JPWO2006064628A1 - Method for producing vinyl silane - Google Patents
Method for producing vinyl silane Download PDFInfo
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- JPWO2006064628A1 JPWO2006064628A1 JP2006548725A JP2006548725A JPWO2006064628A1 JP WO2006064628 A1 JPWO2006064628 A1 JP WO2006064628A1 JP 2006548725 A JP2006548725 A JP 2006548725A JP 2006548725 A JP2006548725 A JP 2006548725A JP WO2006064628 A1 JPWO2006064628 A1 JP WO2006064628A1
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- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- -1 vinyl halide compound Chemical class 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- ZDNBETOXRXGYFH-UHFFFAOYSA-N trimethyl(3,3,3-trifluoroprop-1-en-2-yl)silane Chemical compound C[Si](C)(C)C(=C)C(F)(F)F ZDNBETOXRXGYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 40
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- QKBKGNDTLQFSEU-UHFFFAOYSA-N 2-bromo-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Br)=C QKBKGNDTLQFSEU-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 2
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical compound FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- VPXWFEWRBGEQKN-UHFFFAOYSA-N dimethyl-phenyl-(3,3,3-trifluoroprop-1-en-2-yl)silane Chemical compound FC(F)(F)C(=C)[Si](C)(C)C1=CC=CC=C1 VPXWFEWRBGEQKN-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 1
- LHRSMHZCHIDYBT-UHFFFAOYSA-N 3,3,3-trifluoro-2-iodoprop-1-ene Chemical compound FC(F)(F)C(I)=C LHRSMHZCHIDYBT-UHFFFAOYSA-N 0.000 description 1
- ZOYDPLAHKCEZIE-UHFFFAOYSA-N FC(C(F)(F)F)(C(=C)[Si](C)(C)C)F Chemical compound FC(C(F)(F)F)(C(=C)[Si](C)(C)C)F ZOYDPLAHKCEZIE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
【課題】 ビニルハロゲン化合物とハロゲン化ケイ素化合物から、安全かつ容易で高選択的に主生成物として生産し得る一般式（１）で示されるビニルシランの製造方法を提供する。【解決手段】 非プロトン性溶媒中、アルミニウム存在下でビニルハロゲン化合物とハロゲン化ケイ素化合物を反応させて、一般式（１）で示されるビニルシラン［代表例：（１−トリフルオロメチルビニル）トリメチルシラン］を得ることを特徴とする製造方法。【化１】【選択図】なしPROBLEM TO BE SOLVED: To provide a method for producing vinylsilane represented by the general formula (1), which can be produced safely and easily as a main product from a vinyl halide compound and a silicon halide compound with high selectivity. SOLUTION: A vinyl halogen compound and a silicon halide compound are reacted in an aprotic solvent in the presence of aluminum to give a vinyl silane represented by the general formula (1) [typical example: (1-trifluoromethylvinyl) trimethylsilane. ] Is obtained. [Chemical 1] [Selected figure] None
Description
本発明はビニルシランの製造方法に関する。 The present invention relates to a method for producing vinyl silane.
有機ケイ素化合物は反応試剤として有機合成分野、あるいは高分子分野において有用である。アルキルシラン類である、（トリフルオロメチル）トリメチルシランの合成法は文献に公知である（非特許文献１参照）。一方、アルケンにケイ素基の置換したビニルシラン類は通常のアルケンにない多様な反応性を示す。ビニルシラン類は、求電子試薬との反応、ビニル基へのカルボアニオンの付加、ビニル基の官能基変換等の合成化学的利用法があり、利用価値は高い。 Organosilicon compounds are useful as reaction reagents in the field of organic synthesis or in the field of polymers. Methods for synthesizing (trifluoromethyl) trimethylsilane, which are alkylsilanes, are known in the literature (see Non-Patent Document 1). On the other hand, vinyl silanes in which alkene is substituted with a silicon group exhibit various reactivity not found in ordinary alkene. Vinyl silanes have high utility value because of synthetic chemical methods such as reaction with electrophiles, addition of carbanions to vinyl groups, and functional group conversion of vinyl groups.
