JP4135205B2 - Multimers of silacyclopentadiene derivatives - Google Patents
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- 0 CCc(cc1)ccc1C1=C(C)[Si](C)(*C)C(C)=C1c1ccc(CC)cc1 Chemical compound CCc(cc1)ccc1C1=C(C)[Si](C)(*C)C(C)=C1c1ccc(CC)cc1 0.000 description 1
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【０００１】
【発明の属する技術分野】
本発明は、シラシクロペンタジエン誘導体の多量体に関する。
【０００２】
【従来の技術】
π電子系有機化合物を光機能材料若しくは電子機能材料に応用しようとする試みは、多種多彩で多くの研究機関で行われている。これらの中で代表的な化合物群の１つとして、基本構造にヘテロ５員環構造を持つ１群のπ電子系有機化合物、例えば、チオフェンあるいはピロールなどが知られている。しかしながら、これらの大部分のヘテロ５員環は電子供与性であるため、その特徴から材料への応用に制限があった。このため、電子受容性の化合物が求められていた。
【０００３】
最近、ヘテロ元素がケイ素であるシラシクロペンタジエン環が電子受容性を示すことが報告され、種々の機能性材料への応用が予測されている。例えば、特開平６−１００６６９号公報あるいは特開平６−１６６７４６号公報に導電性ポリマーへの応用を意図した報告が見られる。また、日本化学会第７０春季年会講演予稿集II、７００ページ、２Ｄ１０２、日本化学会第７０春季年会講演予稿集II、７０１ページ、２Ｄ１０３、日本化学会第７１秋季年会講演予稿集、３２ページ、２Ｐ１α２１及び日本化学会第７１秋季年会講演予稿集、３２ページ、２Ｐ１α２２には、シラシクロペンタジエン誘導体を有機ＥＬ素子に応用した例が報告されている。
【０００４】
この様な種々の機能性材料にシラシクロペンタジエン誘導体を応用する場合、目的に応じて複数のシラシクロペンタジエン環を導入することは、化合物の性質をコントロールすることに繋がり、結果として機能性材料の性能が向上するために、非常に重要な技術の１つと考えられる。
【０００５】
ところが、以前のシラシクロペンタジエン環の多量体の合成法は、ケミカルレビュウ、９０巻、２１５〜２６３ページ、１９９０年(Chem.Rev.,90,215-263(1990).)及びその参考文献、あるいはオルガノメタリックス、１４巻、１０８９〜１０９１ページ、１９９５年（Organometallics,14,1089-91(1995)）に記載されているように特定のものに限定されており、種々の誘導体を自由に合成することはできなかった。また、特開平７−１７９４７７及び特開平７−３００４８９には、シラシクロペンタジエン環の２，５位に反応性の置換基を導入し、シラシクロペンタジエン誘導体の多量体を合成する例が示されているが、２，５位のみに限定されている事に加えて、２，５位に反応性の臭素が残り機能性材料には不向きであった。
【０００６】
【発明が解決しようとする課題】
機能性材料としてシラシクロペンタジエン誘導体の多量体を用いる場合に、目的に適した化合物の選択が可能となるように、新規なシラシクロペンタジエンの誘導体およびその多量体を提供すること。
【０００７】
【課題を解決するための手段】
種々の機能性材料に繋がる新規なシラシクロペンタジエン誘導体の多量体を見いだすべく鋭意検討した結果、シラシクロペンタジエン環のケイ素上で縮合した場合、上記問題点が解決されることを見いだし本発明を完成した。
【０００８】
本発明は、下記［１］、［２］、［３］、［４］、および［５］の各構成を有する。
【０００９】
[１]繰り返し単位がシラシクロペンタジエン誘導体である下記一般式（１）で表される多量体。
【００１０】
【化６】
