JP2002088089A - Method for manufacturing 5- vinylnorbornyltrichlorosilane - Google Patents
Method for manufacturing 5- vinylnorbornyltrichlorosilaneInfo
- Publication number
- JP2002088089A JP2002088089A JP2000273838A JP2000273838A JP2002088089A JP 2002088089 A JP2002088089 A JP 2002088089A JP 2000273838 A JP2000273838 A JP 2000273838A JP 2000273838 A JP2000273838 A JP 2000273838A JP 2002088089 A JP2002088089 A JP 2002088089A
- Authority
- JP
- Japan
- Prior art keywords
- vinylnorbornyltrichlorosilane
- norbornene
- palladium
- vinyl
- general formula
- 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
- UWTKEMYGEQEJGG-UHFFFAOYSA-N trichloro-(2-ethenyl-4-bicyclo[2.2.1]heptanyl)silane Chemical compound C1CC2C(C=C)CC1([Si](Cl)(Cl)Cl)C2 UWTKEMYGEQEJGG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 14
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 11
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- ALVNNCNXYMELRG-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)ethyl-trichlorosilane Chemical compound C1C2C(CC[Si](Cl)(Cl)Cl)CC1C=C2 ALVNNCNXYMELRG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- -1 2-trichlorosilylethyl Chemical group 0.000 description 11
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 description 4
- CJIKCIXUSNKIAV-UHFFFAOYSA-N 2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl-trichlorosilane Chemical compound C1CC2C=CC1(CC[Si](Cl)(Cl)Cl)C2 CJIKCIXUSNKIAV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 210000003918 fraction a Anatomy 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- YLXAHVVGOSHZPA-UHFFFAOYSA-N 1,2-dichlorocycloocta-1,3-diene Chemical compound ClC1=C(Cl)C=CCCCC1 YLXAHVVGOSHZPA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MAZHHIIZNUNFDT-UHFFFAOYSA-N C1CC2CC(C=C)C1([Si](Cl)(Cl)Cl)C2 Chemical compound C1CC2CC(C=C)C1([Si](Cl)(Cl)Cl)C2 MAZHHIIZNUNFDT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- VPLLTGLLUHLIHA-UHFFFAOYSA-N dicyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1CCCCC1 VPLLTGLLUHLIHA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 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
- DZQQRNFLQBSVBN-UHFFFAOYSA-N tri(butan-2-yl)phosphane Chemical compound CCC(C)P(C(C)CC)C(C)CC DZQQRNFLQBSVBN-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、５−ビニル−２−
ノルボルネンをヒドロシリル化して、５−ビニルノルボ
ルニルトリクロロシランを製造する方法に関する。TECHNICAL FIELD The present invention relates to 5-vinyl-2-
The present invention relates to a method for producing 5-vinylnorbornyltrichlorosilane by hydrosilylation of norbornene.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】５−ビ
ニルノルボルニルトリクロロシランは、ビニル基及び反
応性シリル基を有しているため、シランカップリング
剤、各種高分子の改質剤として有用である。2. Description of the Related Art Since 5-vinylnorbornyltrichlorosilane has a vinyl group and a reactive silyl group, it is used as a silane coupling agent and a modifier for various polymers. Useful.
【０００３】５−ビニルノルボルニルトリクロロシラン
を製造する方法としては、５−ビニル−２−ノルボルネ
ンに白金触媒下トリクロロシランを付加させる方法
（Ｊ．Ｇｅｎ．Ｃｈｅｍ．ＵＳＳＲ．３１，（４），１
１０９）が知られている。As a method for producing 5-vinylnorbornyltrichlorosilane, a method of adding trichlorosilane to 5-vinyl-2-norbornene in the presence of a platinum catalyst (J. Gen. Chem. USSR. 31, (4), 1
109) are known.
