JPH0684381B2 - Method for producing organosilicon compound - Google Patents
Method for producing organosilicon compoundInfo
- Publication number
- JPH0684381B2 JPH0684381B2 JP2245121A JP24512190A JPH0684381B2 JP H0684381 B2 JPH0684381 B2 JP H0684381B2 JP 2245121 A JP2245121 A JP 2245121A JP 24512190 A JP24512190 A JP 24512190A JP H0684381 B2 JPH0684381 B2 JP H0684381B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- organosilicon compound
- organic
- reaction
- complex
- 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.)
- Expired - Lifetime
Links
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- -1 erkirthio Chemical group 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- WTPDCCLDUUWFKK-UHFFFAOYSA-N phenyl(1-phenylethyl)silane Chemical compound C=1C=CC=CC=1C(C)[SiH2]C1=CC=CC=C1 WTPDCCLDUUWFKK-UHFFFAOYSA-N 0.000 description 4
- JLSYTXUXBUMLKN-UHFFFAOYSA-N phenyl(2-phenylethyl)silane Chemical compound C=1C=CC=CC=1[SiH2]CCC1=CC=CC=C1 JLSYTXUXBUMLKN-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZWYCTGLWNKJOTD-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Nd](C([Si](C)(C)C)[Si](C)(C)C)C1(C(=C(C(=C1C)C)C)C)C)C)C)C Chemical compound CC1=C(C(=C(C1(C)[Nd](C([Si](C)(C)C)[Si](C)(C)C)C1(C(=C(C(=C1C)C)C)C)C)C)C)C ZWYCTGLWNKJOTD-UHFFFAOYSA-N 0.000 description 1
- UQUMMQCBCUHYFT-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Nd])C)C)C Chemical compound CC1=C(C(=C(C1(C)[Nd])C)C)C UQUMMQCBCUHYFT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- KRZXWIWNHRUKDF-UHFFFAOYSA-N hexylsilicon Chemical compound CCCCCC[Si] KRZXWIWNHRUKDF-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- QFXXGTZVYQQGFZ-UHFFFAOYSA-N phenyl(phenylsilyl)silane Chemical compound C=1C=CC=CC=1[SiH2][SiH2]C1=CC=CC=C1 QFXXGTZVYQQGFZ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 150000005671 trienes Chemical class 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は有機ケイ素化合物の製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a method for producing an organosilicon compound.
有機ケイ素化合物は、シリコーンポリマー原料、シリコ
ンカーバイド繊維原料、シランカップリング剤、有機合
成試薬、医農薬中間体等として用いられる有用な化合物
である。The organosilicon compound is a useful compound used as a raw material of silicone polymer, a raw material of silicon carbide fiber, a silane coupling agent, an organic synthetic reagent, an intermediate for medicine and agricultural chemicals.
従来、有機ケイ素化合物の合成法としてはケイ素単体と
有機ハロゲン化物を反応させるいわゆる直接法、ハロシ
ランとグリニャール試薬を反応させる方法、ヒドロシラ
ンと不飽和有機化合物を反応させるヒドロシリル化反応
等が知られている。Conventionally known methods for synthesizing organosilicon compounds include a so-called direct method for reacting a simple substance of silicon and an organic halide, a method for reacting a halosilane and a Grignard reagent, and a hydrosilylation reaction for reacting a hydrosilane and an unsaturated organic compound. .
このうち、ヒドロシリル化反応はオレフィン等の安価な
原料を用いて種々多様な有機ケイ素化合物を得ることが
できる有用な反応である。通常ヒドロシリル化反応は、
白金、ロジウム等を含む遷移金属化合物やラジカル発生
剤を触媒として実施されるが、反応の位置選択性が低
い、ヒドロシランの再分配や不飽和化合物の重合が多
い、触媒活性が低い、等様々な問題があった。Among them, the hydrosilylation reaction is a useful reaction that can obtain various organosilicon compounds using inexpensive raw materials such as olefins. Usually the hydrosilylation reaction is
It is carried out using a transition metal compound containing platinum, rhodium, etc. or a radical generator as a catalyst, but the regioselectivity of the reaction is low, the redistribution of hydrosilane or the polymerization of unsaturated compounds is large, the catalytic activity is low, etc. There was a problem.
一方、近年、資源量の乏しい貴金属錯体に代えて豊富に
存在するランタノイド金属の錯体を触媒反応に利用しよ
うとする試みが活発になりつつあるが、触媒活性が報告
されていのは水素化、エチレン重合などごく少数の反応
に限られている。On the other hand, in recent years, attempts to utilize abundant lanthanoid metal complexes in place of precious metal complexes, which are poor in resources, for catalytic reactions have become active, but catalytic activity has been reported to be due to hydrogenation and ethylene. Limited to very few reactions, such as polymerization.