［式中、Ｒ1及びＲ4は、それぞれ独立に水素、ハロゲン、置換あるいは無置換のアルキル基、パーフルオロアルキル基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはシアノ基を示し、Ｒ2及びＲ3は、置換あるいは無置換のアルキル基、アリール基あるいはヘテロ環基を示し、ｋは２から１００００の整数を示すが、Ｒ1及びＲ4が、フェニル基の場合、ｋは３から１００００の整数を示す］
【００１２】
[２]繰り返し単位がシラシクロペンタジエン誘導体である下記一般式（２）で表される多量体。
【００１３】
【化７】
［式中、Ｒ1、Ｒ4、Ｒ5、Ｒ8、Ｒ9、及びＲ12は、それぞれ独立に水素、ハロゲン、置換あるいは無置換のアルキル基、パーフルオロアルキル基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはシアノ基を示し、Ｒ2、Ｒ3、Ｒ6、Ｒ7、Ｒ10、及びＲ11は、置換あるいは無置換のアルキル基、アリール基あるいはヘテロ環基を示し、Ｘ1及びＹ1は、それぞれ独立に水素、ハロゲン、置換あるいは無置換のアルキル基、アルコキシ基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはアミノ基を示し、ｍは０から８の整数を示すが、Ｒ1、Ｒ4、Ｒ5、Ｒ8、Ｒ9、及びＲ12がフェニル基の場合、ｍは１から８の整数を示す］
【００１５】
[３]繰り返し単位がシラシクロペンタジエン誘導体である下記一般式（３）で表される多量体。
【００１６】
【化８】
［式中、Ｒ1及びＲ4は、それぞれ独立に水素、置換あるいは無置換のアルキル基、パーフルオロアルキル基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはシアノ基を示し、Ｒ2及びＲ3は、置換あるいは無置換のアルキル基、アリール基あるいはヘテロ環基を示し、Ｘ1及びＹ1は、アルカリ金属を示し、ｎは２から１００００の整数を示すが、Ｒ1及びＲ4が、フェニル基の場合、ｎは３から１００００の整数を示す］
【００１８】
［４］下記一般式（４）で表されるシラシクロペンタジエン誘導体にアルカリ金属を反応させることを特徴とする繰り返し単位がシラシクロペンタジエン誘導体である上記一般式（３）で表される多量体の製造法。
【化９】
【００１９】
［５］上記一般式（３）で表される化合物に、下記一般式（５）で表される化合物を反応させることを特徴とする請求項２記載の多量体の製造方法。
【００２０】
【化１０】
［式中、Ｒ1及びＲ4は、それぞれ独立に水素、置換あるいは無置換のアルキル基、パーフルオロアルキル基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはシアノ基を示し、Ｒ2及びＲ3は、置換あるいは無置換のアルキル基、アリール基あるいはヘテロ環基を示し、Ｘ1は、水素、置換あるいは無置換のアルキル基、アルコキシ基、シリル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基あるいはアミノ基を示す］
【００２２】
本発明の化合物の具体例を、化学式（６）から化学式（１７）として列挙する。
【００２３】
【化１１】
【化１２】
【化１３】
【化１４】
本発明のシラシクロペンタジエン誘導体の多量体は、本発明の製造法により例えば下記の様にして得ることができる。すなわち、上記一般式（４）で表されるシラシクロペンタジエン誘導体にアルカリ金属を反応させることによって、上記一般式（１）で表される多量体を得ることができる。
【００２８】
ここで用いられるアルカリ金属としては、例えば、リチウム、ナトリウムあるいはカリウムなどがあげられる。溶媒としては、アルカリ金属に不活性なものなら特に制限はなく、通常、エーテルあるいはテトラヒドロフランのようなエーテル系の溶媒が用いられる。添加するアルカリ金属の量は任意で、これを調整することによって重合の割合を調節できる。さらに、得られた化合物を、通常知られている合成法により変換することによっても本発明のシラシクロペンタジエン誘導体の多量体に誘導できる。この反応は、不活性ガス中で行うことが好ましく、窒素あるいはアルゴンガスなどが使われる。反応温度は、特に制限はないが、通常、０℃〜室温程度が好ましい。
【００２９】
