JPH08325273A - Production of trimethylsilylpropynal - Google Patents
Production of trimethylsilylpropynalInfo
- Publication number
- JPH08325273A JPH08325273A JP7135142A JP13514295A JPH08325273A JP H08325273 A JPH08325273 A JP H08325273A JP 7135142 A JP7135142 A JP 7135142A JP 13514295 A JP13514295 A JP 13514295A JP H08325273 A JPH08325273 A JP H08325273A
- Authority
- JP
- Japan
- Prior art keywords
- reaction solution
- trimethylsilylpropinal
- dimethylformamide
- reaction
- trimethylsilylethynylmagnesium
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- LJRWLSKYGWLYIM-UHFFFAOYSA-N 3-trimethylsilylprop-2-ynal Chemical compound C[Si](C)(C)C#CC=O LJRWLSKYGWLYIM-UHFFFAOYSA-N 0.000 title abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- -1 2-trimethylsilylethynylmagnesium halide Chemical class 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- ZNZVMHOETYIKCJ-UHFFFAOYSA-M [Cl-].C[Si](C)(C)C#C[Mg+] Chemical compound [Cl-].C[Si](C)(C)C#C[Mg+] ZNZVMHOETYIKCJ-UHFFFAOYSA-M 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- LJFFSUDBBGOBGT-UHFFFAOYSA-M [Br-].C[Si](C)(C)C#C[Mg+] Chemical compound [Br-].C[Si](C)(C)C#C[Mg+] LJFFSUDBBGOBGT-UHFFFAOYSA-M 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 229910018540 Si C Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZVGCJDPEKKEYES-UHFFFAOYSA-N 3-trimethylsilylprop-2-yn-1-ol Chemical compound C[Si](C)(C)C#CCO ZVGCJDPEKKEYES-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CDKFWIMBZAUBRS-UHFFFAOYSA-M [I-].CC[Mg+] Chemical compound [I-].CC[Mg+] CDKFWIMBZAUBRS-UHFFFAOYSA-M 0.000 description 1
- ZVXXEONXFWSCIZ-UHFFFAOYSA-N [Li]C#C[Si](C)(C)C Chemical compound [Li]C#C[Si](C)(C)C ZVXXEONXFWSCIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医薬品、農薬等の原料
であるトリメチルシリルプロピナールを製造する方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing trimethylsilylpropinal, which is a raw material for drugs, agricultural chemicals and the like.
【０００２】[0002]
【従来の技術】トリメチルシリルプロピナールは医薬
品、農薬の原料として有効に利用されている。2. Description of the Related Art Trimethylsilylpropinal has been effectively used as a raw material for pharmaceuticals and agricultural chemicals.
【０００３】トリメチルシリルプロピナールを製造する
手段として、３−トリメチルシリル−２−プロピン−１
−オールを酸化する方法、２−トリメチルシリルエチニ
ルリチウムとギ酸エチルとの反応を利用する方法があ
る。３−トリメチルシリル−２−プロピン−１−オール
を酸化する方法は、重金属類を添加するため廃棄処理が
難しい。２−トリメチルシリルエチニルリチウムとギ酸
エチルとの反応を利用する方法は、高価な有機リチウム
試薬を使用しなければならず経済的に好ましくない。そ
れに加えて２−トリメチルシリルエチニルリチウムが発
火しやすいため、反応には細心の注意を必要とする。従
って、これら二つの方法は、安全面を考慮すると工業的
に有効な方法ではない。As a means for producing trimethylsilylpropinal, 3-trimethylsilyl-2-propyne-1
There are methods of oxidizing ol and methods of utilizing the reaction of 2-trimethylsilylethynyl lithium and ethyl formate. The method of oxidizing 3-trimethylsilyl-2-propyn-1-ol is difficult to dispose of because it adds heavy metals. The method utilizing the reaction of 2-trimethylsilylethynyllithium and ethyl formate is not economically preferable because an expensive organolithium reagent must be used. In addition to that, 2-trimethylsilylethynyllithium is easily ignited, and therefore the reaction requires extreme caution. Therefore, these two methods are not industrially effective methods in terms of safety.