一般式（１） General formula (1)
（式中、Ｒは炭素数１〜４の含フッ素有機基を表し、Ａ１，Ａ２，Ａ３はそれぞれ互いに独立し、同一又は異なって、水素原子又は置換基を有してもよい直鎖状若しくは分岐した炭素数１〜４のアルキル基を表す。）
で示されるビニルシランの製造方法に関しては、アセチレン系化合物を少なくとも１個の水素原子を含むシラン化合物と反応させるヒドロシリル化反応により合成する方法が公知である。その製造方法として、ＵＶ光照射下で３，３，３−トリフルオロプロピンとトリメチルシランを反応させて（Ｅ）−３，３，３−トリフルオロプロペニル−１−トリメチルシラン、（Ｚ）−３，３，３−トリフルオロプロペニル−１−トリメチルシラン、（１−トリフルオロメチルビニル）トリメチルシランの混合物、又は（Ｅ）−３，３，３−トリフルオロプロペニル−１−トリメチルシラン、１，１，１−トリフルオロ−３，３−ビストリメチルシリルプロパン、（１−トリフルオロメチルビニル）トリメチルシランの混合物を合成した例があるのみである（非特許文献２参照）。(In the formula, R represents a fluorine-containing organic group having 1 to 4 carbon atoms, and A 1 , A 2 , and A 3 are each independently the same or different and may have a hydrogen atom or a substituent. Represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
Regarding the method for producing vinyl silane represented by the above, a method of synthesizing by a hydrosilylation reaction in which an acetylene compound is reacted with a silane compound containing at least one hydrogen atom is known. As its production method, (E) -3,3,3-trifluoropropenyl-1-trimethylsilane is reacted with 3,3,3-trifluoropropyne and trimethylsilane under UV light irradiation, (Z) -3, 3,3-trifluoropropenyl-1-trimethylsilane, a mixture of (1-trifluoromethylvinyl) trimethylsilane, or (E) -3,3,3-trifluoropropenyl-1-trimethylsilane, 1,1, There is only an example in which a mixture of 1-trifluoro-3,3-bistrimethylsilylpropane and (1-trifluoromethylvinyl) trimethylsilane was synthesized (see Non-Patent Document 2).
当該文献では混合物中の主生成物は共に（Ｅ）−３，３，３−トリフルオロプロペニル−１−トリメチルシランである。副生成物として得られる（１−トリフルオロメチルビニル）トリメチルシランの割合は低く、収率は原料である３，３，３−トリフルオロプロピン基準で２．０〜６．３％と極めて低い。さらに混合物を精製して単離するまでには至っていない。ヒドロシリル化反応は異性体との混合物として得られるため収率が低い上に、分離が困難で工業的には利用価値が低いという課題がある。またガス状アセチレン系化合物を取り扱う際は危険性を伴い、使用できる容器の材質にも制限があるといった問題がある。 In this document, the main product in the mixture is both (E) -3,3,3-trifluoropropenyl-1-trimethylsilane. The proportion of (1-trifluoromethylvinyl) trimethylsilane obtained as a by-product is low, and the yield is as extremely low as 2.0 to 6.3% based on 3,3,3-trifluoropropyne as a raw material. Further, the mixture has not yet been purified and isolated. Since the hydrosilylation reaction is obtained as a mixture with isomers, the yield is low, and there are problems that separation is difficult and industrial utility value is low. Moreover, when handling a gaseous acetylene-type compound, there exists a problem that there exists a danger and the material of the container which can be used also has a restriction | limiting.
上記一般式（１）で示されるビニルシラン以外の化合物として、ケイ素上にフェニル基を有するビニルシランである（１−トリフルオロメチルビニル）ジメチルフェニルシランをテトラヒドロフラン溶媒中、２−ブロモ−３，３，３−トリフルオロプロペンとクロロジメチルフェニルシランからＧｒｉｇｎａｒｄ合成する方法が知られている（非特許文献３）。その手法においては、テトラヒドロフラン溶媒中にマグネシウムとクロロジメチルフェニルシランを加え、−１０℃の冷却条件下において８時間で２−ブロモ−３，３，３−トリフルオロプロペンを滴下している。反応終了後、反応液にリン酸緩衝液（ｐＨ７）を加えた後にジエチルエーテルにて抽出し、減圧下（３０ｋＰａ）で溶媒留去して、残渣をカラムクロマトグラフ法により精製して（１−トリフルオロメチルビニル）ジメチルフェニルシランを得ている。 As a compound other than the vinylsilane represented by the general formula (1), (1-trifluoromethylvinyl) dimethylphenylsilane which is a vinylsilane having a phenyl group on silicon is added to 2-bromo-3,3,3 in a tetrahydrofuran solvent. A method of synthesizing Grignard from trifluoropropene and chlorodimethylphenylsilane is known (Non-patent Document 3). In this method, magnesium and chlorodimethylphenylsilane are added to a tetrahydrofuran solvent, and 2-bromo-3,3,3-trifluoropropene is added dropwise over 8 hours under a cooling condition of −10 ° C. After completion of the reaction, a phosphate buffer solution (pH 7) was added to the reaction solution, followed by extraction with diethyl ether, the solvent was distilled off under reduced pressure (30 kPa), and the residue was purified by column chromatography (1- Trifluoromethylvinyl) dimethylphenylsilane has been obtained.
その手法においては長時間かけて−１０℃の冷却条件下で２−ブロモ−３，３，３−トリフルオロプロペンを滴下している。しかしながら、激しい発熱反応となるために工業スケールで製造した場合は極めて長時間を要し、また温度制御が困難である。さらに引火性が高く爆発性ガスを形成しやすいジエチルエーテルを使用している点、およびカラムクロマトグラフ法により精製を行う点から工業規模での製造において有意ではない。 In this method, 2-bromo-3,3,3-trifluoropropene is dropped over a long period of time under cooling at −10 ° C. However, since it becomes a violent exothermic reaction, when it manufactures on an industrial scale, it requires a very long time and temperature control is difficult. Furthermore, it is not significant in industrial scale production because it uses diethyl ether, which is highly flammable and easily forms explosive gas, and is purified by column chromatography.
