JPH10130335A - Polymer of new acetylene derivative having boric acid residue - Google Patents
Polymer of new acetylene derivative having boric acid residueInfo
- Publication number
- JPH10130335A JPH10130335A JP28503896A JP28503896A JPH10130335A JP H10130335 A JPH10130335 A JP H10130335A JP 28503896 A JP28503896 A JP 28503896A JP 28503896 A JP28503896 A JP 28503896A JP H10130335 A JPH10130335 A JP H10130335A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acid residue
- boric acid
- formula
- acetylene derivative
- Prior art date
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- 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、ホウ酸残基を有す
る新規なアセチレン誘導体の重合体に関するものであ
る。本発明のホウ酸残基を有するアセチレン誘導体の重
合体は、立体規則性を有し、光学活性化合物存在下円偏
光二色性を示すという独特な性質があり、キラルセンサ
ー、光学分割剤等の機能材料としての利用が期待され
る。TECHNICAL FIELD The present invention relates to a novel acetylene derivative polymer having a boric acid residue. The polymer of the acetylene derivative having a boric acid residue of the present invention has a stereoregular property, has a unique property of exhibiting circular dichroism in the presence of an optically active compound, and has a chiral sensor, an optical resolving agent, and the like. It is expected to be used as a functional material.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】光学分
割剤、液晶、非線形光学材料等の機能材料として利用さ
れている高分子物質は、従来から多く知られている。例
えば、特開昭５６−１０６９０７号公報には光学活性な
メタクリル酸トリフェニルメチルの重合体が開示され、
この物質はらせん構造を有しており、高い旋光性を示
し、光学分割剤として有用であることが記載されてい
る。また、特開昭５６−１６７７０８号公報には光学活
性なアクリル酸アミドの重合体が開示され、この物質は
その分子不斉に基づいて大きな旋光性を示し、光学分割
剤として有用であることが記載されている。更に特開昭
６３−１４４６号公報には光学活性なポリ（メタ）アク
リルアミド化合物が開示され、この物質は側鎖に光学活
性基を有しており、ラセミ体混合物をそれらの光学対掌
体に分離するための吸着剤として有用であることが記載
されている。そして、特開平１−７９２３０号公報には
光学活性な高分子化合物を用いた液晶組成物が開示され
ている。2. Description of the Related Art Many polymer substances used as functional materials such as optical resolving agents, liquid crystals, and nonlinear optical materials have been known. For example, JP-A-56-106907 discloses an optically active polymer of triphenylmethyl methacrylate,
It is described that this substance has a helical structure, exhibits high optical rotation, and is useful as an optical resolving agent. JP-A-56-167708 discloses an optically active polymer of acrylic acid amide, which exhibits a large optical rotation based on its molecular asymmetry and is useful as an optical resolving agent. Have been described. Further, JP-A-63-1446 discloses an optically active poly (meth) acrylamide compound, which has an optically active group in a side chain, and is capable of converting a racemic mixture into an optically enantiomer thereof. It is described as being useful as an adsorbent for separation. JP-A-1-79230 discloses a liquid crystal composition using an optically active polymer compound.
【０００３】このように、各種の高分子物質が光学的な
独特の機能を有しており、いろいろな用途に応用されて
いる。そして、現在、ますます社会的ニーズが多様化し
て、研究が盛んになってきている。本発明の目的は、こ
のような背景の下に、ユニークな光学的機能を持つ新規
な高分子物質を提供することにある。As described above, various polymer substances have unique optical functions and are applied to various uses. And now, social needs are diversifying more and more and more and more research is being done. An object of the present invention is to provide a novel polymer having a unique optical function under such a background.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため、鋭意研究を重ねた結果、本発明を完
成するに至った。即ち、本発明は、下記の式（Ｉ）で表
される構成単位を主体とし、重合度が５以上であるホウ
酸残基を有する新規なアセチレン誘導体の重合体を提供
するものである。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides a novel acetylene derivative polymer having a boric acid residue having a degree of polymerization of 5 or more, mainly comprising a structural unit represented by the following formula (I).