【０００４】トリメチルシリルプロピナールの安全な製
造方法として、Tetrahedron 39,3073(1983) 、特開平6-
316584号公報に２−トリメチルシリルエチニルマグネシ
ウムブロミドとジメチルホルムアミドとの反応を利用す
る方法が記載されている。As a safe method for producing trimethylsilylpropinal, Tetrahedron 39, 3073 (1983), JP-A-6-
Japanese Patent No. 316584 describes a method utilizing the reaction of 2-trimethylsilylethynylmagnesium bromide and dimethylformamide.
【０００５】Tetrahedron 39,3073(1983)に記載されて
いる方法は以下の通りである。ジメチルホルムアミド3.
5当量に、２−トリメチルシリルエチニルマグネシウム
ブロミドを滴下する。滴下終了後、得られた白色のサス
ペンジョンを、０℃の５％硫酸水溶液に加えて加水分解
を行ない、トリメチルシリルプロピナールを合成する。
この方法を工業的規模で行う場合には、サスペンジョン
を配管内に通して、硫酸水溶液に滴下する。しかしなが
ら滴下の際に、サスペンジョンが配管内部で詰まること
がある。The method described in Tetrahedron 39, 3073 (1983) is as follows. Dimethylformamide 3.
2-Trimethylsilylethynylmagnesium bromide is added dropwise to 5 equivalents. After completion of the dropping, the obtained white suspension is added to a 5% aqueous solution of sulfuric acid at 0 ° C. for hydrolysis to synthesize trimethylsilylpropinal.
When this method is carried out on an industrial scale, the suspension is passed through the pipe and added dropwise to the aqueous sulfuric acid solution. However, the suspension may become clogged inside the pipe during dripping.
【０００６】特開平6-316584号公報に記載されている方
法は以下の通りである。２−トリメチルシリルエチニル
マグネシウムブロミドの溶液に、ジメチルホルムアミド
１当量を滴下して反応液とする。反応液に、−１０℃で
５％硫酸を加えてpＨ２に調整し加水分解を行ない、ト
リメチルシリルプロピナールを合成する。The method described in JP-A-6-316584 is as follows. To a solution of 2-trimethylsilylethynyl magnesium bromide, 1 equivalent of dimethylformamide is added dropwise to obtain a reaction solution. To the reaction solution, 5% sulfuric acid is added at -10 ° C to adjust the pH to 2, and hydrolysis is performed to synthesize trimethylsilylpropinal.
【０００７】反応液に硫酸水溶液を滴下していくので、
滴下初期では、反応液と硫酸とが塩基性下で反応するこ
とになる。このためＳi-Ｃ≡Ｃ結合が加水分解されて副
生成物が生じ、トリメチルシリルプロピナールの収率が
低下してしまう。それに加えて温度およびｐＨの制御が
難しい。Since sulfuric acid aqueous solution is added dropwise to the reaction solution,
At the initial stage of dropping, the reaction solution and sulfuric acid react with each other under basic conditions. Therefore, the Si—C≡C bond is hydrolyzed to generate a by-product, and the yield of trimethylsilylpropinal is reduced. In addition, it is difficult to control temperature and pH.
【０００８】[0008]
【発明が解決しようとする課題】前記に示されているよ
うに、従来の２−トリメチルシリルエチニルマグネシウ
ムブロミドとジメチルホルムアミドとの反応を利用する
方法も実用的ではない。このため、トリメチルシリルプ
ロピナールを有効に製造できる方法の開発が待ち望まれ
ている。As described above, the conventional method utilizing the reaction of 2-trimethylsilylethynylmagnesium bromide and dimethylformamide is not practical. Therefore, development of a method capable of effectively producing trimethylsilylpropinal has been awaited.