【０００４】[0004]
【化１】 Embedded image
【０００５】しかしこの方法では、目的物である５−ビ
ニルノルボルニルトリクロロシラン（２）の他に、ビニ
ル基にヒドロシリル化された生成物である５−（２−ト
リクロロシリルエチル）−２−ノルボルネン（３）が生
成し、かつその反応率も３５．８％と低いものである。
また、５−ビニルノルボルニルトリクロロシランと５−
（２−トリクロロシリルエチル）−２−ノルボルネンは
分子量が同じであるため、沸点が極めて近く、蒸留によ
る分離が困難である。そのため、ヒドロシリル化反応で
の５−ビニルノルボルニルトリクロロシラン生成の選択
率の向上が必要であった。反応の選択性を向上させる例
として、ジクロロビストリフェニルホスフィンパラジウ
ムを触媒として用いる方法（特開平１−９６１８８号公
報）が提案されている。しかしながら、具体的な選択性
の記載はなく、更に５−ビニルノルボルニルトリクロロ
シランと５−（２−トリクロロシリルエチル）−２−ノ
ルボルネンの両者が分離可能な条件で分析を行った結果
では、満足のいく選択性が得られないことが明らかとな
った。However, in this method, in addition to the desired product, 5-vinylnorbornyltrichlorosilane (2), 5- (2-trichlorosilylethyl) -2-, which is a product hydrosilylated to a vinyl group, is used. Norbornene (3) is produced, and its reaction rate is as low as 35.8%.
Also, 5-vinylnorbornyltrichlorosilane and 5-vinylnorbornyltrichlorosilane
Since (2-trichlorosilylethyl) -2-norbornene has the same molecular weight, it has a very close boiling point and is difficult to separate by distillation. Therefore, it is necessary to improve the selectivity for producing 5-vinylnorbornyltrichlorosilane in the hydrosilylation reaction. As an example of improving the selectivity of the reaction, a method using dichlorobistriphenylphosphine palladium as a catalyst (JP-A-1-96188) has been proposed. However, there is no description of specific selectivity. Further, as a result of performing analysis under conditions where both 5-vinylnorbornyltrichlorosilane and 5- (2-trichlorosilylethyl) -2-norbornene can be separated, It became clear that satisfactory selectivity could not be obtained.
【０００６】ここで、選択性よく５−ビニルノルボルニ
ルトリクロロシランを得ることが必要である理由は、反
応性が高い高分子の改質剤を得ることが望まれているた
めである。つまり、一般的に、ラジカル開始剤を用いた
重合性モノマー、例えばエチレン、プロピレン、（メ
タ）アクリル酸、（メタ）アクリル酸エステルとの共重
合の反応性は、ビニル基の方が環状炭化水素の環内に存
在する二重結合よりも高い。即ち、高分子の改質剤とし
て５−ビニルノルボルニルトリクロロシラン（２）と５
−（２−トリクロロシリルエチル）−２−ノルボルネン
（３）の混合物を用いて重合性モノマーと共重合を行っ
た場合、５−ビニルノルボルニルトリクロロシランのみ
が共重合体として取り込まれ、反応性の低い５−（２−
トリクロロシリルエチル）−２−ノルボルネンは未反応
のまま残存するため、より多くの量が必要となってしま
う。The reason why it is necessary to obtain 5-vinylnorbornyltrichlorosilane with high selectivity is that it is desired to obtain a highly reactive polymer modifier. That is, in general, the reactivity of copolymerization with a polymerizable monomer using a radical initiator, for example, ethylene, propylene, (meth) acrylic acid, or (meth) acrylate, is such that a vinyl group is a cyclic hydrocarbon. Higher than the double bond present in the ring. That is, 5-vinyl norbornyl trichlorosilane (2) and 5
When copolymerization with a polymerizable monomer is performed using a mixture of-(2-trichlorosilylethyl) -2-norbornene (3), only 5-vinylnorbornyltrichlorosilane is incorporated as a copolymer, and the reactivity is reduced. 5- (2-
Since trichlorosilylethyl) -2-norbornene remains unreacted, a larger amount is required.
【０００７】本発明は、上記事情に鑑みなされたもの
で、５−ビニルノルボルニルトリクロロシランを高選択
的に、収率よく製造する方法を提供することを目的とす
る。The present invention has been made in view of the above circumstances, and has as its object to provide a method for producing 5-vinylnorbornyltrichlorosilane with high selectivity and high yield.
