化合物を利用したもの（特
公平３−57,816号公報等）、光学活性なアミノ酸を利用
したもの（特公平４−75,218号公報、特公平３−39,047
号公報等）等を挙げることができる。To date, separation of mixtures of optical isomers,
That is, many optical resolution agents have been studied for optical resolution. For example, those using an optically active (meth) acrylamide polymer (JP-A-63-1446, etc.) and those using an optically active methacrylic acid triphenylmethyl ester polymer (JP-B-63-56,208). Etc.), those using a polysaccharide derivative (Japanese Patent Publication No. 63-12850, Japanese Patent Publication No. 4-30,376, Japanese Patent Publication No. 4-30,377, etc.), those utilizing an optically active crown compound (Japanese Patent Publication No. 57,816), those utilizing optically active amino acids (Japanese Patent Publication No. 4-75,218, Japanese Patent Publication No. 3-39,047).
Publications, etc.) and the like.
【０００４】しかしながら、これらの光学分割剤は光学
分割を行う対象物が限られており、光学分割できない化
合物が多くあることも事実である。従って、光学分割を
行う対象物の範囲を広げるためには、既存の光学分割剤
とは異なった化学構造を持ち、そのことによって異なっ
た光学分割特性を示す光学分割剤の開発が望まれてい
た。However, it is a fact that many of these optical resolving agents cannot be optically resolved because the objects to be optically resolved are limited. Therefore, in order to broaden the range of objects to be optically resolved, it has been desired to develop an optical resolving agent having a chemical structure different from that of the existing optical resolving agents and thereby exhibiting different optical resolving properties. .
【０００５】[0005]
【課題を解決するための手段】本発明者らは、こうした
課題を解決しようと鋭意研究を進めた結果、光学活性な
ノルボルネン誘導体の重合体が優れた不斉識別能を有す
ることを見い出し、本発明を完成するに至った。As a result of intensive research aimed at solving these problems, the present inventors have found that a polymer of an optically active norbornene derivative has excellent asymmetric discrimination ability, and The invention was completed.
【０００６】即ち、本発明は、一般式（Ｉ）又は（II）
で表される構成単位からなり、重合度が５以上である光
学活性なノルボルネン誘導体の重合体、及びこの光学活
性なノルボルネン誘導体の重合体からなる光学分割剤を
提供するものである。That is, the present invention has the general formula (I) or (II)
A polymer of an optically active norbornene derivative having a degree of polymerization of 5 or more and an optical resolving agent comprising the polymer of this optically active norbornene derivative.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】（式中、R1及びR2は炭素数６〜30の芳香族
基又は置換芳香族基を示し、同一又は異なっていてもよ
い。） 本発明の重合体は、下記一般式(III) 又は (IV) で表さ
れる光学活性なノルボルネン誘導体を重合することによ
り得られる。(In the formula, R 1 and R 2 represent an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group, and may be the same or different.) The polymer of the present invention has the following general formula ( It is obtained by polymerizing the optically active norbornene derivative represented by III) or (IV).
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】（式中、R1及びR2は前記と同じ意味を示
す。） 上記一般式(III) 又は (IV) で表される光学活性なノル
ボルネン誘導体は、公知の製造方法（Tetrahedron Lett
ers, 27，4507（1986））により、容易に得ることがで
きる。(In the formula, R 1 and R 2 have the same meanings as described above.) The optically active norbornene derivative represented by the general formula (III) or (IV) is prepared by a known method (Tetrahedron Lett).
ers, 27 , 4507 (1986)).
【００１１】上記一般式(III) 又は (IV) において、R1
及びR2で示される炭素数６〜30の芳香族基又は置換芳香
族基としては、具体的には、In the above general formula (III) or (IV), R 1
And the aromatic group or substituted aromatic group having 6 to 30 carbon atoms represented by R 2 specifically includes
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】（ここで X, Y 及びZ はアルキル基又はア
ルコキシル基、好ましくは炭素数１〜20のアルキル基又
はアルコキシル基であり、p, q及びr は置換基の個数を
示し、１〜５の整数である。）等の基が挙げられる。上
記一般式(III) 又は (IV) で表される光学活性なノルボ
ルネン誘導体の中でも、R1及びR2が共にフェニル基であ
るものが特に好ましい。(Where X, Y and Z are alkyl groups or alkoxyl groups, preferably alkyl groups or alkoxyl groups having 1 to 20 carbon atoms, p, q and r represent the number of substituents, and 1 to 5 Is an integer of 1.) and the like. Among the optically active norbornene derivatives represented by the above general formula (III) or (IV), those in which both R 1 and R 2 are phenyl groups are particularly preferable.
