JPH06345779A - Organosilione compound having oxygen-containing ring and its production - Google Patents
Organosilione compound having oxygen-containing ring and its productionInfo
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- JPH06345779A JPH06345779A JP5140296A JP14029693A JPH06345779A JP H06345779 A JPH06345779 A JP H06345779A JP 5140296 A JP5140296 A JP 5140296A JP 14029693 A JP14029693 A JP 14029693A JP H06345779 A JPH06345779 A JP H06345779A
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性及び耐燃焼性材
料の原料として有用な、従来になかった新しい環状有機
ケイ素化合物とその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic organosilicon compound, which has never been used before, and is useful as a raw material for heat resistant and flammable materials, and a process 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。2. Description of the Related Art This compound could not be produced because of no known effective synthetic means.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、新規な酸素
を含む環状の有機ケイ素化合物を合成することを目的と
する。The object of the present invention is to synthesize a novel oxygen-containing cyclic organosilicon compound.
【０００４】[0004]
【課題を解決するための手段】本発明は、化学式（１）
［化３］The present invention provides a compound represented by the chemical formula (1)
[Chemical 3]
【０００５】[0005]
【化３】 （上式中ｎは１〜１０、R は炭素数１〜１０のアルキル
基、アルケニル基または低級アルキル基、低級アルケニ
ル基、低級アルコキシ基もしくはハロゲンで置換されて
いてもよいフェニル基である。）で表される化合物であ
る。R は例えば-CH3, -C2H5, -C3H7, -CH(CH3)2, -C4H
9, -CH=CH2, -CH2-CH=CH2,-C6H13, -C8H17, -C10H21, -
C6H5, -C6H4(CH3), -C6H4(CH=CH2), -C6H4(OCH3),-C6H4
Brなどである。また本発明は、化学式（２）［化４］[Chemical 3] (In the above formula, n is 1 to 10 and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) Is a compound represented by. R is for example -CH 3, -C 2 H 5, -C 3 H 7, -CH (CH 3) 2, -C 4 H
9 , -CH = CH 2 , -CH 2 -CH = CH 2 , -C 6 H 13 , -C 8 H 17 , -C 10 H 21 ,-
C 6 H 5 ,, -C 6 H 4 (CH 3 ), -C 6 H 4 (CH = CH 2 ), -C 6 H 4 (OCH 3 ), -C 6 H 4
Br and so on. Further, the present invention provides the chemical formula (2) [Chemical Formula 4]
【０００６】[0006]
【化４】 （上式中ｎは１〜１０、R は炭素数１〜１０のアルキル
基、アルケニル基または低級アルキル基、低級アルケニ
ル基、低級アルコキシ基もしくはハロゲンで置換されて
いてもよいフェニル基である。）で表される環状の有機
ケイ素化合物を、触媒の存在下に水と反応させることを
特徴とする化学式（１）で表される含酸素環状有機ケイ
素化合物の製造方法である。化学式（１）で表される含
酸素環状有機ケイ素化合物は、化学式（３）［化５］[Chemical 4] (In the above formula, n is 1 to 10 and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) The method for producing an oxygen-containing cyclic organosilicon compound represented by the chemical formula (1) is characterized in that the cyclic organosilicon compound represented by the formula (1) is reacted with water in the presence of a catalyst. The oxygen-containing cyclic organosilicon compound represented by the chemical formula (1) has the chemical formula (3)
【０００７】[0007]
【化５】 （上式中ｎは１〜１０、R は炭素数１〜１０のアルキル
基、アルケニル基または低級アルキル基、低級アルケニ
ル基、低級アルコキシ基もしくはハロゲンで置換されて
いてもよいフェニル基である。）により製造される。化
学式（１）で表される化合物を製造するのに必要な化学
式（２）で表される化合物とその製造法については本発
明者らが別に出願中である。[Chemical 5] (In the above formula, n is 1 to 10 and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) Manufactured by. The present inventors have separately filed a patent for the compound represented by the chemical formula (2) necessary for producing the compound represented by the chemical formula (1) and the production method thereof.
