JP3937862B2 - Hydrosilylation catalyst and method for producing alkylsilane compound using the same - Google Patents
Hydrosilylation catalyst and method for producing alkylsilane compound using the same Download PDFInfo
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- JP3937862B2 JP3937862B2 JP2002039809A JP2002039809A JP3937862B2 JP 3937862 B2 JP3937862 B2 JP 3937862B2 JP 2002039809 A JP2002039809 A JP 2002039809A JP 2002039809 A JP2002039809 A JP 2002039809A JP 3937862 B2 JP3937862 B2 JP 3937862B2
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- -1 alkylsilane compound Chemical class 0.000 title claims description 46
- 239000003054 catalyst Substances 0.000 title claims description 40
- 238000006459 hydrosilylation reaction Methods 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 150000003058 platinum compounds Chemical class 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- FKHNZQFCDGOQGV-UHFFFAOYSA-N 2,3-dimethylquinoxaline Chemical compound C1=CC=C2N=C(C)C(C)=NC2=C1 FKHNZQFCDGOQGV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 6
- 150000004687 hexahydrates Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、不飽和炭化水素化合物とヒドロシラン化合物からヒドロシリル化反応により高付加価値なアルキルシラン化合物を製造する際に用いるヒドロシリル化触媒、およびこの触媒を用いるアルキルシラン化合物の製造方法に関するものである。
【０００２】
【従来技術】
ヒドロシリル化反応は、＞Ｃ＝Ｃ＜，−Ｃ≡Ｃ−，＞Ｃ＝Ｏ，＞Ｃ＝Ｎ−などの不飽和結合を有する化合物に、ヒドロシリル化合物が後者のＳｉ−Ｈ結合の開列を伴って付加する反応であり、有機合成上重要な反応の一つである。特に、炭素・炭素間二重結合を有する化合物のヒドロシリル化により得られるアルキルシラン化合物は、化学品の製造中間体として工業的に重要である。
【０００３】
炭素・炭素間二重結合を有する化合物とヒドロシラン化合物からヒドロシリル化反応によりアルキルシラン化合物を得る方法は、下記反応式[1]に示される通りである。
【０００４】
【化３】
炭素・炭素間二重結合を有する化合物がアリルクロライドのようなハロゲン化アリル化合物である場合は、３−ハロプロピルシラン化合物が生成するが、この反応生成物は接着剤やプラスチック架橋剤などの製造に用いられるきわめて重要な化合物である。アリルクロライドの場合の反応を下記反応式［２］で示す。
【０００６】
【化４】
一般に、ハロゲン化アリル化合物のヒドロシリル化により３−ハロプロピルシラン化合物を製造する際には、主に白金化合物、例えば塩化白金酸６水和物のイソプロパノ−ル溶液（Spier,s Catalyst）等が触媒として用いられるが、その際、ヒドロシリル化反応と同時に副反応が起こり、３−ハロプロピルシラン生成物の収率低下を招く。アリルクロライドの場合の副反応を下記反応式[3]に示す。
【０００８】
【化５】