【００１４】上記一般式(III) 又は (IV) で表される光
学活性なノルボルネン誘導体を重合する際に用いられる
重合触媒としては、W 、Mo、Ru等の遷移金属が適当であ
るが、好ましくは、WCl6−Ph4Sn、MoCl5−Ph4Sn、RuCl3
等の遷移金属錯体触媒であり、更に好ましくはWCl6−Ph
4Sn である。なお、ここで、Phはフェニル基を示す。As the polymerization catalyst used for polymerizing the optically active norbornene derivative represented by the above general formula (III) or (IV), transition metals such as W, Mo and Ru are suitable, but are preferable. Is WCl 6 −Ph 4 Sn, MoCl 5 −Ph 4 Sn, RuCl 3
Transition metal complex catalyst such as WCl 6 -Ph
4 Sn. Here, Ph represents a phenyl group.
【００１５】上記一般式(III) 又は (IV) で表される光
学活性なノルボルネン誘導体の重合反応における溶媒と
しては、ベンゼン、トルエン、テトラヒドロフラン、ジ
オキサン、ジメトキシエタン、ジエチルエーテル、ピリ
ジン、テトラヒドロピラン、ジメチルスルホキシド、ジ
メチルホルムアミド等のような一般的な溶媒が使用可能
であるが、反応原料のモノマー、得られる重合体及び上
記触媒との反応性があるものについては適当でない。重
合温度は−98〜＋120 ℃、好ましくは−78〜＋80℃であ
る。The solvent in the polymerization reaction of the optically active norbornene derivative represented by the above general formula (III) or (IV) is benzene, toluene, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether, pyridine, tetrahydropyran, dimethyl. Although a general solvent such as sulfoxide or dimethylformamide can be used, it is not suitable for a monomer as a reaction raw material, a polymer to be obtained, and a substance having reactivity with the above catalyst. The polymerization temperature is -98 to + 120 ° C, preferably -78 to + 80 ° C.
【００１６】上記のようにして得られる本発明の光学活
性なノルボルネン誘導体の重合体の重合度は、５以上、
好ましくは５〜1000の範囲、更に好ましくは30〜500 の
範囲である。The degree of polymerization of the polymer of the optically active norbornene derivative of the present invention obtained as described above is 5 or more,
The range is preferably 5 to 1000, more preferably 30 to 500.
【００１７】本発明の重合体を光学分割剤として用いる
場合、単独でも、担体に担持させてもよいが、好ましく
は担体に担持させて用いる。単独で用いるときは、粉砕
状あるいはビーズ状の粉体としてカラムに充填する。担
体に担持させる方法としては、化学的方法でも物理的方
法でもよいが、通常は物理的方法であり、本発明の重合
体を可溶性の溶剤に溶解させ、担体とよく混和し、減圧
下、加温下又は気流下で溶剤を留去させる。担体として
は、無機担体又は有機担体が使われるが、好ましくは無
機担体であり、更に好ましくはシリカゲルである。本発
明の光学分割剤は、優れた光学分割識別能を有し、各種
の光学異性体の分離に用いることができる。When the polymer of the present invention is used as an optical resolving agent, it may be used alone or on a carrier, but it is preferably used on a carrier. When used alone, it is packed in a column as a pulverized or beaded powder. The method of loading on the carrier may be a chemical method or a physical method, but it is usually a physical method, in which the polymer of the present invention is dissolved in a soluble solvent, mixed well with the carrier, and added under reduced pressure. The solvent is distilled off under warm or air flow. As the carrier, an inorganic carrier or an organic carrier is used, preferably an inorganic carrier, and more preferably silica gel. The optical resolving agent of the present invention has excellent optical resolution discriminating ability and can be used for separation of various optical isomers.
【００１８】[0018]
【発明の効果】本発明の重合体は、旋光度を有し、光学
異性体や幾何異性体の分割剤として有効な物質である。
そして、本発明の重合体からなる光学分割剤は、優れた
光学分割識別能を有しており、光学分割の対象とする化
合物の範囲を広げられる可能性を秘めている。The polymer of the present invention has optical rotation and is a substance effective as a resolving agent for optical isomers and geometric isomers.
The optical resolving agent comprising the polymer of the present invention has excellent optical resolution discriminating ability, and has a possibility of expanding the range of compounds to be subjected to optical resolution.
【００１９】[0019]
【実施例】以下、実施例によって本発明を具体的に説明
するが、本発明がこれらに限定されるものでないことは
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.
