JP5321414B2 - Method for producing dimethylvinylsilyl triflate - Google Patents
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本発明は、ジメチルビニルシリルトリフラートの製造方法に関する。 The present invention relates to a method for producing dimethylvinylsilyl triflate.
ジメチルビニルシリルトリフラート、及びこれが含まれるトリオルガノシリルトリフラートは強力なシリル化能を有するシリル化剤である。この特性は、シランカップリング剤、ガラス繊維への処理、合成樹脂塗料、接着剤、無機質の充填剤、研削剤などに応用されている。また、アルコール、カルボン酸、アミン、メルカプタン等の活性水素を持つ有機化合物と容易に反応し、その化合物の安定性の向上、精製の簡便化、合成反応時における収率の向上をもたらすだけではなく、強力なルイス酸として医薬、農薬、香料等のファインケミカル製造に用いられている。 Dimethylvinylsilyl triflate and triorganosilyl triflate containing the same are silylating agents having a strong silylation ability. This characteristic is applied to silane coupling agents, processing to glass fibers, synthetic resin paints, adhesives, inorganic fillers, abrasives, and the like. In addition, it easily reacts with organic compounds with active hydrogen such as alcohols, carboxylic acids, amines, mercaptans, etc., not only improving the stability of the compounds, simplifying the purification, and improving the yield during the synthesis reaction. It is used as a powerful Lewis acid for the production of fine chemicals such as pharmaceuticals, agricultural chemicals and fragrances.
従来よく用いられている方法として、トリアルキルシリルトリフラート、特にトリメチルシリルトリフラート及びｔｅｒｔ−ブチルジメチルシリルトリフラートは、以下の方法により合成されている。
（１）トリアルキルクロロシランとトリフルオロメタンスルホン酸を脱塩酸条件下で反応させ、蒸留により目的物を得る方法。
（２）強酸性条件下、脱離しやすいフェニル基やビニル基等のオルガノ基（特に、芳香族基や脂肪族不飽和基）を有するテトラオルガノシランとトリフルオロメタンスルホン酸を反応させ、選択的にオルガノ基脱離反応を行い、蒸留により目的物を得る方法。
As a conventionally used method, trialkylsilyl triflate, particularly trimethylsilyl triflate and tert-butyldimethylsilyl triflate, are synthesized by the following method.
(1) A method in which a trialkylchlorosilane and trifluoromethanesulfonic acid are reacted under dehydrochlorination conditions to obtain a target product by distillation.
(2) By reacting tetraorganosilane having an organo group (especially aromatic group or aliphatic unsaturated group) such as phenyl group or vinyl group which is easily eliminated under strongly acidic conditions, trifluoromethanesulfonic acid is selectively reacted. A method in which an organogroup elimination reaction is carried out to obtain the desired product by distillation.
しかしながら、ジメチルビニルシリルトリフラートなど、シリル基上の置換基としてアルケニル基等の脂肪族不飽和基を有するトリオルガノシリルトリフラートの合成に上記方法を適応しようとすると、トリフルオロメタンスルホン酸と塩酸が共存する強酸条件下反応となるために、ビニル基等のアルケニル基が脱離してしまい、合成が困難であった。 However, when the above method is applied to the synthesis of triorganosilyl triflate having an aliphatic unsaturated group such as alkenyl group as a substituent on the silyl group such as dimethylvinylsilyl triflate, trifluoromethanesulfonic acid and hydrochloric acid coexist. Since the reaction is carried out under strong acid conditions, alkenyl groups such as vinyl groups are eliminated, making synthesis difficult.