【０００９】本発明は前記の課題を解決するためなされ
たもので、安全に効率よくトリメチルシリルプロピナー
ルを製造する方法を提供することを目的とする。The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for safely and efficiently producing trimethylsilylpropinal.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、鋭意研究
を重ねた結果、通常、ジメチルホルムアミドの様な極性
溶媒を多く用いた方が塩は溶解しやすいと考えられる
が、トリメチルシリルエチ二ルマグネシウムハライドと
ジメチルホルムアミドの反応においては、ジメチルホル
ムアミドが少ないときに塩は溶解して均一溶液となり、
ジメチルホルムアミドを多くすると塩が析出することを
発見した。このことからトリメチルシリルエチ二ルマグ
ネシウムハライドに所定量のジメチルホルムアミドを加
えて均一反応液とし、前記均一反応液と酸とを酸性下で
反応させると、副反応が抑制されてトリメチルシリルプ
ロピナールを収率よく製造できることを見いだし、本発
明を完成させた。Means for Solving the Problems As a result of intensive studies, the present inventors have found that it is usually easier to dissolve a salt by using a large amount of a polar solvent such as dimethylformamide. In the reaction between rumagnesium halide and dimethylformamide, when the amount of dimethylformamide is small, the salt dissolves and becomes a homogeneous solution,
It was discovered that salt was precipitated when the amount of dimethylformamide was increased. From this, a predetermined amount of dimethylformamide was added to trimethylsilylethynylmagnesium halide to form a homogeneous reaction solution, and when the homogeneous reaction solution and the acid were reacted under acidic conditions, side reactions were suppressed and trimethylsilylpropinal was obtained in a yield. The inventors have found that they can be manufactured well and completed the present invention.
【００１１】即ち、本発明のトリメチルシリルプロピナ
ールの製造方法は、（CH3)3SiC≡CMgXで表される２−ト
リメチルシリルエチニルマグネシウムハライド１当量
に、ジメチルホルムアミド1.0〜2.0当量を加えて均一反
応液とし、酸を２当量以上含む水溶液に、この均一反応
液を加えて加水分解する方法である。尚、化学式中のX
は塩素、臭素またはヨウ素である。That is, the method for producing trimethylsilylpropinal according to the present invention is carried out by adding 1.0 to 2.0 equivalents of dimethylformamide to 1 equivalent of 2-trimethylsilylethynylmagnesium halide represented by (CH 3 ) 3 SiC≡CMgX. In this method, the homogeneous reaction solution is added to an aqueous solution containing 2 equivalents or more of an acid to perform hydrolysis. In addition, X in the chemical formula
Is chlorine, bromine or iodine.
【００１２】前記製造方法における反応は以下の式で表
される。The reaction in the above production method is represented by the following formula.
【００１３】[0013]
【数１】 [Equation 1]
【００１４】ジメチルホルムアミドが1.0当量未満の場
合には、トリメチルシリルプロピナールの収率が低くな
ってしまう。2.0当量を超える場合には、反応液中に多
量の塩が析出するので、反応液を配管等で移送させると
配管が詰まることがある。If the amount of dimethylformamide is less than 1.0 equivalent, the yield of trimethylsilylpropinal will be low. If the amount exceeds 2.0 equivalents, a large amount of salt will be precipitated in the reaction solution, and thus the piping may be clogged when the reaction solution is transferred through the piping or the like.
【００１５】水溶液中に含まれている酸が２当量未満の
場合には、塩基性下で、反応液と酸とが反応してしまう
ことがある。When the acid contained in the aqueous solution is less than 2 equivalents, the reaction solution may react with the acid under basic conditions.
【００１６】２−トリメチルシリルエチニルマグネシウ
ムハライドは、トリメチルシリルアセチレンと、RMgXで
表されるグリニャール試薬によって合成される。Rは炭
化水素基であり、具体的にはメチル基、エチル基、プロ
ピル基、ブチル基等のアルキル基、フェニル基、トリル
基等のアリール基である。2-Trimethylsilylethynylmagnesium halide is synthesized by trimethylsilylacetylene and a Grignard reagent represented by RMgX. R is a hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and an aryl group such as a phenyl group and a tolyl group.
【００１７】RMgXには、具体的にメチルマグネシウムク
ロリド、メチルマグネシウムブロミド、メチルマグネシ
ウムヨージド、エチルマグネシウムクロリド、エチルマ
グネシウムブロミド、エチルマグネシウムヨージド、ｎ
−プロピルマグネシウムクロリド、ｎ−プロピルマグネ
シウムブロミド、ｎ−ブチルマグネシウムクロリド、ｎ
−ブチルマグネシウムブロミド、フェニルマグネシウム
クロリド、フェニルマグネシウムブロミドが挙げられ
る。Specific examples of RMgX include methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, and n.
-Propyl magnesium chloride, n-propyl magnesium bromide, n-butyl magnesium chloride, n
-Butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide.
