JPH0678343B2 - Novel octaalkyltetrasila [2.2] paracyclophane compound and method for producing the same - Google Patents
Novel octaalkyltetrasila [2.2] paracyclophane compound and method for producing the sameInfo
- Publication number
- JPH0678343B2 JPH0678343B2 JP21155586A JP21155586A JPH0678343B2 JP H0678343 B2 JPH0678343 B2 JP H0678343B2 JP 21155586 A JP21155586 A JP 21155586A JP 21155586 A JP21155586 A JP 21155586A JP H0678343 B2 JPH0678343 B2 JP H0678343B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- general formula
- novel
- octaalkyltetrasila
- paracyclophane
- 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.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0624—Heterocyclic compounds containing one hetero ring
- G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規オクタアルキルテトラシラ〔2.2〕パラ
シクロファン系化合物およびその製造方法に関する。TECHNICAL FIELD The present invention relates to a novel octaalkyltetrasila [2.2] paracyclophane compound and a method for producing the same.
光電変換性をもつ材料として、有機材料は無機材料に比
べて安価、量産性などの点ですぐれている。従来、代表
的な有機光電変換材料としてはフタロシアニン系化合物
などがある（「導電性高分子材料」、雀部博之 編、第
２章、シーエムシー刊、1984年）。これらの物質の光起
電力の発生機構は、金属等との接合による電位勾配の形
成、空間電荷層およびその近傍での光吸収にもとずくキ
ャリヤ生成の２つの過程からなる。後者のキャリヤ生成
過程においてはOnsagerモデルにもとずき、光励起状態
からのイオン対の生成が重要な役割を果たすと考えられ
ている。As a material having a photoelectric conversion property, an organic material is superior to an inorganic material in terms of cost and mass productivity. Conventionally, phthalocyanine compounds have been known as typical organic photoelectric conversion materials (“Conductive polymer materials”, edited by Hiroyuki Sparrow, Chapter 2, published by CMC, 1984). The photoelectromotive force generation mechanism of these substances consists of two processes: formation of a potential gradient by bonding with a metal or the like, and generation of carriers based on light absorption in the space charge layer and its vicinity. In the latter carrier generation process, based on the Onsager model, the generation of ion pairs from the photoexcited state is considered to play an important role.
光電変換材料としてはキャリヤ生成密度の高い材料が好
ましいが、従来その要求を満たす有機材料はごく限られ
ていた。本発明の目的は、上記従来の有機光電変換材料
のの光起電力発生機構中、特に光励起によるイオン対生
成が容易であるため光電変換材料に適すると考えられ
る、新規なオクタアルキルテトラシラ〔2.2〕パラシク
ロファン系化合物およびその製造方法を提供することに
ある。As the photoelectric conversion material, a material having a high carrier generation density is preferable, but conventionally, only a limited number of organic materials satisfy the requirements. The object of the present invention, during the photovoltaic generation mechanism of the conventional organic photoelectric conversion material, considered to be suitable for the photoelectric conversion material because ion pair generation by photoexcitation is particularly easy, novel octaalkyl tetrasila (2.2 ] It is to provide a paracyclophane compound and a method for producing the same.
〔問題点を解決するための手段〕 従来、フェニルペンタメチルジシランが分子内電荷移動
による光の吸収を示すことが知られていた。そのフェニ
ルペンタメチルジシランの２分子が環状に結合した形形
をもつ、以下に示す新規なオクタアルキルテトラシラ
〔2.2〕パラシクロファン系化合物においては、さらに
強い分子内電荷移動が生じることを見出した。[Means for Solving Problems] It has been conventionally known that phenylpentamethyldisilane exhibits light absorption by intramolecular charge transfer. It has been found that even stronger intramolecular charge transfer occurs in the novel octaalkyltetrasila [2.2] paracyclophane compound shown below, which has a form in which two molecules of phenylpentamethyldisilane are cyclically bonded. .
本発明の新規オクタアルキルテトラシラ〔2.2〕パラシ
クロファン系化合物は、以下の一般式（１）で示され
る。The novel octaalkyltetrasila [2.2] paracyclophane compound of the present invention is represented by the following general formula (1).
ただし、一般式（１）中の1R、2R、3R、4R、5R、6R、
7R、および8Rはそれぞれ水素あるいはアルキルキ基を、
ＡおよびＢは芳香族系化合物を示す。 However, in the general formula (1), 1 R, 2 R, 3 R, 4 R, 5 R, 6 R,
7 R and 8 R are each hydrogen or an alkyl group,
A and B represent aromatic compounds.