そこで、トリフルオロメタンスルホン酸ではなく、トリフルオロメタンスルホン酸銀をジエチルエーテル中、ジメチルビニルクロロシランと反応させる方法（非特許文献１：Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ １９８８， ７， ２１５８−２１６２．）がある。同方法では、安定的にジメチルビニルシリルトリフラートを得ることができるが、高価なトリフルオロメタンスルホン酸銀を用い、水分に不安定なジメチルビニルシリルトリフラートから塩化銀をろ過により取り除かなければならない。また、反応溶媒もジエチルエーテルであることから、工業的な生産には適しているとはいい難い。 Therefore, there is a method of reacting silver trifluoromethanesulfonate with dimethylvinylchlorosilane in diethyl ether instead of trifluoromethanesulfonic acid (Non-patent Document 1: Organometallics 1988, 7, 2158-2162.). In this method, dimethylvinylsilyl triflate can be stably obtained, but expensive silver trifluoromethanesulfonate must be used, and silver chloride must be removed from the water-unstable dimethylvinylsilyl triflate by filtration. Further, since the reaction solvent is also diethyl ether, it is difficult to say that it is suitable for industrial production.
本発明は、ジメチルビニルシリルトリフラートの製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing dimethylvinylsilyl triflate.
本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、トリフルオロメタンスルホン酸と１，３−ジビニル−１，１，３，３−テトラメチルジシラザンを反応させた中和塩を熱分解させ、アンモニア、ジメチルビニルシリルアミン又は１，３−ジビニル−１，１，３，３−テトラメチルジシラザンを留去させることにより、ジメチルシリルトリフラートが得られることを確認して、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a neutralized salt obtained by reacting trifluoromethanesulfonic acid with 1,3-divinyl-1,1,3,3-tetramethyldisilazane. After confirming that dimethylsilyl triflate is obtained by pyrolyzing and distilling off ammonia, dimethylvinylsilylamine or 1,3-divinyl-1,1,3,3-tetramethyldisilazane, the present invention It came to make.
従って、本発明は、シリル基上の置換基としてアルケニル基等の脂肪族不飽和基を有するトリオルガノシリルトリフラートの代表的シリル化剤である下記のジメチルビニルシリルトリフラートの製造方法を提供する。
請求項１：
トリフルオロメタンスルホン酸と１，３−ジビニル−１，１，３，３−テトラメチルジシラザンとを混合して中和塩を生成させた後、該中和塩を熱分解させ、蒸留することを特徴とするジメチルビニルシリルトリフラートの製造方法。
請求項２：
トリフルオロメタンスルホン酸と１，３−ジビニル−１，１，３，３−テトラメチルジシラザンとの中和塩を２０〜２００℃の温度で熱分解する請求項１記載のジメチルビニルシリルトリフラートの製造方法。
Accordingly, the present invention provides the following method for producing dimethylvinylsilyl triflate, which is a typical silylating agent of triorganosilyl triflate having an aliphatic unsaturated group such as an alkenyl group as a substituent on the silyl group.
Claim 1:
Trifluoromethanesulfonic acid and 1,3-divinyl-1,1,3,3-tetramethyldisilazane are mixed to form a neutralized salt, and then the neutralized salt is thermally decomposed and distilled. A method for producing dimethylvinylsilyl triflate, which is characterized.
Claim 2:
The production of dimethylvinylsilyl triflate according to claim 1, wherein a neutralized salt of trifluoromethanesulfonic acid and 1,3-divinyl-1,1,3,3-tetramethyldisilazane is pyrolyzed at a temperature of 20 to 200 ° C. Method.
本発明の方法により製造されるジメチルビニルシリルトリフラートは、高価なトリフルオロメタンスルホン酸銀や引火点の低いジエチルエーテルを用いることなく、トリフルオロメタンスルホン酸から溶媒を用いることなく、安価に安定的にジメチルビニルシリルトリフラートを得ることができる。 The dimethylvinylsilyl triflate produced by the method of the present invention can be stably and inexpensively used without using an expensive silver trifluoromethanesulfonate or diethyl ether having a low flash point and without using a solvent from trifluoromethanesulfonic acid. Vinylsilyl triflate can be obtained.
