JP3715358B2 - Novel optically active phenylacetylene polymer and process for producing the same - Google Patents
Novel optically active phenylacetylene polymer and process for producing the same Download PDFInfo
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- JP3715358B2 JP3715358B2 JP31079795A JP31079795A JP3715358B2 JP 3715358 B2 JP3715358 B2 JP 3715358B2 JP 31079795 A JP31079795 A JP 31079795A JP 31079795 A JP31079795 A JP 31079795A JP 3715358 B2 JP3715358 B2 JP 3715358B2
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims description 54
- 229920000642 polymer Polymers 0.000 title claims description 27
- 238000000034 method Methods 0.000 title description 15
- 229920000858 Cyclodextrin Polymers 0.000 claims description 13
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 0 *c(cc1)ccc1C#C Chemical compound *c(cc1)ccc1C#C 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- XDNWPGKDHDBJJD-UHFFFAOYSA-M [Rh]Cl.C1=CC2C=CC1C2 Chemical class [Rh]Cl.C1=CC2C=CC1C2 XDNWPGKDHDBJJD-UHFFFAOYSA-M 0.000 description 1
- -1 acrylamide compound Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、アキラルなｐ−置換基を有する新規な光学活性フェニルアセチレンポリマー及びその製造方法に関するものであり、本発明のポリマーは、光学異性体分離用材料などの光学的機能材料として期待できるものである。
【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光学活性な高分子物質は、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。さらに、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な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。
【０００３】
また、光学活性なポリアセチレンポリマーについても特開平７−６２０３０号公報にペンダント基に光学活性なピナリル基を有するものが開示され、これは光学分割膜として利用されることが記載されている。
【０００４】
このように、各種の光学活性な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。物質が異なれば、異なる機能が期待できることは言うまでもない。そして、現在、ますます社会的ニーズが多様化して、新しい光学活性ポリマーの開発研究が盛んになってきている。
【０００５】
本発明の目的は、このような背景の下に、光学材料としての利用が期待できる新規な光学活性ポリマーを提供することにある。
【０００６】
【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。すなわち、本発明は、下記の式（Ｉ）で表される構成単位を主体とする新規な光学活性フェニルアセチレンポリマー、及びその製造方法を提供するものである。
【０００７】
【化４】
（式中、 Rはアキラルな置換基を示す。）
【０００９】
【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。
【００１０】
本発明のアキラルなｐ−置換基を有する新規な光学活性フェニルアセチレンポリマーは、上記の式（Ｉ）で表される構成単位を主体とするものであるが、 Rで示されるアキラルな置換基としては、具体的には下記の式(a) 〜(e) で表される基等が挙げられる。
【００１１】
【化５】
本発明の光学活性フェニルアセチレンポリマーの重合度は５以上であるが、好ましくは10以上である。また重量平均分子量（以下Ｍｗと略記）は10,000〜500,000 である。
【００１３】
本発明の光学活性フェニルアセチレンポリマーは、下記の式（II）で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマーを重合することにより得られる。
【００１４】
【化６】
（式中、 Rは前記の意味を示す。）
本発明のポリマーのペンダント基はキラリティーを持たないため、ポリマーにキラリティーを持たせるには、特別な重合方法を採用しなければならない。本発明における重合方法の具体例としては、下記の２種類の方法が挙げられる。
【００１６】
第１の方法
上記式（II）で表されるフェニルアセチレンと、キラルなシクロデキストリンとの包接錯体を形成し、この包接錯体を重合させた後、キラルなシクロデキストリンを除去する方法。
【００１７】
第２の方法
式 [Ｒｈ（ＮＢＤ−Ｐ* ) Ｃｌ]2
（式中、ＮＢＤ−Ｐ* は、ノルボルナジエンとジメチルピナリルクロロシランとの反応生成物を示す。）
で表されるキラルなロジウム錯体触媒を用い、上記式（II）で表されるフェニルアセチレンを重合する方法。
【００１８】
以下、各方法について詳細に説明する。
第１の方法は、キラルなシクロデキストリン（ＣＤ）と、式（II）で表されるフェニルアセチレンとの包接錯体をモノマーに用いる方法であるが、この方法のスキームは次の通りである。
【００１９】
【化７】
上記のスキームに示すように、先ず、ＣＤの水溶液に、式（II）で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマーを滴下して沈殿を得、これを水洗し未包接のＣＤを除き、ＣＤとフェニルアセチレンとの包接錯体を得る。次に、この包接錯体の状態で重合を行う。重合は、触媒として、式
[Ｒｈ（ＮＢＤ）Ｃｌ]2
（式中、ＮＢＤはノルボルナジエンを示す。）