特開平９−１５７２７６号公報には、その副反応を抑えるべく三級フォスフィンと塩化白金酸を触媒として用いてハロゲン化アリル化合物とヒドロシラン化合物から３−ハロプロピルシラン化合物を得る方法が記載されている。
【００１０】
また、特開平９−１９２４９４号公報には、同様に副反応を抑えるべく三級アミンと白金コロイドを触媒として用いてハロゲン化アリル化合物とヒドロシラン化合物から３−ハロプロピルシラン化合物を得る方法が記載されている。
【００１１】
これらの触媒を用いれば、三級フォスフィンを持たない塩化白金酸や三級アミンを持たない白金コロイドを触媒として使用した時と比べ、３−ハロプロピルシラン化合物の収率は向上するが副反応の割合は依然大きく、これらは３−ハロプロピルシラン化合物を高収率で得るにはまだ満足の行く触媒ではない。
【００１２】
【発明が解決しようとする課題】
反応式［２］で得られる３−ハロプロピルシラン化合物は、上述の如く接着剤やプラスチック架橋剤などの原料としてきわめて重要な化合物であるため、ヒドロシリル化反応における収率の向上はわずかであっても工業的には大きな意味があり、また、収率の向上は廃棄物の減少をもたらす点からも要望されている。
【００１３】
よって、本発明はヒドロシリル化反応における収率向上を達成することができる触媒を提供することを課題とする。
【００１４】
【課題を解決するための手段】
本発明の第１のものは、２，３−ジメチルキノキサリンと白金化合物とからなることを特徴とする、不飽和結合を有する化合物のヒドロシリル化触媒に関する。
白金化合物としては、塩化白金酸無水物、塩化白金酸６水和物等の塩化白金酸や、白金コロイドなどがよく用いられ、特に塩化白金酸６水和物が好ましい。
【００１５】
本発明の第２のものは、不飽和結合を有する化合物とヒドロシラン化合物を触媒の存在下に反応させてアルキルシラン化合物を製造するに当たり、該触媒として、下記一般式［Ｉ］
【化６】
で表される環状アミンと白金化合物とからなるヒドロシリル化触媒を用い、
反応前に不飽和結合を有する化合物に環状アミンと白金化合物を添加し、これらを含む混合液にヒドロシラン化合物を添加するか、反応前にヒドロシラン化合物に環状アミンと白金化合物を添加し、これらを含む混合液に不飽和化合物を添加するか、または、反応前に溶媒に環状アミンと白金化合物を添加し、これらを含む混合液に不飽和化合物とヒドロシラン化合物を添加することを特徴とするアルキルシラン化合物の製造方法に関する。
【００１６】
第２発明において、環状アミンとしては、キノキサリンや２，３−ジメチルキノキサリンなどがよく用いられ、特に２，３−ジメチルキノキサリンが好ましい。
【００１７】
第２発明においても、白金化合物としては、塩化白金酸無水物、塩化白金酸６水和物等の塩化白金酸や、白金コロイドなどがよく用いられ、特に塩化白金酸６水和物が好ましい。
【００１８】
上記ヒドロシリル化触媒の存在下に、不飽和結合を有する化合物とヒドロシラン化合物を反応させてアルキルシラン化合物を製造する。
【００１９】
本発明による触媒を用いるヒドロシリル化反応は、＞Ｃ＝Ｃ＜，−Ｃ≡Ｃ−，＞Ｃ＝Ｏ，＞Ｃ＝Ｎ−などの不飽和結合を有する化合物のヒドロシリル化に適用可能であるが、炭素・炭素間二重結合を有する化合物、とりわけ炭素・炭素間二重結合を有するハロゲン含有化合物、特にハロゲン化アリル化合物のヒドロシリル化に好適である。ハロゲン化アリル化合物のヒドロシリル化により、下記一般式［II］
【化７】
（式中、Xはハロゲン原子であり、R4、R5 、R6、 R7および R8は、互いに同一または異なり、水素原子またはアルキル基であり、R9、R10およびR11は、互いに同一または異なり、水素原子、ハロゲン原子、アルキル基またはアルコキシル基である）
で表される３−ハロプロピルシラン化合物が得られる。例えばアリルクロライドを本発明による触媒の存在下にヒドロシリル化することにより、上記反応式［２］で示すように、３−クロロプロピルトリクロロシランが得られる。この反応では上述したような副反応［３］を抑えて目的物を高収率で得ることができる。
【００２１】
環状アミンと 白金化合物とからなる触媒を反応系に存在させるには、ヒドロシリル化反応前に原料である不飽和結合を有する化合物に触媒を添加しておき、ついでここへヒドロシラン化合物を添加することが好ましい。場合によっては、反応前にヒドロシラン化合物に触媒を添加しておき、ついでここに不飽和化合物を添加してもよい。また、不飽和化合物とヒドロシラン化合物の混合溶液に触媒を添加してもよい。さらには反応液に触媒を添加しておき、ここに不飽和化合物とヒドロシラン化合物の混合溶液を添加してもよい。