【０００８】[0008]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を重ねた結
果、５−ビニル−２−ノルボルネンとトリクロロシラン
とを反応させ、５−ビニルノルボルニルトリクロロシラ
ンを製造する方法において、触媒としてパラジウム化合
物と下記一般式（１） ＰＲ1Ｒ2Ｒ3 （１） （式中、Ｒ1，Ｒ2，Ｒ3は炭素数１〜１０の非置換又は
置換の１価炭化水素基であるが、Ｒ1，Ｒ2，Ｒ3のうち
少なくとも２つ以上は同一又は異種の炭素数３〜１０の
二級脂肪族炭化水素基である。）で示される有機リン化
合物、又は、上記一般式（１）で示される有機リン化合
物を配位子として持つパラジウム錯体を用いることによ
り、５−ビニルノルボルニルトリクロロシランが高選択
的に得られることを知見し、本発明を完成するに至った
ものである。Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, reacted 5-vinyl-2-norbornene with trichlorosilane, In the method for producing vinylnorbornyltrichlorosilane, a palladium compound is used as a catalyst together with the following general formula (1) PR 1 R 2 R 3 (1) (wherein R 1 , R 2 , and R 3 each have 1 to 10 carbon atoms) Is an unsubstituted or substituted monovalent hydrocarbon group, wherein at least two or more of R 1 , R 2 , and R 3 are the same or different secondary aliphatic hydrocarbon groups having 3 to 10 carbon atoms. ) Or a palladium complex having an organophosphorus compound represented by the above general formula (1) as a ligand enables 5-vinylnorbornyltrichlorosilane to be obtained with high selectivity. Know that , Which has led to the completion of the present invention.
【０００９】従って、本発明は、５−ビニル−２−ノル
ボルネンとトリクロロシランとを反応させ、５−ビニル
ノルボルニルトリクロロシランを製造する方法におい
て、触媒としてパラジウム化合物と下記一般式（１） ＰＲ1Ｒ2Ｒ3 （１） （式中、Ｒ1，Ｒ2，Ｒ3は炭素数１〜１０の非置換又は
置換の１価炭化水素基であるが、Ｒ1，Ｒ2，Ｒ3のうち
少なくとも２つ以上は同一又は異種の炭素数３〜１０の
二級脂肪族炭化水素基である。）で示される有機リン化
合物、又は、上記一般式（１）で示される有機リン化合
物を配位子として持つパラジウム錯体を用いることを特
徴とする５−ビニルノルボルニルトリクロロシランの製
造方法を提供するものである。Accordingly, the present invention provides a method for producing 5-vinylnorbornyltrichlorosilane by reacting 5-vinyl-2-norbornene with trichlorosilane, wherein a palladium compound and a catalyst represented by the following general formula (1): 1 R 2 R 3 (1) ( wherein, although R 1, R 2, R 3 is a monovalent hydrocarbon radical unsubstituted or substituted having 1 to 10 carbon atoms, the R 1, R 2, R 3 At least two or more of which are the same or different secondary aliphatic hydrocarbon groups having 3 to 10 carbon atoms.) Or an organic phosphorus compound represented by the general formula (1). It is intended to provide a method for producing 5-vinylnorbornyltrichlorosilane, which comprises using a palladium complex having a ligand.
【００１０】以下、本発明につき更に詳しく説明する。
本発明において、トリクロロシランと５−ビニル−２−
ノルボルネンとを反応させる場合、その配合比は特に限
定されないが、反応性、生産性の点から、５−ビニル−
２−ノルボルネン１モルに対し、トリクロロシラン０．
５〜２．０モル、特に０．８〜１．２モルの範囲が好ま
しい。Hereinafter, the present invention will be described in more detail.
In the present invention, trichlorosilane and 5-vinyl-2-
When reacting with norbornene, the compounding ratio is not particularly limited, but from the viewpoint of reactivity and productivity, 5-vinyl-
Trichlorosilane is added in an amount of 0.1 mol per mol of 2-norbornene.
The range of 5 to 2.0 mol, particularly 0.8 to 1.2 mol is preferable.
【００１１】本発明におけるパラジウム化合物として
は、酢酸パラジウム、塩化パラジウム、塩化パラジウム
ナトリウム、ジクロロビス（ベンゾニトリル）パラジウ
ム、ジクロロ（１，５−シクロオクタジエン）パラジウ
ム、ジ−μ−クロロビス（π−アリル）二パラジウム等
が例示される。As the palladium compound in the present invention, palladium acetate, palladium chloride, sodium palladium chloride, dichlorobis (benzonitrile) palladium, dichloro (1,5-cyclooctadiene) palladium, di-μ-chlorobis (π-allyl) Dipalladium and the like are exemplified.