【０００５】[0005]
【化５】 Embedded image
【０００６】アリール基又はヘテロアリール基を示
す。）An aryl group or a heteroaryl group is shown. )
【０００７】[0007]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。式（Ｉ）において、式Embodiments of the present invention will be described below in detail. In the formula (I), the formula
【０００８】[0008]
【化６】 Embedded image
【０００９】で表される基は、炭素数５〜14のアリール
基又はヘテロアリール基を示すが、具体的には下記の式
で表される基等が挙げられる。The group represented by the formula represents an aryl group or a heteroaryl group having 5 to 14 carbon atoms, and specific examples include a group represented by the following formula.
【００１０】[0010]
【化７】 Embedded image
【００１１】上記の式（Ｉ）で表される構成単位を主体
とするホウ酸残基を有するアセチレン誘導体の重合体の
中でも、Among the polymers of the acetylene derivative having a boric acid residue mainly composed of the structural unit represented by the above formula (I),
【００１２】[0012]
【化８】 Embedded image
【００１３】であるものが特に好ましい。本発明のホウ
酸残基を有するアセチレン誘導体の重合体の重合度は５
以上であるが、好ましくは 100 以上である。Is particularly preferred. The polymerization degree of the polymer of the acetylene derivative having a boric acid residue of the present invention is 5
However, it is preferably 100 or more.
【００１４】本発明のホウ酸残基を有するアセチレン誘
導体の重合体は、下記の式（II）で表されるホウ酸残基
を有するアセチレン誘導体モノマーを重合することによ
り得られる。The polymer of an acetylene derivative having a boric acid residue of the present invention can be obtained by polymerizing an acetylene derivative monomer having a boric acid residue represented by the following formula (II).
【００１５】[0015]
【化９】 Embedded image
【００１６】上記の式（II）で表されるホウ酸残基を有
するアセチレン誘導体モノマーを重合する際に用いられ
る重合触媒としては、Ｗ、Ｍｏ、Ｒｕ、Ｒｈ等の遷移金
属の化合物が適当であるが、好ましくは、〔ＲｈＣｌ
（ＮＢＤ）〕2 のような遷移金属錯体触媒である。な
お、ここで、ＮＢＤはノルボルナジエンを示す。As a polymerization catalyst used for polymerizing the acetylene derivative monomer having a boric acid residue represented by the above formula (II), a compound of a transition metal such as W, Mo, Ru, Rh is suitable. However, preferably, [RhCl
(NBD)] 2 . Here, NBD represents norbornadiene.
【００１７】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の触媒との反応性が
あるものについては適当でない。重合反応温度は−98℃
〜＋120 ℃が好ましく、−78℃〜＋80℃が更に好まし
い。重合反応時間は１〜50時間が好ましい。As the solvent in the polymerization reaction, general solvents such as benzene, toluene, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether, pyridine, tetrahydropyran, dimethyl sulfoxide, dimethylformamide and the like can be used. It is not suitable for monomers, the resulting polymer and those which are reactive with the above-mentioned catalysts. Polymerization reaction temperature is -98 ° C
To + 120 ° C, more preferably -78 ° C to + 80 ° C. The polymerization reaction time is preferably 1 to 50 hours.
【００１８】本発明によるホウ酸残基を有する新規なア
セチレン誘導体の重合体は、光学活性な様々の化合物、
例えば、ジオール、アミノアルコール、ヒドロキシカル
ボン酸、炭水化物、ステロイド等に対して、分裂型の誘
起円偏光二色性（ＩＣＤ）を示す。この独特な性質によ
り、特にキラルセンサーとして利用できる。また、上記
の光学活性な化合物の存在下、シリカゲルに担持するこ
とによりＨＰＬＣ用のキラル固定相としても利用でき
る。The novel polymer of an acetylene derivative having a boric acid residue according to the present invention includes various optically active compounds,
For example, it exhibits split-type induced circular dichroism (ICD) with respect to diols, amino alcohols, hydroxycarboxylic acids, carbohydrates, steroids and the like. Due to this unique property, it can be used especially as a chiral sensor. Further, it can be used as a chiral stationary phase for HPLC by supporting on silica gel in the presence of the above optically active compound.