【００２２】
触媒を構成する環状アミンと 白金化合物の比は、白金化合物中の白金１モルにつき環状アミン０．１〜３．０当量が好ましく、より好ましくは０．５〜２．０当量である。
【００２３】
反応系中の白金化合物の量は、ヒドロシラン化合物1モルに対して好ましくは１×１０−８〜１×１０−３当量、より好ましくは１×１０−６〜１×１０−４である。
【００２４】
本発明方法の好ましい実施形態は、ハロゲン化アリル化合物とヒドロシラン化合物を上記触媒の存在下にヒドロシリル化反応させて３−ハロプロピルシラン化合物を得る方法である。その反応では反応前に触媒をハロゲン化アリル化合物に添加しておき、ついでここへヒドロシラン化合物を添加することが好ましい。場合によっては、反応前にヒドロシラン化合物に触媒を添加しておき、ついでここにハロゲン化アリル化合物を添加してもよい。また、ハロゲン化アリル化合物とヒドロシラン化合物の混合溶液に触媒を添加してもよい。さらには反応液に触媒を添加しておき、ここにヒドロシラン化合物とハロゲン化アリル化合物の混合溶液を添加してもよい。
【００２５】
ハロゲン化アリル化合物とヒドロシラン化合物とを上記触媒の存在下にヒドロシリル化反応させる時の温度は、好ましくは２０℃〜２００℃、より好ましくは３０℃〜１５０℃である。
【００２６】
ハロゲン化アリル化合物とヒドロシラン化合物とを上記触媒の存在下にヒドロシリル化反応させる時の雰囲気および圧力は、好ましくは乾燥空気雰囲気下大気圧、より好ましくは窒素雰囲気下大気圧である。
【００２７】
【発明の効果】
本発明によれば、環状アミン［Ｉ］と白金化合物からなる触媒を用いることにより、副反応の割合を抑えることができる。よって、３−ハロプロピルシラン化合物のようなアルキルシラン化合物の収率を向上させることができると共に、廃棄物軽減に寄与することができる。
【００２８】
【発明の実施の形態】
以下に実施例を挙げて本発明を説明するが、本発明はこれらに限定されるものではない。反応操作は全て窒素雰囲気下にて行った。
【００２９】
実施例１
温度計、滴下ロ−トおよび−１０℃ブラインコンデンサ−を備え付けた５００ｍL ４つ口フラスコにアリルクロライド１２４．６ｇ（１．６３mol ）、０．１M 塩化白金酸６水和物のイソプロパノ−ル溶液 １４８μL （白金原子１．４８×１０−５mol ）および０．４M ２，３−ジメチルキノキサリンの イソプロパノ−ル溶液１８μL （０．７４×１０−５mol ）を入れ、マグネチックスタ−ラ−を用いて混合液を３０℃で３０分攪拌した。その後、温度を６０℃へ上げアリルクロライドを十分に還流させた後、トリクロロシラン２００．０ｇ（１．４８mol ）を２．５時間かけて滴下した。トリクロロシラン滴下中は反応液が還流するように加熱を続けた。トリクロロシラン滴下終了後３０分還流を続けて熟成し、トリクロロシランが消失したことをガスクロマトグラフィ−により確認した後に、生成物を蒸留により単離した。純度９９．７％の３−クロロプロピルトリクロロシランが２２９．８５ｇ（収率７３％）得られた。
【００３０】
実施例２
２，３−ジメチルキノキサリンの イソプロパノ−ル溶液に代えて同量のキノキサリンのイソプロパノ−ル溶液を用い、その他の点を実施例１と同じにして操作を繰返した。純度９９．５％の３−クロロプロピルトリクロロシランが２１９．６ｇ（収率７０％）得られた。
【００３１】
比較例１
２，３−ジメチルキノキサリンの イソプロパノール溶液を使用せず、その他の点を実施例１と同じにして操作を繰返した。純度９９．４％の３−クロロプロピルトリクロロシランが１５６．８ｇ（収率５５％）得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrosilylation catalyst used for producing a high value-added alkylsilane compound from an unsaturated hydrocarbon compound and a hydrosilane compound by a hydrosilylation reaction, and a method for producing an alkylsilane compound using this catalyst.