【００１２】パラジウム化合物の配合比は特に限定され
ないが、反応性、生産性の点から、５−ビニル−２−ノ
ルボルネン１モルに対し、０．０００００１〜０．０１
モル、特に０．００００１〜０．００１モルの範囲が好
ましい。パラジウム化合物の配合比が０．０００００１
モル未満だと触媒の充分な効果が発現しない可能性があ
り、０．０１モルを超えると、触媒の量に見合うだけの
反応促進効果がみられない可能性がある。The mixing ratio of the palladium compound is not particularly limited, but from the viewpoint of reactivity and productivity, 0.000001 to 0.01 per mol of 5-vinyl-2-norbornene.
Moles, preferably in the range of 0.00001 to 0.001 mole. The compounding ratio of the palladium compound is 0.000001
If the amount is less than the mole, there is a possibility that a sufficient effect of the catalyst may not be exhibited. If the amount is more than 0.01 mole, there is a possibility that a reaction promoting effect corresponding to the amount of the catalyst may not be obtained.
【００１３】本発明における有機リン化合物は、下記一
般式（１）で示される化合物である。 ＰＲ1Ｒ2Ｒ3 （１） 式中、Ｒ1，Ｒ2，Ｒ3は炭素数１〜１０の非置換又は置
換の１価炭化水素基であるが、Ｒ1，Ｒ2，Ｒ3のうち少
なくとも２つ以上、好ましくは全部が、同一又は異種の
炭素数３〜１０の二級脂肪族炭化水素基である。ここ
で、二級脂肪族炭化水素基としては、分岐状又は環状の
アルキル基が好ましく、イソプロピル基、ｓ−ブチル
基、シクロペンチル基、シクロへキシル基などが挙げら
れる。また、残りの１価炭化水素基としては、メチル、
エチル、ｎ−プロピル、ｎ−ブチル、イソブチル、ｔｅ
ｒｔ−ブチル、ｎ−ペンチル、ネオペンチル、ｔｅｒｔ
−アミル、ｎ−ヘキシル、エチルヘキシル、ｎ−オクチ
ル等のアルキル基、フェニル、トリル、キシリル、メシ
チル、ベンジル等のアリール基やアラルキル基、更にこ
れらの基の水素原子をハロゲン原子などで置換したもの
などが挙げられる。The organic phosphorus compound in the present invention is a compound represented by the following general formula (1). PR in 1 R 2 R 3 (1) formula, but R 1, R 2, R 3 is a monovalent hydrocarbon radical unsubstituted or substituted having 1 to 10 carbon atoms, the R 1, R 2, R 3 At least two or more, and preferably all of them, are the same or different secondary aliphatic hydrocarbon groups having 3 to 10 carbon atoms. Here, as the secondary aliphatic hydrocarbon group, a branched or cyclic alkyl group is preferable, and examples thereof include an isopropyl group, an s-butyl group, a cyclopentyl group, and a cyclohexyl group. The remaining monovalent hydrocarbon groups include methyl,
Ethyl, n-propyl, n-butyl, isobutyl, te
rt-butyl, n-pentyl, neopentyl, tert
Alkyl groups such as amyl, n-hexyl, ethylhexyl, and n-octyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, and benzyl, aralkyl groups, and those in which hydrogen atoms in these groups are substituted with halogen atoms and the like. Is mentioned.
【００１４】上記式で表される有機リン化合物として、
具体的にはトリイソプロピルホスフィン、トリｓ−ブチ
ルホスフィン、トリシクロペンチルホスフィン、トリシ
クロヘキシルホスフィン等が例示され、反応性、選択性
の点からトリシクロヘキシルホスフィンを用いることが
好ましい。As the organic phosphorus compound represented by the above formula,
Specific examples include triisopropylphosphine, tris-butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, and the like. It is preferable to use tricyclohexylphosphine from the viewpoint of reactivity and selectivity.