また反応溶媒は収率よく目的物である上記一般式（１）のビニルシランを生成し、さらに反応生成物との分離が容易なことが望まれる。一般式（１）に示されるビニルシランは、反応溶媒としてテトラヒドロフラン等の低沸点溶媒を使用した場合は反応生成物と溶媒との分離が困難となり望ましくない。 Further, it is desired that the reaction solvent produces the vinylsilane of the above general formula (1), which is the target product, in a high yield and can be easily separated from the reaction product. The vinyl silane represented by the general formula (1) is not desirable when a low boiling point solvent such as tetrahydrofuran is used as a reaction solvent because it is difficult to separate the reaction product from the solvent.
従って、安全かつ容易に、収率良く高選択的に主生成物として一般式（１）で示されるビニルシランが得られる製造方法が望まれていた。
本発明は、上記課題を解決するためになされたものであり、その目的は、安全かつ容易に、収率良く高選択的に主生成物として製造することが可能な上記一般式（１）で示されるビニルシランの製造方法を提供することである。 The present invention has been made to solve the above-mentioned problems, and the object thereof is the general formula (1) that can be produced safely and easily as a main product with high yield and high selectivity. It is to provide a method for producing the indicated vinylsilane.
本発明者らは、上記課題を解決するため鋭意研究を行った結果、ビニルハロゲン化合物とハロゲン化ケイ素化合物を非プロトン性溶媒中でアルミニウム存在下に反応させることで一般式（1）に示されるビニルシランを得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have shown that the general formula (1) is obtained by reacting a vinyl halogen compound and a silicon halide compound in the presence of aluminum in an aprotic solvent. The present inventors have found that vinylsilane can be obtained and have completed the present invention.
すなわち、本発明は、以下の通りである。
（１） 一般式（１）That is, the present invention is as follows.
(1) General formula (1)
（式中、Ｒは炭素数１〜４の含フッ素有機基を表し、Ａ１，Ａ２，Ａ３はそれぞれ互いに独立し、同一又は異なって、水素原子又は置換基を有してもよい直鎖状若しくは分岐した炭素数１〜４のアルキル基を表す。）
で示されるビニルシランの製造方法であり、非プロトン性溶媒中、アルミニウム存在下、一般式（２）(In the formula, R represents a fluorine-containing organic group having 1 to 4 carbon atoms, and A 1 , A 2 , and A 3 are each independently the same or different and may have a hydrogen atom or a substituent. Represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
In the presence of aluminum in an aprotic solvent in the presence of aluminum.
（式中、Ｘ1はハロゲン原子を表し、Ｒは前記定義に同じ。）
で示されるビニルハロゲン化合物と、一般式（３）(In the formula, X 1 represents a halogen atom, and R is the same as defined above.)
A vinyl halide compound represented by the general formula (3)
（式中Ｘ２はＸ１とは互いに独立し、同一又は異なるハロゲン原子を表し、Ａ１，Ａ２及びＡ３は前記定義に同じ）
で示されるハロゲン化ケイ素化合物を反応させて、上記一般式（１）で示されるビニルシランを生成することを特徴とするビニルシランの製造方法。(In the formula, X 2 is independent of X 1 and represents the same or different halogen atom, and A 1 , A 2 and A 3 are the same as defined above)
A method for producing vinyl silane, characterized in that a vinyl silane represented by the general formula (1) is produced by reacting a silicon halide compound represented by formula (1).
（２） 前記一般式（２）において、Ｘ1は臭素原子、Ｒは炭素数１〜４の含フッ素有機基を表すビニルハロゲン化合物であり、
前記一般式（３）において、Ａ１，Ａ２及びＡ３はメチル基を表し、Ｘ２は塩素原子を表すハロゲン化ケイ素化合物であることを特徴とする前記一般式（１）のＲが炭素数１〜４の含フッ素有機基、Ａ１，Ａ２およびＡ３がメチル基を表すビニルシランである（１）に記載のビニルシランの製造方法。(2) In the general formula (2), X 1 is a bromine atom, R is a vinyl halogen compound representing a fluorine-containing organic group having 1 to 4 carbon atoms,
In the general formula (3), A 1 , A 2 and A 3 each represent a methyl group, and X 2 is a halogenated silicon compound representing a chlorine atom, wherein R in the general formula (1) is carbon. The method for producing vinyl silane according to (1), wherein the fluorine-containing organic group of formulas 1 to 4, A 1 , A 2 and A 3 are vinyl silanes representing a methyl group.
（３） 前記一般式（２）で示されるビニルハロゲン化合物が２−ブロモ−３，３，３−トリフルオロプロペンであり、前記一般式（３）で示されるハロゲン化ケイ素化合物がクロロトリメチルシランであることを特徴とする前記一般式（１）で示される化合物が（１−トリフルオロメチルビニル）トリメチルシランである（１）又は（２）に記載のビニルシランの製造方法。 (3) The vinyl halogen compound represented by the general formula (2) is 2-bromo-3,3,3-trifluoropropene, and the silicon halide compound represented by the general formula (3) is chlorotrimethylsilane. The method for producing vinylsilane according to (1) or (2), wherein the compound represented by the general formula (1) is (1-trifluoromethylvinyl) trimethylsilane.