これらの一連の反応には、特に反応時間に制限はなく、反応が十分に進行している時点で反応を止めればよい。ＮＭＲあるいはクロマトグラフィー等の一般的な分析手段により反応を追跡し、最適の時点で反応の終点を決定することができる。
【００３０】
置換基の導入方法は、シラシクロペンタジエン環の形成前に導入しても良いし、シラシクロペンタジエン環形成後に導入しても良い。
【００３１】
このようにして得られた本発明のシラシクロペンタジエン誘導体の多量体に付く置換基としては、水素、フッ素あるいは塩素等のハロゲン、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、シクロペンチル基、あるいはターシャリーブチル基のようなアルキル基、ビニル基、アリル基、ブテニル基あるいはスチリル基のようなアルケニル基、エチニル基、プロパギル基あるいはフェニルアセチニル基のようなアルキニル基、メトキシ基、エトキシ基、イソプロポキシ基あるいはターシャリーブトキシ基のようなアルコキシ基、ビニルオキシ基あるいはアリルオキシ基のようなアルケニルオキシ基、エチニルオキシ基あるいはフェニルアセチルオキシ基のようなアルキニルオキシ基、フェノキシ基、ナフトキシ基、ビフェニルオキシ基あるいはピレニルオキシ基のようなアリールオキシ基、トリフルオロメチル基、トリフルオロメトキシ基あるいはペンタフルオロエトキシ基のようなパーフルオロ基、ジメチルアミノ基、ジエチルアミノ基あるいはジフェニルアミノ基のようなアミノ基、トリメチルシリル基、ジメチルターシャリーブチルシリル基、トリメトキシシリル基あるいはトリフェニルシリル基のようなシリル基、フェニル基、ナフチル基、アントラセニル基、ビフェニル基、トルイル基、ピレニル基、ペリレニル基、アニシル基、ターフェニル基あるいはフェナンスレニル基等のアリール基、ヒドロフリル基、ヒドロピレニル基、ジオキサニル基、チエニル基、フリル基、オキサゾリル基、オキサジアゾリル基、チアゾリル基、チアジアゾリル基、アクリジニル基、キノリル基、キノキサロイル基、フェナンスロリル基、ベンゾチエニル基、ベンゾチアゾリル基、インドリル基、シラシクロペンタジエニル基あるいはピリジル基等のヘテロ環等があげられる。さらに、これらの置換基がお互いに任意の場所で結合して環を形成していても良い。
【００３２】
本発明のシラシクロペンタジエン誘導体の多量体は、ケイ素上で直接となりのシラシクロペンタジエン環と結合されているために、シラシクロペンタジエン環の特性ばかりでなく、ケイ素−ケイ素結合に特有の性質も付与されるために、機能性材料等に有効である。さらに、本発明の製造法によると、シラシクロペンタジエン環の２，５位にも種々の置換基が導入できるため、広範な化合物が合成できる特徴を有する。
【００３３】
例えば、繰り返し単位がシラシクロペンタジエン誘導体である下記一般式（１８）で表される多量体において、ｋが６である下記化学式（１８）で表される環状化合物などが挙げられる。
【００３４】
【化１５】
【実施例】
以下に実施例にて本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。
【００３６】
（実施例１）上記化学式（７）表される化合物の合成
アルゴン気流下、１，１’−ジクロロ−２，５−ジメチル−３，４−ジフェニルシラシクロペンタジエン８９．４ｍｇとリチウム９．４ｍｇの２ｍｌテトラヒドロフラン（以下ＴＨＦと略記する。）溶液を１０℃で１０時間撹拌した。その後、−７８℃で１−クロロ−１，２，５−トリメチル−３，４−ジフェニルシラシクロペンタジエン１６８ｍｇの３ｍｌＴＨＦ溶液を滴下した。２時間撹拌後、室温に戻し、反応溶液を濃縮した。これに水を加え、エーテルにて抽出した。さらに、エーテル層を水で洗浄後、硫酸マグネシウムにて乾燥し濃縮した。ヘキサンへの再沈殿により精製し、１０１ｍｇの３量体を得た。収率は４６％で、融点は２１３〜２１５℃であった。
得られた化合物のＮＭＲによる測定結果を以下に示す。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）δ＝0.60(s,6H), 1.95(s,12H), 1.96(s,6H), 6.72-6.89(m,12H), 6.98-7.17(m,18H).
