JP3249966B2 - Cyclic bishydrosilyl compound - Google Patents
Cyclic bishydrosilyl compoundInfo
- Publication number
- JP3249966B2 JP3249966B2 JP27460692A JP27460692A JP3249966B2 JP 3249966 B2 JP3249966 B2 JP 3249966B2 JP 27460692 A JP27460692 A JP 27460692A JP 27460692 A JP27460692 A JP 27460692A JP 3249966 B2 JP3249966 B2 JP 3249966B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ppm
- bishydrosilyl
- cyclic
- reaction vessel
- 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 - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性及び対燃焼性ポ
リマーの原料等として有用な、新規な環状ビスヒドロシ
リル化合物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic bishydrosilyl compound useful as a raw material of a heat-resistant and combustible polymer and a method for producing the same.
【０００２】[0002]
【従来の技術】本化合物は有効な合成手段が知られてお
らず、製造できなかった。BACKGROUND OF THE INVENTION The present compound could not be produced because no effective synthetic means was known.
【０００３】[0003]
【発明は解決しようとする課題】本発明は、有機ケイ素
ポリマーの原料として有用な新規な環状ビスヒドロシリ
ル化合物を合成することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to synthesize a novel cyclic bishydrosilyl compound useful as a raw material for an organosilicon polymer.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成する本発
明は、化学式（１）To achieve the above object, the present invention provides a compound of the formula (1)
【０００５】[0005]
【化３】 で示される環状ビスヒドロシリル化合物（ベンゾ［ｂ］
−５，６−ビス（ジメチルヒドロシリル）−１，１，
４，４−テトラメチル−１，４−ジシラシクロヘキサ−
２，５−ジエン）である。Embedded image (Benzo [b])
-5,6-bis (dimethylhydrosilyl) -1,1,
4,4-tetramethyl-1,4-disilacyclohexa-
2,5-diene).
【０００６】また、本発明は、化学式（２）Further, the present invention provides a compound represented by the following chemical formula (2):
【０００７】[0007]
【化４】 で示される化合物と金属水素化物とを反応させることを
特徴とする上記環状ビスヒドロシリル化合物の製造方法
である。Embedded image And reacting the compound represented by the formula (1) with a metal hydride.
【０００８】以下、化学式（１）で示される環状ビスヒ
ドロシリル化合物の製造方法を説明する。Hereinafter, a method for producing the cyclic bishydrosilyl compound represented by the chemical formula (1) will be described.
【０００９】まず、反応容器内に化学式（２）で示され
るビスフロロシリル化合物と金属水素化物、更に溶媒を
仕込む。First, a bisfluorosilyl compound represented by the chemical formula (2), a metal hydride, and a solvent are charged in a reaction vessel.
【００１０】金属水素化物としては、例えば、ＬｉＨ、
ＮａＨ、ＫＨ、ＲｂＨ、ＣｓＨ等のアルカリ金属水素化
物、ＭｇＨ2、ＣａＨ2、ＳｒＨ2、ＢａＨ2等のアルカリ
土類金属水素化物、ＢＨ3錯体、ＡｌＨ3錯体等の１３族
金属水素化物、ＬｉＡｌＨ4、ＮａＡｌＨ4、ＫＡｌ
Ｈ4、ＬｉＢＨ4、ＮａＢＨ4、ＫＢＨ4、Ｍｇ（Ｂ
Ｈ4）2、Ｃａ（ＢＨ4）2、Ｂａ（ＢＨ4）2、Ｓｒ（ＢＨ
4）2、Ａｌ（ＢＨ4）3等の複合水素化物等が使用でき
る。該金属水素化物は、還元に用い得る水素原子として
該ビスフロロシリル化合物に対して０．１〜１００当
量、より好ましくは０．５〜１０当量、更に好ましくは
１〜５当量とする。As the metal hydride, for example, LiH,
Group 13 metal hydrides such as alkali metal hydrides such as NaH, KH, RbH and CsH, alkaline earth metal hydrides such as MgH 2 , CaH 2 , SrH 2 and BaH 2 , BH 3 complex and AlH 3 complex, LiAlH 4, NaAlH 4, KAl
H 4 , LiBH 4 , NaBH 4 , KBH 4 , Mg (B
H 4 ) 2 , Ca (BH 4 ) 2 , Ba (BH 4 ) 2 , Sr (BH
4 ) Complex hydrides such as 2 and Al (BH 4 ) 3 can be used. The metal hydride is used in an amount of 0.1 to 100 equivalents, more preferably 0.5 to 10 equivalents, and still more preferably 1 to 5 equivalents to the bisfluorosilyl compound as a hydrogen atom usable for reduction.