（４） 前記非プロトン性溶媒が、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチル−２−ピロリドンおよびＮ，Ｎ−ジメチルホルムアミドからなる群より選ばれる少なくとも１種である（１）ないし（３）のいずれか１項に記載のビニルシランの製造方法。 (4) The aprotic solvent is at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and N, N-dimethylformamide (1) Thru | or the manufacturing method of vinyl silane of any one of (3).
（５） 反応温度が０〜６０℃である（１）ないし（３）のいずれか１項に記載のビニルシランの製造方法。 (5) The method for producing vinyl silane according to any one of (1) to (3), wherein the reaction temperature is 0 to 60 ° C.
（６） 反応圧力が０〜０．２０ＭＰａ（ゲージ圧力）である（１）ないし（３）のいずれか１項に記載のビニルシランの製造方法。 (6) The method for producing vinyl silane according to any one of (1) to (3), wherein the reaction pressure is 0 to 0.20 MPa (gauge pressure).
一般式（１）で示されるビニルシランに関しては、従来技術としてアセチレン系化合物のヒドロシリル化が挙げられる。しかしながら、ヒドロシリル化法は異性体との混合物として得られるため収率が低い上に、分離が難しく、工業的には利用価値が低いという課題がある。またガス状アセチレン系化合物を取り扱う際は危険性を伴い、使用できる容器の材質にも制限があるといった問題がある。 As for the vinyl silane represented by the general formula (1), hydrosilylation of acetylene compounds can be mentioned as a conventional technique. However, since the hydrosilylation method is obtained as a mixture with isomers, there is a problem that the yield is low, separation is difficult, and industrial utility value is low. Moreover, when handling a gaseous acetylene-type compound, there exists a problem that there exists a danger and the material of the container which can be used also has a restriction | limiting.
従来法と比較して、本発明におけるビニルシランの製造方法は原料をアセチレン系化合物に替えてビニルハロゲン化合物を用いるため、安全かつ容易に、収率良く主生成物としてビニルシランを得ることが可能であり、工業的に利用価値は高い。 Compared with the conventional method, the method for producing vinyl silane in the present invention uses a vinyl halogen compound instead of the acetylene compound, so it is possible to obtain vinyl silane as a main product safely and easily in a high yield. Industrial utility value is high.
以下、本発明を詳細に説明する。本発明は前記一般式（１）に示されたビニルシランの製造方法に関するものであり、非プロトン性溶媒中、アルミニウム存在下、一般式（２）で示されるビニルハロゲン化合物と、一般式（３）で示されるハロゲン化ケイ素化合物を反応させてビニルシランを生成することを特徴とする製造方法である。 Hereinafter, the present invention will be described in detail. The present invention relates to a process for producing the vinylsilane represented by the general formula (1), and in the presence of aluminum in an aprotic solvent, the vinyl halogen compound represented by the general formula (2) and the general formula (3) A vinyl silane is produced by reacting a silicon halide compound represented by the formula:
前記一般式（１）で示されるビニルシランにおいて、Ｒで示される炭素数１〜４の含フッ素有機基としては、例えば炭素数１〜２の低級含フッ素有機基であることが好ましく、炭素数１の含フッ素有機基がさらに好ましい。で示される含フッ素有機基の例としては、特に制限するわけではないが、トリフルオロメチル基、２，２，２−トリフルオロエチル基、パーフルオロエチル基等が挙げられる。Ａ１，Ａ２，Ａ３における炭素数１〜４のアルキル基としては、炭素数１〜２の低級アルキル基であることが好ましく、炭素数１がさらに好ましい。アルキル基の例としては、特に制限するわけではないが、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられる。In the vinylsilane represented by the general formula (1), the fluorinated organic group having 1 to 4 carbon atoms represented by R is preferably, for example, a lower fluorinated organic group having 1 to 2 carbon atoms. The fluorine-containing organic group is more preferable. Examples of the fluorine-containing organic group represented by (2) include, but are not limited to, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, and the like. The alkyl group having 1 to 4 carbon atoms in A 1 , A 2 and A 3 is preferably a lower alkyl group having 1 to 2 carbon atoms, and more preferably 1 carbon atom. Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group and the like.
前記一般式（１）で示されるビニルシランとしては、例えば（１−トリフルオロメチルビニル）トリメチルシラン、（１−ペンタフルオロエチルビニル）トリメチルシラン、［１−（２，２，２−トリフルオロエチル）ビニル］トリメチルシランであることが好ましく、（１−トリフルオロメチルビニル）トリメチルシランがさらに好ましい。 Examples of the vinyl silane represented by the general formula (1) include (1-trifluoromethylvinyl) trimethylsilane, (1-pentafluoroethylvinyl) trimethylsilane, and [1- (2,2,2-trifluoroethyl). Vinyl] trimethylsilane is preferred, and (1-trifluoromethylvinyl) trimethylsilane is more preferred.
前記一般式（２）で示されるビニルハロゲン化合物において、Ｒは前記一般式（１）に同じである。また、Ｘ１で表されるハロゲン原子は塩素、臭素、ヨウ素が好ましく、さらに臭素が好ましい。In the vinyl halogen compound represented by the general formula (2), R is the same as the general formula (1). The halogen atom represented by X 1 is preferably chlorine, bromine or iodine, and more preferably bromine.
