JPS58152892A - Novel ethynylenepolysilane compound and its preparation - Google Patents
Novel ethynylenepolysilane compound and its preparationInfo
- Publication number
- JPS58152892A JPS58152892A JP3382382A JP3382382A JPS58152892A JP S58152892 A JPS58152892 A JP S58152892A JP 3382382 A JP3382382 A JP 3382382A JP 3382382 A JP3382382 A JP 3382382A JP S58152892 A JPS58152892 A JP S58152892A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- novel
- general formula
- silylene
- compound represented
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は、新規エチニレンボリシラン系化合物およびそ
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ethynyleneborisilane compound and a method for producing the same.
二価の反応性中間体であるシリレンは、極めて反応性に
富むことから、高分子の架橋剤や新しい有機合成反応へ
の利用が期待され、広く研究されている。有機シリレン
（： ＳｉＲ，）の発生法としては、各種の方法が公知
であり、例えばポリン２ン類を光分解する方法がある。Silylene, a divalent reactive intermediate, is extremely reactive and is therefore widely studied as it is expected to be used as a crosslinking agent for polymers and in new organic synthesis reactions. Various methods are known for generating organic silylene (SiR), such as a method of photolyzing porin di-phosphones.
この方法は操作が容易であることから応用範囲が広い。This method has a wide range of applications because it is easy to operate.
上記の方法の一つに鎮状フェニルジシラン類を光分解す
る方法が知られているが、この方法によると１，３−ケ
イ素転位したシラエテンを主に生成し、有機シリレンの
生成収率は低い。またその感光波長が紫外線領域に限ら
れる。One of the above-mentioned methods is known to photolyze decomposed phenyldisilanes, but this method mainly produces 1,3-silicon rearranged silaethene, and the yield of organic silylene is low. . Furthermore, its sensitivity wavelength is limited to the ultraviolet region.
本発明の目的は、光分解で有機シリレンを高収率で発生
する新規なエチニ、レンポリシラン系化合物およびその
負遣方法を提供するＫある。An object of the present invention is to provide a novel ethylene polysilane compound that generates organic silylene in high yield through photolysis, and a method for producing the same.
上記目的のために各種のポリエチニレンボリシラン系化
合物を合成し、有機シリレンの発生収率を調べた結果、
以下に示される新規なエチニレンボリシラｙ系化合物が
有用であることを見出した。As a result of synthesizing various polyethynylene polysilane compounds for the above purpose and investigating the yield of organic silylene,
It has been found that the novel ethynyleneborisyl y-based compounds shown below are useful.
本発明の蛾規エチニレンボリシラン系化合物は、以下の
一般式（１）で示される。The ethylene polysilane compound of the present invention is represented by the following general formula (1).
（但シ、一般式＋１１中のＲはアルキル基を表わす。(However, R in general formula +11 represents an alkyl group.
本発明の新規エチニレンボリシ２ン系化合物としては、
例えば、ｙ ＃ ７ ｐ ｓ ｔ ａ Ｉ ９ ｙ ？
−へキサメチル−７，８，？ −）リシラシクロー１，
５−ノナジインなどがあげられる。The novel ethynylene boricin compounds of the present invention include:
For example, y # 7 p s t a I 9 y?
-hexamethyl-7,8,? -) Rishira cyclo 1,
Examples include 5-nonadiyne.
本発明による新規ポリエチニレンボリシラン系化合物は
、例えば次のような反応により合成できる。The novel polyethynylene polysilane compound according to the present invention can be synthesized, for example, by the following reaction.