【００１１】溶媒としては、ジエチルエーテル、ＴＨＦ
等のエーテル系溶剤、ベンゼン、トルエン等の芳香族系
溶剤、シクロヘキサン、ノルマルヘプタン等の飽和炭化
水素系溶剤、又はこれらの溶剤の混合溶剤等が好まし
い。該溶媒は該ビスフロロシリル化合物１ｍｍｏｌに対
して１〜１００ｍｌ、より好ましくは２〜１０ｍｌとす
る。As a solvent, diethyl ether, THF
Preferred are ether solvents such as benzene, aromatic solvents such as benzene and toluene, saturated hydrocarbon solvents such as cyclohexane and normal heptane, and mixed solvents of these solvents. The solvent is used in an amount of 1 to 100 ml, more preferably 2 to 10 ml, per 1 mmol of the bisfluorosilyl compound.
【００１２】上記各原料の反応容器内への仕込順序は特
に限定されるものではない。混合の仕方は、全ての原料
を同時に混合してもよいし、ビスフロロシリル及び金属
水素化物の内どちらか一方もしくは両方の原料を反応中
に連続にもしくは断続的に反応容器内へ供給してもよ
い。反応中は、反応容器を所定の反応温度に制御しつ
つ、所定の反応時間攪拌する。The order of charging the raw materials into the reaction vessel is not particularly limited. As for the method of mixing, all the raw materials may be mixed at the same time, or one or both raw materials of bisfluorosilyl and metal hydride may be continuously or intermittently supplied into the reaction vessel during the reaction. Is also good. During the reaction, the reaction vessel is stirred for a predetermined reaction time while controlling the reaction vessel at a predetermined reaction temperature.
【００１３】反応温度は−３０〜２００℃、より好まし
くは０〜１００℃、更に好ましくは２０〜６０℃が適当
である。The reaction temperature is -30 to 200 ° C, more preferably 0 to 100 ° C, and further preferably 20 to 60 ° C.
【００１４】反応時間は、反応温度や原料の量に依存す
るが、好ましくは１０分〜１０時間、より好ましくは３
０分〜５時間が適当である。The reaction time depends on the reaction temperature and the amount of raw materials, but is preferably 10 minutes to 10 hours, more preferably 3 minutes.
0 minutes to 5 hours is appropriate.
【００１５】目的の化合物は反応液のデカンテーショ
ン、濾過、溶媒抽出、蒸留、又はクロマトグラフィー等
の通常の方法で、容易に分離精製することができる。The target compound can be easily separated and purified by a conventional method such as decantation, filtration, solvent extraction, distillation, or chromatography of the reaction solution.
【００１６】[0016]
【実施例】以下、実施例により本発明を具体的に説明す
る。The present invention will be described below in detail with reference to examples.
【００１７】実施例１ ２００ｍｌのガラス製反応容器にコンデンサーを取り付
け、該反応容器の内部に磁気攪拌子を投入した後、該反
応容器内を高純度窒素ガスで置換した。続いて、該ビス
フロロシリル化合物４．７５ｇ（１２．８ｍｍｏｌ）
と、金属水素化物としてＬｉＡｌＨ4１．０８ｇ（２
８．５ｍｍｏｌ）と、ジエチルエーテル５０ｍｌとを該
反応容器内に投入した。温度を３５℃に設定した油浴に
該反応容器を浸し、磁気攪拌子で攪拌しながら３時間反
応させた。ガスクロマトグラフィーにより、原料がほぼ
消失したことを確認した後、該反応容器を油浴から外
し、反応液にノルマルヘキサン５０ｍｌを加えて未反応
のＬｉＡｌＨ4を沈澱させ、分液ロートで有機層と沈澱
層とを分離した。該有機層を飽和塩化アンモニウム水で
洗浄後、無水硫酸ナトリウムで乾燥させた。乾燥後の該
有機層をシリカゲルカラムに担持させ、ベンゼン溶媒で
生成物を溶出させた。該ベンゼン溶液中のベンゼンを減
圧蒸発させ、生成物をエタノールから再結晶させること
により化学式（１）で示される環状ビスヒドロシリル化
合物を得た。該化合物の収量は２．１６ｇ（６．５ｍｏ
ｌ）、収率は５２％であった。Example 1 A condenser was attached to a 200 ml glass reaction vessel, a magnetic stirrer was put into the reaction vessel, and the inside of the reaction vessel was replaced with high-purity nitrogen gas. Subsequently, 4.75 g (12.8 mmol) of the bisfluorosilyl compound was used.