前記一般式（２）で示されるビニルハロゲン化合物としては、例えば２−クロロ−３，３，３−トリフルオロプロペン、２−ブロモ−３，３，３−トリフルオロプロペン、２−ヨード−３，３，３−トリフルオロプロペンであることが好ましく、２−ブロモ−３，３，３−トリフルオロプロペンがさらに好ましい。 Examples of the vinyl halogen compound represented by the general formula (2) include 2-chloro-3,3,3-trifluoropropene, 2-bromo-3,3,3-trifluoropropene, 2-iodo-3, 3,3-trifluoropropene is preferred, and 2-bromo-3,3,3-trifluoropropene is more preferred.
前記一般式（３）で示されるハロゲン化ケイ素化合物において、Ｘ1及びＡ１，Ａ２，
Ａ３は前記一般式（１）に同じである。またＸ２で表されるハロゲン原子は塩素、臭素、ヨウ素が好ましく、さらに塩素が好ましい。In the silicon halide compound represented by the general formula (3), X 1 and A 1 , A 2 ,
A 3 is the same as the general formula (1). The halogen atom represented by X 2 is preferably chlorine, bromine or iodine, and more preferably chlorine.
前記一般式（３）で示されるハロゲン化ケイ素化合物としては、例えばクロロトリメチルシラン、ブロモトリメチルシラン、ヨードトリメチルシランであることが好ましく、クロロトリメチルシランがさらに好ましい。 The halogenated silicon compound represented by the general formula (3) is preferably, for example, chlorotrimethylsilane, bromotrimethylsilane, or iodotrimethylsilane, and more preferably chlorotrimethylsilane.
本発明の反応は、アルミニウムもしくはアルミニウムを含有する金属のいずれも使用可能である。通常に市販のアルミニウムを直接用いることができる。アルミニウムの形状としては、粒状品、粉末品のいずれも使用することができるが、有機溶媒への分散性の面から粉末品が好ましい。 In the reaction of the present invention, either aluminum or a metal containing aluminum can be used. Usually, commercially available aluminum can be used directly. As the shape of aluminum, either a granular product or a powder product can be used, but a powder product is preferable from the viewpoint of dispersibility in an organic solvent.
本発明の反応は、溶媒として非プロトン性溶媒を用いることが好ましい。非プロトン性溶媒の具体例としてはジメトキシエタン（ＤＭＥ）、ジエチレングリコールジメチルエーテル（ＤＧＭ）、ヘキサメチルリン酸トリアミド（ＨＭＰＡ）、テトラヒドロフラン（ＴＨＦ）、１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等が挙げられる。中でも反応の収率が高く、また蒸留精製工程において反応生成物と溶媒の蒸留分離が容易である点から、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミドが好ましい。これらは単独で使用し得るのみならず、２種類以上を混合して用いることも可能である。 In the reaction of the present invention, an aprotic solvent is preferably used as the solvent. Specific examples of the aprotic solvent include dimethoxyethane (DME), diethylene glycol dimethyl ether (DGM), hexamethylphosphoric triamide (HMPA), tetrahydrofuran (THF), 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) and the like can be mentioned. Among them, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N, and the like, because the reaction yield is high and the reaction product and the solvent are easily separated by distillation in the distillation purification step. N-dimethylformamide is preferred. These can be used alone or in combination of two or more.
本発明で用いられる試薬はあらゆる慣用の方法に従って導入することができ、ビニルハロゲン化合物とハロゲン化ケイ素化合物を、同時にまたは混合物として、溶媒およびアルミニウムから成る混合物に投入することができる。またビニルハロゲン化合物を溶媒、アルミニウム、ハロゲン化ケイ素化合物から成る三成分の混合物中に投入すること、あるいはハロゲン化ケイ素化合物を溶媒、アルミニウム、ビニルハロゲン化合物から成る三成分の混合物中に投入することも可能である。 The reagent used in the present invention can be introduced according to any conventional method, and the vinyl halide compound and the silicon halide compound can be introduced into a mixture comprising a solvent and aluminum simultaneously or as a mixture. Alternatively, the vinyl halide compound may be put into a ternary mixture consisting of a solvent, aluminum and a silicon halide compound, or the silicon halide compound may be put into a ternary mixture consisting of a solvent, aluminum and a vinyl halide compound. Is possible.
本発明で使用する試薬の量は、前記一般式（２）で示されるビニルハロゲン化合物１ｍｏｌに対して前記一般式（３）で示されるハロゲン化ケイ素化合物０．１〜５０ｍｏｌであるのが好ましく、さらに好ましくは０．５〜２ｍｏｌである。また前記一般式（２）で示されるビニルハロゲン化合物１ｍｏｌに対してアルミニウムは０．１〜５ｍｏｌであるのが好ましく、さらに好ましくは０．５〜２ｍｏｌである。溶媒量は特に制限するわけではないが、使用するビニルハロゲン化合物１ｇに対して溶媒１〜１００ｇが好ましく、３〜２０ｇがさらに好ましい。 The amount of the reagent used in the present invention is preferably 0.1 to 50 mol of the silicon halide compound represented by the general formula (3) with respect to 1 mol of the vinyl halogen compound represented by the general formula (2). More preferably, it is 0.5-2 mol. Moreover, it is preferable that aluminum is 0.1-5 mol with respect to 1 mol of vinyl halogen compounds shown by the said General formula (2), More preferably, it is 0.5-2 mol. The amount of the solvent is not particularly limited, but is preferably 1 to 100 g, more preferably 3 to 20 g, with respect to 1 g of the vinyl halogen compound to be used.