【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、本発明がこれらの実施例に限定されるものでな
いことは言うまでもない。EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.
【００２０】実施例１：ポリ（４−ジヒドロキシボロフ
ェニルアセチレン）の合成 合成のスキームは次の通りである。Example 1 Synthesis of Poly (4-dihydroxyborophenylacetylene) The synthesis scheme is as follows.
【００２１】[0021]
【化１０】 Embedded image
【００２２】(1) 式（１）で表されるモノマーの合成 式（２）で表される４−ブロモフェニルボロン酸 9.2ｇ
(45.8mmol)をトルエン(100ml) 中、 110℃で１時間、
２，２−ジメチル−１，３−プロパンジオール5.01ｇ(4
8.1mmol)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、酢酸エチル：ヘキサン＝
１：１）で分離し、式（３）で表される化合物を得た。(1) Synthesis of monomer represented by formula (1) 9.2 g of 4-bromophenylboronic acid represented by formula (2)
(45.8 mmol) in toluene (100 ml) at 110 ° C. for 1 hour,
5.0 g of 2,2-dimethyl-1,3-propanediol (4
8.1 mmol), and the product is subjected to column chromatography on silica gel (eluent, ethyl acetate: hexane =
1: 1) to obtain a compound represented by the formula (3).
【００２３】これをパラジウム触媒存在下、トリエチル
アミン(200ml) 中、90℃で 7.5時間、室温で14.5時間、
トリメチルシリルアセチレン 9.2ml(65.0mmol)と反応さ
せ、反応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、酢酸エチル：ヘキサン＝１：１）で分
離することにより、式（４）で表される化合物12.9ｇ(4
5.1mmol)を得た（収率98.5％）。This was mixed with triethylamine (200 ml) in the presence of a palladium catalyst at 90 ° C. for 7.5 hours, at room temperature for 14.5 hours,
Reaction with 9.2 ml (65.0 mmol) of trimethylsilylacetylene and separation of the reaction product by column chromatography on silica gel (eluent, ethyl acetate: hexane = 1: 1) gave the compound 12.9 represented by the formula (4). g (4
5.1 mmol) (98.5% yield).
【００２４】この化合物の内 4.9ｇ(17.1mmol)をテトラ
ヒドロフラン(49ml)中、テトラブチルアンモニウムフル
オリド（１mol/リットル）と、室温で20分間反応させ
た。シリカゲルによるカラムクロマトグラフィー（溶離
液、酢酸エチル：ヘキサン＝１：１）で分離することに
より、目的の式（１）で表される２，２−ジメチルプロ
パン−１，３−ジイル〔ｐ−（エチニル）フェニル〕ボ
ロネート（以下、モノマー１と略記）を得た。収量 2.0
ｇ（収率55％） 融点：73.5〜75℃1 Ｈ−ＮＭＲ(CDCl3) ：δ 1.02(s,CH3,6H), 3.12(s,≡
CH,1H), 3.77(s,CH2,4H), 7.47(d,aromatic,2H), 7.75
(d,aromatic,2H) 図１に得られたモノマー１の 1Ｈ−ＮＭＲスペクトルを
示す。4.9 g (17.1 mmol) of this compound was reacted with tetrabutylammonium fluoride (1 mol / l) in tetrahydrofuran (49 ml) for 20 minutes at room temperature. Separation by column chromatography on silica gel (eluent, ethyl acetate: hexane = 1: 1) gives the desired 2,2-dimethylpropane-1,3-diyl [p- ( [Ethynyl) phenyl] boronate (hereinafter abbreviated as monomer 1) was obtained. Yield 2.0
g (55% yield) Melting point: 73.5-75 ° C 1 H-NMR (CDCl 3 ): δ 1.02 (s, CH 3 , 6H), 3.12 (s, ≡)
CH, 1H), 3.77 (s , CH 2, 4H), 7.47 (d, aromatic, 2H), 7.75
(d, aromatic, 2H) FIG. 1 shows the 1 H-NMR spectrum of the obtained monomer 1.