【００１５】有機リン化合物の使用量は特に限定されな
いが、パラジウム化合物のパラジウム原子１モルに対
し、１〜４モルの範囲が好ましい。有機リン化合物の使
用量がパラジウム化合物のパラジウム原子１モルに対し
１モル未満だと、反応の選択性が低下する可能性があ
り、４モルを超えると、触媒活性が低下する可能性があ
る。The amount of the organic phosphorus compound to be used is not particularly limited, but is preferably in the range of 1 to 4 mol per mol of palladium atom of the palladium compound. If the amount of the organic phosphorus compound is less than 1 mol per 1 mol of the palladium atom of the palladium compound, the selectivity of the reaction may decrease, and if it exceeds 4 mol, the catalytic activity may decrease.
【００１６】また、上記パラジウム化合物と上記一般式
（１）で示される有機リン化合物を用いるに際し、あら
かじめ、パラジウム化合物と上記一般式（１）で示され
る有機リン化合物を混合、反応させて錯体としたもの、
また必要ならば単離精製したものを用いてもよい。When the palladium compound and the organic phosphorus compound represented by the general formula (1) are used, the palladium compound and the organic phosphorus compound represented by the general formula (1) are mixed and reacted in advance to form a complex with the complex. What did
If necessary, an isolated and purified product may be used.
【００１７】上記錯体として、具体的にはジクロロビス
トリイソプロピルホスフィンパラジウム、ジクロロビス
トリｓ−ブチルホスフィンパラジウム、ジクロロビスト
リシクロペンチルホスフィンパラジウム、ジクロロビス
トリシクロヘキシルホスフィンパラジウム等が例示され
る。Specific examples of the complex include dichlorobistriisopropylphosphinepalladium, dichlorobistris-butylphosphinepalladium, dichlorobistricyclopentylphosphinepalladium, and dichlorobistricyclohexylphosphinepalladium.
【００１８】本発明において、トリクロロシランと５−
ビニル−２−ノルボルネンとを反応させる場合の反応温
度は特に限定されないが、常圧又は加圧下で、０〜２０
０℃、特に１０〜１４０℃が好ましい。In the present invention, trichlorosilane and 5-
The reaction temperature when reacting with vinyl-2-norbornene is not particularly limited, but is 0 to 20 at normal pressure or under pressure.
0 ° C, particularly preferably 10 to 140 ° C, is preferred.
【００１９】なお、反応は無溶媒でも進行するが、溶媒
を用いることもできる。用いられる溶媒としては、ペン
タン、ヘキサン、シクロヘキサン、ベンゼン、トルエ
ン、キシレン等の炭化水素系溶媒、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系溶媒、
酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニ
トリル等の非プロトン性極性溶媒、ジクロロメタン、ク
ロロホルム等の塩素化炭化水素溶媒等が挙げられる。ま
た、これらの溶媒は単独で使用してもよく、あるいは２
種以上を混合して使用してもよい。The reaction proceeds without solvent, but a solvent can be used. As the solvent used, pentane, hexane, cyclohexane, benzene, toluene, hydrocarbon solvents such as xylene, diethyl ether,
Ether solvents such as tetrahydrofuran and dioxane,
Examples thereof include ester solvents such as ethyl acetate and butyl acetate, aprotic polar solvents such as acetonitrile, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or 2
A mixture of more than one species may be used.
【００２０】本発明では、上記反応によって高純度の５
−ビニルノルボルニルトリクロロシランを得ることがで
きる。In the present invention, high purity 5
-Vinyl norbornyl trichlorosilane can be obtained.