本発明のジメチルビニルシリルトリフラートの製造方法は、下記に示すようにトリフルオロメタンスルホン酸ＣＦ3ＳＯ3Ｈと下記式
ここで、上記中和塩を得るためのトリフルオロメタンスルホン酸と１，３−ジビニル−１，１，３，３−テトラメチルジシラザンとの混合は、通常、室温下、具体的には−３０〜５０℃、特に０〜３５℃で行われる。混合時間は、通常１分〜２４時間、特に２分〜１２時間である。混合割合は、トリフルオロメタンスルホン酸１モルに対して１，３−ジビニル−１，１，３，３−テトラメチルジシラザンをほぼ等モル量、例えば０．８〜１．３モル、好ましくは１．０〜１．２モル程度とすることができる。また、雰囲気は１，３−ジビニル−１，１，３，３−テトラメチルジシラザン等の加水分解を防ぐために、例えば、窒素、ネオン、アルゴン等の不活性ガス雰囲気下であることが好ましい。 Here, the mixture of trifluoromethanesulfonic acid and 1,3-divinyl-1,1,3,3-tetramethyldisilazane to obtain the neutralized salt is usually at room temperature, specifically -30. It is carried out at -50 ° C, especially 0-35 ° C. The mixing time is usually 1 minute to 24 hours, particularly 2 minutes to 12 hours. The mixing ratio is approximately equimolar amount of 1,3-divinyl-1,1,3,3-tetramethyldisilazane, for example, 0.8 to 1.3 mol, preferably 1 with respect to 1 mol of trifluoromethanesulfonic acid. It can be about 0.0-1.2 mol. In order to prevent hydrolysis of 1,3-divinyl-1,1,3,3-tetramethyldisilazane or the like, the atmosphere is preferably an inert gas atmosphere such as nitrogen, neon, or argon.
トリフルオロメタンスルホン酸と１，３−ジビニル−１，１，３，３−テトラメチルジシラザンの中和塩を熱分解する温度は２０〜２００℃、好ましくは５０〜１９０℃、より好ましくは１００〜１７０℃である。なお、この熱処理（熱分解）時間は通常５分〜２４時間である。また、雰囲気は加水分解を防ぐために、前記と同様の不活性ガス雰囲気下であることが好ましい。加熱条件下に、減圧や窒素パージ、その他これに相当する手段を用いてもよい。 The temperature for thermally decomposing the neutralized salt of trifluoromethanesulfonic acid and 1,3-divinyl-1,1,3,3-tetramethyldisilazane is 20 to 200 ° C., preferably 50 to 190 ° C., more preferably 100 to 170 ° C. The heat treatment (thermal decomposition) time is usually 5 minutes to 24 hours. In order to prevent hydrolysis, the atmosphere is preferably an inert gas atmosphere similar to that described above. Under heating conditions, reduced pressure, nitrogen purge, or other equivalent means may be used.
熱分解により発生したジメチルビニルシリルアミン二分子の縮合と共にアンモニアと１，３−ジビニル−１，１，３，３−テトラメチルジシラザンが生成する。これらの副生物のうち、アンモニアは容易に揮発してしまうが、１，３−ジビニル−１，１，３，３−テトラメチルジシラザンと目的物であるジメチルビニルシリルトリフラートの沸点が近いため、精留を行って１，３−ジビニル−１，１，３，３−テトラメチルジシラザンを除去する必要がある。 Ammonia and 1,3-divinyl-1,1,3,3-tetramethyldisilazane are produced together with the condensation of two dimethylvinylsilylamine molecules generated by thermal decomposition. Among these by-products, ammonia easily volatilizes, but the boiling points of 1,3-divinyl-1,1,3,3-tetramethyldisilazane and the target product, dimethylvinylsilyl triflate, are close, It is necessary to perform rectification to remove 1,3-divinyl-1,1,3,3-tetramethyldisilazane.