３．３，４，４，７，７，８，８，１１．１１．１２，
１２−ドデカメチル−５，４，７，８，１１，１２−へ
キサシラシクロドデカ−１，５，９−）リイン（一般式
４においてＲ＝メチル基、ル＝１である化合物）は、エ
ーテル溶液中５，５，４，４−テトラメチル−３，４−
ジシラー１．５−へキサジインと７エールマグネシウム
ブｐマイトから導びかれるジグリニャール試薬を１．６
−ジクロロ−１，１，２，２，５，５，ｄ、（Ｓ−オク
タメチル−１，２，５，６−テトラシツヘキサンー５−
インを加え、室温にて反応させ、さらに還流させること
により合成できる。3.3,4,4,7,7,8,8,11.11.12,
12-dodecamethyl-5,4,7,8,11,12-hexasilacyclododeca-1,5,9-)lyne (a compound in which R = methyl group and R = 1 in general formula 4) is an ether 5,5,4,4-tetramethyl-3,4- in solution
The digrignard reagent derived from disylar 1.5-hexadiyne and 7 ale magnesium bumite is 1.6
-dichloro-1,1,2,2,5,5,d, (S-octamethyl-1,2,5,6-tetracituhexane-5-
It can be synthesized by adding yne, reacting at room temperature, and further refluxing.
実施例ｔ
） ２００５ｗ１５つロフラスコを窒素置換した
後、その中に５．Ｓ、４．４−テトラメチル−３，４−
ジシツー１，５−へキサジイン２１（α０１２モル）を
入れ、。Example t) After purging a 2005W15 flask with nitrogen, 5. S, 4,4-tetramethyl-3,4-
Add 1,5-hexadiyne 21 (α012 mol).
４０ｍのジエチルエーテルを加え、フラスコを氷冷した
。次にこの溶液を攪拌しながら、フェニルマグネシウム
ブロマイドの２規定ＴＨＦ溶箪１２ｗｌ１（フェニルマ
グネシウムブロマイドとしてα０２４モル）を約１０分
間で滴下し、さらＫｍ温で２０分間攪拌した。これに１
，６−ジクロロ−１，１゜２，２，５，５，６．６−オ
クタメチル−１，２，５，６−テトラシラヘキサン−３
−イン５，９５ （０，０１２モル）トジエチルエーテ
ル２０ｍの混合溶液を一度に添加し、室温にて１時間攪
拌した後、１時間還流させた。反応混合物を常法により
処理した後、粗生成物を再結晶により精製し、白色固体
を得た。40 m of diethyl ether was added and the flask was cooled on ice. Next, while stirring this solution, 12 ml of 2N THF solution of phenylmagnesium bromide (α024 mol as phenylmagnesium bromide) was added dropwise over about 10 minutes, and the mixture was further stirred at a temperature of Km for 20 minutes. 1 for this
,6-dichloro-1,1゜2,2,5,5,6.6-octamethyl-1,2,5,6-tetrasilahexane-3
A mixed solution of 20 ml of -yne 5,95 (0,012 mol) todiethyl ether was added at once, stirred at room temperature for 1 hour, and then refluxed for 1 hour. After the reaction mixture was treated in a conventional manner, the crude product was purified by recrystallization to obtain a white solid.
この固体が本発明の３，３，４，４，７；７，８，８，
１１．１１．１２１２−ドデカメチル−３，４，７，８
，１１，１２−へキサシラシクロドデカ−１，５，９−
）リインであることは核磁気共鳴スペクトル（’Ｈ−Ｎ
ＭＲ）および高分解能マススペクトルにおける以下の結
果から確認された。収率５５ ％ ｍｌ 、 １４５〜
１４７ ’０（１） Ｈ−ＮＭＲ（ａ ｐｐｍ／Ｃ
ＤＣｌ、 ）（Ｌ２５ （５６Ｍ 、シングレット、
メチル基）（２） 高分解能マススペクトル
Ｃ１＠Ｈ＠＠Ｓｉ＠の計算値＝ ４２１００２実測値＝
４２１．００１
実施例２
実施例１の方法により合成した５、５，４，４，７．７
８．８，１１．１１．１２，１２−ドデカメチル−５，
４，７，Ｂ、１１１２−へキサシラシクロドデカ−１，
５，９−）リイン２ｔをベン４フ５０ｗｔＫ溶かし、さ
らにシリレン捕捉剤としてジエチルメチルシラン２．９
ｆを加え、３００Ｗ低圧水銀燈で１０分間光照射した。This solid is the 3,3,4,4,7;7,8,8,
11.11.1212-dodecamethyl-3,4,7,8
,11,12-hexasilacyclododeca-1,5,9-
) Rein is nuclear magnetic resonance spectrum ('H-N
This was confirmed from the following results in MR) and high-resolution mass spectra. Yield 55% ml, 145~
147 '0(1) H-NMR (a ppm/C
DCl, )(L25 (56M, singlet,
Methyl group) (2) Calculated value of high-resolution mass spectrum C1@H@@Si@= 421002 Actual measurement value=
421.001 Example 2 5, 5, 4, 4, 7.7 synthesized by the method of Example 1
8.8,11.11.12,12-dodecamethyl-5,
4,7,B, 1112-hexasilacyclododeca-1,
5,9-) 2t of lyne was dissolved in 50wtK of ben4, and 2.9% of diethylmethylsilane was added as a silylene scavenger.