本発明の反応は窒素、アルゴン等の不活性ガス気流下で行うのが好ましい。反応温度は−２０℃〜１２０℃で可能であるが、０℃〜６０℃が好ましい。温度が−２０℃未満であると反応速度が遅いため、反応が充分に進行しない傾向があるために好ましくない。また１２０℃を超えると目的物であるビニルシランの収率が低下して、還元生成物の割合が増加する傾向があるために好ましくない。 The reaction of the present invention is preferably carried out under an inert gas stream such as nitrogen or argon. The reaction temperature can be −20 ° C. to 120 ° C., preferably 0 ° C. to 60 ° C. If the temperature is lower than −20 ° C., the reaction rate is slow, and the reaction tends not to proceed sufficiently, which is not preferable. Moreover, when it exceeds 120 degreeC, since the yield of the target vinylsilane falls and there exists a tendency for the ratio of a reduction product to increase, it is unpreferable.
反応器は大気開放型の反応器、またはオートクレーブ等の密閉型の反応器のいずれも可能である。反応圧力は大気圧下、または加圧下のいずれも可能であるが、０〜０．２０ＭＰａ（ゲージ圧力）が好ましい。 The reactor can be either an open-air reactor or a closed reactor such as an autoclave. The reaction pressure can be either atmospheric or pressurized, but is preferably 0 to 0.20 MPa (gauge pressure).
反応生成物は直接、または水を加えた後に精製することが可能である。常圧下、または減圧下で蒸留することにより単離および精製することができ、本発明の目的化合物を得ることができる。 The reaction product can be purified directly or after adding water. It can be isolated and purified by distillation under normal pressure or under reduced pressure, and the target compound of the present invention can be obtained.
実施例
以下、実施例により本発明をさらに詳細に説明するが、本発明は下記の実施例に限定されるものではない。Examples Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
還流冷却管、温度計、攪拌機を備えた５００ｍＬフラスコに窒素気流下、１，３−ジメチル−２−イミダゾリジノン２６０ｍＬ、アルミニウム６．３ｇ（０．２３ｍｏｌ）を加え、クロロトリメチルシラン４０ｇ（０．３７ｍｏｌ）を添加した。２−ブロモ−３，３，３−トリフルオロプロペン４１ｇ（０．２３ｍｏｌ）を加え、反応温度３０℃で４３時間反応した。反応終了後、水１００ｍＬを滴下した。単蒸留して（１−トリフルオロメチルビニル）トリメチルシラン２２ｇを含む生成物を得た（収率５７％）。 Under a nitrogen stream, 260 mL of 1,3-dimethyl-2-imidazolidinone and 6.3 g (0.23 mol) of aluminum were added to a 500 mL flask equipped with a reflux condenser, a thermometer, and a stirrer, and 40 g of chlorotrimethylsilane (0. 37 mol) was added. 2-Bromo-3,3,3-trifluoropropene (41 g, 0.23 mol) was added and reacted at a reaction temperature of 30 ° C. for 43 hours. After completion of the reaction, 100 mL of water was added dropwise. By simple distillation, a product containing 22 g of (1-trifluoromethylvinyl) trimethylsilane was obtained (yield 57%).
５Ｌオートクレーブに窒素気流下、１，３−ジメチル−２−イミダゾリジノン３１００ｍＬ、アルミニウム７７ｇ（２．９ｍｏｌ）を加え、クロロトリメチルシラン３１０ｇ（２．９ｍｏｌ）を添加した。２−ブロモ−３，３，３−トリフルオロプロペン５００ｇ（２．９ｍｏｌ）を加え、反応温度３０℃で６８時間反応した。反応終了時点での圧力は０．１７ＭＰａ（ゲージ圧）であった。反応液を単蒸留して（１−トリフルオロメチルビニル）トリメチルシランを含む生成物３７４ｇを得た。１９Ｆ−ＮＭＲ内部標準法により定量分析したところ、（１−トリフルオロメチルビニル）トリメチルシランおよび還元生成物である３，３，３−トリフルオロプロペンの収率がそれぞれ５９％，１２％であった。定量分析の際、内部標準物質として２，２，２−トリフルオロエタノールを添加して分析した。Under a nitrogen stream, 3100 mL of 1,3-dimethyl-2-imidazolidinone and 77 g (2.9 mol) of aluminum were added to a 5 L autoclave, and 310 g (2.9 mol) of chlorotrimethylsilane was added. 2-Bromo-3,3,3-trifluoropropene (500 g, 2.9 mol) was added, and the mixture was reacted at a reaction temperature of 30 ° C. for 68 hours. The pressure at the end of the reaction was 0.17 MPa (gauge pressure). The reaction solution was simply distilled to obtain 374 g of a product containing (1-trifluoromethylvinyl) trimethylsilane. The quantitative analysis by the 19 F-NMR internal standard method revealed that the yields of (1-trifluoromethylvinyl) trimethylsilane and the reduction product 3,3,3-trifluoropropene were 59% and 12%, respectively. It was. During quantitative analysis, 2,2,2-trifluoroethanol was added as an internal standard substance for analysis.