【００１８】トリメチルシリルプロピナールの製造方法
は、具体的には以下の通りである。テトラヒドロフラン
中にマグネシウムを加え、さらにメチルクロリドをマグ
ネシウムが消失するまで加えてメチルマグネシウムクロ
リドを合成する。得られたメチルマグネシウムクロリド
にトリメチルシリルアセチレンを滴下し、さらに撹拌し
てトリメチルシリルエチニルマグネシウムクロリドを合
成する。反応温度は２０〜８０℃、特に４０〜６０℃に
調整するのが好ましく、反応時間は３０分〜５時間が好
ましい。The method for producing trimethylsilylpropinal is specifically as follows. Magnesium is added to tetrahydrofuran, and methyl chloride is further added until magnesium disappears to synthesize methyl magnesium chloride. Trimethylsilylacetylene is added dropwise to the obtained methylmagnesium chloride and further stirred to synthesize trimethylsilylethynylmagnesium chloride. The reaction temperature is preferably adjusted to 20 to 80 ° C, particularly 40 to 60 ° C, and the reaction time is preferably 30 minutes to 5 hours.
【００１９】得られたトリメチルシリルエチニルマグネ
シウムクロリドに、ジメチルホルムアミドを滴下し撹拌
して均一反応液とする。反応温度は−３０〜６０℃、特
に２０〜４０℃に調整するのが好ましく、反応時間は３
０分〜３時間が好ましい。Dimethylformamide was added dropwise to the obtained trimethylsilylethynylmagnesium chloride, and the mixture was stirred to form a homogeneous reaction solution. The reaction temperature is preferably adjusted to -30 to 60 ° C, particularly 20 to 40 ° C, and the reaction time is 3
0 minutes to 3 hours is preferable.
【００２０】この均一反応液を塩酸水溶液に滴下して撹
拌する。加水分解が起こり、均一反応液および塩酸水溶
液からなる反応系が、有機層と水層とに分離する。加水
分解の際の反応温度は−３０〜６０℃、特に１０〜３０
℃に調整するのが好ましく、反応時間は３０分〜５時間
が好ましい。This homogeneous reaction solution is dropped into a hydrochloric acid aqueous solution and stirred. Hydrolysis occurs, and the reaction system composed of the homogeneous reaction solution and the hydrochloric acid aqueous solution separates into an organic layer and an aqueous layer. The reaction temperature during hydrolysis is -30 to 60 ° C, especially 10 to 30 ° C.
The temperature is preferably adjusted to 0 ° C, and the reaction time is preferably 30 minutes to 5 hours.
【００２１】水層を分離した後、有機層を脱水剤で乾燥
させてから蒸留し、トリメチルシリルプロピナールを得
る。脱水剤には、例えば無水塩化カルシウム、無水硫酸
ナトリウム、無水塩化マグネシウムが挙げられる。蒸留
は１０〜２００ｍｍＨｇの減圧下で行うことが好まし
い。After separating the aqueous layer, the organic layer is dried with a dehydrating agent and then distilled to obtain trimethylsilylpropinal. Examples of the dehydrating agent include anhydrous calcium chloride, anhydrous sodium sulfate, and anhydrous magnesium chloride. The distillation is preferably performed under a reduced pressure of 10 to 200 mmHg.
【００２２】[0022]
【作用】２−トリメチルシリルエチニルマグネシウムハ
ライド１当量にジメチルホルムアミド1.0〜2.0当量が加
えられた反応液中には塩が析出することがない。このた
め反応液は均一溶液となる。トリメチルシリルプロピナ
ールを合成する際、酸が２当量以上含まれている水溶液
に前記反応液を加えるので、反応液と酸とは、常に酸性
下で反応することになる。このためＳi-Ｃ≡Ｃ結合の加
水分解が抑制され、副生成物の生成が低下する。Function: No salt is precipitated in the reaction solution obtained by adding 1.0-2.0 equivalents of dimethylformamide to 1 equivalent of 2-trimethylsilylethynylmagnesium halide. Therefore, the reaction solution becomes a uniform solution. When trimethylsilylpropinal is synthesized, the reaction solution is added to an aqueous solution containing 2 equivalents or more of the acid, so that the reaction solution and the acid always react under acidic conditions. Therefore, hydrolysis of the Si-C≡C bond is suppressed, and the production of by-products is reduced.