【００２０】実施例１ (1) (S,S)−(＋)−トランス−2,3 −ジカルボフェノキ
シノルボルネンの合成 公知の文献(Tetrahedron Letters, 27, 4507（1986))に
基づき、（−）−ジメンチルフマレートとシクロペンタ
ジエンから、不斉ディールス−アルダー (Diels−Alde
r)反応によって、ノルボルネンのジメンチルエステルを
合成した(5.6ｇ、収率96％）。この中の３ｇをメタノー
ル中で、水酸化カリウムにより加水分解し、ジカルボン
酸を得た（0.89ｇ、収率76％）。過剰量の塩化チオニル
を用いて、カルボン酸を酸クロリドに変換した後、乾燥
ベンゼン中、トリエチルアミン存在下、フェノールと反
応させ、生成物をシリカゲルによるカラムクロマトグラ
フィー（溶離液 ジエチルエーテル：ヘキサン＝１：
４）で精製してから、ヘキサンで再結晶し、精製された
目的物を得た（1.02ｇ、収率47％）。Example 1 (1) Synthesis of (S, S)-(+)-trans-2,3-dicarbophenoxynorbornene Based on known literature (Tetrahedron Letters, 27 , 4507 (1986)), (- ) -Dimenthyl fumarate and cyclopentadiene from Diels-Alde
The r) reaction produced the dimenthyl ester of norbornene (5.6 g, 96% yield). 3 g of this was hydrolyzed in methanol with potassium hydroxide to obtain a dicarboxylic acid (0.89 g, yield 76%). After converting the carboxylic acid to an acid chloride with an excess amount of thionyl chloride, the product was reacted with phenol in the presence of triethylamine in dry benzene, and the product was subjected to column chromatography on silica gel (eluent diethyl ether: hexane = 1: 1).
After purification in 4), it was recrystallized from hexane to obtain a purified target product (1.02 g, yield 47%).
【００２１】アミローストリス(3,5−ジメチルフェニル
カルバメート）を担持したキラルカラムを用いたHPLC分
析により光学純度を求めたところ、86％eeであった。HP
LC分析の使用機器及び使用条件は次の通りである。 カラム ：25cm×0.46(i.d.)cm ＵＶ検出器：日本分光株式会社製 875−ＵＶ（波長25
4nm) 旋光検出器：日本分光株式会社製 DIP−181 溶離液 ：ヘキサン／２−プロパノール＝９／１ 温度 ：室温 次に、光学純度を上げるために、アミローストリス(3,5
−ジメチルフェニルカルバメート）を担持したキラルカ
ラム（50cm×２(i.d.)cm）を用いたHPLCにより分取し、
光学的に純粋な下記式（Ｖ）で表される (S,S)− (＋)
−トランス−2,3 −ジカルボフェノキシノルボルネンを
得た。mp. 69−72℃、[α]D 25＝148(CHCl3、ｃ＝1.0 ｇ
／dl）。The optical purity was 86% ee as determined by HPLC analysis using a chiral column supporting amylose tris (3,5-dimethylphenylcarbamate). HP
The equipment and conditions for LC analysis are as follows. Column: 25cm × 0.46 (id) cm UV detector: JASCO Corporation 875-UV (wavelength 25
Optical rotation detector: DIP-181 made by JASCO Corporation Eluent: Hexane / 2-propanol = 9/1 Temperature: Room temperature Next, in order to improve optical purity, amylose tris (3,5)
-Dimethylphenyl carbamate) -prepared by HPLC using a chiral column (50 cm x 2 (id) cm),
Optically pure represented by the following formula (V) (S, S)-(+)
-Trans-2,3-dicarbophenoxynorbornene was obtained. mp. 69-72 ° C, [α] D 25 = 148 (CHCl 3 , c = 1.0 g
/ Dl).
【００２２】[0022]
【化５】 [Chemical 5]
【００２３】（式中、Phはフェニル基を示す。） (2) (S,S)−(＋)−トランス−2,3 −ジカルボフェノキ
シノルボルネンの重合次の条件で、上記(1) の合成で得
た (S,S)− (＋) −トランス−2,3 −ジカルボフェノキ
シノルボルネンの重合を行った。触媒としてWCl6−Ph4S
n を用い、 (S,S)− (＋) −トランス−2,3 −ジカルボ
フェノキシノルボルネン(0.9ｇ）をトルエン中（９m
l）、60℃で、72時間重合反応させ、下記式 (VI) で表
される、光学活性なノルボルネンの誘導体の重合体を得
た（0.43ｇ、収率48％）。 [α]D 25＝−23(CHCl3、ｃ＝
0.95ｇ／dl）。この重合の反応式を以下に示す。(In the formula, Ph represents a phenyl group.) (2) Polymerization of (S, S)-(+)-trans-2,3-dicarbophenoxynorbornene Under the following conditions, The (S, S)-(+)-trans-2,3-dicarbophenoxynorbornene obtained in the synthesis was polymerized. WCl 6 -Ph 4 S as a catalyst
Using n, (S, S)-(+)-trans-2,3-dicarbophenoxynorbornene (0.9 g) in toluene (9 m
l), a polymerization reaction was carried out at 60 ° C. for 72 hours to obtain a polymer of an optically active norbornene derivative represented by the following formula (VI) (0.43 g, yield 48%). [α] D 25 = -23 (CHCl 3 , c =
0.95 g / dl). The reaction formula of this polymerization is shown below.