本発明の新規オクタアルキルテトラシラ〔2.2〕パラシ
クロファン系化合物としては、たとえばオクタメチルテ
トラシラ〔2.2〕パラシクロファンがあげられる。本発
明の新規オクタアルキルテトラシラ〔2.2〕パラシクロ
ファン系化合物はSi−−Si間のσ結合と芳香族環のπ結
合とが相互作用しやすい位置関係にある。そのため、光
励起により結合間の電荷移動をおこしイオン対を高密度
で生成して、多数のキャリヤを生ずると考えられる。Examples of the novel octaalkyltetrasila [2.2] paracyclophane compound of the present invention include octamethyltetrasila [2.2] paracyclophane. The novel octaalkyltetrasila [2.2] paracyclophane compound of the present invention has a positional relationship in which the σ bond between Si and Si and the π bond of the aromatic ring easily interact with each other. Therefore, it is considered that photoexcitation causes charge transfer between bonds to generate ion pairs at a high density, resulting in a large number of carriers.
本発明による新規オクタアルキルテトラシラ〔2.2〕パ
ラシクロファン系化合物は、たとえば次のような反応に
より合成できる。The novel octaalkyltetrasila [2.2] paracyclophane compound according to the present invention can be synthesized, for example, by the following reaction.
オクタメチルテトラシラ〔2.2〕パラシクロファン（一
般式（１）において1R＝2R＝3R＝4R＝5R＝6R＝7R＝8R＝
メチル基、Ａ＝Ｂ＝フェニル基であり、２つのフェニル
基ともパラの位置でSiと結合している化合物）は、パラ
ジブロモベンゼン（一般式（４）および（５）Ｘ＝Ｙ＝
臭素、Ａ＝Ｂ＝フェニル基で、２つのフェニル基ともパ
ラの位置でSiと結合している化合物）を1,2−ジクロロ
テトラメチルジシラン（一般式（３）で1R＝2R＝3R＝4R
＝メチル基、Ｘ＝Ｙ＝塩素である化合物）と反応させて
得られるジ（パラブロモフェニル）テトラメチルジシラ
ン（一般式（２）で1R＝2R＝3R＝4R＝メチル基、Ｘ＝Ｙ
＝臭素、Ａ＝Ｂ＝フェニル基で、２つのフェニル基とも
パラの位置でSiと結合している化合物）をグリニャール
試薬とし、それを1,2−ジクロロテトラメチルジシラン
（一般式（３）で1R＝2R＝3R＝4R＝メチル基、Ｘ＝Ｙ＝
塩素である化合物）と反応させることにより合成でき
る。Octamethyltetrasila [2.2] paracyclophane ( 1 R = 2 R = 3 R = 4 R = 5 R = 6 R = 7 R = 8 R = in the general formula (1)
A methyl group, A = B = phenyl group, and a compound in which both two phenyl groups are bonded to Si at the para position) is paradibromobenzene (general formulas (4) and (5) X = Y =
Bromine, A = B = phenyl group, a compound in which two phenyl groups are bonded to Si at the para position) is 1,2-dichlorotetramethyldisilane ( 1 R = 2 R = 3 in the general formula (3)). R = 4 R
= Methyl group, X = Y = compound of chlorine), and obtained by reacting with di (parabromophenyl) tetramethyldisilane ( 1 R = 2 R = 3 R = 4 R = methyl group in the general formula (2), X = Y
= Bromine, A = B = phenyl group, a compound in which two phenyl groups are bonded to Si at the para position) is used as a Grignard reagent, and it is treated with 1,2-dichlorotetramethyldisilane (in the general formula (3)). 1 R = 2 R = 3 R = 4 R = methyl group, X = Y =
It can be synthesized by reacting with a compound which is chlorine.
以下、本発明の合成例および実施例を示す。 Hereinafter, synthesis examples and examples of the present invention will be shown.