で表されるロジウム触媒を用いて、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）等の溶媒中で行い、反応温度は室温、反応時間は１〜10時間である。重合は、反応溶液をメタノールに投入することにより停止し、水洗を十分に行うことによりＣＤを除去する。ポリマーは再沈殿によって精製する。
【００２１】
第２の方法は、上記のキラルなロジウム錯体触媒を用いる方法であるが、このキラルなロジウム錯体触媒を合成するには、ノルボルナジエンとジメチルピナリルクロロシランとを反応させて得られたＮＢＤ−Ｐ* を三塩化ロジウムとエタノール中で反応させ、ヘキサンに対する溶解性の違いを利用して精製する方法を用いる。上記式（II）で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマーの重合は、このキラルなロジウム錯体触媒を用いて、トリエチルアミン中で行い、反応温度は−52℃〜室温、反応時間は１〜 180時間である。重合は、メタノールで停止し、ポリマーは再沈殿によって精製する。
【００２２】
上記の第１の方法又は第２の方法により得られたポリマーは、Ｍｗが10,000〜500,000 であり、高い旋光度を示し、キラル識別能を有する。
【００２３】
【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。
【００２４】
実施例１
β−シクロデキストリン（β−ＣＤ）3.82ｇ(3.36mmol)をイオン交換水 220mlに溶かし、飽和水溶液（1.76ｇ／100ml)を調製した。これにゲスト分子である、式（II-(a))
【００２５】
【化８】
で表されるフェニルアセチレン0.36ｇ(3.52mmol)を徐々に滴下させて、室温で12時間攪拌した。得られた白色固体を吸引濾過で濾別し、イオン交換水で洗浄後、24時間真空乾燥を行った。包接錯体の収量は3.49ｇ（収率91.3％）であり、200MHz 1Ｈ−ＮＭＲ分析のプロトン比より包接比を測定した結果、〔β−ＣＤ〕：〔II-(a)〕＝１：１であった。
【００２７】
次に、この包接錯体3.21ｇ（このうちII-(a)は0.26ｇ、2.59mmol) を取り、窒素置換後、ジメチルホルムアミド（ＤＭＦ）を加えて、完全に溶解させた。別途に30ml二口ナスフラスコに（ビシクロ〔２，２，１〕ヘプタ−２，５−ジエン）ロジウム（Ｉ）クロライドダイマー 3.6mg（0.0078mmol) を取り、窒素置換後、トリエチルアミン 4.0mlを加えて溶かし、この触媒溶液をモノマー溶液に加えて（モノマー／触媒＝332(モル比）) 、室温で24時間攪拌した。攪拌終了後、重合系をメタノール中に滴下し、生じた沈殿物を濾別し、イオン交換水で洗浄してβ−ＣＤを除去してから、真空乾燥した。得られたポリマーをクロロホルムに溶かし、メタノールで再沈殿後、濾別して真空乾燥した。ポリマーの収量は0.22ｇ（収率84.6％）であり、200MHz 1Ｈ−ＮＭＲ分析によりβ−ＣＤの除去を確認した。ＧＰＣ分析により、Ｍｗ＝2.20×105 、Ｍｗ／Ｍｎ（ここでＭｎは数平均分子量を示す）＝2.12であり、旋光度は〔α〕D 20＝−31.2°（ｃ 0.565ｇ／dl、ＣＨＣｌ3)であった。これらの結果を表１に示す。
【００２８】
実施例２
モノマーとして、式（II-(b))
【００２９】
【化９】
で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマー、ＣＤとしてβ−ＣＤを用いて、実施例１と同様にして重合を行った。結果を表１に示す。
【００３１】
実施例３
モノマーとして、上記式（II-(b)) で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマー、ＣＤとしてγ−ＣＤを用いて、実施例１と同様にして重合を行った。結果を表１に示す。
【００３２】
実施例４
モノマーとして、式（II-(e))
【００３３】
【化１０】
で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマー、ＣＤとしてβ−ＣＤを用いて、実施例１と同様にして重合を行った。結果を表１に示す。
【００３５】
実施例５
モノマーとして、上記式（II-(e)) で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマー、ＣＤとしてγ−ＣＤを用いて、実施例１と同様にして重合を行った。結果を表１に示す。
【００３６】
【表１】
実施例６〜７
上記式（II-(a)) で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマーを、キラルな [Ｒｈ（ＮＢＤ−Ｐ* ) Ｃｌ]2を重合触媒として用い、表２に示す反応条件でトリエチルアミン中で重合した。結果を表２に示す。
【００３８】
実施例８〜１３
上記式（II-(b)) で表されるアキラルなｐ−置換基を有するフェニルアセチレンモノマーを、キラルな [Ｒｈ（ＮＢＤ−Ｐ* ) Ｃｌ]2を重合触媒として用い、表２に示す反応条件でトリエチルアミン中で重合した。結果を表２に示す。
【００３９】
【表２】
応用例１
実施例３で得られたポリマーを用いて、α−フェニルエチルアルコールのラセミ体の吸着分離実験を行った結果、96.2％e.e.（Ｓ体）が得られた。
【００４１】
【発明の効果】
本発明によるアキラルなｐ−置換基を有する新規な光学活性フェニルアセチレンポリマーは、高い旋光度を示し、キラル識別能を有しており、光学異性体分離用充填剤や光学分割膜等への応用が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel optically active phenylacetylene polymer having an achiral p-substituent and a method for producing the same, and the polymer of the present invention can be expected as an optical functional material such as a material for separating optical isomers. It is.
[0002]
[Prior art and problems to be solved by the invention]