したがって本発明の目的は高活性、高選択率で有機ケイ
素化合物を製造しうる方法を提供することにある。Therefore, an object of the present invention is to provide a method capable of producing an organosilicon compound with high activity and high selectivity.
すなわち、本発明は有機ネオジム錯体存在下、オレフィ
ンとヒドロシラン化合物を反応させることを特徴とする
有機ケイ素化合物の製造方法を提供するものである。That is, the present invention provides a method for producing an organosilicon compound, which comprises reacting an olefin with a hydrosilane compound in the presence of an organic neodymium complex.
本発明で触媒として用いられる有機ネオジム錯体の配位
子としては、ハロゲン、水素、アルキル、アラルキル、
アリール、アルキルシリル、アリールシリル、オレフィ
ン、ジエン、トリエン、テトラエン、シクロジエン、シ
クロトリエン、シクロテトラエン、アリル、アルコキ
シ、アリールオキシ、エルキルチオ、アリールチオ、シ
クロペンタジエニル、アルキルアミン、アリールアミ
ン、ピリジル、アルキルホスフィン、アリールホスフィ
ン、アルキルアリールホスフィン、アルキルイソシアニ
ド、アリールイソシアニド、エーテル、環状エーテル等
を用いることができる。これらの配位子は置換基を有し
ているものも包含する。The ligand of the organic neodymium complex used as a catalyst in the present invention includes halogen, hydrogen, alkyl, aralkyl,
Aryl, alkylsilyl, arylsilyl, olefin, diene, triene, tetraene, cyclodiene, cyclotriene, cyclotetraene, allyl, alkoxy, aryloxy, erkirthio, arylthio, cyclopentadienyl, alkylamine, arylamine, pyridyl, alkyl Phosphine, arylphosphine, alkylarylphosphine, alkylisocyanide, arylisocyanide, ether, cyclic ether and the like can be used. These ligands also include those having a substituent.
本発明で触媒として用いられる金属錯体の構造として下
記一般式（Ｉ）で表わされるもの、またはその会合体が
好ましいが、これらに限定されるものではない。The structure of the metal complex used as a catalyst in the present invention is preferably one represented by the following general formula (I) or an associated body thereof, but is not limited thereto.
Cp* 2NdR （Ｉ） （なお式中、Cp*はシクロペンタジエニル基またはその
置換体、Ｒは水素、１価の有機基または１価のシリル基
を表す。） 一般式（Ｉ）における配位子Ｒをさらに具体的に例示す
ると、水素、メチル、ビス（トリメチルシリル）メチ
ル、ベンジル、フェニル、トリル、ジメチルシリル、フ
ェニルシリル、フェニルメチルシリル等である。また、
配位子Cp*としてはペンタメチルシクロペンタジエニ
ル、メチルシクロペンタジエニル、シクロペンタジエニ
ル等を例示することができる。Cp * 2 NdR (I) (In the formula, Cp * represents a cyclopentadienyl group or a substituted product thereof, and R represents hydrogen, a monovalent organic group or a monovalent silyl group.) In formula (I) More specific examples of the ligand R are hydrogen, methyl, bis (trimethylsilyl) methyl, benzyl, phenyl, tolyl, dimethylsilyl, phenylsilyl, phenylmethylsilyl and the like. Also,
Examples of the ligand Cp * include pentamethylcyclopentadienyl, methylcyclopentadienyl, cyclopentadienyl and the like.
本発明で用いられるヒドロシラン化合物は、下記一般式
（III） R1R2R3SiH （III） （式中、R1R2R3は、水素、ハロゲン、炭化水素基、また
はシリル基であり、互いに同じであっても異なっていて
もよい）で表わされる。The hydrosilane compound used in the present invention is represented by the following general formula (III) R 1 R 2 R 3 SiH (III) (wherein R 1 R 2 R 3 is hydrogen, halogen, a hydrocarbon group, or a silyl group). , Which may be the same as or different from each other).
このようなヒドロシラン化合物として、具体的にはテト
ラヒドロシラン、メチルシラン、エチルシラン、ｎ−ヘ
キシルシラン、フェニルシラン、ジメチルシラン、ジエ
チルシラン、ジフェニルシラン、フェニルジメチルシラ
ン、トリクロロシラン、1,2−ジフェニルジシラン等を
挙げることができる。Specific examples of such hydrosilane compounds include tetrahydrosilane, methylsilane, ethylsilane, n-hexylsilane, phenylsilane, dimethylsilane, diethylsilane, diphenylsilane, phenyldimethylsilane, trichlorosilane, and 1,2-diphenyldisilane. Can be mentioned.
