JP3671281B2 - Method for producing trimethylsilyl azide - Google Patents
Method for producing trimethylsilyl azide Download PDFInfo
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- JP3671281B2 JP3671281B2 JP22595196A JP22595196A JP3671281B2 JP 3671281 B2 JP3671281 B2 JP 3671281B2 JP 22595196 A JP22595196 A JP 22595196A JP 22595196 A JP22595196 A JP 22595196A JP 3671281 B2 JP3671281 B2 JP 3671281B2
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- azide
- trimethylsilyl
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- trimethylsilyl azide
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- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 16
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical group [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VBCKYDVWOPZOBA-UHFFFAOYSA-N 2-(oxolan-2-ylmethoxymethyl)oxolane Chemical compound C1CCOC1COCC1CCCO1 VBCKYDVWOPZOBA-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XFWZWUGZZIYSLL-UHFFFAOYSA-L tributyl-[16-(tributylazaniumyl)hexadecyl]azanium;dibromide Chemical compound [Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC XFWZWUGZZIYSLL-UHFFFAOYSA-L 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
Description
【０００１】
【発明の属する技術分野】
本発明は、アミノ化剤、アジド化剤あるいはヘテロ環化合物の合成に有用な、トリメチルシリルアジドを製造する方法に関する。
【０００２】
【従来の技術】
従来、トリメチルシリルアジドを製造する方法としては、トリメチルシリルクロライドとアジ化水素の無機塩とを、溶媒中で反応させる方法が知られている［シンセシス（Ｓｙｎｔｈｅｓｉｓ）２，１０６〜１０７（１９８８）］［オルガニック・シンセシス（Ｏｒｇ．Ｓｙｎｔｈ．）５０，１０７〜（１９７０）］［ジャーナル・オブ・ケミカル・フィジックス（Ｊ．Ｃｈｅｍ．Ｐｈｙｓ．）２８，１９６２〜１９６４（１９５８）］。
【０００３】
また、トリメチルシリルクロライドとマクロポーラスポリマーに担持させたアジ化水素の無機塩とを、溶媒中で反応させる方法も知られている［特開平１ー１４３８７８］。
【０００４】
しかしながら、上記の製法においては次の（１）〜（２）のような問題がある。
【０００５】
（１） 反応完結までに６〜６０時間という長時間を必要としている。又、反応時間を短縮するためには、アジ化水素の無機塩をマクロポーラスポリマーに担持させて使用する必要がある。
【０００６】
（２） 生成したトリメチルシリルアジドの単離方法としては、蒸留による方法しかなく、その蒸留ではトリメチルシリルアジドと溶媒とが十分に分離せず、トリメチルシリルアジド中に溶媒が混入するために純度が低下する。すなわち、高純度なトリメチルシリルアジドを得るには、多段数の精密蒸留装置が必要であり、そのための設備が必要となり、製造コストの上昇の原因となる。
【０００７】
【発明が解決しようとする課題】
本発明の課題は、上記した従来技術の問題点を解決し、トリメチルシリルクロライドから、容易にしかも高収率で、高品質のトリメチルシリルアジドを製造する方法を提供する。
【０００８】
【課題を解決するための手段】
上記の課題を解決するために、本発明者らは鋭意研究したところ、相間移動触媒を用いることによって、無溶媒で且つ短時間でトリメチルシリルアジドが得られることを見出した。さらに、無溶媒で反応を行うことにより、生成したトリメチルシリルアジドの単離においては多段数の精密蒸留装置を必要せず、単蒸留あるいは濾過により、容易に、高純度なトリメチルシリルアジドが得られることを見出し、本発明を完成させるに至った。
【０００９】
すなわち、本発明は、下記式（１）で表されるトリメチルシリルクロライドと下記式（２）で表されるアジ化水素の無機塩とを、相間移動触媒の存在下、無溶媒で反応させることを特徴とする、下記式（３）で表されるトリメチルシリルアジドを容易に、高純度で単離することのできる製造方法である。
（ＣＨ3）3ＳｉＣｌ （１）
Ｍ（Ｎ3）n （２）
（式中、Ｍはアルカリ金属またはアルカリ土類金属であり、ｎは１または２である。）
（ＣＨ3）3ＳｉＮ3 （３）