Many optically active polymer substances that have been used as functional materials such as optical resolution agents, liquid crystals, and nonlinear optical materials have been conventionally known. For example, JP-A-56-106907 discloses an optically active polymer of triphenylmethyl methacrylate, which has a helical structure, exhibits high optical rotation, and is useful as an optical resolution agent. It is described that there is. 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. Has been described. Furthermore, Japanese Patent Application Laid-Open No. 63-1446 discloses an optically active poly (meth) acrylamide compound, which has an optically active group in the side chain, and the racemic mixture is converted to an optical antipode thereof. It is described that it is useful as an adsorbent for separation. JP-A-1-79230 discloses a liquid crystal composition using an optically active polymer compound.
[0003]
As for the optically active polyacetylene polymer, JP-A-7-62030 discloses an optically active pinaryl group in a pendant group, which is described as being used as an optical resolution film.
[0004]
Thus, various optically active polymer substances have optically unique functions and are applied to various applications. It goes without saying that different materials can be expected to have different functions. Currently, social needs are diversifying more and more, and research and development of new optically active polymers are becoming active.
[0005]
An object of the present invention is to provide a novel optically active polymer that can be expected to be used as an optical material under such a background.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, the present invention has been completed. That is, the present invention is to provide new optically active phenylacetylene polymers consisting mainly of structural units represented by the following formula (I), and a manufacturing method thereof.
[0007]
[Formula 4]
(In the formula, R represents an achiral substituent.)
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0010]
The novel optically active phenylacetylene polymer having an achiral p-substituent of the present invention is mainly composed of the structural unit represented by the above formula (I), but as an achiral substituent represented by R, Specific examples include groups represented by the following formulas (a) to (e).
[0011]
[Chemical formula 5]
The degree of polymerization of the optically active phenylacetylene polymer of the present invention is 5 or more, preferably 10 or more. The weight average molecular weight (hereinafter abbreviated as Mw) is 10,000 to 500,000.
[0013]
The optically active phenylacetylene polymer of the present invention can be obtained by polymerizing a phenylacetylene monomer having an achiral p-substituent represented by the following formula (II).
[0014]
[Chemical 6]
(Wherein R represents the above-mentioned meaning)
Since the pendant group of the polymer of the present invention does not have chirality, a special polymerization method must be employed to give the polymer chirality. Specific examples of the polymerization method in the present invention include the following two methods.