【００２５】(2) モノマー１の重合 モノマー−１(2.0g, 9.4mmol) を、触媒として〔ＲｈＣ
ｌ（ＮＢＤ) 〕2 （ＮＢＤ＝ノルボルナジエン)(22mg)
を用いて、テトラヒドロフラン(18.9ml)中、30℃で44時
間重合させ、側鎖が保護されたポリマーを得た。収量0.
66ｇ（収率48％）であった。これを少量の塩酸を含むメ
タノール(300ml) 中で攪拌し、側鎖の保護基をはずし、
ポリ（４−ジヒドロキシボロフェニルアセチレン）（以
下、ポリマー１と略記する）を定量的に得た。(2) Polymerization of Monomer 1 Monomer-1 (2.0 g, 9.4 mmol) was used as a catalyst [RhC
l (NBD)] 2 (NBD = norbornadiene) (22mg)
Was used to polymerize in tetrahydrofuran (18.9 ml) at 30 ° C. for 44 hours to obtain a polymer having a protected side chain. Yield 0.
It was 66 g (yield 48%). This was stirred in methanol (300 ml) containing a small amount of hydrochloric acid to remove the side chain protecting group,
Poly (4-dihydroxyborophenylacetylene) (hereinafter abbreviated as polymer 1) was obtained quantitatively.
【００２６】ポリスチレンを標準サンプルとするゲルパ
ーミエーションクロマトグラフィー（溶離液、クロロホ
ルム）より求めたポリマー１の数平均分子量（Ｍｎ）は
約37,000であった。ポリマー１の 1Ｈ−ＮＭＲスペクト
ルより、立体規則性はほぼ 100％シス−トランソイドで
ある可能性が強い。図２にポリマー１の 1Ｈ−ＮＭＲス
ペクトルを示す。The number average molecular weight (Mn) of Polymer 1 determined by gel permeation chromatography (eluent, chloroform) using polystyrene as a standard sample was about 37,000. From the 1 H-NMR spectrum of polymer 1, the stereoregularity is likely to be almost 100% cis-transoid. FIG. 2 shows the 1 H-NMR spectrum of the polymer 1.
【００２７】(3) 誘起ＣＤ 得られたポリマー１は、黄褐色の固体で、紫外−可視領
域に吸収を有し、光学活性なジオールや糖の存在下、こ
の領域に分裂型の誘起円偏光二色性（ＩＣＤ）ピークを
示した。これは、下記の反応式に示すように、光学活性
な二官能性化合物がポリマー１のボロン酸残基と共有結
合を介した錯体を形成し、そのため主鎖が左右どちらか
一方向にねじれたらせん構造を形成したため、ＩＣＤが
現れたものと考えられる。(3) Induced CD The obtained polymer 1 is a tan solid, has an absorption in the ultraviolet-visible region, and has a split type induced circularly polarized light in this region in the presence of an optically active diol or sugar. A dichroic (ICD) peak was shown. This is because, as shown in the following reaction formula, the optically active bifunctional compound forms a complex via a covalent bond with the boronic acid residue of the polymer 1, so that the main chain is twisted in one direction, left or right. It is probable that ICD appeared because the spiral structure was formed.
【００２８】[0028]
【化１１】 Embedded image
【００２９】図３にポリマー１の紫外−可視吸収スペク
トルを、図４に下記(a) 〜(e) に示す各種の光学活性ジ
オール存在下でのポリマー１のＣＤスペクトルを、図５
に下記(f) 〜(m) に示す各種の糖存在下でのポリマー１
のＣＤスペクトルを示す。FIG. 3 shows an ultraviolet-visible absorption spectrum of polymer 1, and FIG. 4 shows a CD spectrum of polymer 1 in the presence of various optically active diols shown in the following (a) to (e).
The polymer 1 in the presence of various sugars shown in (f) to (m) below
2 shows the CD spectrum of the sample.
【００３０】[0030]
【化１２】 Embedded image
【００３１】[0031]
【化１３】 Embedded image
【００３２】[0032]
【化１４】 Embedded image
【００３３】尚、ＣＤスペクトルの測定条件は以下の通
りである。The conditions for measuring the CD spectrum are as follows.