And 1.08 g of LiAlH 4 as metal hydride (2
8.5 mmol) and 50 ml of diethyl ether were charged into the reaction vessel. The reaction vessel was immersed in an oil bath whose temperature was set at 35 ° C., and reacted for 3 hours while stirring with a magnetic stirrer. After confirming that the raw materials had almost disappeared by gas chromatography, the reaction vessel was removed from the oil bath, 50 ml of normal hexane was added to the reaction solution to precipitate unreacted LiAlH 4 , and the organic layer was separated with a separating funnel. The precipitate layer was separated. The organic layer was washed with saturated aqueous ammonium chloride and dried over anhydrous sodium sulfate. The dried organic layer was supported on a silica gel column, and the product was eluted with a benzene solvent. The benzene in the benzene solution was evaporated under reduced pressure, and the product was recrystallized from ethanol to obtain a cyclic bishydrosilyl compound represented by the chemical formula (1). The yield of the compound was 2.16 g (6.5 mo).
1), the yield was 52%.
【００１８】得られた化合物の形態は、無色の針状結晶
で、融点は５０．９〜５１．０℃であった。The obtained compound was in the form of colorless needle crystals and had a melting point of 50.9 to 51.0 ° C.
【００１９】以下、元素分析、質量分析、ＩＲ、ＮＭＲ
により得られた化合物を同定した結果を示す。Hereinafter, elemental analysis, mass spectrometry, IR, NMR
3 shows the results of identifying the compound obtained by the method described above.
【００２０】元素分析の結果、炭素５７．６２％（理論
値５７．４１％）、水素９．２７％（理論値９．０３
％）となり、測定値は、測定誤差の範囲で理論値とよく
一致した。As a result of elemental analysis, carbon was 57.62% (theoretical 57.41%), and hydrogen was 9.27% (theoretical 9.03%).
%), And the measured value was in good agreement with the theoretical value within the range of the measurement error.
【００２１】質量分析の結果、マススペクトル（ＥＩ＝
７０ｅＶ）の主なピークのｍ／ｅ値が３３４（１６
％）、３１９（１１％）、２７５（１００％）、２６１
（２２％）、１７７（４１％）であった。ｍ／ｅ値の最
大値３３４は、Ｍ+の理論値３３４と一致した。As a result of mass spectrometry, the mass spectrum (EI =
The m / e value of the main peak at 70 eV) is 334 (16
%), 319 (11%), 275 (100%), 261
(22%) and 177 (41%). The maximum value 334 of the m / e value was consistent with the theoretical value 334 of M + .
【００２２】ＫＢｒ錠剤法により赤外吸収スペクトルを
測定した結果、主な吸収ピーク波数（単位はｃｍ-1）
は、３０５０、２９５０、２９００、２１５０、２１２
０、１４００、１２４０、１１２０、１０６０、１０４
０であった。２１５０、２１２０はＳｉＨ結合の吸収を
示すものである。As a result of measuring the infrared absorption spectrum by the KBr tablet method, the main absorption peak wave number (unit: cm -1 )
Are 3050, 2950, 2900, 2150, 212
0, 1400, 1240, 1120, 1060, 104
It was 0. Reference numerals 2150 and 2120 indicate absorption of SiH bonds.