[0002]
[Prior art]
The hydrosilylation reaction involves a compound having an unsaturated bond, such as> C = C <, -C≡C-,> C = O,> C = N-, and the hydrosilyl compound is accompanied by the opening of the latter Si-H bond. This reaction is an important reaction in organic synthesis. In particular, an alkylsilane compound obtained by hydrosilylation of a compound having a carbon-carbon double bond is industrially important as an intermediate for producing a chemical product.
[0003]
A method for obtaining an alkylsilane compound from a compound having a carbon-carbon double bond and a hydrosilane compound by a hydrosilylation reaction is as shown in the following reaction formula [1].
[0004]
[Chemical 3]
When the compound having a carbon-carbon double bond is an allyl halide compound such as allyl chloride, a 3-halopropylsilane compound is produced, and this reaction product is used to produce an adhesive, a plastic cross-linking agent, etc. It is a very important compound used in The reaction in the case of allyl chloride is shown by the following reaction formula [2].
[0006]
[Formula 4]
Generally, when a 3-halopropylsilane compound is produced by hydrosilylation of an allyl halide compound, a platinum compound, for example, an isopropanol solution of chloroplatinic acid hexahydrate (Spier , s Catalyst) or the like is mainly used as a catalyst. In this case, a side reaction occurs simultaneously with the hydrosilylation reaction, resulting in a decrease in the yield of the 3-halopropylsilane product. The side reaction in the case of allyl chloride is shown in the following reaction formula [3].
[0008]
[Chemical formula 5]
JP-A-9-157276 describes a method for obtaining a 3-halopropylsilane compound from an allyl halide compound and a hydrosilane compound by using tertiary phosphine and chloroplatinic acid as a catalyst in order to suppress the side reaction. .
[0010]
JP-A-9-192494 also describes a method for obtaining a 3-halopropylsilane compound from an allyl halide compound and a hydrosilane compound using a tertiary amine and a platinum colloid as a catalyst in order to suppress side reactions. ing.
[0011]
When these catalysts are used, the yield of the 3-halopropylsilane compound is improved compared with the case where chloroplatinic acid without tertiary phosphine or platinum colloid without tertiary amine is used as a catalyst. The proportions are still large and these are not yet satisfactory catalysts for obtaining high yields of 3-halopropylsilane compounds.
[0012]
[Problems to be solved by the invention]
Since the 3-halopropylsilane compound obtained by the reaction formula [2] is a very important compound as a raw material for adhesives, plastic crosslinkers and the like as described above, the yield improvement in the hydrosilylation reaction is slight. However, there is a significant meaning industrially, and an improvement in yield is demanded from the viewpoint of reducing waste.
[0013]
Therefore, an object of the present invention is to provide a catalyst that can achieve an improvement in yield in the hydrosilylation reaction.
[0014]
[Means for Solving the Problems]
The first of the present invention relates to a hydrosilylation catalyst for a compound having an unsaturated bond, characterized by comprising 2,3-dimethylquinoxaline and a platinum compound.
As the platinum compound, chloroplatinic acid such as chloroplatinic anhydride and chloroplatinic acid hexahydrate, platinum colloid, and the like are often used, and chloroplatinic acid hexahydrate is particularly preferable.
[0015]
In the second aspect of the present invention, when a compound having an unsaturated bond and a hydrosilane compound are reacted in the presence of a catalyst to produce an alkylsilane compound, the catalyst is represented by the following general formula [I].