【００２３】[0023]
【発明の効果】本発明のトリメチルシリルプロピナール
の製造方法によると、トリメチルシリルエチニルマグネ
シウムクロリドとジメチルホルムアミドからなる反応液
中には塩が析出することがないので、反応液は均一であ
る。均一反応液を配管に通しても、配管が詰まることは
ない。EFFECTS OF THE INVENTION According to the method for producing trimethylsilylpropinal of the present invention, a salt is not precipitated in the reaction solution containing trimethylsilylethynylmagnesium chloride and dimethylformamide, so that the reaction solution is uniform. Even if the homogeneous reaction liquid is passed through the pipe, the pipe is not clogged.
【００２４】トリメチルシリルプロピナールを合成する
際、塩酸水溶液等に、均一反応液を滴下する。常に酸性
下で均一反応液と酸とが反応するため、副反応が起こり
にくく、トリメチルシリルプロピナールを効率よく製造
することができる。At the time of synthesizing trimethylsilylpropinal, a homogeneous reaction solution is dropped into an aqueous solution of hydrochloric acid or the like. Since the homogeneous reaction solution and the acid always react under acidic conditions, side reactions hardly occur and trimethylsilylpropinal can be efficiently produced.
【００２５】[0025]
【実施例】以下、本発明の実施例を詳細に説明する。EXAMPLES Examples of the present invention will be described in detail below.
【００２６】実施例１ 冷却管、温度計、ガス吹き込み管、撹拌機を４口フラス
コに備え付け、マグネシウム４０．１ｇ（１．６５ｍｏ
ｌ）と、テトラヒドロフラン９００ｍｌを仕込んだ。ガ
ス吹き込み管からメチルクロリドをマグネシウムが消失
するまで導入し、メチルマグネシウムクロリドを合成し
た。ガス吹き込み管を外して滴下管を付け、滴下管より
トリメチルシリルアセチレン１４７．３ｇ（１．５ｍｏ
ｌ）をメチルマグネシウムクロリドへ４０〜５０℃で滴
下した。そのままの温度でさらに１時間撹拌しトリメチ
ルシリルエチニルマグネシウムクロリド（１．５ｍｏ
ｌ：１当量）を合成した。Example 1 A four-necked flask was equipped with a cooling tube, a thermometer, a gas blowing tube, and a stirrer, and 40.1 g of magnesium (1.65 mo)
1) and 900 ml of tetrahydrofuran were charged. Methyl chloride was introduced from the gas blowing tube until magnesium disappeared, and methyl magnesium chloride was synthesized. Remove the gas blowing tube and attach the dropping tube. From the dropping tube, 147.3 g of trimethylsilylacetylene (1.5 mo
1) was added dropwise to methylmagnesium chloride at 40 to 50 ° C. The mixture was stirred at the same temperature for 1 hour, and trimethylsilylethynylmagnesium chloride (1.5mo
1: 1 equivalent) was synthesized.
【００２７】トリメチルシリルエチニルマグネシウムク
ロリドに、ジメチルホルムアミド１６４．５ｇ（２．２
５ｍｏｌ：１．５当量）を２０〜３０℃で滴下し、その
ままの温度でさらに１時間撹拌して均一反応液とした。
冷却管、温度計、ガス滴下管、撹拌機を備え付けた別の
フラスコに１５％塩酸８８２．１ｇを仕込み、前記均一
反応液を２０〜２５℃で塩酸に滴下した。加水分解反応
が起こり、均一反応液および塩酸からなる反応系が有機
層と水層とに分離した。フラスコ内から水層を除去した
後、無水塩化カルシウムで有機層を乾燥してから蒸留
し、トリメチルシリルプロピナール１４７．６ｇを得
た。トリメチルシリルプロピナールは、収率が７８％で
あり、沸点が８０℃／１００ｍｍＨｇであった。164.5 g (2.2 of dimethylformamide) was added to trimethylsilylethynyl magnesium chloride.
5 mol: 1.5 equivalent) was added dropwise at 20 to 30 ° C., and the mixture was stirred at the same temperature for 1 hour to give a uniform reaction solution.