f was added and irradiated with a 300W low-pressure mercury lamp for 10 minutes.
反応混合物をガスクロマトグラフィーで分離し、標準試
料との比較ならびにマススペクトルによって分析した。The reaction mixture was separated by gas chromatography and analyzed by comparison with standard samples and by mass spectroscopy.
その結果、シリレンの捕捉によって生じたｔｌ−ジエチ
ル−１，２，２−）リメチルジシラン（シリレン捕捉剤
に対して、収率８５−）を得た。As a result, tl-diethyl-1,2,2-)limethyldisilane produced by scavenging of silylene (yield 85- with respect to silylene scavenger) was obtained.
以上述べたように１本発明の新規エチニレンポリシラン
系化合物は、σ（Ｓｉ−５ｉ）−π共役に基づく強い吸
収を紫外線領域に有するため光分解による有機シリレン
の発生効率が高く、新しいシリレン発生剤として有用で
ある。As mentioned above, the novel ethynylene polysilane compound of the present invention has strong absorption in the ultraviolet region based on σ(Si-5i)-π conjugation, so it has a high efficiency of generating organic silylene through photolysis, and generates new silylene. It is useful as a drug.
また、次のように光電変換膜の形成に使用できる。例え
ば、３，３，４，４，７，７，８，８，１１．１１．１
２．１２−ドデカメチル−３，４，７，８，１１，１２
−へキサシラシクロドデカ−１，５，？−トリインのト
ルエン溶＊（５〜１０重量Ｉｓ）を導電性基板上に塗布
し、乾燥成膜の後、全面を低圧水鋼溶で照射すれ＆ｆ不
溶性の光電変換薄膜を形成できる。Moreover, it can be used to form a photoelectric conversion film as follows. For example, 3, 3, 4, 4, 7, 7, 8, 8, 11.11.1
2.12-dodecamethyl-3,4,7,8,11,12
-hexasilacyclododeca-1,5,? - A toluene solution of triyne (5 to 10 weight Is) is applied on a conductive substrate, and after drying and film formation, the entire surface is irradiated with a low pressure water steel solution to form an insoluble photoelectric conversion thin film.
さらに、同様の方法により、レーザービームパターニン
グシステムにおける感光体として用い５る。即ち上記と
同様の方法により作製した本新規吻質薄膜に対して、レ
ーザービーム照射により光電導性の不溶性薄膜ノ（ター
ンを形成できる。Furthermore, it can be used as a photoreceptor in a laser beam patterning system by a similar method. That is, photoconductive insoluble thin film turns can be formed on the novel rostral thin film produced by the same method as described above by laser beam irradiation.
代理人弁理士 薄 １）字ＪＪ、、Representative Patent Attorney Susuki 1) JJ,...