[Chemical 6]
Using a hydrosilylation catalyst comprising a cyclic amine represented by
Add cyclic amine and platinum compound to compound with unsaturated bond before reaction and add hydrosilane compound to mixed solution containing these, or add cyclic amine and platinum compound to hydrosilane compound before reaction An alkylsilane compound characterized in that an unsaturated compound is added to a liquid mixture, or a cyclic amine and a platinum compound are added to a solvent before the reaction, and an unsaturated compound and a hydrosilane compound are added to a liquid mixture containing them. It relates to the manufacturing method.
[0016]
In the second invention, as the cyclic amine, quinoxaline, 2,3-dimethylquinoxaline and the like are often used, and 2,3-dimethylquinoxaline is particularly preferable.
[0017]
Also in the second invention, as the platinum compound, chloroplatinic acid such as chloroplatinic acid anhydride and chloroplatinic acid hexahydrate, platinum colloid and the like are often used, and chloroplatinic acid hexahydrate is particularly preferable.
[0018]
In the presence of the hydrosilylation catalyst, an alkylsilane compound is produced by reacting a compound having an unsaturated bond with a hydrosilane compound.
[0019]
The hydrosilylation reaction using the catalyst according to the present invention is applicable to the hydrosilylation of a compound having an unsaturated bond such as> C═C <, —C≡C—,>C═O,> C═N—. It is suitable for hydrosilylation of a compound having a carbon-carbon double bond, particularly a halogen-containing compound having a carbon-carbon double bond, particularly an allyl halide compound. By hydrosilylation of an allyl halide compound, the following general formula [II]
[Chemical 7]
(In the formula, X is a halogen atom, R 4 , R 5 , R 6 , R 7 and R 8 are the same or different from each other, and are a hydrogen atom or an alkyl group, and R 9 , R 10 and R 11 are Are the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group)
The 3-halopropyl silane compound represented by these is obtained. For example, by hydrosilylation of allyl chloride in the presence of the catalyst according to the present invention, 3-chloropropyltrichlorosilane is obtained as shown in the above reaction formula [2]. In this reaction, the target product can be obtained in a high yield while suppressing the side reaction [3] described above.
[0021]
In order for a catalyst comprising a cyclic amine and a platinum compound to be present in the reaction system, the catalyst is added to the compound having an unsaturated bond as a raw material before the hydrosilylation reaction, and then a hydrosilane compound is added thereto. preferable. In some cases, a catalyst may be added to the hydrosilane compound before the reaction, and then an unsaturated compound may be added thereto. Moreover, you may add a catalyst to the mixed solution of an unsaturated compound and a hydrosilane compound. Furthermore, a catalyst may be added to the reaction solution, and a mixed solution of an unsaturated compound and a hydrosilane compound may be added thereto.
[0022]
The ratio of the cyclic amine constituting the catalyst to the platinum compound is preferably from 0.1 to 3.0 equivalents, more preferably from 0.5 to 2.0 equivalents, per mole of platinum in the platinum compound.
[0023]
The amount of the platinum compound in the reaction system is preferably 1 × 10 −8 to 1 × 10 −3 equivalent, more preferably 1 × 10 −6 to 1 × 10 −4 with respect to 1 mol of the hydrosilane compound.
[0024]
A preferred embodiment of the method of the present invention is a method for obtaining a 3-halopropylsilane compound by hydrosilylation reaction of an allyl halide compound and a hydrosilane compound in the presence of the above catalyst. In the reaction, it is preferable to add a catalyst to the allyl halide compound before the reaction, and then add the hydrosilane compound thereto. In some cases, a catalyst may be added to the hydrosilane compound before the reaction, and then the allyl halide compound may be added thereto. Moreover, you may add a catalyst to the mixed solution of an allyl halide compound and a hydrosilane compound. Furthermore, a catalyst may be added to the reaction solution, and a mixed solution of a hydrosilane compound and an allyl halide compound may be added thereto.
[0025]
The temperature for the hydrosilylation reaction between the halogenated allyl compound and the hydrosilane compound in the presence of the catalyst is preferably 20 ° C to 200 ° C, more preferably 30 ° C to 150 ° C.