【００３７】
（実施例２）上記化学式（８）で表される化合物の合成
窒素気流下、１，１’−ジクロロ−２，５−ジメチル−３，４−ジフェニルシラシクロペンタジエン３４６ｍｇの８ｍｌＴＨＦ溶液に室温でナトリウム７２．２ｍｇを添加した。３８時間撹拌後、−７８℃で１−クロロ−１’，２，５−トリメチル−３，４−ジフェニルシラシクロペンタジエン４６６ｍｇの５ｍｌＴＨＦ溶液を滴下した。３時間撹拌後、反応溶液を濃縮した。これに水を加え、エーテルにて抽出した。さらに、エーテル層を水で洗浄後、硫酸マグネシウムにて乾燥し濃縮した。ヘキサンを加え析出した沈殿をゲルパーミエイションクロマトグラフィーにより精製し、１０９ｍｇの４量体を得た。収率は２０％で、融点は１５３〜１５５℃であった。
得られた化合物のＮＭＲによる測定結果を以下に示す。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）δ＝0.63(s,6H), 1.90(s,12H), 2.11(s,12H), 6.68-6.89(m,16H), 6.97-7.17(m,24H).
【００３８】
（実施例３）上記化学式（６）で表される化合物の合成
アルゴン気流下、１−クロロ−１，２，５−トリメチル−３，４−ジフェニルシラシクロペンタジエン４６６ｍｇとリチウム１０．４ｍｇの６ｍｌＴＨＦ溶液を室温で１５時間撹拌した。その後、これに水を加え、ヘキサンにて抽出した。さらに、ヘキサン層を水で洗浄後、硫酸マグネシウムにて乾燥し濃縮した。濃縮物をゲルパーミエイションクロマトグラフィーにより精製し、１０８ｍｇの２量体を得た。収率は２６％で、融点は１７８〜１８０℃であった。
得られた化合物のＮＭＲによる測定結果を以下に示す。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）δ＝0.52(s,6H), 1.90(s,12H), 6.71-6.86(m,8H), 6.94-7.15(m,12H).
【００３９】
（実施例４）上記一般式（１８）で表される多量体、および上記化学式（１９）表される環状化合物の合成
窒素気流下、１，１’−ジクロロ−２，５−ジメチル−３，４−ビス（エチルフェニル）シラシクロペンタジエン２２３ｍｇとリチウム８ｍｇの３ｍｌＴＨＦ溶液を−２０℃で１０時間攪拌した。次いで、１００ｍｌのメタノールに反応混合物を加え、沈殿物をろ過した。この沈殿物を水およびメタノールで洗浄した。再度、沈殿物をＴＨＦに溶かし、１００ｍｌのイソプロパノールに滴下し再沈殿させた。ろ過後、一般式（１８）で表される目的の多量体１１０ｍｇを得た。この多量体の分子量はゲルパーミエイションクロマトグラフィーから、Ｍｎ=４６００、Ｍｗ=６４００であった。
また、ろ液を濃縮後、酢酸エチルにて再結晶を行った。化学式（１９）で表される目的の環状化合物１４ｍｇを得た。
得られた化合物のＮＭＲによる測定結果を以下に示す。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）δ＝1.14(t,36H), 2.12(s,36H), 2.53(q,24H), 6.69(d,24H), 6.91(d,24H).
【００４０】
【発明の効果】
本発明のシラシクロペンタジエン誘導体の多量体は、ケイ素上で直接結合しているために、シラシクロペンタジエン環の持つ特性ばかりでなく、ケイ素−ケイ素結合に由来する特性も有するために、非線形光学材料、導電性材料、有機ＥＬ素子あるいは電子写真などの光電子機能材料あるいはその原料として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multimer of a silacyclopentadiene derivative.
[0002]
[Prior art]
Attempts to apply π-electron organic compounds to optical functional materials or electronic functional materials are being carried out in a wide variety of research institutions. Among these, a group of π-electron organic compounds having a hetero 5-membered ring structure in the basic structure, such as thiophene or pyrrole, is known as one of the representative compound groups. However, since most of these hetero 5-membered rings are electron-donating, their characteristics have limited their application to materials. For this reason, an electron-accepting compound has been desired.
[0003]
Recently, it has been reported that a silacyclopentadiene ring in which the hetero element is silicon exhibits electron accepting properties, and application to various functional materials is predicted. For example, a report intended for application to a conductive polymer can be found in Japanese Patent Application Laid-Open No. 6-1000066 or Japanese Patent Application Laid-Open No. 6-166746. The Chemical Society of Japan 70th Spring Annual Meeting Proceedings II, 700 pages, 2D102, The Chemical Society of Japan 70th Spring Annual Meeting Proceedings II, pages 701, 2D103, The 71st Annual Meeting of the Chemical Society of Japan 71st Autumn Meeting, Examples of the application of silacyclopentadiene derivatives to organic EL devices are reported on page 32, 2P1α21 and the 71st Autumn Meeting of the Chemical Society of Japan, page 32, 2P1α22.