本発明で用いられる不飽和化合物としては、オレフィ
ン、ジエン、アセチレン、アレン等を挙げることがで
き、さらに具体的には、エチレン、プロピレン、ブテ
ン、ｎ−ヘキセン、シクロヘキセン、ブタジエン、イソ
プレン、スチレン、フェニルアセチレン等である。Examples of the unsaturated compound used in the present invention include olefins, dienes, acetylenes, allenes, and the like, and more specifically, ethylene, propylene, butene, n-hexene, cyclohexene, butadiene, isoprene, styrene, phenyl. Acetylene and the like.
上記のような有機ネオジム錯体を触媒とするヒドロシリ
ル化反応は以下のような反応条件下に行うことが望まし
い。The hydrosilylation reaction using the above-mentioned organic neodymium complex as a catalyst is preferably carried out under the following reaction conditions.
反応温度は−50℃から300℃、通常は20℃から200℃であ
る。The reaction temperature is -50 ° C to 300 ° C, usually 20 ° C to 200 ° C.
反応に際しては、溶媒は必ずしも必要ではないが、トル
エン、ベンゼン等の芳香族化合物、ジエチルエーテル、
テトラヒドロフラン、ジオキサン等のエーテル類、ペン
タン、ヘキサン、デカン等の脂肪族炭化水素等を溶媒と
して用いることができる。A solvent is not always necessary for the reaction, but an aromatic compound such as toluene or benzene, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, aliphatic hydrocarbons such as pentane, hexane, and decane can be used as a solvent.
ヒドロシラン化合物とオレフィンのモル比は任意に設定
することができるが、好ましくは１対１である。The molar ratio of the hydrosilane compound to the olefin can be set arbitrarily, but it is preferably 1: 1.
触媒としての前記金属錯体は、ヒドロシラン化合物また
はオレフィンの少ない方１モルに対して0.001から0.5モ
ル、好ましくは0.001から0.05モル程度の量用いられ
る。The metal complex as a catalyst is used in an amount of about 0.001 to 0.5 mol, preferably about 0.001 to 0.05 mol, based on 1 mol of the less hydrosilane compound or olefin.
本発明の反応によりヒドロシラン化合物にオレフィンが
結合し、いわゆるアルキル化される。By the reaction of the present invention, an olefin is bonded to the hydrosilane compound and so-called alkylation is performed.
生成物の分離は、反応液を蒸留、クロマトグラフィー、
再結晶等の通常の精製操作に付することによって容易に
実施される。The products can be separated by distilling the reaction solution, chromatography,
It is easily carried out by subjecting it to a usual purification operation such as recrystallization.
本発明のヒドロシリル化反応では、有機ネオジム錯体を
触媒として室温付近の温和な条件下で高収率で種々の有
機ケイ素化合物が得られる。しかも、白金、ロジウム等
の錯体を用いる従来のヒドロシリル化法に比べ高い位置
選択性が容易に達成され、また、ヒドロシランの再分配
などの副反応も少ない。In the hydrosilylation reaction of the present invention, various organosilicon compounds can be obtained in high yield under mild conditions near room temperature using an organic neodymium complex as a catalyst. Moreover, higher regioselectivity is easily achieved as compared with the conventional hydrosilylation method using a complex such as platinum or rhodium, and side reactions such as redistribution of hydrosilane are few.
次に本発明を実施例によってさらに具体的に説明する。
なお、生成物はガスクロマトグラフィーを用いて内部標
準法により定量し、また、分取ガスクロマトグラフ等で
単離精製後、1H−NMR、13C−NMR、1R、GC−MSにより構
造を確認した。Next, the present invention will be described more specifically by way of examples.
The product is quantified by the internal standard method using gas chromatography, and after isolation and purification by preparative gas chromatography, etc., the structure is confirmed by 1 H-NMR, 13 C-NMR, 1R, and GC-MS. did.
実施例１ ビス（ペンタメチルシクロペンタジエニル）（ビス（ト
リメチルシリル）メチル）ネオジム（0.01mmol）、フェ
ニルシラン（1.00mmol）及びスチレン（1.00mmol）のベ
ンゼン（1.0ml）溶液を窒素雰囲気下、30℃で２日間攪
拌したところ、１−フェニル−１−フェニルシリルエタ
ンと１−フェニル−２−フェニルシリルエタンが各々68
％及び６％の収率で生成した。Example 1 A solution of bis (pentamethylcyclopentadienyl) (bis (trimethylsilyl) methyl) neodymium (0.01 mmol), phenylsilane (1.00 mmol) and styrene (1.00 mmol) in benzene (1.0 ml) under a nitrogen atmosphere at 30 After stirring for 2 days at ℃, 1-phenyl-1-phenylsilylethane and 1-phenyl-2-phenylsilylethane each 68
% And 6% yield.