【０００８】化学式（１）で表される化合物を製造する
際に用いる触媒は白金、パラジウムまたはルテニウムの
錯体である。具体例としては白金触媒として、Pt(db
a)2、Pt(CH2=CH2)(PPh3)2、PtCl2(PPh3)2、PtCl2(PO3C6
H11)2、Pt(PPh3)4、Pt(PO3C6H11)4、Pt(CO)2(PPh3)2、P
t(PhCCPh)(PPh3)2、Pt(C8H12)2、H2PtCl6、パラジウム
触媒として、Pd(dba)2、Pd(CH2=CH2)(PPh3)2、Pd(PO3C6
H11)2、Pd(CH2=CH2)(PO3C6H11)2、Pd(PPh3)4、Pd(PO3C6
H11)4、PdCl2、Pd(CH3COO)2、ルテニウム触媒として、R
uCl2(PPh3)3、RuCl2(PO3C6H11)3、RuCl2(CO)3、Ru3(CO)
12などが挙げられる。特に好ましくは、Pt(dba)2、Pt(C
H2=CH2)(PPh3)2、Ru3(CO)12である。またこれらの触媒
は助触媒として触媒の１〜１０等量のNEt3、PPh3等の配
位子を加えて用いてもよい。例を挙げれば、PtCl2(PP
h3)2にNEt3を２等量加えて用いる、Pd(dba)2にPPh3を２
等量加えて用いる等である。The catalyst used in producing the compound represented by the chemical formula (1) is a complex of platinum, palladium or ruthenium. As a specific example, Pt (db
a) 2 , Pt (CH 2 = CH 2 ) (PPh 3 ) 2 , PtCl 2 (PPh 3 ) 2 , PtCl 2 (PO 3 C 6
H 11 ) 2 , Pt (PPh 3 ) 4 , Pt (PO 3 C 6 H 11 ) 4 , Pt (CO) 2 (PPh 3 ) 2 , P
t (PhCCPh) (PPh 3) 2, Pt (C 8 H 12) 2, H 2 PtCl 6, as a palladium catalyst, Pd (dba) 2, Pd (CH 2 = CH 2) (PPh 3) 2, Pd ( PO 3 C 6
H 11) 2, Pd (CH 2 = CH 2) (PO 3 C 6 H 11) 2, Pd (PPh 3) 4, Pd (PO 3 C 6
H 11 ) 4 , PdCl 2 , Pd (CH 3 COO) 2 , as a ruthenium catalyst, R
uCl 2 (PPh 3 ) 3 , RuCl 2 (PO 3 C 6 H 11 ) 3 , RuCl 2 (CO) 3 , Ru 3 (CO)
12 and so on. Particularly preferably, Pt (dba) 2 and Pt (C
H 2 = CH 2 ) (PPh 3 ) 2 and Ru 3 (CO) 12 . Further, these catalysts may be used as a cocatalyst by adding 1 to 10 equivalents of a ligand such as NEt 3 or PPh 3 to the catalyst. For example, PtCl 2 (PP
Use 2 equivalents of NEt 3 to h 3 ) 2 , and use PPh 3 to Pd (dba) 2 2
It is used by adding an equal amount.
【０００９】製造法を説明する。反応容器内に化学式
（２）で表される環状化合物、水、触媒および必要に応
じて溶媒を仕込む。これらの反応容器への仕込みの順序
は特に限定するものではない。これらを同時に、あるい
は原料や触媒ないしは両方を反応中に連続してもしくは
断続的に反応容器内に供給してもよい。反応容器内は反
応前に高純度窒素、高純度アルゴン等の不活性ガスで置
換することが好ましい。反応容器を所定の反応温度に制
御しつつ、攪拌しながら所定の時間反応させる。目的の
化合物は反応液からデカンテーション、濾過、溶媒によ
る抽出、蒸留、クロマトグラフィーなど通常の方法で容
易に分離精製することができる。The manufacturing method will be described. A cyclic compound represented by the chemical formula (2), water, a catalyst and, if necessary, a solvent are charged into a reaction vessel. The order of charging these reaction vessels is not particularly limited. These may be supplied to the reaction vessel at the same time, or the raw material and / or the catalyst may be continuously or intermittently supplied during the reaction. Before the reaction, the inside of the reaction vessel is preferably replaced with an inert gas such as high-purity nitrogen or high-purity argon. The reaction is performed for a predetermined time while stirring while controlling the reaction container to a predetermined reaction temperature. The desired compound can be easily separated and purified from the reaction solution by a usual method such as decantation, filtration, extraction with a solvent, distillation and chromatography.
