JPH04124189A - Production of organosilicon compound - Google Patents
Production of organosilicon compoundInfo
- Publication number
- JPH04124189A JPH04124189A JP2245121A JP24512190A JPH04124189A JP H04124189 A JPH04124189 A JP H04124189A JP 2245121 A JP2245121 A JP 2245121A JP 24512190 A JP24512190 A JP 24512190A JP H04124189 A JPH04124189 A JP H04124189A
- Authority
- JP
- Japan
- Prior art keywords
- complex
- compound
- olefin
- organic
- hydrosilane
- 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
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 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
- 238000000034 method Methods 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- -1 ethylene, propylene Chemical group 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 2
- 229920005573 silicon-containing polymer Polymers 0.000 abstract description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 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
- 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
- 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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
- 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 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-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
- 230000000052 comparative effect Effects 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
- 150000002170 ethers Chemical class 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
- 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 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
- 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
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000002253 acid 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
- 125000004414 alkyl thio 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 150000004696 coordination complex Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 239000000543 intermediate Substances 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
- 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl 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
- 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
- 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
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 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
Abstract
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 [Field of Industrial Application] The present invention relates to a method for producing organosilicon compounds.
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、打機合
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。Organosilicon compounds are useful compounds used as silicone polymer raw materials, silicon carbide fiber raw materials, silane coupling agents, batter synthesis reagents, pharmaceutical and agricultural intermediates, and the like.
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、へロシ
ランとグリニヤ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 the so-called direct method in which silicon itself is reacted with an organic halide, the method in which herosilane is reacted with a Grignard reagent, and the hydrosilylation reaction in which hydrosilane is reacted with an unsaturated organic compound. There is.
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 these, the hydrosilylation reaction is a useful reaction that can produce a wide variety of organosilicon compounds using inexpensive raw materials such as olefins. The hydrosilylation reaction is usually
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, and there are many redistribution of hydrosilane and polymerization of unsaturated compounds.
There were various problems such as low catalytic activity.
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な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
されているのは水素化、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 have been made to use abundant lanthanoid metals in complex catalytic reactions instead of precious metal complexes, which are scarce in resources, but only hydrogenation, It is limited to a few reactions such as ethylene polymerization.
〔発明が解決しようとする課題１
したがって本発明の目的は高活性、高選択率で有機ケイ
素化合物を製造しつる方法を提供することにある。[Problem to be Solved by the Invention 1] Therefore, an object of the present invention is to provide a method for producing an organosilicon compound with high activity and high selectivity.
〔課題を解決するための手段］
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。[Means for Solving the Problems] That is, the present invention provides a method for producing an organosilicon compound, which is characterized by 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、アルキルチオ、アリールチオ、シク
ロペンタジェニル、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、アリールボスフィン、
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 ligands of the organic neodymium complex used as a catalyst in the present invention include halogen, hydrogen, alkyl, aralkyl,
Aryl, alkylsilyl, arylsilyl, olefin, diene, triene, tetraene, cyclodiene, cyclotriene, cyclotetraene, allyl, alkoxy, aryloxy, alkylthio, arylthio, cyclopentadienyl, alkylamine, arylamine,
pyridyl, alkylphosphine, arylbosphine,
alkylarylphosphine, alkyl isocyanide,
Aryl isocyanides, ethers, cyclic ethers, etc. can be used. These ligands also include those having substituents.
本発明で触媒として用いられる金Ｒ錯体の構造としては
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 gold R complex used as a catalyst in the present invention is preferably represented by the following general formula (I) or an aggregate thereof, but is not limited thereto.
Ｃｐ ’ ＊ Ｎ ｄ、 Ｒ（Ｉ ）
（なお式中、Ｃｐｏはシクロペンタジェニル基またはそ
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ェニル
、メチルシクロペンタジェニル、シクロペンタジェニル
等を例示することができる。Cp'*Nd, R(I) (In the formula, Cpo represents a cyclopentadienyl group or a substituted product thereof, R represents hydrogen, a monovalent organic group, or a monovalent silyl group.) General formula (I More specific examples of the ligand R in ) include hydrogen, methyl, bis(trimethylsilyl)methyl, benzyl, phenyl, tolyl, dimethylsilyl, phenylsilyl, phenylmethylsilyl, and the like. Furthermore, examples of the ligand Cp° include pentamethylcyclopentagenyl, methylcyclopentagenyl, cyclopentagenyl, 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）
Ｒ’ Ｒ” Ｒ” ＳｉＨ（ｍ）
（式中、Ｒ’ 、Ｒ” 、Ｒ”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 has the following general formula (III) R'R"R" SiH (m) (wherein R', R" and R" are hydrogen, halogen, hydrocarbon group, or silyl group). and may be the same 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−へ
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、フエニルジメチルシラ
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, 1,2-diphenyldisilane, etc. 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、ブタジェン、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 compounds used in the present invention include olefins, dienes, acetylenes, allenes, etc.
More specifically, ethylene, propylene, butene, n
-hexene, cyclohexene, butadiene, isoprene, styrene, phenylacetylene, etc.
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 an organic neodymium complex as a catalyst as described above is preferably carried out under the following reaction conditions.
