JP3456658B2 - Cyclic organosilicon compounds having a fluorosilyl group - Google Patents
Cyclic organosilicon compounds having a fluorosilyl groupInfo
- Publication number
- JP3456658B2 JP3456658B2 JP03859893A JP3859893A JP3456658B2 JP 3456658 B2 JP3456658 B2 JP 3456658B2 JP 03859893 A JP03859893 A JP 03859893A JP 3859893 A JP3859893 A JP 3859893A JP 3456658 B2 JP3456658 B2 JP 3456658B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- cyclic organosilicon
- chemical formula
- reaction
- 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
- -1 Cyclic organosilicon compounds Chemical class 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 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 16
- 150000001875 compounds Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910019032 PtCl2 Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SWJXYIHLHXRZNT-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;platinum Chemical compound [Pt].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 SWJXYIHLHXRZNT-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WLXDJYZDTGKMSI-UHFFFAOYSA-N fluoro-[2-[fluoro(dimethyl)silyl]ethynyl]-dimethylsilane Chemical group C[Si](C)(F)C#C[Si](C)(C)F WLXDJYZDTGKMSI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性及び耐燃焼性材
料の原料等として有用な、従来になかった新しい環状の
有機ケイ素化合物とその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unprecedented new cyclic organosilicon compound which is useful as a raw material for heat resistant and combustible materials and a method for producing the same.
【０００２】[0002]
【従来の技術】本化合物は有効な合成手段が知られてお
らず製造できなかった。2. Description of the Related Art This compound could not be produced because of no known effective synthetic means.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、含ケイ素高
分子材料の原料として有用な新規の環状の有機ケイ素化
合物を合成することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to synthesize a novel cyclic organosilicon compound useful as a raw material for a silicon-containing polymer material.
【０００４】[0004]
【課題を解決するための手段】本発明は化学式（１）The present invention has the chemical formula (1)
【０００５】[0005]
【化４】
（上式中、Ｒ1 ，Ｒ2 は炭素数１〜１０のアルキル基、
アルケニル基または低級アルキル基、低級アルケニル
基、低級アルコキシ基もしくはハロゲンで置換されてい
てもよいフェニル基である。例えば−ＣＨ3 ，−Ｃ2 Ｈ
5 ，−Ｃ3 Ｈ7 ，−ＣＨ（ＣＨ3 ）2 ，−Ｃ4 Ｈ9 ，−
ＣＨ＝ＣＨ2 ，−ＣＨ2 −ＣＨ＝ＣＨ2 ，−Ｃ6 Ｈ13，
−Ｃ8 Ｈ17，−Ｃ10Ｈ21，−Ｃ6 Ｈ5 ，−Ｃ6 Ｈ4 （Ｃ
Ｈ3 ），−Ｃ6 Ｈ4 （ＣＨ＝ＣＨ2 ），−Ｃ6 Ｈ4 （Ｏ
ＣＨ3 ），−Ｃ6 Ｈ4 Ｂｒ等である。）で示されるフロ
ロシリル基を有する新規な環状有機ケイ素化合物であ
る。[Chemical 4] (In the above formula, R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms,
It is an alkenyl group or a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen. For example -CH 3, -C 2 H
5, -C 3 H 7, -CH (CH 3) 2, -C 4 H 9, -
CH = CH 2, -CH 2 -CH = CH 2, -C 6 H 13,
-C 8 H 17, -C 10 H 21, -C 6 H 5, -C 6 H 4 (C
H 3), - C 6 H 4 (CH = CH 2), - C 6 H 4 (O
CH 3), - a C 6 H 4 Br and the like. ) Is a novel cyclic organosilicon compound having a fluorosilyl group.