実施例２ ヒドロビス（ペンタメチルシクロペンタジエニル）ネオ
ジム（0.005mmol）、フェニルシラン（0.25mmol）及び
スチレン（0.25mmol）のベンゼン（1.0ml）溶液を窒素
雰囲気下、80℃で２日攪拌したところ、１−フェニル−
１−フェニルシリルエタンと１−フェニル−２−フェニ
ルシリルエタンが各々60％及び27％の収率で得られた。
またヒドロシランの再分配反応によりジフェニルシラン
が２％生成した。Example 2 A solution of hydrobis (pentamethylcyclopentadienyl) neodymium (0.005 mmol), phenylsilane (0.25 mmol) and styrene (0.25 mmol) in benzene (1.0 ml) was stirred at 80 ° C. for 2 days under a nitrogen atmosphere. , 1-phenyl-
1-Phenylsilylethane and 1-phenyl-2-phenylsilylethane were obtained in yields of 60% and 27%, respectively.
Further, 2% of diphenylsilane was produced by the redistribution reaction of hydrosilane.
比較例１ 実施例２と同様の反応をネオジム錯体の代わりに塩化白
金酸を触媒として行ったところ、１−フェニル−１−フ
ェニルシリルエタンと１−フェニル−２−フェニルシリ
ルエタン及びジフェニルシランが各々、１％、４％、11
％の収率で生成した。Comparative Example 1 When the same reaction as in Example 2 was carried out using chloroplatinic acid as a catalyst instead of the neodymium complex, 1-phenyl-1-phenylsilylethane, 1-phenyl-2-phenylsilylethane and diphenylsilane were obtained, respectively. 1%, 4%, 11
Produced in% yield.
比較例２ 実施例２と同様の反応をネオジム錯体の代わりにクロロ
トリス（トリフェニルホスフィン）ロジウムを触媒とし
て行ったところ、１−フェニル−１−フェニルシリルエ
タン、１−フェニル−２−フェニルシリルエタンの収率
は各々１％以下であり、またジフェニルシランが17％の
収率で生成した。Comparative Example 2 When the same reaction as in Example 2 was carried out using chlorotris (triphenylphosphine) rhodium as a catalyst instead of the neodymium complex, 1-phenyl-1-phenylsilylethane and 1-phenyl-2-phenylsilylethane were obtained. Yields were less than 1% each and diphenylsilane was produced in 17% yield.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔ ｓ，95〔３〕（1981），25190ｍ. Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔ ｓ，106〔７〕（1987），50284ｙ. ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Chemical Abstracts, 95 [3] (1981), 25190m. Chemical Abstracts, 106 [7] (1987), 50284y.
Claims (2)
ドロシラン化合物を反応させることを特徴とする有機ケ
イ素化合物の製造方法。1. A method for producing an organosilicon compound, which comprises reacting an olefin with a hydrosilane compound in the presence of an organic neodymium complex.
される錯体、またはその会合体である請求項１の方法。 Cp* 2NdR （Ｉ） （式中、Cp*はシクロペンタジエニル基またはその置換
体、Ｒは水素、１価の有機基または１価のシリル基を表
す。）2. The method according to claim 1, wherein the organic neodymium complex is a complex represented by the following general formula (I) or an aggregate thereof. Cp * 2 NdR (I) (In the formula, Cp * represents a cyclopentadienyl group or a substituted product thereof, and R represents hydrogen, a monovalent organic group or a monovalent silyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2245121A JPH0684381B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing organosilicon compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2245121A JPH0684381B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing organosilicon compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04124189A JPH04124189A (en) | 1992-04-24 |
| JPH0684381B2 true JPH0684381B2 (en) | 1994-10-26 |
Family
ID=17128935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2245121A Expired - Lifetime JPH0684381B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing organosilicon compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0684381B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2560247B2 (en) * | 1994-03-11 | 1996-12-04 | 工業技術院長 | Method for producing polycarbosilanes |
| JP2666208B2 (en) * | 1994-03-11 | 1997-10-22 | 工業技術院長 | Production method of organic silanes |
| JP4597406B2 (en) * | 2000-03-14 | 2010-12-15 | 独立行政法人科学技術振興機構 | Method for producing organosilicon compound |
| JP6869333B2 (en) * | 2016-09-02 | 2021-05-12 | 株式会社ブリヂストン | Preparation of cis-1,4-polydiene with multiple silane functional groups prepared by in-situ hydrosilylation of polymer cements |
-
1990
- 1990-09-14 JP JP2245121A patent/JPH0684381B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| ＣｈｅｍｉｃａｌＡｂｓｔｒａｃｔｓ，１０６〔７〕（１９８７），５０２８４ｙ． |
| ＣｈｅｍｉｃａｌＡｂｓｔｒａｃｔｓ，９５〔３〕（１９８１），２５１９０ｍ． |
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| Publication number | Publication date |
|---|---|
| JPH04124189A (en) | 1992-04-24 |
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