[0026]
The atmosphere and pressure when the hydrosilylation reaction of the allyl halide compound and the hydrosilane compound in the presence of the catalyst is preferably atmospheric pressure in a dry air atmosphere, more preferably atmospheric pressure in a nitrogen atmosphere.
[0027]
【The invention's effect】
According to the present invention, by using a catalyst composed of cyclic amine [I] and a platinum compound, the ratio of side reactions can be suppressed. Therefore, the yield of the alkylsilane compound such as the 3-halopropylsilane compound can be improved, and the waste can be reduced.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. All reaction operations were performed under a nitrogen atmosphere.
[0029]
Example 1
In a 500 mL four-necked flask equipped with a thermometer, a dropping funnel and a −10 ° C. brine condenser, 124.6 g (1.63 mol) of allyl chloride, 148 μL of 0.1 M chloroplatinic acid hexahydrate in isopropanol (Platinum atom 1.48 × 10 −5 mol) and 0.4 μm of 2,3-dimethylquinoxaline isopropanol solution 18 μL (0.74 × 10 −5 mol) were put in, and a magnetic stirrer was used. The mixture was stirred at 30 ° C. for 30 minutes. Thereafter, the temperature was raised to 60 ° C. and allyl chloride was sufficiently refluxed, and then 200.0 g (1.48 mol) of trichlorosilane was added dropwise over 2.5 hours. During the dropwise addition of trichlorosilane, heating was continued so that the reaction solution was refluxed. After completion of the dropwise addition of trichlorosilane, aging was continued for 30 minutes. After confirming that trichlorosilane had disappeared by gas chromatography, the product was isolated by distillation. 229.85 g (yield 73%) of 3-chloropropyltrichlorosilane having a purity of 99.7% was obtained.
[0030]
Example 2
The same procedure as in Example 1 was repeated except that the same amount of the isopropanol solution of quinoxaline was used instead of the isopropanol solution of 2,3-dimethylquinoxaline. 219.6 g (yield 70%) of 3-chloropropyltrichlorosilane having a purity of 99.5% was obtained.
[0031]
Comparative Example 1
The operation was repeated in the same manner as in Example 1 except that an isopropanol solution of 2,3-dimethylquinoxaline was not used. 156.8 g (yield 55%) of 3-chloropropyltrichlorosilane having a purity of 99.4% was obtained.
Claims (10)
で表される環状アミンと白金化合物とからなるヒドロシリル化触媒を用い、
反応前に不飽和結合を有する化合物に環状アミンと白金化合物を添加し、これらを含む混合液にヒドロシラン化合物を添加するか、反応前にヒドロシラン化合物に環状アミンと白金化合物を添加し、これらを含む混合液に不飽和化合物を添加するか、または、反応前に溶媒に環状アミンと白金化合物を添加し、これらを含む混合液に不飽和化合物とヒドロシラン化合物を添加することを特徴とするアルキルシラン化合物の製造方法。In producing an alkylsilane compound by reacting a compound having an unsaturated bond with a hydrosilane compound in the presence of a catalyst, the catalyst is represented by the following general formula [I].
Using a hydrosilylation catalyst comprising a cyclic amine represented by
Add cyclic amine and platinum compound to compound with unsaturated bond before reaction and add hydrosilane compound to mixed solution containing these, or add cyclic amine and platinum compound to hydrosilane compound before reaction An alkylsilane compound characterized in that an unsaturated compound is added to a liquid mixture, or a cyclic amine and a platinum compound are added to a solvent before the reaction, and an unsaturated compound and a hydrosilane compound are added to a liquid mixture containing them. Manufacturing method.
で表される３−ハロプロピルシラン化合物であることを特徴とする請求項８記載のアルキルシラン化合物の製造方法。The halogen-containing compound having a carbon-carbon double bond is an allyl halide compound, and the alkylsilane compound is represented by the following general formula [II]:
The method for producing an alkylsilane compound according to claim 8 , wherein the compound is a 3-halopropylsilane compound represented by the formula:
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