[0016]
First method: An inclusion complex of phenylacetylene represented by the above formula (II) and a chiral cyclodextrin is formed, the inclusion complex is polymerized, and then the chiral cyclodextrin is removed. how to.
[0017]
Second method Formula [Rh (NBD-P * ) Cl] 2
(In the formula, NBD-P * represents a reaction product of norbornadiene and dimethylpinalylchlorosilane.)
A method of polymerizing phenylacetylene represented by the above formula (II) using a chiral rhodium complex catalyst represented by formula (II).
[0018]
Hereinafter, each method will be described in detail.
The first method is a method using an inclusion complex of chiral cyclodextrin (CD) and phenylacetylene represented by the formula (II) as a monomer. The scheme of this method is as follows.
[0019]
[Chemical 7]
As shown in the above scheme, first, a phenylacetylene monomer having an achiral p-substituent represented by the formula (II) is dropped into an aqueous solution of CD to obtain a precipitate, which is washed with water and unincluded. Excluding CD, an inclusion complex of CD and phenylacetylene is obtained. Next, polymerization is performed in the state of the inclusion complex. Polymerization can be used as a catalyst
[Rh (NBD) Cl] 2
(In the formula, NBD represents norbornadiene.)
Is carried out in a solvent such as dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) using a rhodium catalyst represented by the formula: The reaction temperature is room temperature and the reaction time is 1 to 10 hours. The polymerization is stopped by adding the reaction solution to methanol, and CD is removed by sufficiently washing with water. The polymer is purified by reprecipitation.
[0021]
The second method uses the above chiral rhodium complex catalyst. To synthesize this chiral rhodium complex catalyst, NBD-P * obtained by reacting norbornadiene with dimethylpinalylchlorosilane is used . A method is used in which rhodium trichloride is reacted with ethanol in ethanol and purified using the difference in solubility in hexane. Polymerization of the phenylacetylene monomer having an achiral p-substituent represented by the above formula (II) is carried out in triethylamine using this chiral rhodium complex catalyst, and the reaction temperature is -52 ° C to room temperature, reaction time. Is 1 to 180 hours. The polymerization is stopped with methanol and the polymer is purified by reprecipitation.
[0022]
The polymer obtained by the first method or the second method has an Mw of 10,000 to 500,000, exhibits high optical rotation, and has chiral discrimination ability.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it cannot be overemphasized that this invention is not what is limited to these Examples.
[0024]
Example 1
β-cyclodextrin (β-CD) 3.82 g (3.36 mmol) was dissolved in ion-exchanged water 220 ml to prepare a saturated aqueous solution (1.76 g / 100 ml). This is the guest molecule, formula (II- (a))
[0025]
[Chemical 8]
Then, 0.36 g (3.52 mmol) of phenylacetylene represented by the above formula was gradually added dropwise and stirred at room temperature for 12 hours. The obtained white solid was separated by suction filtration, washed with ion-exchanged water, and then vacuum-dried for 24 hours. The yield of the inclusion complex was 3.49 g (yield 91.3%). As a result of measuring the inclusion ratio from the proton ratio of 200 MHz 1 H-NMR analysis, [β-CD]: [II- (a)] = 1 : 1.
[0027]
Next, 3.21 g of this inclusion complex (of which 0.26 g, 2.59 mmol of II- (a) was taken), and after nitrogen substitution, dimethylformamide (DMF) was added and completely dissolved. Separately, 3.6 mg (0.0078 mmol) of (bicyclo [2,2,1] hepta-2,5-diene) rhodium (I) chloride dimer was placed in a 30 ml two-necked eggplant flask, and after purging with nitrogen, 4.0 ml of triethylamine was added. After dissolution, this catalyst solution was added to the monomer solution (monomer / catalyst = 332 (molar ratio)) and stirred at room temperature for 24 hours. After completion of the stirring, the polymerization system was dropped into methanol, and the resulting precipitate was filtered off, washed with ion-exchanged water to remove β-CD, and then vacuum-dried. The obtained polymer was dissolved in chloroform, reprecipitated with methanol, filtered and dried in vacuum. The yield of the polymer was 0.22 g (yield 84.6%), and removal of β-CD was confirmed by 200 MHz 1 H-NMR analysis. According to GPC analysis, Mw = 2.20 × 10 5 , Mw / Mn (where Mn represents the number average molecular weight) = 2.12, and the optical rotation is [α] D 20 = −31.2 ° (c 0.565 g / dl, CHCl 3 ). These results are shown in Table 1.