反応温度は一５０℃から３００℃、通常は２０℃から２
００℃である。The reaction temperature is -50℃ to 300℃, usually 20℃ to 2℃.
It is 00℃.
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。During the reaction, a solvent is not necessarily required, but aromatic compounds such as toluene and benzene, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, aliphatic hydrocarbons such as pentane, hexane, and decane, etc. can be used as the 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 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０．０００１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 0.0001 to 0.5 mol, preferably about 0.001 to 0.05 mol, per 1 mol of the hydrosilane compound or olefin, whichever is smaller.
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。Through the reaction of the present invention, an olefin is bonded to a hydrosilane compound, resulting in so-called alkylation.
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 product can be separated by distillation of the reaction solution, chromatography,
This can be easily carried out by subjecting it to ordinary purification operations 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 around room temperature using an organo-neodymium complex as a catalyst. Moreover, higher regioselectivity can be easily achieved compared to conventional hydrosilylation methods using complexes of platinum, rhodium, etc., and there are fewer side reactions such as redistribution of hydrosilane.
〔実施例１ 次に本発明を実施例によってさらに具体的に説明する。[Example 1 Next, the present invention will be explained in more detail with reference to Examples.
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、 ’Ｈ−ＮＭＲ１”Ｃ−ＮＭＲｌＩＲ，Ｇ
Ｃ−ＭＳにより構造を確認した。The product was quantified by internal standard method using gas chromatography, and after isolation and purification using preparative gas chromatography, 'H-NMR1''C-NMRlIR,G
The structure was confirmed by C-MS.
実施例１
ビス（ペンタメチルシクロペンタジェニル）（ビス（ト
リメチルシリル）メチル）ネオジム（０、０１，ｍｍｏ
ｌ） 、フェニルシラン（１，００ｍ＋ａｏｌ）及びス
チレン（１、ＯＯｍｍｏｌ）のベンゼン（１，０１７ｄ
）溶液を窒素雰囲気下、３０℃で２日間撹拌したところ
、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 Bis(pentamethylcyclopentadienyl)(bis(trimethylsilyl)methyl)neodymium (0,01,mmo
l), phenylsilane (1,00 m+aol) and styrene (1,00 mmol) in benzene (1,017 d
) When the solution was stirred at 30°C for 2 days under a nitrogen atmosphere, 1-phenyl-1-phenylsilylethane and 1-phenyl-2-phenylsilylethane were 68% and 6%, respectively.
was produced in a yield of .
実施例２
ヒドロビス（ペンタメチルシクロペンタジェニル）ネオ
ジム（０、００５ｍｍｏｌ） 、フェニルシラン（０、
２５ｍｍｏｌ）及びスチレン（０，２５ｒｎｍｏｌ）の
ベンゼン（１，０ＴＩｉ）溶液を窒素雰囲気下、８０℃
で２日撹拌したところ、ｌ−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 Hydrobis(pentamethylcyclopentadienyl) neodymium (0,005 mmol), phenylsilane (0,
A solution of 25 mmol) and styrene (0.25 rnmol) in benzene (1,0TIi) was heated at 80°C under a nitrogen atmosphere.
After stirring for 2 days, l-phenyl-1-phenylsilylethane and 1-phenyl-2-phenylsilylethane were obtained in yields of 60% and 27%, respectively. Furthermore, 2% 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、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％、１
１％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 produced, respectively. , 1%, 4%, 1
Produced in 1% 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. The yield is less than 1% for each, and diphenylsilane is 17%.
was produced in a yield of .
Claims (2)
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 organo-neodymium complex.
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^*_2NdR(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 true JPH04124189A (en) | 1992-04-24 |
| JPH0684381B2 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252267A (en) * | 1994-03-11 | 1995-10-03 | Agency Of Ind Science & Technol | Production of organosilanes |
| US5605998A (en) * | 1994-03-11 | 1997-02-25 | Director-General Of Agency Of Industrial Science And Technology | Method for producing polycarbosilanes |
| JP2001328990A (en) * | 2000-03-14 | 2001-11-27 | Japan Science & Technology Corp | Method for producing organosilicone compound |
| JP2019526675A (en) * | 2016-09-02 | 2019-09-19 | 株式会社ブリヂストン | Production of cis-1,4-polydienes having multiple silane functional groups prepared by in situ hydrosilylation of polymer cement |
-
1990
- 1990-09-14 JP JP2245121A patent/JPH0684381B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252267A (en) * | 1994-03-11 | 1995-10-03 | Agency Of Ind Science & Technol | Production of organosilanes |
| US5605998A (en) * | 1994-03-11 | 1997-02-25 | Director-General Of Agency Of Industrial Science And Technology | Method for producing polycarbosilanes |
| JP2001328990A (en) * | 2000-03-14 | 2001-11-27 | Japan Science & Technology Corp | Method for producing organosilicone compound |
| JP2019526675A (en) * | 2016-09-02 | 2019-09-19 | 株式会社ブリヂストン | Production of cis-1,4-polydienes having multiple silane functional groups prepared by in situ hydrosilylation of polymer cement |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0684381B2 (en) | 1994-10-26 |
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