【００１０】化学式（２）で表される環状化合物に対す
る触媒の量は化合物１ｍｏｌに対して０．０００１〜
０．５ｍｏｌ、より好ましくは０．００１〜０．１ｍｏ
ｌである。溶媒はベンゼンやトルエン等の芳香族系溶
剤、シクロヘキサンや正ヘプタン等の飽和炭化水素系溶
剤、ジエチルエーテルやテトラヒドロフラン等のエーテ
ル系溶剤等が有効に用いられる。化学式（２）で表され
る環状化合物に対する溶媒の量は、該化合物１ｍｍｏｌ
に対して０．２〜１００００ｍｌ、より好ましくは２〜
５０００ｍｌが適当である。The amount of the catalyst for the cyclic compound represented by the chemical formula (2) is 0.0001 to 1 mol of the compound.
0.5 mol, more preferably 0.001-0.1 mo
It is l. As the solvent, aromatic solvents such as benzene and toluene, saturated hydrocarbon solvents such as cyclohexane and normal heptane, ether solvents such as diethyl ether and tetrahydrofuran are effectively used. The amount of the solvent for the cyclic compound represented by the chemical formula (2) is 1 mmol of the compound.
0.2 to 10,000 ml, more preferably 2 to
5000 ml is suitable.
【００１１】反応に用いる水の量は化学式（２）で表さ
れる環状化合物１ｍｏｌに対して０．１〜１００ｍｏ
ｌ、より好ましくは１〜５０ｍｏｌが適当である。反応
温度は０℃〜２００℃、より好ましくは０℃〜１Ｏ０℃
である。反応時間は仕込んだ化合物や触媒の量にもよる
が１〜１００時間、より好ましくは１〜２０時間が適当
である。原料である化学式（２）で表される化合物が、
化学式（２）においてｎが大きい化合物ほど反応時間を
長くする必要がある。The amount of water used in the reaction is 0.1 to 100 mo with respect to 1 mol of the cyclic compound represented by the chemical formula (2).
1 and more preferably 1 to 50 mol. The reaction temperature is 0 ° C to 200 ° C, more preferably 0 ° C to 100 ° C.
Is. The reaction time is 1 to 100 hours, more preferably 1 to 20 hours, though it depends on the amounts of the compound and the catalyst charged. The compound represented by the chemical formula (2), which is a raw material,
In the chemical formula (2), it is necessary to increase the reaction time for a compound having a larger n.