【００１０】
【発明の実施の形態】
以下に本発明を詳細に説明する。
【００１１】
本発明の製造方法において用いうるアジ化水素の無機塩の具体例としては、ナトリウム、カリウム、リチウム、カルシウム、マグネシウム等のアルカリ金属またはアルカリ土類金属のアジ化物が挙げられる。好ましくはアジ化ナトリウムが工業的に好適である。これらのアジ化水素の無機塩の使用量は、トリメチルシリルクロライド１モルに対して、アジ化水素換算で通常１．０〜１．５モルの範囲、好ましくは１．０〜１．０５モルである。
【００１２】
また、本発明の製造方法において用いうる相間移動触媒の具体例としては、従来公知の４級アンモニウム塩、４級アンモニウム塩源となり得る３級アミン、ポリエーテル化合物を使用することができる。例えば、テトラエチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、ヘキサデシルトリブチルアンモニウムブロマイド、メチルトリオクチルアンモニウムクロライド、トリエチルアミン塩酸塩、ポリエチレングリコールメチルエーテル、ポリエチレングリコールテトラヒドロフルフリルエーテル、ポリエチレングリコールジステアリン酸エステル、ポリエチレングリコール、および、ポリエチレングリコールメチルエーテル、ポリエチレングリコールテトラヒドロフルフリルエーテル、ポリエチレングリコールのシリル化物等を挙げられるが、これらに限定されるものではない。好ましい相間移動触媒は、工業的で安価な点より、ポリエチレングリコールおよびそのシリル化物である。これらの相間移動触媒の使用量は、トリメチルシリルクロライドに対し、通常０．１重量％以上、好ましくは２〜６重量％の範囲である。
【００１３】
反応温度は、通常０〜６０℃、好ましくは４５〜５５℃の範囲である。また、反応時間は触媒の添加量、反応温度により影響を受けるが、通常０．５〜２０時間、好ましくは１〜１０時間である。
【００１４】
反応終了後にトリメチルシリルアジドを単離するには、蒸留あるいは無機塩等を濾過によって除けばよい。単離は、溶媒を使用していないのでトリメチルシリルアジドへの溶媒の混入がなく、容易に、高純度なトリメチルシリルアジドを得ることができる。
【００１５】
従って、本発明は、従来の溶媒を用いる合成法に比べて、短時間の反応で、高純度なトリメチルシリルアジドを製造するのに非常に有利な方法である。
【００１６】
【実施例】
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらに限定されるものではない。
【００１７】
実施例１
還流冷却器、温度計および撹拌機を設けたフラスコに、トリメチルシリルクロライド４２３．７ｇ（３．９モル）、アジ化ナトリウム２６６．２ｇ（４．１モル）、および、ポリエチレングリコール８．５ｇを入れ、５０〜５５℃に加熱して１時間反応させた。反応終了後、内温を９６〜９７℃まで昇温し、トリメチルシリルアジドを蒸留によって、単離した。その結果、無色透明液体のトリメチルシリルアジド３９２．３ｇ（３．４モル）を得た。これはトリメチルシリルクロライドに対して収率８７．３％に相当する。また、ガスクロマトグラフィ−（ＧＣ）分析による純度は９７．９％であった。
【００１８】
実施例２
実施例１と同様な装置に、トリメチルシリルクロライド１０．９ｇ（０．１モル）、アジ化ナトリウム６．８ｇ（０．１１モル）、および、テトラエチルアンモニウムブロマイド０．４４ｇを入れ、５５〜６０℃に加熱して５時間反応させた。反応終了後、内温を９７〜９８℃まで昇温し、トリメチルシリルアジドを蒸留によって、単離した。その結果、無色透明液体のトリメチルシリルアジド９．９ｇ（０．８６モル）を得た。これはトリメチルシリルクロライドに対して収率８６．１％に相当する。また、ＧＣ分析による純度は９６．７％であった。
【００１９】
実施例３
実施例１と同様な装置に、トリメチルシリルクロライド２１．８ｇ（０．２モル）、アジ化ナトリウム１３．４ｇ（０．２１モル）、および、テトラブチルアンモニウムブロマイド０．６６ｇを入れ、５０〜５５℃に加熱して９時間反応させた。反応終了後、内温を９６〜９７℃まで昇温し、トリメチルシリルアジドを蒸留によって、単離した。その結果、無色透明液体のトリメチルシリルアジド２０．６ｇ（０．１８モル）を得た。これはトリメチルシリルクロライドに対して収率８９．６％に相当する。また、ＧＣ分析による純度は９７．１％であった。
【００２０】
実施例４
実施例１と同様な装置に、トリメチルシリルクロライド２１．８ｇ（０．２モル）、アジ化ナトリウム１３．４ｇ（０．２１モル）、および、トリエチルアミン塩酸塩１．３ｇを入れ、５０〜５５℃に加熱して１０時間反応させた。反応終了後、内温を９４〜９７℃まで昇温し、トリメチルシリルアジドを蒸留によって、単離した。その結果、無色透明液体のトリメチルシリルアジド１９．６ｇ（０．１７モル）を得た。これはトリメチルシリルクロライドに対して収率８５．０％に相当する。また、ＧＣ分析による純度は９６．５％であった。
【００２１】
【発明の効果】
本発明の製造方法によれば、トリメチルシリルクロライドから溶媒を使用することなく、トリメチルシリルアジドを製造し、容易、且つ高純度で単離することができる。従って、工業的に有利かつ好適な方法である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing trimethylsilyl azide useful for the synthesis of aminating agents, azidating agents or heterocyclic compounds.