【００２３】測定溶媒として重クロロホルム溶液を用い
て、1Ｈ−ＮＭＲ測定を行った結果、化学シフト（δ
値）は、ＴＭＳを基準として０．３３ｐｐｍ（１２Ｈ、
２重項）、０．３９ｐｐｍ（１２Ｈ、１重項）、４．５
ｐｐｍ（２Ｈ、多重項）、７．３７ｐｐｍ（２Ｈ、多重
項）、７．５６ｐｐｍ（２Ｈ、多重項）であった。０．
３３ｐｐｍ及び０．３９ｐｐｍの位置に確認された合計
２４個の水素は８個のメチル基を形成する合計２４個の
水素、４．５ｐｐｍの位置に確認された２個の水素はＳ
ｉＨ結合の合計２個の水素、７．３７ｐｐｍ及び７．５
６ｐｐｍの位置に確認された合計４個の水素はベンゼン
環上の合計４個の水素と考えられる。As a result of 1 H-NMR measurement using a heavy chloroform solution as a measuring solvent, the chemical shift (δ
Value) is 0.33 ppm (12H,
Doublet), 0.39 ppm (12H, singlet), 4.5
ppm (2H, multiplet), 7.37 ppm (2H, multiplet), and 7.56 ppm (2H, multiplet). 0.
A total of 24 hydrogens found at the 33 ppm and 0.39 ppm positions are a total of 24 hydrogens forming 8 methyl groups, two hydrogens found at the 4.5 ppm position are S
a total of two hydrogens at the iH bond, 7.37 ppm and 7.5
The total of four hydrogens identified at the position of 6 ppm are considered to be a total of four hydrogens on the benzene ring.
【００２４】測定溶媒として重クロロホルム溶液を用い
て、13Ｃ−ＮＭＲ測定を行った結果、化学シフト（δ
値）は、ＴＭＳを基準として、−１．３２ｐｐｍ、０．
７１ｐｐｍ、１２８．０６ｐｐｍ、１３２．６６ｐｐ
ｍ、１４５．２０ｐｐｍ、１８５．５５ｐｐｍであっ
た。As a result of 13 C-NMR measurement using a heavy chloroform solution as a measuring solvent, the chemical shift (δ
Values) are -1.32 ppm, 0.
71 ppm, 128.06 ppm, 132.66 pp
m, 145.20 ppm, and 185.55 ppm.
【００２５】測定溶媒として重クロロホルム溶液を用い
て、29Ｓｉ−ＮＭＲ測定を行った結果、化学シフト（δ
値）はＴＭＳを基準として、−２６．７９ｐｐｍ、−２
４．３５ｐｐｍであった。As a result of 29 Si-NMR measurement using a heavy chloroform solution as a measuring solvent, the chemical shift (δ
Values) are -26.79 ppm, -2 based on TMS.
It was 4.35 ppm.
【００２６】[0026]
【発明の効果】本発明によれば、耐熱性及び耐燃焼性ポ
リマー原料として有用な新規な環状ビスヒドロシリル化
合物を提供できる。According to the present invention, it is possible to provide a novel cyclic bishydrosilyl compound useful as a heat-resistant and flame-resistant polymer raw material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 正人 茨城県つくば市東１丁目１番地 工業技 術院化学技術研究所内 (72)発明者 内丸 祐子 茨城県つくば市東１丁目１番地 工業技 術院化学技術研究所内 審査官 星野 紹英 (56)参考文献 特開 平５−345825（ＪＰ，Ａ) 特開 平５−85719（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07F 7/08 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masato Tanaka 1-1-1 Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Yuko Uchimaru 1-1-1 Higashi, Tsukuba, Ibaraki Pref. Examiner in the Technical Research Laboratory Shohide Hoshino (56) References JP-A-5-345825 (JP, A) JP-A-5-85719 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) ) C07F 7/08 CA (STN) REGISTRY (STN)
Claims (2)
特徴とする請求項１に記載の環状ビスヒドロシリル化合
物の製造方法。2. Chemical formula (2) The method for producing a cyclic bishydrosilyl compound according to claim 1, wherein the compound represented by the formula (1) is reacted with a metal hydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27460692A JP3249966B2 (en) | 1992-10-13 | 1992-10-13 | Cyclic bishydrosilyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27460692A JP3249966B2 (en) | 1992-10-13 | 1992-10-13 | Cyclic bishydrosilyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06128272A JPH06128272A (en) | 1994-05-10 |
| JP3249966B2 true JP3249966B2 (en) | 2002-01-28 |
Family
ID=17544079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27460692A Expired - Lifetime JP3249966B2 (en) | 1992-10-13 | 1992-10-13 | Cyclic bishydrosilyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3249966B2 (en) |
-
1992
- 1992-10-13 JP JP27460692A patent/JP3249966B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06128272A (en) | 1994-05-10 |
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