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１］
ジメチルビニルシリルトリフラートを下記方法で合成した。
１００ｍＬの三口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシラザン６７．９１ｇ（０．３７モル）を入れ、窒素ガス雰囲気下で、トリフルオロメタンスルホン酸４９．９３ｇ（０．３３モル）を滴下し、透明な液体を得た。１００ｍＬ三口フラスコに、ト字管、温度計、冷却管等の蒸留装置を組み、窒素ガス雰囲気下で加熱を行った。加熱によりアミン臭気体が発生した。気体の発生が止まったところで、常圧蒸留（沸点１３０〜１４０℃）によりジメチルビニルシリルトリフラート５６．６ｇ、収率７２．６％を得た。
1Ｈ−ＮＭＲ（σ，３００ＭＨｚ，ＣＤＣｌ3）：６．０２−５．５９（ｍ，３Ｈ），０．１６（ｓ，６Ｈ）．
[Example 1]
Dimethylvinylsilyl triflate was synthesized by the following method.
In a 100 mL three-necked flask, 67.91 g (0.37 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisilazane was placed, and under a nitrogen gas atmosphere, 49.93 g (0 .33 mol) was added dropwise to obtain a transparent liquid. A 100 mL three-necked flask was combined with a distillation apparatus such as a T-tube, a thermometer, and a cooling tube, and heated in a nitrogen gas atmosphere. An amine odor gas was generated by heating. When gas generation stopped, atmospheric distillation (boiling point 130-140 ° C.) gave 56.6 g of dimethylvinylsilyl triflate, yield 72.6%.
1 H-NMR (σ, 300 MHz, CDCl 3 ): 6.02-5.59 (m, 3H), 0.16 (s, 6H).
［比較例１］
ジメチルビニルシリルトリフラートを下記方法で合成を試みた。
１００ｍＬの三口フラスコにジメチルビニルクロロシラン４４．６６ｇ（０．３７モル）を入れ、窒素ガス雰囲気下で、トリフルオロメタンスルホン酸４９．９３ｇ（０．３３モル）を滴下し、気体の発生を確認した。ガスクロマトグラフィーによる成分分析を行ったところ、複数の化合物が確認され、効率よくジメチルビニルシリルトリフラートを得ることができないことを確認した。
[Comparative Example 1]
Synthesis of dimethylvinylsilyl triflate was attempted by the following method.
In a 100 mL three-necked flask, 44.66 g (0.37 mol) of dimethylvinylchlorosilane was added, and 49.93 g (0.33 mol) of trifluoromethanesulfonic acid was dropped in a nitrogen gas atmosphere, and gas generation was confirmed. When component analysis was performed by gas chromatography, a plurality of compounds were confirmed, and it was confirmed that dimethylvinylsilyl triflate could not be obtained efficiently.
［比較例２］
ジメチルビニルシリルトリフラートを下記方法で合成を試みた。
２００ｍＬの三口フラスコにジメチルビニルクロロシラン１３．２７ｇ（０．１１モル）、トリエチルアミン２０．３６ｇ（０．２０ｍｏｌ）、ヘキサン２２．８１ｇ（０．２６ｍｏｌ）を入れ、窒素ガス雰囲気下で、トリフルオロメタンスルホン酸１５．０６ｇ（０．１０ｍｏｌ）を滴下し、撹拌したところ、二相に分離した。ガスクロマトグラフィーによる各相の分析を行った結果、ジメチルビニルクロロシランは消費されておらず、トリエチルアミントリフルオロメタンスルホン酸塩が生成したことを確認した。
[Comparative Example 2]
Synthesis of dimethylvinylsilyl triflate was attempted by the following method.
A 200 mL three-necked flask is charged with 13.27 g (0.11 mol) of dimethylvinylchlorosilane, 20.36 g (0.20 mol) of triethylamine and 22.81 g (0.26 mol) of hexane, and trifluoromethanesulfonic acid in a nitrogen gas atmosphere. When 15.06 g (0.10 mol) was added dropwise and stirred, it was separated into two phases. As a result of analyzing each phase by gas chromatography, it was confirmed that dimethylvinylchlorosilane was not consumed and triethylamine trifluoromethanesulfonate was formed.
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