（合成例） パラジブロモベンゼンをエーテル中でｔ−ブチルリチウ
ムでリチオ化したあと、1,2−ジクロロテトラメチルジ
シランと反応させて得られるジ（パラブロモフェニル）
テトラメチルジシランをテトラハイドロフラン中でマグ
ネシウムと反応させてジグリニャール試薬とし、1,2−
ジクロロテトラメチルジシランと縮合反応させた。これ
により収率1.6％で無色の本発明のオクタメチルテトラ
シラ〔2.2〕パラシクロファン結晶が得られた。同定は1
H、13C、29Siそれぞれの核磁気共鳴（1H、13C、29Si−N
MR）、質量分析（MS）、およびＸ線構造解析によった。
その結果を以下に示す。(Synthesis example) Di (parabromophenyl) obtained by lithiation of paradibromobenzene with t-butyllithium in ether and reaction with 1,2-dichlorotetramethyldisilane
Tetramethyldisilane was reacted with magnesium in tetrahydrofuran to give a DiGrignard reagent, 1,2-
It was condensed with dichlorotetramethyldisilane. As a result, colorless octamethyltetrasila [2.2] paracyclophane crystals of the present invention were obtained with a yield of 1.6%. Identification is 1
H, 13 C, 29 Si nuclear magnetic resonance ( 1 H, 13 C, 29 Si-N
MR), mass spectrometry (MS), and X-ray structural analysis.
The results are shown below.
m.p. 268〜269℃1 H−NMR（δppm/CCl4） 6.75 （8H,シングレット） 0.50 （24H,シングレット）13 C−NMR（δppm/CCl4） 138.58 （シングレット） 133.36 （ダブレット） −4.77 （カルルテット）29 Si−NMR（δppm/CCl4） 6.45 MS C20H32Si4の実測値＝384 計算値＝384.816 Ｘ線構造解析の結果を第１図に示す。mp 268 to 269 ° C 1 H-NMR (δppm / CCl 4 ) 6.75 (8H, singlet) 0.50 (24H, singlet) 13 C-NMR (δppm / CCl 4 ) 138.58 (singlet) 133.36 (doublet) -4.77 (quartet) 29 Si-NMR (δppm / CCl 4 ) 6.45 MS C 20 H 32 Si 4 measured value = 384 calculated value = 384.816 The result of X-ray structural analysis is shown in FIG.
（実施例） 上記合成例により合成したオクタメチルテトラシラ〔2.
2〕パラシクロフアンの可視外吸収スペクトルを第２図
に示す。263nmに分子内σ（Si−Si）−π電荷移動吸収
帯が観測された。これは光の吸収によって分子内の電子
が分極して分子内でイオン対が生成することを示してい
る。(Example) Octamethyltetrasila synthesized according to the above synthesis example [2.
2] The non-visible absorption spectrum of paracyclophane is shown in FIG. An intramolecular σ (Si-Si) -π charge transfer absorption band was observed at 263 nm. This indicates that absorption of light polarizes electrons in the molecule to generate ion pairs in the molecule.
以上述べたように、本発明の新規オクタアルキルテトラ
シラ〔2.2〕パラシクロフアン系化合物は、その光励起
状態が強く分極して容易にイオン対を生成し光起電力の
原因であるキャリヤを生成する。したがって本新規化合
物を光電変換素子に適用できる。As described above, in the novel octaalkyltetrasila [2.2] paracyclophane compound of the present invention, its photoexcited state is strongly polarized to easily generate an ion pair to generate a carrier which is a cause of photovoltaic power. . Therefore, the novel compound can be applied to a photoelectric conversion device.
たとえば上記合成例の方法で合成した化合物を、金の電
極表面に100〜300Åの厚さに真空蒸着し、次にアルミニ
ウムを真空蒸着した素子は、光を照射することにより金
電極とアルミニウム電極との間に起電力を生じる。この
起電力を用いて外部回路に電流を流すことができる。ま
た光電変換効率の制御は、各種の芳香族系化合物を含む
本発明の新規化合物を合成することにより達成できる。For example, a compound synthesized by the method of the above Synthesis Example is vacuum-deposited on the surface of a gold electrode to a thickness of 100 to 300Å, and then aluminum is vacuum-deposited. Generates an electromotive force. This electromotive force can be used to pass a current through an external circuit. The control of photoelectric conversion efficiency can be achieved by synthesizing the novel compound of the present invention containing various aromatic compounds.
第１図は本発明の一合成例により得られた、オクタメチ
ルテトラシラ〔2.2〕パラシクロフアンのＸ線構造解析
による構造図（図中、角度以外の数字の単位はÅであ
る）、第２図はこのオクタメチルテトラシラ〔2.2〕パ
ラシクロファンの可紫外吸収スペクトルである。 C3〜C8,C11〜C24……炭素原子 SI1、SI2、SI3、SI4……ケイ素原子FIG. 1 is a structural diagram obtained by an X-ray structural analysis of octamethyltetrasila [2.2] paracyclophane obtained by one synthesis example of the present invention (in the figure, the unit of numbers other than angles is Å), Figure 2 is the UV absorption spectrum of this octamethyltetrasila [2.2] paracyclophane. C3 ~ C8, C11 ~ C24 ... carbon atom SI1, SI2, SI3, SI4 ... silicon atom
Claims (3)
7R、および8Rはそれぞれ水素あるいはアルキルキ基を、
ＡおよびＢは芳香族系化合物を示す）で表される化合物
よりなることを特徴とする新規オクタアルキルテトラシ
ラ〔2.2〕パラシクロファン系化合物。1. A general formula (1) (However, in the general formula (1), 1 R, 2 R, 3 R, 4 R, 5 R, 6 R,
7 R and 8 R are each hydrogen or an alkyl group,
A and B each represent an aromatic compound), which is a novel octaalkyltetrasila [2.2] paracyclophane compound.