【００３４】＜測定条件＞ ポリマー１（1.0mg/ml：１モノマー単位当たり5.4 mmol
／リットル) 光学活性化合物 27mmol／リットル（５倍ｍｏｌ）<Measurement Conditions> Polymer 1 (1.0 mg / ml: 5.4 mmol per monomer unit)
/ Liter) Optically active compound 27mmol / liter (5 times mol)
【００３５】[0035]
【発明の効果】本発明によるホウ酸残基を有する新規な
アセチレン誘導体の重合体は、光学活性な低分子化合物
との相互作用で、ポリマーの不斉が規則的に誘起される
ことを利用した一種のキラルセンサーとして用いること
ができる。また、光学分割剤としても有用である。Industrial Applicability The novel acetylene derivative polymer having a boric acid residue according to the present invention utilizes the fact that asymmetry of the polymer is regularly induced by interaction with an optically active low molecular weight compound. It can be used as a kind of chiral sensor. It is also useful as an optical resolving agent.
【図１】 モノマー１の １Ｈ−ＮＭＲスペクトルであ
る。FIG. 1 is a 1 H-NMR spectrum of Monomer 1.
【図２】 ポリマー１の 1Ｈ−ＮＭＲスペクトルであ
る。FIG. 2 is a 1 H-NMR spectrum of polymer 1.
【図３】 ポリマー１の紫外−可視吸収スペクトルであ
る。FIG. 3 is an ultraviolet-visible absorption spectrum of polymer 1.
【図４】 各種光学活性ジオール存在下でのポリマー１
のＣＤスペクトルである。FIG. 4 Polymer 1 in the presence of various optically active diols
3 is a CD spectrum of the sample.
【図５】 各種糖存在下でのポリマー１のＣＤスペクト
ルである。FIG. 5 is a CD spectrum of polymer 1 in the presence of various sugars.
Claims (3)
体とし、重合度が５以上であるホウ酸残基を有する新規
なアセチレン誘導体の重合体。 【化１】 アリール基又はヘテロアリール基を示す。）1. A novel acetylene derivative polymer having a boric acid residue having a degree of polymerization of 5 or more, mainly comprising a structural unit represented by the following formula (I). Embedded image Indicates an aryl group or a heteroaryl group. )
ばれる請求項１記載のホウ酸残基を有する新規なアセチ
レン誘導体の重合体。 【化３】 2. The formula: The polymer of a novel acetylene derivative having a boric acid residue according to claim 1, wherein the group represented by is selected from any group represented by the following formula: Embedded image
レン誘導体の重合体。(3) 2. The polymer of a novel acetylene derivative having a boric acid residue according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28503896A JPH10130335A (en) | 1996-10-28 | 1996-10-28 | Polymer of new acetylene derivative having boric acid residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28503896A JPH10130335A (en) | 1996-10-28 | 1996-10-28 | Polymer of new acetylene derivative having boric acid residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10130335A true JPH10130335A (en) | 1998-05-19 |
Family
ID=17686365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28503896A Pending JPH10130335A (en) | 1996-10-28 | 1996-10-28 | Polymer of new acetylene derivative having boric acid residue |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10130335A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294626A (en) * | 2000-04-13 | 2001-10-23 | Japan Science & Technology Corp | Poly(phosphonoarylacetylene) and chiral sensor using the same |
| JP2003055410A (en) * | 2001-08-13 | 2003-02-26 | Japan Science & Technology Corp | New polyacetylene derivative and chiral sensor using the same |
-
1996
- 1996-10-28 JP JP28503896A patent/JPH10130335A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294626A (en) * | 2000-04-13 | 2001-10-23 | Japan Science & Technology Corp | Poly(phosphonoarylacetylene) and chiral sensor using the same |
| JP4598229B2 (en) * | 2000-04-13 | 2010-12-15 | 独立行政法人科学技術振興機構 | Poly (phosphonoarylacetylene) and chiral sensor using the same |
| JP2003055410A (en) * | 2001-08-13 | 2003-02-26 | Japan Science & Technology Corp | New polyacetylene derivative and chiral sensor using the same |
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