【００２１】[0021]
【実施例】以下、実施例及び比較例を示して本発明を具
体的に説明するが、本発明は下記の実施例に制限される
ものではない。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００２２】［比較例１］撹拌機、還流冷却器、滴下ロ
ート及び温度計を備えたフラスコに、５−ビニル−２−
ノルボルネン２４．０ｇ（０．２０ｍｏｌ）、ジクロロ
ビストリフェニルホスフィンパラジウム２８．１ｍｇを
仕込み、８０℃に加熱した。内温が安定した後、トリク
ロロシラン２９．８ｇ（０．２２ｍｏｌ）を４時間かけ
て滴下した。滴下終了後、反応液を８０℃で２時間撹拌
した。反応液を蒸留し、沸点９４−９８℃／０．６７ｋ
Ｐａの留分を４４．３ｇ得た。留分をＧＣ−ＭＳにて分
析したところ、目的物である５−ビニルノルボルニルト
リクロロシランと、不純物である５−（２−トリクロロ
シリルエチル）−２−ノルボルネンが含まれていること
が明らかとなった。ガスクロマトグラフィーにて純度を
測定すると、目的物である５−ビニルノルボルニルトリ
クロロシランの純度は６０％であり、不純物である５−
（２−トリクロロシリルエチル）−２−ノルボルネンが
ＧＣ面積％で４０％含まれていた。[Comparative Example 1] 5-Vinyl-2-vinyl was placed in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
24.0 g (0.20 mol) of norbornene and 28.1 mg of dichlorobistriphenylphosphine palladium were charged and heated to 80 ° C. After the internal temperature was stabilized, 29.8 g (0.22 mol) of trichlorosilane was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours. Distill the reaction solution, boiling point 94-98 ° C / 0.67k
44.3 g of a fraction of Pa was obtained. When the fraction was analyzed by GC-MS, it was clear that the target product contained 5-vinylnorbornyltrichlorosilane and the impurity 5- (2-trichlorosilylethyl) -2-norbornene. It became. When the purity was measured by gas chromatography, the purity of the target substance, 5-vinylnorbornyltrichlorosilane, was 60%, and the impurity, 5-vinylnorbornyltrichlorosilane.
(2-Trichlorosilylethyl) -2-norbornene was contained by 40% by GC area%.
【００２３】［実施例１］撹拌機、還流冷却器、滴下ロ
ート及び温度計を備えたフラスコに、５−ビニル−２−
ノルボルネン２４．０ｇ（０．２０ｍｏｌ）、ジクロロ
（１，５−シクロオクタジエン）パラジウム１１．４ｍ
ｇ、トリシクロヘキシルホスフィン２２．４ｍｇを仕込
み、８０℃に加熱した。内温が安定した後、トリクロロ
シラン２９．８ｇ（０．２２ｍｏｌ）を４時間かけて滴
下した。滴下終了後、反応液を８０℃で２時間撹拌し
た。反応液を蒸留し、沸点９４−９７℃／０．６７ｋＰ
ａの留分を４６．１ｇ得た（収率９０．２％）。留分を
ガスクロマトグラフィーにて分析したところ、５−ビニ
ルノルボルニルトリクロロシランの純度は９８％であ
り、不純物である５−（２−トリクロロシリルエチル）
−２−ノルボルネンはＧＣ面積％で２％しか生成してい
なかった。Example 1 In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 5-vinyl-2-
24.0 g (0.20 mol) of norbornene, 11.4 m of dichloro (1,5-cyclooctadiene) palladium
g, 22.4 mg of tricyclohexylphosphine, and heated to 80 ° C. After the internal temperature was stabilized, 29.8 g (0.22 mol) of trichlorosilane was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours. The reaction solution is distilled and has a boiling point of 94-97 ° C / 0.67 kP.
46.1 g of the fraction a was obtained (90.2% yield). When the fraction was analyzed by gas chromatography, the purity of 5-vinylnorbornyltrichlorosilane was 98%, and the impurity 5- (2-trichlorosilylethyl) was detected.
-2-Norbornene was produced only at 2% by GC area%.
【００２４】［実施例２］撹拌機、還流冷却器、滴下ロ
ート及び温度計を備えたフラスコに、５−ビニル−２−
ノルボルネン２４．０ｇ（０．２０ｍｏｌ）、ジクロロ
（１，５−シクロオクタジエン）パラジウム１１．４ｍ
ｇ、トリイソプロピルホスフィン１２．８ｍｇを仕込
み、８０℃に加熱した。内温が安定した後、トリクロロ
シラン２９．８ｇ（０．２２ｍｏｌ）を４時間かけて滴
下した。滴下終了後、反応液を８０℃で２時間撹拌し
た。反応液を蒸留し、沸点９４−９７℃／０．６７ｋＰ
ａの留分を３７．０ｇ得た（収率７２．３％）。留分を
ガスクロマトグラフィーにて分析したところ、５−ビニ
ルノルボルニルトリクロロシランの純度は９７％であ
り、不純物である５−（２−トリクロロシリルエチル）
−２−ノルボルネンはＧＣ面積％で３％しか生成してい
なかった。Example 2 In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 5-vinyl-2-
24.0 g (0.20 mol) of norbornene, 11.4 m of dichloro (1,5-cyclooctadiene) palladium
g and triisopropylphosphine (12.8 mg) were charged and heated to 80 ° C. After the internal temperature was stabilized, 29.8 g (0.22 mol) of trichlorosilane was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours. The reaction solution is distilled and has a boiling point of 94-97 ° C / 0.67 kP.