[0004]
When silacyclopentadiene derivatives are applied to such various functional materials, introduction of a plurality of silacyclopentadiene rings depending on the purpose leads to control of the properties of the compound, and as a result, It is considered one of the most important technologies for improving performance.
[0005]
However, previous methods for synthesizing multimers of silacyclopentadiene rings are described in Chemical Review, 90, 215-263, 1990 (Chem. Rev., 90, 215-263 (1990)) and its references, or organo As described in Metallics, 14, 1089-1091, 1995 (Organometallics, 14, 1089-91 (1995)), it is limited to a specific thing, and various derivatives are freely synthesize | combined. I couldn't. JP-A-7-179477 and JP-A-7-300489 show examples of synthesizing multimers of silacyclopentadiene derivatives by introducing reactive substituents at the 2- and 5-positions of the silacyclopentadiene ring. However, in addition to being limited to the 2nd and 5th positions, reactive bromine remains at the 2nd and 5th positions, which is unsuitable for functional materials.
[0006]
[Problems to be solved by the invention]
To provide a novel silacyclopentadiene derivative and its multimer so that a compound suitable for the purpose can be selected when a multimer of silacyclopentadiene derivative is used as a functional material.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to find a novel multimer of silacyclopentadiene derivatives that lead to various functional materials, it was found that the above problems can be solved when the silacyclopentadiene ring is condensed on silicon. did.
[0008]
The present invention has the following configurations [1], [2], [3], [4], and [5].
[0009]
[1] A multimer represented by the following general formula (1), wherein the repeating unit is a silacyclopentadiene derivative.
[0010]
[Chemical 6]
[Wherein R 1 and R 4 each independently represents hydrogen, halogen, a substituted or unsubstituted alkyl group, a perfluoroalkyl group, a silyl group, an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group or a cyano group. R 2 and R 3 represent a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, k represents an integer of 2 to 10,000, and when R 1 and R 4 are phenyl groups, Represents an integer from 3 to 10,000]
[0012]
[2] A multimer represented by the following general formula (2), wherein the repeating unit is a silacyclopentadiene derivative.
[0013]
[Chemical 7]
[Wherein R 1, R 4, R 5, R 8, R 9, and R 12 are each independently hydrogen, halogen, substituted or unsubstituted alkyl group, perfluoroalkyl group, silyl group, aryl group, Represents a heterocyclic group, an alkenyl group, an alkynyl group or a cyano group, and R 2, R 3, R 6, R 7, R 10 and R 11 represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. X 1 and Y 1 each independently represent hydrogen, halogen, substituted or unsubstituted alkyl group, alkoxy group, silyl group, aryl group, heterocyclic group, alkenyl group, alkynyl group or amino group, and m is Represents an integer of 0 to 8, but when R 1, R 4, R 5, R 8, R 9 and R 12 are phenyl groups, m represents an integer of 1 to 8]
[0015]
[3] A multimer represented by the following general formula (3), wherein the repeating unit is a silacyclopentadiene derivative.
[0016]
[Chemical 8]
[Wherein R 1 and R 4 each independently represent hydrogen, a substituted or unsubstituted alkyl group, a perfluoroalkyl group, a silyl group, an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, or a cyano group, R 2 and R 3 represent a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, X 1 and Y 1 represents an alkali metal, n represents represents an integer of 2 to 10000, R 1 and When R 4 is a phenyl group, n represents an integer of 3 to 10,000]
[0018]
[4] A multimer represented by the above general formula (3), wherein the repeating unit is a silacyclopentadiene derivative, wherein the silacyclopentadiene derivative represented by the following general formula (4) is reacted with an alkali metal. Manufacturing method.
[Chemical 9]
[0019]
[5] The method for producing a multimer according to claim 2, wherein the compound represented by the general formula (3) is reacted with the compound represented by the following general formula (5).
[0020]
[Chemical Formula 10]
[Wherein R 1 and R 4 each independently represent hydrogen, a substituted or unsubstituted alkyl group, a perfluoroalkyl group, a silyl group, an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, or a cyano group, R 2 and R 3 represent a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and X 1 represents hydrogen, a substituted or unsubstituted alkyl group, an alkoxy group, a silyl group, an aryl group or a heterocyclic group. Represents an alkenyl group, an alkynyl group or an amino group]
[0022]
Specific examples of the compound of the present invention are listed as chemical formula (6) to chemical formula (17).