882.1 g of 15% hydrochloric acid was charged into another flask equipped with a cooling tube, a thermometer, a gas dropping tube, and a stirrer, and the homogeneous reaction solution was added dropwise to hydrochloric acid at 20 to 25 ° C. A hydrolysis reaction occurred and the reaction system consisting of the homogeneous reaction solution and hydrochloric acid separated into an organic layer and an aqueous layer. After removing the aqueous layer from the flask, the organic layer was dried with anhydrous calcium chloride and then distilled to obtain 147.6 g of trimethylsilylpropinal. Trimethylsilylpropinal had a yield of 78% and a boiling point of 80 ° C./100 mmHg.
【００２８】実施例２ ジメチルホルムアミド２１９．３ｇ（３．０ｍｏｌ：
２．０当量）を用い、その他の条件を実施例１と同様に
してトリメチルシリルプロピナール１４５．７ｇを得
た。収率は７７％であった。Example 2 219.3 g (3.0 mol: dimethylformamide)
(2.0 equivalents) and other conditions were the same as in Example 1 to obtain 145.7 g of trimethylsilylpropinal. The yield was 77%.
【００２９】比較例１ 実施例１と同様の方法で、トリメチルシリルエチニルマ
グネシウムクロライドを合成し、ジメチルホルムアミド
と反応させた。得られた反応液に、１５％塩酸８８２．
１ｇを２０〜２５℃で滴下した。水層を除去した後、無
水塩化カルシウムで有機層を乾燥してから蒸留し、トリ
メチルシリルプロピナール６６．２ｇを得た。トリメチ
ルシリルプロピナールの収率はわずか３５％であり、他
に多量の副生成物が合成されていた。Comparative Example 1 In the same manner as in Example 1, trimethylsilylethynyl magnesium chloride was synthesized and reacted with dimethylformamide. 15% hydrochloric acid 882.
1 g was added dropwise at 20 to 25 ° C. After removing the aqueous layer, the organic layer was dried over anhydrous calcium chloride and then distilled to obtain 66.2 g of trimethylsilylpropinal. The yield of trimethylsilylpropinal was only 35%, and a large amount of by-products were also synthesized.
【００３０】比較例２ 実施例１と同様の方法で、トリメチルシリルエチニルマ
グネシウムクロライドを合成した。ジメチルホルムアミ
ド３２９．０ｇ（４．５ｍｏｌ：３．０当量）を２０℃
〜３０℃でトリメチルシリルエチニルマグネシウムクロ
ライドに滴下し、そのままの温度で１時間撹拌して反応
液とした。Comparative Example 2 In the same manner as in Example 1, trimethylsilylethynyl magnesium chloride was synthesized. Dimethylformamide 329.0 g (4.5 mol: 3.0 equivalent) was added at 20 ° C.
The solution was added dropwise to trimethylsilylethynylmagnesium chloride at -30 ° C and stirred at the same temperature for 1 hour to obtain a reaction solution.
【００３１】冷却管、温度計、ガス滴下管、撹拌機を備
え付けた別のフラスコに１５％塩酸８８２．１ｇを仕込
み、前記反応液を滴下管から塩酸に滴下したが、途中で
滴下管が詰まってしまった。882.1 g of 15% hydrochloric acid was charged into another flask equipped with a cooling tube, a thermometer, a gas dropping tube, and a stirrer, and the reaction solution was dropped into the hydrochloric acid from the dropping tube, but the dropping tube was clogged in the middle. I got it.
【００３２】比較例３ 実施例１と同様にして、反応液を得た。冷却管、温度
計、ガス滴下管、撹拌機を備え付けた別のフラスコに１
５％塩酸３６４．６ｇ（１．５ｍｏｌ：１．０当量）を
仕込み、前記均一反応液を２０〜２５℃で塩酸に滴下し
た。加水分解反応が起こり、反応液および塩酸からなる
反応系が有機層と水層とに分離した。この時水層は塩基
性であった。フラスコ内から水層を除去した後、無水塩
化カルシウムで有機層を乾燥してから蒸留し、トリメチ
ルシリルプロピナール９０．９ｇを得た。収率は４８％
であり、他の副生成物が合成されていた。Comparative Example 3 In the same manner as in Example 1, a reaction solution was obtained. 1 in a separate flask equipped with a cooling tube, thermometer, gas dropping tube and stirrer
364.6 g (1.5 mol: 1.0 equivalent) of 5% hydrochloric acid was charged, and the homogeneous reaction solution was added dropwise to hydrochloric acid at 20 to 25 ° C. A hydrolysis reaction occurred and the reaction system consisting of the reaction solution and hydrochloric acid separated into an organic layer and an aqueous layer. At this time, the aqueous layer was basic. After removing the aqueous layer from the inside of the flask, the organic layer was dried with anhydrous calcium chloride and then distilled to obtain 90.9 g of trimethylsilylpropinal. 48% yield
And other by-products were synthesized.