【００２４】[0024]
【化６】 [Chemical 6]
【００２５】（式中、Phはフェニル基、ｎは重合度を示
す。） ポリスチレンを標準サンプルとするGPC （溶離液 クロ
ロホルム）より求めた数平均分子量（Mn）は 5.1×1
04 、分子量分布（Mw／Mn）は5.0 であった。(In the formula, Ph represents a phenyl group and n represents a degree of polymerization.) The number average molecular weight (Mn) determined from GPC (eluent: chloroform) using polystyrene as a standard sample is 5.1 × 1.
0 4 , and the molecular weight distribution (Mw / Mn) was 5.0.
【００２６】(3) (S,S)−(＋)−トランス−2,3 −ジカ
ルボフェノキシノルボルネンの重合体を用いた光学分割 上記(2)で得た光学活性なノルボルネンの誘導体の重合
体(0.3ｇ)を３−アミノプロピルトリエトキシシランで
表面処理したシリカゲル(2.8ｇ、粒径７μm、孔径100n
m)に担持した後、ステンレスカラム（25cm×0.46(i.d.)
cm) に充填し、キラルカラムとした。このカラムを用い
て、表１に示す各種分離対象物の光学分割実験を行っ
た。結果を表１に示す。なお、表１における容量比
(k1') 及び分離係数（α）の定義は次の通りである。(3) Optical resolution using a polymer of (S, S)-(+)-trans-2,3-dicarbophenoxynorbornene A polymer of the optically active norbornene derivative obtained in (2) above. (0.3g) silica gel surface-treated with 3-aminopropyltriethoxysilane (2.8g, particle size 7μm, pore size 100n
m), then stainless steel column (25cm × 0.46 (id)
cm) and used as a chiral column. Using this column, optical separation experiments of various separation objects shown in Table 1 were conducted. The results are shown in Table 1. The capacity ratio in Table 1
The definitions of (k 1 ') and separation factor (α) are as follows.
【００２７】[0027]
【数１】 [Equation 1]
【００２８】[0028]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 32/08 ＭＮＶ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C08F 32/08 MNV
Claims (2)
単位からなり、重合度が５以上である光学活性なノルボ
ルネン誘導体の重合体。 【化１】 （式中、R1及びR2は炭素数６〜30の芳香族基又は置換芳
香族基を示し、同一又は異なっていてもよい。）1. A polymer of an optically active norbornene derivative having a degree of polymerization of 5 or more, which comprises a structural unit represented by the general formula (I) or (II). [Chemical 1] (In the formula, R 1 and R 2 represent an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group, and may be the same or different.)
誘導体の重合体からなる光学分割剤。2. An optical resolving agent comprising the polymer of the optically active norbornene derivative according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26061993A JP3403469B2 (en) | 1993-10-19 | 1993-10-19 | Optically active norbornene derivative polymer and optical resolving agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26061993A JP3403469B2 (en) | 1993-10-19 | 1993-10-19 | Optically active norbornene derivative polymer and optical resolving agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07118172A true JPH07118172A (en) | 1995-05-09 |
| JP3403469B2 JP3403469B2 (en) | 2003-05-06 |
Family
ID=17350446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26061993A Expired - Fee Related JP3403469B2 (en) | 1993-10-19 | 1993-10-19 | Optically active norbornene derivative polymer and optical resolving agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3403469B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998027423A1 (en) * | 1996-12-18 | 1998-06-25 | Michael Rudolf Buchmeiser | Separation polymers |
| WO1999042502A1 (en) * | 1998-02-23 | 1999-08-26 | The B.F. Goodrich Company | Polycyclic resist compositions with increased etch resistance |
-
1993
- 1993-10-19 JP JP26061993A patent/JP3403469B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998027423A1 (en) * | 1996-12-18 | 1998-06-25 | Michael Rudolf Buchmeiser | Separation polymers |
| WO1999042502A1 (en) * | 1998-02-23 | 1999-08-26 | The B.F. Goodrich Company | Polycyclic resist compositions with increased etch resistance |
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| Publication number | Publication date |
|---|---|
| JP3403469B2 (en) | 2003-05-06 |
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