Claims (1)
表わされる化合物よりなることを特徴とする新規エチニ
レンボリシラン系化合物。 ２、 ３．！Ｓ、４，４，７，７，８，８，１１，１１
，１２，１２−ドデカメチル−３，４，７，８，１１，
１２−ヘキサシラシクロドデカ−１，５，？ −）リイ
ンであることを特徴とする特許請求の範囲第１項記載の
新規エチニレンボリシラン系化合物。 五 一般式（２）で表わされる化合物と、一般式（３）
で表わされる化合物とを反応させて、一般式（１１で示
される化合物を得ることを特徴とする新規エチニレンポ
リシラｙ系化合物の製造方法。 但し、一般式（１）〜（３）中のＲはアルキル基であり
、一般式（２）〜（４）中のＸはＣ４もしくはＢｙであ
り、一般式＋１１〜（３）中の３は１以上の整数である
。 ４、一般式（２）で示される化合物が （３）で表わされる化合−が ＣＩＳ ｉ （ＣＨ，）、 Ｓ ｉ （ＣＨ，）、−ｆ
Ｃ＝Ｃ−）−５ｉ （ＣＭｓ）、 Ｓｉ （ＣＭ、）、
ＣＩもしくは ＢｒＳｉ （ＣＥ、 ）ｔ Ｓｉ （ＣＨ，）１＋Ｃ＝
Ｃ’＋Ｓｉ （ＣＢ、 ）ｔ Ｓｉ （ＣＨ，）、
Ｂｒであり、一般式（１）で表わされる化合物が、であ
ることを特徴とする特許請求の範囲第３項記載の新規エ
チニレンボリシラン系化合物の製造方法。[Scope of Claims] t A novel ethynyleneborisilane compound characterized by comprising a compound represented by the general formula (11 (wherein, R in the general formula (1) represents an alkyl group). 2. 3.!S, 4, 4, 7, 7, 8, 8, 11, 11
,12,12-dodecamethyl-3,4,7,8,11,
12-hexasilacyclododeca-1,5,? -) The novel ethynyleneborisilane compound according to claim 1, which is lyne. (5) A compound represented by general formula (2) and general formula (3)
A method for producing a novel ethynylene polysilane compound, which is characterized in that a compound represented by general formula (11) is obtained by reacting with a compound represented by R is an alkyl group, X in general formulas (2) to (4) is C4 or By, and 3 in general formulas +11 to (3) is an integer of 1 or more. 4. General formula (2) ), the compound represented by (3) is CIS i (CH,), S i (CH,), -f
C=C-)-5i (CMs), Si (CM, ),
CI or BrSi (CE, )t Si (CH,)1+C=
C'+Si (CB, )t Si (CH,),
4. The method for producing a novel ethynyleneborisilane compound according to claim 3, wherein the compound represented by general formula (1) is Br.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382382A JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382382A JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58152892A true JPS58152892A (en) | 1983-09-10 |
| JPS6340435B2 JPS6340435B2 (en) | 1988-08-11 |
Family
ID=12397202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3382382A Granted JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58152892A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996341A (en) * | 1990-07-05 | 1991-02-26 | Kanegafuchi Chemical Industry Co., Ltd. | Condensed bicyclic disilanylene-acetylene compound and method for preparing the same |
| JPH0671989B2 (en) * | 1988-10-28 | 1994-09-14 | ヒユーズ・エアクラフト・カンパニー | High density filament winding and method of forming improved intersection and internal payouts |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0227462U (en) * | 1988-08-10 | 1990-02-22 | ||
| JPH0268961U (en) * | 1988-11-14 | 1990-05-24 |
-
1982
- 1982-03-05 JP JP3382382A patent/JPS58152892A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0671989B2 (en) * | 1988-10-28 | 1994-09-14 | ヒユーズ・エアクラフト・カンパニー | High density filament winding and method of forming improved intersection and internal payouts |
| US4996341A (en) * | 1990-07-05 | 1991-02-26 | Kanegafuchi Chemical Industry Co., Ltd. | Condensed bicyclic disilanylene-acetylene compound and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6340435B2 (en) | 1988-08-11 |
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