これを常圧で精密蒸留して、沸点が８８℃の（１−トリフルオロメチルビニル）トリメチルシラン１８５ｇを得た（収率３８％）。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，内部基準ＴＭＳ）δ０．１３（ｓ，９Ｈ），５．７４（ｄ，１Ｈ，Ｊ＝１．６Ｈｚ），６．２５（ｍ，１Ｈ）
１９Ｆ−ＮＭＲ（ＣＤＣｌ３，内部基準ＣＦＣｌ３）δ−６２．３（ｓ，ＣＦ３）This was subjected to precision distillation at normal pressure to obtain 185 g of (1-trifluoromethylvinyl) trimethylsilane having a boiling point of 88 ° C. (yield 38%).
1 H-NMR (CDCl 3 , internal reference TMS) δ 0.13 (s, 9H), 5.74 (d, 1H, J = 1.6 Hz), 6.25 (m, 1H)
19 F-NMR (CDCl 3 , internal reference CFCl 3 ) δ-62.3 (s, CF 3 )
還流冷却管、温度計、攪拌機を備えた１００ｍＬフラスコに窒素気流下、１，３−ジメチル−２−イミダゾリジノン２５ｍＬ、アルミニウム０．６２ｇ（２３ｍｍｏｌ）を加え、２０℃においてクロロトリメチルシラン２．５ｇ（２３ｍｍｏｌ）を添加した。２−ブロモ−３，３，３−トリフルオロプロペン４．０ｇ（２３ｍｍｏｌ）を加えた後、反応温度３０℃、４２時間反応した。水２５ｍＬを加えて反応を停止させた後にトルエン２５ｍＬで２回抽出した。本溶液を定量分析したところ、（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は５９％であった。定量分析の際、内部標準物質として２，２，２−トリフルオロエタノールを添加して分析した。Under a nitrogen stream, 25 mL of 1,3-dimethyl-2-imidazolidinone and 0.62 g (23 mmol) of aluminum were added to a 100 mL flask equipped with a reflux condenser, thermometer, and stirrer, and 2.5 g of chlorotrimethylsilane at 20 ° C. (23 mmol) was added. After adding 4.0 g (23 mmol) of 2-bromo-3,3,3-trifluoropropene, the mixture was reacted at a reaction temperature of 30 ° C. for 42 hours. The reaction was stopped by adding 25 mL of water, and then extracted twice with 25 mL of toluene. When this solution was quantitatively analyzed, the 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 59%. During quantitative analysis, 2,2,2-trifluoroethanol was added as an internal standard substance for analysis.
実施例３において２−ブロモ−３，３，３−トリフルオロプロペン４．０ｇ（２３ｍｍｏｌ）を加えた後、反応温度５０℃、４１時間反応した以外は同様な反応を行った。（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は４２％であった。In Example 3, after adding 4.0 g (23 mmol) of 2-bromo-3,3,3-trifluoropropene, the same reaction was performed except that the reaction was performed at a reaction temperature of 50 ° C. for 41 hours. The 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 42%.
実施例３において２−ブロモ−３，３，３−トリフルオロプロペン４．０ｇ（２３ｍｍｏｌ）を加えた後、反応温度５℃、１２０時間反応した以外は同様な反応を行った。（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は５０％であった。In Example 3, the same reaction was carried out except that 4.0 g (23 mmol) of 2-bromo-3,3,3-trifluoropropene was added and the reaction was conducted at a reaction temperature of 5 ° C. for 120 hours. The 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 50%.
実施例３においてアルミニウム１．２ｇ（４４ｍｍｏｌ）を加えた以外は同様な反応を行った。（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は５６％であった。A similar reaction was carried out except that 1.2 g (44 mmol) of aluminum was added in Example 3. The 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 56%.
実施例３においてアルミニウム０．４１ｇ（１５ｍｍｏｌ）を加えた後、反応温度３０℃、４６時間反応した以外は同様な反応を行った。（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は４１％であった。In Example 3, 0.41 g (15 mmol) of aluminum was added, and then the same reaction was performed except that the reaction was performed at a reaction temperature of 30 ° C. for 46 hours. The 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 41%.
実施例３において１，３−ジメチル−２−イミダゾリジノン２８ｍＬ、アルミニウム０．２３ｇ（８．６ｍｍｏｌ）、クロロトリメチルシラン０．９３ｇ（８．６ｍｍｏｌ）、２−ブロモ−３，３，３−トリフルオロプロペン１．５ｇ（８．６ｍｍｏｌ）を用いた以外は同様な反応を行った。（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は５９％であった。In Example 3, 28 mL of 1,3-dimethyl-2-imidazolidinone, 0.23 g (8.6 mmol) of aluminum, 0.93 g (8.6 mmol) of chlorotrimethylsilane, 2-bromo-3,3,3-tri A similar reaction was performed except that 1.5 g (8.6 mmol) of fluoropropene was used. The 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 59%.