37.0 g of the fraction a was obtained (yield: 72.3%). When the fraction was analyzed by gas chromatography, the purity of 5-vinylnorbornyltrichlorosilane was 97%, and the impurity 5- (2-trichlorosilylethyl) was detected.
-2-Norbornene produced only 3% by GC area%.
【００２５】［比較例２］撹拌機、還流冷却器、滴下ロ
ート及び温度計を備えたフラスコに、５−ビニル−２−
ノルボルネン２４．０ｇ（０．２０ｍｏｌ）、ジクロロ
（１，５−シクロオクタジエン）パラジウム１１．４ｍ
ｇ、トリフェニルホスフィン２１．０ｍｇを仕込み、８
０℃に加熱した。内温が安定した後、トリクロロシラン
２９．８ｇ（０．２２ｍｏｌ）を４時間かけて滴下し
た。滴下終了後、反応液を８０℃で２時間撹拌した。反
応液を蒸留し、沸点９４−９８℃／０．６７ｋＰａの留
分を４５．２ｇ得た。留分をガスクロマトグラフィーに
て分析したところ、５−ビニルノルボルニルトリクロロ
シランの純度は６０％であり、不純物である５−（２−
トリクロロシリルエチル）−２−ノルボルネンがＧＣ面
積％で４０％含まれていた。[Comparative Example 2] In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 5-vinyl-2-
24.0 g (0.20 mol) of norbornene, 11.4 m of dichloro (1,5-cyclooctadiene) palladium
g, 21.0 mg of triphenylphosphine, and 8
Heated to 0 ° C. After the internal temperature was stabilized, 29.8 g (0.22 mol) of trichlorosilane was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours. The reaction solution was distilled to obtain 45.2 g of a fraction having a boiling point of 94-98 ° C./0.67 kPa. When the fraction was analyzed by gas chromatography, the purity of 5-vinylnorbornyltrichlorosilane was 60%, and the impurity 5- (2-
Trichlorosilylethyl) -2-norbornene was contained by 40% by GC area%.
【００２６】［実施例３］撹拌機、還流冷却器、滴下ロ
ート及び温度計を備えたフラスコに、５−ビニル−２−
ノルボルネン２４．０ｇ（０．２０ｍｏｌ）、ジクロロ
（シクロオクタジエン）パラジウム１１．４ｍｇ、ジシ
クロヘキシルフェニルホスフィン２２．０ｍｇを仕込
み、８０℃に加熱した。内温が安定した後、トリクロロ
シラン２９．８ｇ（０．２０ｍｏｌ）を４時間かけて滴
下した。滴下終了後、反応液を８０℃で２時間撹拌し
た。反応液を蒸留し、沸点９４−９７℃／０．６７ｋＰ
ａの留分を４５．０ｇ得た。留分をガスクロマトグラフ
ィーにて分析したところ、５−ビニルノルボルニルトリ
クロロシランの純度は９０％であり、不純物である５−
（２−トリクロロシリルエチル）−２−ノルボルネンが
ＧＣ面積％で１０％含まれていた。Example 3 In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 5-vinyl-2-
24.0 g (0.20 mol) of norbornene, 11.4 mg of dichloro (cyclooctadiene) palladium, and 22.0 mg of dicyclohexylphenylphosphine were charged and heated to 80 ° C. After the internal temperature was stabilized, 29.8 g (0.20 mol) of trichlorosilane was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours. The reaction solution is distilled and has a boiling point of 94-97 ° C / 0.67 kP.
45.0 g of the fraction a was obtained. When the fraction was analyzed by gas chromatography, the purity of 5-vinylnorbornyltrichlorosilane was 90%,
(2-Trichlorosilylethyl) -2-norbornene was contained at 10% by GC area%.