【００１２】[0012]
【実施例】以下に実施例に基づいて説明する。 実施例１ 化学式（１）においてｎ＝１、R がメチル基である多環
式有機ケイ素化合物の製造方法を示す。反応容器の上部
にコンデンサートを付け、１００ｍｌのガラス製反応容
器の内部に磁気攪拌子を設置する。反応容器内を高純度
窒素ガスで置換した。続いて反応容器内に化学式（２）
においてｎ＝１、R がメチル基である化合物１４．４ｍ
ｇ（０．０２４４ｍｍｏｌ）、ビス（ジベンジリデンア
セトン）白金（Pt(dba)2）触媒７．２ｍｇ（０．０１１
ｍｍｏｌ）、水１４．４μｌ（０．８ｍｍｏｌ）とテト
ラヒドロフラン３２ｍｌを仕込んだ。反応器を加温し、
還流下にて３時間、攪拌しながら反応を行った。反応終
了後、室温にまで反応容器を冷却し生成物をガスクロマ
トグラフィーで分析、定量した。さらに生成物を液体ク
ロマトグラフィーを用いて分取し、各成分の構造決定を
行った。EXAMPLES Examples will be described below. Example 1 A method for producing a polycyclic organosilicon compound in which n = 1 in the chemical formula (1) and R 2 is a methyl group will be described. A condenser is attached to the upper part of the reaction vessel, and a magnetic stir bar is installed inside the 100 ml glass reaction vessel. The inside of the reaction vessel was replaced with high-purity nitrogen gas. Then, in the reaction vessel, the chemical formula (2)
14.4m in which n = 1 and R is a methyl group
g (0.0244 mmol), bis (dibenzylideneacetone) platinum (Pt (dba) 2 ) catalyst 7.2 mg (0.011)
mmol), 14.4 μl of water (0.8 mmol) and 32 ml of tetrahydrofuran were charged. Warm the reactor,
The reaction was carried out with stirring under reflux for 3 hours. After completion of the reaction, the reaction vessel was cooled to room temperature, and the product was analyzed and quantified by gas chromatography. Furthermore, the product was fractionated using liquid chromatography, and the structure of each component was determined.
【００１３】目的の化学式（１）においてｎ＝１、R が
メチル基である多環式有機ケイ素化合物の収量は４．５
ｍｇで、その収率は３０％であった。得られた化合物の
形態は無色の結晶で、ＴＧＡ−ＤＴＡによれば２７５〜
３０５℃で該化合物は昇華した。元素分析の測定値は、
炭素５０．３４％（理論値５０．４２％）、水素８．２
６％（理論値８．１４％）であり、測定値は、測定誤差
の範囲で理論値とよく一致している。マススペクトル
（ＦＤーＭＳ）よりＭ+;は６１８であった。これは理論
値と一致している。In the target chemical formula (1), the yield of the polycyclic organosilicon compound in which n = 1 and R is a methyl group is 4.5.
In mg, the yield was 30%. The obtained compound is in the form of colorless crystals, and according to TGA-DTA, 275-
The compound sublimed at 305 ° C. The elemental analysis measurements are
Carbon 50.34% (theoretical 50.42%), hydrogen 8.2
6% (theoretical value 8.14%), and the measured value is in good agreement with the theoretical value within the range of measurement error. From the mass spectrum (FD-MS), M + ; was 618. This is in agreement with the theoretical value.
【００１４】赤外吸収スペクトルをＫＢｒ錠剤法により
測定した。主な吸収ピーク波数（単位はｃｍ-1）は、２
９５０、２９００（以上νC-H）、１４００、１２５０
（以上ArδCH3）、１１５０、１０９０であった。1Ｈ−
ＮＭＲを重クロロホルム溶液で測定した。化学シフト
（δ値）はＴＭＳを基準として、０．２６ｐｐｍ（２４
Ｈ、１重項、ケイ素上のメチル基の水素）、０．３７ｐ
ｐｍ（２４Ｈ、１重項、ケイ素上のメチル基の水素）、
７．７８ｐｐｍ（２Ｈ、１重項、ベンゼン環の水素）で
あった。13Ｃ−ＮＭＲを重クロロホルム溶液で測定し
た。化学シフト（δ値）はＴＭＳを基準として、０．０
９ｐｐｍ、１．３１ｐｐｍ（以上メチル基の炭素）、１
３６．９６ｐｐｍ、１４４．４２ｐｐｍ（以上ベンゼン
環中の炭素）、１８８．０３ｐｐｍ（ケイ素を含む６員
環中の炭素）であった。29Ｓｉ−ＮＭＲを重クロロホル
ム溶液で測定した。化学シフト（δ値）はＴＭＳを基準
として、−２６．６４ｐｐｍ（６員環中のケイ素）、１
８．６７ｐｐｍ（５員環中のケイ素）であった。The infrared absorption spectrum was measured by the KBr tablet method. The main absorption peak wave number (unit: cm -1 ) is 2
950, 2900 (above νC-H), 1400, 1250
(Above Ar δ CH 3 ) was 1150 and 1090. 1 H-
NMR was measured with a heavy chloroform solution. Chemical shift (δ value) is 0.26ppm (24
H, singlet, hydrogen of methyl group on silicon), 0.37p
pm (24H, singlet, hydrogen of a methyl group on silicon),
It was 7.78 ppm (2H, singlet, hydrogen of benzene ring). 13 C-NMR was measured with a heavy chloroform solution. Chemical shift (δ value) is 0.0 based on TMS
9ppm, 1.31ppm (above methyl group carbon), 1
It was 36.96 ppm, 144.42 ppm (the carbon in the benzene ring above), and 188.03 ppm (carbon in the 6-membered ring containing silicon). 29 Si-NMR was measured with a heavy chloroform solution. Chemical shift (δ value) is -26.64 ppm (silicon in 6-membered ring) based on TMS, 1
It was 8.67 ppm (silicon in a 5-membered ring).