素あるいはアルキル基を、ＡおよびＢは芳香族系化合物
を、ＸおよびＹはハロゲン元素を示す）で表されるジ
（パラハロゲノフェニル）テトラアルキルジシラン系化
合物をマグネシウムと反応させて得られるグリニャール
試薬と、一般式（３） （ただし、一般式（３）中の1R、2R、3R、および4Rは水
素あるいはアルキル基を、ＸおよびＹはハロゲン元素を
示す）で表される1,2−ジハロゲノテトラアルキルジシ
ランとを反応させて、一般式（１）で表される化合物を
得ることを特徴とする新規オクタアルキルテトラシラ
〔2.2〕パラシクロファン系化合物の製造方法。2. General formula (2) (However, 1 R, 2 R, 3 R, and 4 R in the general formula (2) are hydrogen or an alkyl group, A and B are aromatic compounds, and X and Y are halogen elements) A Grignard reagent obtained by reacting a di (parahalogenophenyl) tetraalkyldisilane compound with magnesium, and a general formula (3) (However, 1 R, 2 R, 3 R, and 4 R in the general formula (3) represent hydrogen or an alkyl group, and X and Y represent a halogen element). A method for producing a novel octaalkyltetrasila [2.2] paracyclophane compound, which comprises reacting disilane to obtain a compound represented by the general formula (1).
芳香族系化合物を、ＸおよびＹはハロゲン元素を示す）
で表されるパラジハロゲノベンゼン系化合物と、一般式
（３）で表される1,2−ジハロゲノテトラアルキルジシ
ランとを反応させて得られる、一般式（２）で表される
ジ（パラハロゲノフェニル）テトラアルキルジシラン系
化合物を用いることを特徴とする特許請求の範囲第２項
に記載の新規オクタアルキルテトラシラ〔2.2〕パラシ
クロファン系化合物の製造方法。3. General formulas (4) and (5) X-A-X (4) Y-B-Y (5) (wherein A and B in general formulas (4) and (5) are aromatic). System compounds, X and Y represent halogen elements)
A di (parahalogeno represented by the general formula (2) obtained by reacting a paradihalogenobenzene compound represented by the formula (2) with a 1,2-dihalogenotetraalkyldisilane represented by the general formula (3). A method for producing a novel octaalkyltetrasila [2.2] paracyclophane compound according to claim 2, characterized in that a phenyl) tetraalkyldisilane compound is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21155586A JPH0678343B2 (en) | 1986-09-10 | 1986-09-10 | Novel octaalkyltetrasila [2.2] paracyclophane compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21155586A JPH0678343B2 (en) | 1986-09-10 | 1986-09-10 | Novel octaalkyltetrasila [2.2] paracyclophane compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6368588A JPS6368588A (en) | 1988-03-28 |
| JPH0678343B2 true JPH0678343B2 (en) | 1994-10-05 |
Family
ID=16607747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21155586A Expired - Fee Related JPH0678343B2 (en) | 1986-09-10 | 1986-09-10 | Novel octaalkyltetrasila [2.2] paracyclophane compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678343B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100974037B1 (en) | 2008-04-25 | 2010-08-04 | 제이에스아이실리콘주식회사 | Novel silyl substituted 1,4-disilacyclohexane derivatives and preparation method thereof |
| JP5692222B2 (en) * | 2010-04-20 | 2015-04-01 | コニカミノルタ株式会社 | Materials for organic electronics elements, organic electronics elements, lighting devices, display devices, and organic thin film solar cell elements |
| JP5556602B2 (en) * | 2010-11-10 | 2014-07-23 | コニカミノルタ株式会社 | Material for organic electronics element, organic electronics element, lighting device and display device |
-
1986
- 1986-09-10 JP JP21155586A patent/JPH0678343B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6368588A (en) | 1988-03-28 |
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