[0002]
[Prior art]
Conventionally, as a method for producing trimethylsilyl azide, a method in which trimethylsilyl chloride and an inorganic salt of hydrogen azide are reacted in a solvent is known [Synthesis 2 , 106-107 (1988)] [Orga. Nick Synthesis (Org. Synth.) 50 , 107- (1970)] [Journal of Chemical Physics (J. Chem. Phys.) 28 , 1962-1964 (1958)].
[0003]
A method is also known in which trimethylsilyl chloride and an inorganic salt of hydrogen azide supported on a macroporous polymer are reacted in a solvent [Japanese Patent Laid-Open No. Hei 1-143878].
[0004]
However, the above production method has the following problems (1) to (2).
[0005]
(1) It takes a long time of 6 to 60 hours to complete the reaction. Further, in order to shorten the reaction time, it is necessary to use an inorganic salt of hydrogen azide supported on a macroporous polymer.
[0006]
(2) As a method for isolating the produced trimethylsilyl azide, there is only a method by distillation. In the distillation, the trimethylsilyl azide and the solvent are not sufficiently separated, and the purity is lowered because the solvent is mixed in the trimethylsilyl azide. That is, in order to obtain high-purity trimethylsilyl azide, a multistage precision distillation apparatus is required, and equipment for that purpose is required, leading to an increase in manufacturing costs.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems of the prior art and provide a method for producing high-quality trimethylsilyl azide from trimethylsilyl chloride easily and in high yield.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors diligently researched and found that trimethylsilyl azide can be obtained in a short time without a solvent by using a phase transfer catalyst. Furthermore, by performing the reaction in the absence of a solvent, it is possible to easily obtain high-purity trimethylsilyl azide by simple distillation or filtration without the need for a multistage precision distillation apparatus for the isolation of the produced trimethylsilyl azide. The headline and the present invention have been completed.
[0009]
That is, the present invention comprises reacting a trimethylsilyl chloride represented by the following formula (1) with an inorganic salt of hydrogen azide represented by the following formula (2) in the presence of a phase transfer catalyst without solvent. It is a production method characterized by easily isolating trimethylsilyl azide represented by the following formula (3) with high purity.
(CH 3 ) 3 SiCl (1)
M (N 3 ) n (2)
(In the formula, M is an alkali metal or alkaline earth metal, and n is 1 or 2.)
(CH 3 ) 3 SiN 3 (3)
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0011]
Specific examples of the inorganic salt of hydrogen azide that can be used in the production method of the present invention include azides of alkali metals or alkaline earth metals such as sodium, potassium, lithium, calcium, and magnesium. Sodium azide is preferred industrially. The amount of the inorganic salt of hydrogen azide used is usually in the range of 1.0 to 1.5 mol, preferably 1.0 to 1.05 mol in terms of hydrogen azide, relative to 1 mol of trimethylsilyl chloride. .
[0012]
As specific examples of the phase transfer catalyst that can be used in the production method of the present invention, conventionally known quaternary ammonium salts, tertiary amines that can serve as quaternary ammonium salt sources, and polyether compounds can be used. For example, tetraethylammonium bromide, tetrabutylammonium bromide, hexadecyltributylammonium bromide, methyltrioctylammonium chloride, triethylamine hydrochloride, polyethylene glycol methyl ether, polyethylene glycol tetrahydrofurfuryl ether, polyethylene glycol distearate, polyethylene glycol, and polyethylene Examples thereof include, but are not limited to, glycol methyl ether, polyethylene glycol tetrahydrofurfuryl ether, and a silylated product of polyethylene glycol. A preferred phase transfer catalyst is polyethylene glycol and its silylated product from the viewpoint of industrial and low cost. The amount of these phase transfer catalysts used is usually 0.1% by weight or more, preferably 2 to 6% by weight, based on trimethylsilyl chloride.
[0013]
The reaction temperature is usually in the range of 0 to 60 ° C, preferably 45 to 55 ° C. The reaction time is affected by the amount of catalyst added and the reaction temperature, but is usually 0.5 to 20 hours, preferably 1 to 10 hours.
[0014]
In order to isolate trimethylsilyl azide after completion of the reaction, distillation or inorganic salts may be removed by filtration. In the isolation, since no solvent is used, the solvent is not mixed into trimethylsilyl azide, and high-purity trimethylsilyl azide can be easily obtained.