[0028]
Example 2
As a monomer, the formula (II- (b))
[0029]
[Chemical 9]
Polymerization was carried out in the same manner as in Example 1, except that a phenylacetylene monomer having an achiral p-substituent represented by the formula: The results are shown in Table 1.
[0031]
Example 3
Polymerization was carried out in the same manner as in Example 1, using a phenylacetylene monomer having an achiral p-substituent represented by the above formula (II- (b)) as a monomer and γ-CD as a CD. The results are shown in Table 1.
[0032]
Example 4
As a monomer, the formula (II- (e))
[0033]
[Chemical Formula 10]
Polymerization was carried out in the same manner as in Example 1, except that a phenylacetylene monomer having an achiral p-substituent represented by the formula: The results are shown in Table 1.
[0035]
Example 5
Polymerization was carried out in the same manner as in Example 1, using a phenylacetylene monomer having an achiral p-substituent represented by the above formula (II- (e)) as a monomer and γ-CD as a CD. The results are shown in Table 1.
[0036]
[Table 1]
Examples 6-7
Reactions shown in Table 2 using a phenylacetylene monomer having an achiral p-substituent represented by the above formula (II- (a)) using chiral [Rh (NBD-P * ) Cl] 2 as a polymerization catalyst. Polymerized in triethylamine under conditions. The results are shown in Table 2.
[0038]
Examples 8-13
Reactions shown in Table 2 using a phenylacetylene monomer having an achiral p-substituent represented by the above formula (II- (b)) using chiral [Rh (NBD-P * ) Cl] 2 as a polymerization catalyst. Polymerized in triethylamine under conditions. The results are shown in Table 2.
[0039]
[Table 2]
Application example 1
As a result of the adsorption separation experiment of the racemic form of α-phenylethyl alcohol using the polymer obtained in Example 3, 96.2% ee (S form) was obtained.
[0041]
【The invention's effect】
The novel optically active phenylacetylene polymer having an achiral p-substituent according to the present invention exhibits high optical rotation and chiral discrimination ability, and is applied to fillers for optical isomer separation, optical resolution films, etc. Is possible.
Claims (4)
（式中、ＮＢＤ−Ｐ* は、ノルボルナジエンとジメチルピナリルクロロシランとの反応生成物を示す。）
で表されるキラルなロジウム錯体触媒を用い、上記式（II）で表されるフェニルアセチレンを重合することを特徴とする請求項１又は２記載の光学活性フェニルアセチレンポリマーの製造方法。Formula [Rh (NBD-P * ) Cl] 2
(In the formula, NBD-P * represents a reaction product of norbornadiene and dimethylpinalylchlorosilane.)
The method for producing an optically active phenylacetylene polymer according to claim 1 or 2, wherein the phenylacetylene represented by the formula (II) is polymerized using a chiral rhodium complex catalyst represented by formula (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31079795A JP3715358B2 (en) | 1995-11-29 | 1995-11-29 | Novel optically active phenylacetylene polymer and process for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31079795A JP3715358B2 (en) | 1995-11-29 | 1995-11-29 | Novel optically active phenylacetylene polymer and process for producing the same |
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| Publication Number | Publication Date |
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| JPH09151212A JPH09151212A (en) | 1997-06-10 |
| JP3715358B2 true JP3715358B2 (en) | 2005-11-09 |
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| JP3903176B2 (en) * | 2002-09-25 | 2007-04-11 | 独立行政法人産業技術総合研究所 | Method for producing black polyacetylene compound and method for regenerating yellow polyacetylene compound |
| JP2008063360A (en) * | 2006-09-04 | 2008-03-21 | Kyoto Univ | Polyphenylacetylene polymer, process for producing the same, and phenylacetylene derivative |
| JP4853834B2 (en) * | 2007-05-02 | 2012-01-11 | 国立大学法人 新潟大学 | Optical resolution method |
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