還流冷却管、温度計、攪拌機を備えた１００ｍＬフラスコに窒素気流下、Ｎ−メチル−２−ピロリドン（ＮＭＰ）２５ｍＬ、アルミニウム０．６２ｇ（２３ｍｍｏｌ）を加え、２０℃においてクロロトリメチルシラン２．５ｇ（２３ｍｍｏｌ）を添加した。２−ブロモ−３，３，３−トリフルオロプロペン４．０ｇ（２３ｍｍｏｌ）を加えた後、反応温度５０℃、６５時間反応した。水２５ｍＬを加えて反応を停止させた後にトルエン２５ｍＬで２回抽出した。本溶液を定量分析したところ、（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は２１％であった。In a 100 mL flask equipped with a reflux condenser, a thermometer, and a stirrer, 25 mL of N-methyl-2-pyrrolidone (NMP) and 0.62 g (23 mmol) of aluminum were added under a nitrogen stream, and 2.5 g of chlorotrimethylsilane at 20 ° C. 23 mmol) was added. After adding 4.0 g (23 mmol) of 2-bromo-3,3,3-trifluoropropene, the mixture was reacted at a reaction temperature of 50 ° C. for 65 hours. The reaction was stopped by adding 25 mL of water, and then extracted twice with 25 mL of toluene. When this solution was quantitatively analyzed, the 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 21%.
還流冷却管、温度計、攪拌機を備えた１００ｍＬフラスコに窒素気流下、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）２５ｍＬ、アルミニウム０．６２ｇ（２３ｍｍｏｌ）を加え、２０℃においてクロロトリメチルシラン２．５ｇ（２３ｍｍｏｌ）を添加した。２−ブロモ−３，３，３−トリフルオロプロペン４．０ｇ（２３ｍｍｏｌ）を加えた後、反応温度５０℃、６５時間反応した。水２５ｍＬを加えて反応を停止させた後にトルエン２５ｍＬで２回抽出した。本溶液を定量分析したところ、（１−トリフルオロメチルビニル）トリメチルシランの１９Ｆ−ＮＭＲ内部標準収率は３％であった。In a 100 mL flask equipped with a reflux condenser, thermometer, and stirrer, 25 mL of N, N-dimethylformamide (DMF) and 0.62 g (23 mmol) of aluminum were added under a nitrogen stream, and 2.5 g (23 mmol) of chlorotrimethylsilane at 20 ° C. ) Was added. After adding 4.0 g (23 mmol) of 2-bromo-3,3,3-trifluoropropene, the mixture was reacted at a reaction temperature of 50 ° C. for 65 hours. The reaction was stopped by adding 25 mL of water, and then extracted twice with 25 mL of toluene. When this solution was quantitatively analyzed, the 19 F-NMR internal standard yield of (1-trifluoromethylvinyl) trimethylsilane was 3%.
本発明のビニルシランの製造方法は、原料としてビニルハロゲン化合物を用いるため、安全かつ容易に、収率良く主生成物としてビニルシランを得ることが可能であり、工業的に利用価値は高い。
Since the vinyl silane compound of the present invention uses a vinyl halogen compound as a raw material, it is possible to obtain vinyl silane as a main product with good yield in a safe and easy manner, and its industrial utility value is high.
Claims (6)
で示されるビニルシランの製造方法であり、非プロトン性溶媒中、アルミニウム存在下、一般式（２）
で示されるビニルハロゲン化合物と、
一般式（３）
で示されるハロゲン化ケイ素化合物を反応させて、上記一般式（１）で示されるビニルシランを生成することを特徴とするビニルシランの製造方法。General formula (1)
In the presence of aluminum in an aprotic solvent in the presence of aluminum.
A vinyl halide compound represented by
General formula (3)
A method for producing vinyl silane, characterized in that a vinyl silane represented by the general formula (1) is produced by reacting a silicon halide compound represented by formula (1).
前記一般式（３）において、Ａ１，Ａ２およびＡ３はメチル基を表し、Ｘ２は塩素原子を表すハロゲン化ケイ素化合物であることを特徴とする前記一般式（１）のＲが炭素数１〜４の含フッ素有機基、Ａ１，Ａ２及びＡ３がメチル基を表すビニルシランである請求項１に記載のビニルシランの製造方法。In the general formula (2), X 1 is a bromine atom, R is a vinyl halogen compound representing a fluorine-containing organic group having 1 to 4 carbon atoms,
In the general formula (3), A 1 , A 2 and A 3 represent a methyl group, and X 2 is a halogenated silicon compound representing a chlorine atom, wherein R in the general formula (1) is carbon The method for producing a vinyl silane according to claim 1 , wherein the fluorine-containing organic group of formulas 1 to 4, A 1 , A 2 and A 3 are vinyl silanes representing a methyl group.
The method for producing vinylsilane according to any one of claims 1 to 3, wherein the reaction pressure is 0 to 0.20 MPa (gauge pressure).
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