[0023]
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The multimer of the silacyclopentadiene derivative of the present invention can be obtained, for example, as follows by the production method of the present invention. That is, the multimer represented by the general formula (1) can be obtained by reacting the silacyclopentadiene derivative represented by the general formula (4) with an alkali metal.
[0028]
Examples of the alkali metal used here include lithium, sodium, and potassium. The solvent is not particularly limited as long as it is inert to alkali metals, and an ether-based solvent such as ether or tetrahydrofuran is usually used. The amount of alkali metal to be added is arbitrary, and the polymerization rate can be adjusted by adjusting this amount. Furthermore, the obtained compound can be derived into a multimer of the silacyclopentadiene derivative of the present invention by converting it by a generally known synthesis method. This reaction is preferably carried out in an inert gas, and nitrogen or argon gas is used. Although reaction temperature does not have a restriction | limiting in particular, Usually, about 0 degreeC-room temperature are preferable.
[0029]
There is no particular limitation on the reaction time for these series of reactions, and the reaction may be stopped when the reaction is sufficiently advanced. The reaction can be traced by a general analytical means such as NMR or chromatography, and the end point of the reaction can be determined at an optimal time point.
[0030]
The method for introducing the substituent may be introduced before the formation of the silacyclopentadiene ring or after the silacyclopentadiene ring is formed.
[0031]
Substituents attached to the multimer of the silacyclopentadiene derivative of the present invention thus obtained include hydrogen, halogen such as fluorine or chlorine, methyl group, ethyl group, normal propyl group, isopropyl group, cyclopentyl group, or Alkyl group such as tertiary butyl group, alkenyl group such as vinyl group, allyl group, butenyl group or styryl group, alkynyl group such as ethynyl group, propargyl group or phenylacetinyl group, methoxy group, ethoxy group, Alkoxy groups such as propoxy groups or tertiary butoxy groups, alkenyloxy groups such as vinyloxy groups or allyloxy groups, alkynyloxy groups such as ethynyloxy groups or phenylacetyloxy groups, phenoxy groups, naphthoxy groups, biphenyloxy groups. Group or aryloxy group such as pyrenyloxy group, perfluoro group such as trifluoromethyl group, trifluoromethoxy group or pentafluoroethoxy group, amino group such as dimethylamino group, diethylamino group or diphenylamino group, trimethylsilyl group , Dimethyl tertiary butylsilyl group, silyl group such as trimethoxysilyl group or triphenylsilyl group, phenyl group, naphthyl group, anthracenyl group, biphenyl group, toluyl group, pyrenyl group, perylenyl group, anisyl group, terphenyl group Or an aryl group such as a phenanthrenyl group, hydrofuryl group, hydropyrenyl group, dioxanyl group, thienyl group, furyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridin Group, quinolyl group, quinoxaloyl group, Fenansuroriru group, benzothienyl group, benzothiazolyl group, heterocyclic such as indolyl group, sila cyclopentadienyl group or a pyridyl group. Further, these substituents may be bonded to each other at any place to form a ring.
[0032]
Since the multimer of the silacyclopentadiene derivative of the present invention is bonded directly to the silacyclopentadiene ring on the silicon, not only the characteristics of the silacyclopentadiene ring but also the properties specific to the silicon-silicon bond are imparted. Therefore, it is effective for functional materials and the like. Furthermore, according to the production method of the present invention, since various substituents can be introduced into the 2,5-positions of the silacyclopentadiene ring, a wide range of compounds can be synthesized.
[0033]
For example, in the multimer represented by the following general formula (18) in which the repeating unit is a silacyclopentadiene derivative, a cyclic compound represented by the following chemical formula (18) in which k is 6 may be mentioned.