【００３３】上記の実験結果から、実施例１・２のトリ
メチルシリルプロピナールの製造方法は工業的に有利で
あることが予測できるが、比較例１〜３の方法は工業的
に不向きであることが確認された。From the above experimental results, it can be predicted that the method for producing trimethylsilylpropinal of Examples 1 and 2 is industrially advantageous, but the methods of Comparative Examples 1 to 3 are industrially unsuitable. confirmed.
【００３４】比較例１で多量の副生成物が生じたのは、
トリメチルシリルプロピナールを合成する際、反応液に
塩酸を滴下したため、滴下初期では反応系が塩基性とな
り、Ｓi-Ｃ≡Ｃ結合が加水分解されるからである。A large amount of by-products were generated in Comparative Example 1 because
This is because hydrochloric acid was added dropwise to the reaction solution when trimethylsilylpropinal was synthesized, so that the reaction system becomes basic at the initial stage of addition and the Si—C≡C bond is hydrolyzed.
【００３５】比較例２で滴下管が詰まったのは、トリメ
チルシリルエチニルマグネシウムクロライドに対してジ
メチルホルムアミドの量が多すぎ、多量の塩が反応液中
に析出したためである。The reason why the dropping tube was clogged in Comparative Example 2 was that the amount of dimethylformamide was too large for trimethylsilylethynylmagnesium chloride and a large amount of salt was precipitated in the reaction solution.
【００３６】比較例３で多量の副生成物が生じたのは、
トリメチルシリルプロピナールを合成する際、酸の量が
十分でないため、最終的に反応系が塩基性となり、Ｓi-
Ｃ≡Ｃ結合が加水分解されるからである。In Comparative Example 3, a large amount of by-products were produced.
When trimethylsilylpropinal was synthesized, the amount of acid was not sufficient, so that the reaction system finally became basic and Si-
This is because the C≡C bond is hydrolyzed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久保田 透 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toru Kubota Toru Kubota No. 28 Nishi-Fukushima, Chugaku-mura, Nakakubiki-gun, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd.
Claims (1)
素またはヨウ素）で表される２−トリメチルシリルエチ
ニルマグネシウムハライド１当量に対し、ジメチルホル
ムアミド1.0〜2.0当量を加えて均一反応液とし、酸を２
当量以上含む水溶液に、該均一反応液を加えて加水分解
することを特徴とするトリメチルシリルプロピナールの
製造方法。1. 1.0 to 2.0 equivalents of dimethylformamide are added to 1 equivalent of 2-trimethylsilylethynylmagnesium halide represented by (CH 3 ) 3 SiC≡CMgX (where X is chlorine, bromine or iodine) to obtain a uniform mixture. As a reaction solution, acid 2
A method for producing trimethylsilylpropinal, which comprises adding the homogeneous reaction solution to an aqueous solution containing not less than an equivalent amount and performing hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07135142A JP3122334B2 (en) | 1995-06-01 | 1995-06-01 | Method for producing trimethylsilyl propinal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07135142A JP3122334B2 (en) | 1995-06-01 | 1995-06-01 | Method for producing trimethylsilyl propinal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08325273A true JPH08325273A (en) | 1996-12-10 |
| JP3122334B2 JP3122334B2 (en) | 2001-01-09 |
Family
ID=15144793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07135142A Expired - Fee Related JP3122334B2 (en) | 1995-06-01 | 1995-06-01 | Method for producing trimethylsilyl propinal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3122334B2 (en) |
-
1995
- 1995-06-01 JP JP07135142A patent/JP3122334B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3122334B2 (en) | 2001-01-09 |
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