[0015]
Therefore, the present invention is a very advantageous method for producing high-purity trimethylsilyl azide in a short reaction time as compared with a conventional synthesis method using a solvent.
[0016]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these.
[0017]
Example 1
A flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 423.7 g (3.9 mol) of trimethylsilyl chloride, 266.2 g (4.1 mol) of sodium azide, and 8.5 g of polyethylene glycol. The mixture was heated to 50 to 55 ° C. and reacted for 1 hour. After completion of the reaction, the internal temperature was raised to 96 to 97 ° C., and trimethylsilyl azide was isolated by distillation. As a result, 392.3 g (3.4 mol) of trimethylsilylazide was obtained as a colorless transparent liquid. This corresponds to a yield of 87.3% with respect to trimethylsilyl chloride. The purity by gas chromatography (GC) analysis was 97.9%.
[0018]
Example 2
In the same apparatus as in Example 1, 10.9 g (0.1 mol) of trimethylsilyl chloride, 6.8 g (0.11 mol) of sodium azide, and 0.44 g of tetraethylammonium bromide were placed at 55-60 ° C. The reaction was conducted by heating for 5 hours. After completion of the reaction, the internal temperature was raised to 97-98 ° C., and trimethylsilyl azide was isolated by distillation. As a result, 9.9 g (0.86 mol) of trimethylsilylazide was obtained as a colorless transparent liquid. This corresponds to a yield of 86.1% with respect to trimethylsilyl chloride. The purity by GC analysis was 96.7%.
[0019]
Example 3
In the same apparatus as in Example 1, 21.8 g (0.2 mol) of trimethylsilyl chloride, 13.4 g (0.21 mol) of sodium azide, and 0.66 g of tetrabutylammonium bromide were added, and the temperature was 50 to 55 ° C. And reacted for 9 hours. After completion of the reaction, the internal temperature was raised to 96 to 97 ° C., and trimethylsilyl azide was isolated by distillation. As a result, 20.6 g (0.18 mol) of trimethylsilylazide was obtained as a colorless transparent liquid. This corresponds to a yield of 89.6% with respect to trimethylsilyl chloride. The purity by GC analysis was 97.1%.
[0020]
Example 4
In the same apparatus as in Example 1, 21.8 g (0.2 mol) of trimethylsilyl chloride, 13.4 g (0.21 mol) of sodium azide, and 1.3 g of triethylamine hydrochloride were placed at 50 to 55 ° C. The reaction was carried out for 10 hours by heating. After completion of the reaction, the internal temperature was raised to 94-97 ° C., and trimethylsilyl azide was isolated by distillation. As a result, 19.6 g (0.17 mol) of trimethylsilylazide was obtained as a colorless transparent liquid. This corresponds to a yield of 85.0% with respect to trimethylsilyl chloride. The purity by GC analysis was 96.5%.
[0021]
【The invention's effect】
According to the production method of the present invention, trimethylsilyl azide can be produced from trimethylsilyl chloride without using a solvent, and can be easily isolated with high purity. Therefore, this is an industrially advantageous and preferred method.
Claims (4)
（ＣＨ3）3ＳｉＣｌ （１）
Ｍ（Ｎ3）n （２）
（式中、Ｍはアルカリ金属またはアルカリ土類金属であり、ｎは１または２である。）
（ＣＨ3）3ＳｉＮ3 （３）A trimethylsilyl chloride represented by the following formula (1) and an inorganic salt of hydrogen azide represented by the following formula (2) are reacted in the absence of a solvent in the presence of a phase transfer catalyst: A method for producing trimethylsilyl azide represented by 3).
(CH 3 ) 3 SiCl (1)
M (N 3 ) n (2)
(In the formula, M is an alkali metal or alkaline earth metal, and n is 1 or 2.)
(CH 3 ) 3 SiN 3 (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22595196A JP3671281B2 (en) | 1996-08-07 | 1996-08-07 | Method for producing trimethylsilyl azide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22595196A JP3671281B2 (en) | 1996-08-07 | 1996-08-07 | Method for producing trimethylsilyl azide |
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| Publication Number | Publication Date |
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| JPH1045769A JPH1045769A (en) | 1998-02-17 |
| JP3671281B2 true JP3671281B2 (en) | 2005-07-13 |
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| KR101152249B1 (en) * | 2004-09-30 | 2012-06-08 | 도요 보세키 가부시키가이샤 | Method for producing trimethylsilyl azide |
| JP5233127B2 (en) * | 2007-02-06 | 2013-07-10 | セントラル硝子株式会社 | Low dielectric constant film modifier and manufacturing method |
| JP5870713B2 (en) * | 2011-10-31 | 2016-03-01 | 東洋紡株式会社 | Method for recovering solvent in the production of trimethylsilyl azide |
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