[0034]
Embedded image
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
[0036]
(Example 1) Synthesis of the compound represented by the chemical formula (7) Under an argon stream, 89.4 mg of 1,1'-dichloro-2,5-dimethyl-3,4-diphenylsilacyclopentadiene and 9.4 mg of lithium A 2 ml tetrahydrofuran (hereinafter abbreviated as THF) solution was stirred at 10 ° C. for 10 hours. Thereafter, a 3 ml THF solution of 168 mg of 1-chloro-1,2,5-trimethyl-3,4-diphenylsilacyclopentadiene was added dropwise at -78 ° C. After stirring for 2 hours, the reaction solution was returned to room temperature and concentrated. Water was added to this and extracted with ether. Further, the ether layer was washed with water, dried over magnesium sulfate and concentrated. Purification by reprecipitation into hexane gave 101 mg of trimer. The yield was 46% and the melting point was 213 to 215 ° C.
The measurement result by NMR of the obtained compound is shown below.
1 H-NMR (CDCl 3 ) δ = 0.60 (s, 6H), 1.95 (s, 12H), 1.96 (s, 6H), 6.72-6.89 (m, 12H), 6.98-7.17 (m, 18H).
[0037]
(Example 2) Synthesis of the compound represented by the above chemical formula (8) Under a nitrogen stream, sodium was added to an 8 ml THF solution of 346 mg of 1,1'-dichloro-2,5-dimethyl-3,4-diphenylsilacyclopentadiene at room temperature. 72.2 mg was added. After stirring for 38 hours, a 5 ml THF solution of 466 mg of 1-chloro-1 ′, 2,5-trimethyl-3,4-diphenylsilacyclopentadiene was added dropwise at −78 ° C. After stirring for 3 hours, the reaction solution was concentrated. Water was added to this and extracted with ether. Further, the ether layer was washed with water, dried over magnesium sulfate and concentrated. Hexane was added and the deposited precipitate was purified by gel permeation chromatography to obtain 109 mg of a tetramer. The yield was 20% and the melting point was 153 to 155 ° C.
The measurement result by NMR of the obtained compound is shown below.
1 H-NMR (CDCl 3 ) δ = 0.63 (s, 6H), 1.90 (s, 12H), 2.11 (s, 12H), 6.68-6.89 (m, 16H), 6.97-7.17 (m, 24H).
[0038]
Example 3 Synthesis of Compound Represented by Chemical Formula (6) 6 ml THF solution of 466 mg of 1-chloro-1,2,5-trimethyl-3,4-diphenylsilacyclopentadiene and 10.4 mg of lithium in an argon stream Was stirred at room temperature for 15 hours. Then, water was added to this and extracted with hexane. Further, the hexane layer was washed with water, dried over magnesium sulfate and concentrated. The concentrate was purified by gel permeation chromatography to give 108 mg of dimer. The yield was 26% and the melting point was 178-180 ° C.
The measurement result by NMR of the obtained compound is shown below.
1 H-NMR (CDCl 3 ) δ = 0.52 (s, 6H), 1.90 (s, 12H), 6.71-6.86 (m, 8H), 6.94-7.15 (m, 12H).
[0039]
(Example 4) Synthesis of multimer represented by general formula (18) and cyclic compound represented by chemical formula (19) 1,1'-dichloro-2,5-dimethyl-3, A solution of 223 mg of 4-bis (ethylphenyl) silacyclopentadiene and 8 mg of lithium in 3 ml of THF was stirred at −20 ° C. for 10 hours. The reaction mixture was then added to 100 ml of methanol and the precipitate was filtered. The precipitate was washed with water and methanol. Again, the precipitate was dissolved in THF and re-precipitated by adding dropwise to 100 ml of isopropanol. After filtration, 110 mg of the target multimer represented by the general formula (18) was obtained. The molecular weight of this multimer was Mn = 4600 and Mw = 6400 from gel permeation chromatography.
The filtrate was concentrated and recrystallized with ethyl acetate. 14 mg of the target cyclic compound represented by the chemical formula (19) was obtained.
The measurement result by NMR of the obtained compound is shown below.
1 H-NMR (CDCl 3 ) δ = 1.14 (t, 36H), 2.12 (s, 36H), 2.53 (q, 24H), 6.69 (d, 24H), 6.91 (d, 24H).
[0040]
【The invention's effect】
Since the multimer of the silacyclopentadiene derivative of the present invention is directly bonded on silicon, it has not only the characteristics of the silacyclopentadiene ring but also the characteristics derived from the silicon-silicon bond. It is useful as a photoelectron functional material such as a conductive material, an organic EL element or electrophotography, or a raw material thereof.
Claims (5)
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