【００２７】[0027]
【発明の効果】本発明の５−ビニルノルボルニルトリク
ロロシランの製造方法は、蒸留で分離困難な５−（２−
トリクロロシリルエチル）−２−ノルボルネンをほとん
ど生成しない方法であり、高純度の５−ビニルノルボル
ニルトリクロロシランを収率よく得ることができる。According to the method for producing 5-vinylnorbornyltrichlorosilane of the present invention, 5- (2-
This is a method in which trichlorosilylethyl) -2-norbornene is hardly generated, and high-purity 5-vinylnorbornyltrichlorosilane can be obtained in a high yield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 幹夫 新潟県中頸城郡頸城村大字西福島28−１ 信越化学工業株式会社合成技術研究所内 Ｆターム(参考） 4H039 CA92 CD10 4H049 VN01 VP01 VQ12 VR21 VR33 VS12 VT17 VT30 VT52 VU16 VU22 VW02 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Mikio Endo 28-1 Nishifukushima, Kazagi-son, Nakakushiro-gun, Niigata Pref. VS12 VT17 VT30 VT52 VU16 VU22 VW02
Claims (1)
ロロシランとを反応させ、５−ビニルノルボルニルトリ
クロロシランを製造する方法において、触媒としてパラ
ジウム化合物と下記一般式（１） ＰＲ1Ｒ2Ｒ3 （１） （式中、Ｒ1，Ｒ2，Ｒ3は炭素数１〜１０の非置換又は
置換の１価炭化水素基であるが、Ｒ1，Ｒ2，Ｒ3のうち
少なくとも２つ以上は同一又は異種の炭素数３〜１０の
二級脂肪族炭化水素基である。）で示される有機リン化
合物、又は、上記一般式（１）で示される有機リン化合
物を配位子として持つパラジウム錯体を用いることを特
徴とする、５−ビニルノルボルニルトリクロロシランの
製造方法。In a method for producing 5-vinylnorbornyltrichlorosilane by reacting 5-vinyl-2-norbornene and trichlorosilane, a palladium compound is used as a catalyst together with the following general formula (1): PR 1 R 2 R 3 (1) (wherein, R 1 , R 2 , and R 3 are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and at least two of R 1 , R 2 , and R 3 These are the same or different secondary aliphatic hydrocarbon groups having 3 to 10 carbon atoms.) Or the organic phosphorus compound represented by the above general formula (1) as a ligand. A method for producing 5-vinylnorbornyltrichlorosilane, comprising using a palladium complex.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009120573A (en) * | 2007-11-16 | 2009-06-04 | Shin Etsu Chem Co Ltd | Radiation polymerizable functional group-containing organosilicon compound, and method for producing the same |
| JP2009263321A (en) * | 2008-04-30 | 2009-11-12 | Shin Etsu Chem Co Ltd | Method for production of ethyl norbornene compound containing chlorosilyl group |
| US8034965B2 (en) | 2007-11-09 | 2011-10-11 | Shin-Etsu Chemical Co., Ltd. | Norbornane skeleton structure-containing organosilicon compound and method of producing same |
| JP2014009110A (en) * | 2012-06-28 | 2014-01-20 | Shin Etsu Chem Co Ltd | Method for producing 2-(trichlorosilyl)norbornane |
-
2000
- 2000-09-08 JP JP2000273838A patent/JP3856090B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8034965B2 (en) | 2007-11-09 | 2011-10-11 | Shin-Etsu Chemical Co., Ltd. | Norbornane skeleton structure-containing organosilicon compound and method of producing same |
| US8283486B2 (en) | 2007-11-09 | 2012-10-09 | Shin-Etsu Chemical Co., Ltd. | Norbornane skeleton structure-containing organosilicon compound and method of producing same |
| JP2009120573A (en) * | 2007-11-16 | 2009-06-04 | Shin Etsu Chem Co Ltd | Radiation polymerizable functional group-containing organosilicon compound, and method for producing the same |
| JP4520497B2 (en) * | 2007-11-16 | 2010-08-04 | 信越化学工業株式会社 | Radiation-polymerizable functional group-containing organosilicon compound and method for producing the same |
| JP2009263321A (en) * | 2008-04-30 | 2009-11-12 | Shin Etsu Chem Co Ltd | Method for production of ethyl norbornene compound containing chlorosilyl group |
| JP2014009110A (en) * | 2012-06-28 | 2014-01-20 | Shin Etsu Chem Co Ltd | Method for producing 2-(trichlorosilyl)norbornane |
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