【００１５】実施例２ 実施例１において、触媒としてビス（ジベンジリデンア
セトン）白金のかわりに、ルテニウムカルボニル（Ru
3(CO)12）を７．０ｍｇ（０．０１１ｍｍｏｌ）を用い
た以外は実施例１と同様に反応を行った。得られた目的
生成物は３.８ｍｇで、その収率は２５％であった。こ
の場合副生成物として化学式（４）［化６］Example 2 In Example 1, instead of bis (dibenzylideneacetone) platinum as a catalyst, ruthenium carbonyl (Ru) was used.
The reaction was performed in the same manner as in Example 1 except that 7.0 mg (0.011 mmol) of 3 (CO) 12 ) was used. The obtained target product was 3.8 mg, and the yield was 25%. In this case, as a by-product, chemical formula (4)
【００１６】[0016]
【化６】 で表される化合物の生成がかなり認められた（収率４３
％）。[Chemical 6] The formation of the compound represented by
%).
【００１７】[0017]
【発明の効果】本発明は、新しい環状有機ケイ素化合物
を提供するものである。この化合物は熱安定性に優れ、
耐熱性、耐燃焼性材料の構成成分としの利用が期待でき
る。The present invention provides a new cyclic organosilicon compound. This compound has excellent thermal stability,
It can be expected to be used as a constituent component of heat resistant and flammable materials.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井上 浩二 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 三塚 雅彦 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Masahiko Mitsuka 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chem Within the corporation
Claims (3)
基、アルケニル基または低級アルキル基、低級アルケニ
ル基、低級アルコキシ基もしくはハロゲンで置換されて
いてもよいフェニル基である。）で表される化合物。1. A chemical formula (1) [Chemical Formula 1] (In the above formula, n is 1 to 10 and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) The compound represented by.
基、アルケニル基または低級アルキル基、低級アルケニ
ル基、低級アルコキシ基もしくはハロゲンで置換されて
いてもよいフェニル基である。）で表される環状の有機
ケイ素化合物を、触媒の存在下に水と反応させることを
特徴とする請求項１記載の含酸素環状有機ケイ素化合物
の製造方法。2. A chemical formula (2) [Chemical Formula 2] (In the above formula, n is 1 to 10 and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) The method for producing an oxygen-containing cyclic organosilicon compound according to claim 1, wherein the cyclic organosilicon compound represented by the formula (1) is reacted with water in the presence of a catalyst.
ウムの錯体であることを特徴とする請求項２記載の製造
方法。3. The method according to claim 2, wherein the catalyst is a complex of platinum, palladium or ruthenium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5140296A JPH06345779A (en) | 1993-06-11 | 1993-06-11 | Organosilione compound having oxygen-containing ring and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5140296A JPH06345779A (en) | 1993-06-11 | 1993-06-11 | Organosilione compound having oxygen-containing ring and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06345779A true JPH06345779A (en) | 1994-12-20 |
Family
ID=15265490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5140296A Pending JPH06345779A (en) | 1993-06-11 | 1993-06-11 | Organosilione compound having oxygen-containing ring and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06345779A (en) |
-
1993
- 1993-06-11 JP JP5140296A patent/JPH06345779A/en active Pending
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