【０００６】また、本発明は化学式（２）The present invention also has the chemical formula (2)
【０００７】[0007]
【化５】
（上式中、Ｒ1 は炭素数１〜１０のアルキル基、アルケ
ニル基または低級アルキル基、低級アルケニル基、低級
アルコキシ基もしくはハロゲンで置換されていてもよい
フェニル基である。例えば−ＣＨ3 ，−Ｃ2 Ｈ5 ，−Ｃ
3 Ｈ7 ，−ＣＨ（ＣＨ3 ）2 ，−Ｃ4 Ｈ9 ，−ＣＨ＝Ｃ
Ｈ2 ，−ＣＨ2 −ＣＨ＝ＣＨ2 ，−Ｃ6Ｈ13，−Ｃ8 Ｈ
17，−Ｃ10Ｈ21，−Ｃ6 Ｈ5 ，−Ｃ6 Ｈ4 （ＣＨ3 ），
−Ｃ6 Ｈ 4 （ＣＨ＝ＣＨ2 ），−Ｃ6 Ｈ4 （ＯＣＨ
3 ），−Ｃ6 Ｈ4 Ｂｒ等である。）で示されるテトラキ
ス（ヒドロシリル）ベンゼン化合物と、化学式（３）[Chemical 5]
(In the above formula, R1 Is an alkyl group having 1 to 10 carbon atoms, an alk
Nyl group or lower alkyl group, lower alkenyl group, lower
May be substituted with an alkoxy group or halogen
It is a phenyl group. For example -CH3 , -C2 HFive , -C
3 H7 , -CH (CH3 )2 , -CFour H9 , -CH = C
H2 , -CH2 -CH = CH2 , -C6H13, -C8 H
17, -CTenHtwenty one, -C6 HFive , -C6 HFour (CH3 ),
-C6 H Four (CH = CH2 ), -C6 HFour (OCH
3 ), -C6 HFour Br and the like. ) Tetraki
Su (hydrosilyl) benzene compound and chemical formula (3)
【０００８】[0008]
【化６】
（上式中、Ｒ2 は炭素数１〜１０のアルキル基、アルケ
ニル基または低級アルキル基、低級アルケニル基、低級
アルコキシ基もしくはハロゲンで置換されていてもよい
フェニル基である。例えば−ＣＨ3 ，−Ｃ2 Ｈ5 ，−Ｃ
3 Ｈ7 ，−ＣＨ（ＣＨ3 ）2 ，−Ｃ4 Ｈ9 ，−ＣＨ＝Ｃ
Ｈ2 ，−ＣＨ2 −ＣＨ＝ＣＨ2 ，−Ｃ6Ｈ13，−Ｃ8 Ｈ
17，−Ｃ10Ｈ21，−Ｃ6 Ｈ5 ，−Ｃ6 Ｈ4 （ＣＨ3 ），
−Ｃ6 Ｈ 4 （ＣＨ＝ＣＨ2 ），−Ｃ6 Ｈ4 （ＯＣＨ
3 ），−Ｃ6 Ｈ4 Ｂｒ等である。）で示されるビス（フ
ロロシリル）アセチレン化合物とを触媒存在下に反応さ
せることを特徴とする化学式（１）で示されるフロロシ
リル基を有する環状有機ケイ素化合物の製造方法であ
る。[Chemical 6]
(In the above formula, R2 Is an alkyl group having 1 to 10 carbon atoms, an alk
Nyl group or lower alkyl group, lower alkenyl group, lower
May be substituted with an alkoxy group or halogen
It is a phenyl group. For example -CH3 , -C2 HFive , -C
3 H7 , -CH (CH3 )2 , -CFour H9 , -CH = C
H2 , -CH2 -CH = CH2 , -C6H13, -C8 H
17, -CTenHtwenty one, -C6 HFive , -C6 HFour (CH3 ),
-C6 H Four (CH = CH2 ), -C6 HFour (OCH
3 ), -C6 HFour Br and the like. )
(Lorosilyl) acetylene compound in the presence of a catalyst
Florosi represented by the chemical formula (1) characterized by
A method for producing a cyclic organosilicon compound having a rilyl group
It
【０００９】また本発明の化合物を合成する際に用いる
触媒は白金、パラジウムまたはルテニウムいずれかの錯
体である。The catalyst used when synthesizing the compound of the present invention is a complex of platinum, palladium or ruthenium.
【００１０】本発明の化合物を合成する際に用いる触媒
の具体例としてはＰｔ触媒として、Ｐｔ（ｄｂａ）2
（ｄｂａ：ジベンジリデンアセトン），Ｐｔ（ＣＨ2 ＝
ＣＨ2）（ＰＰｈ3 ）2 ，ＰｔＣｌ2 （ＰＰｈ3 ）2 ，
ＰｔＣｌ2 （ＰＯ3 Ｃ6 Ｈ11） 2 ，Ｐｔ（ＰＰｈ3 ）
4 ，Ｐｔ（ＰＯ3 Ｃ6 Ｈ11）4 ，Ｐｔ（ＣＯ2 （ＰＰｈ
3）2 ，Ｐｔ（ＰｈＣＣＰｈ）（ＰＰｈ3 ）2 ，Ｐｔ
（Ｃ8 Ｈ12）2 ，Ｈ2 ＰｔＣｌ6 ，Ｐｄ触媒として、Ｐ
ｄ（ｄｂａ）2 ，Ｐｄ（ＣＨ2 ＝ＣＨ2 ）（ＰＰｈ3）2
，Ｐｄ（ＰＯ3 Ｃ6 Ｈ11）2 ，Ｐｄ（ＣＨ2 ＝ＣＨ
2 ）（ＰＯ3 Ｃ6 Ｈ11）2 ，Ｐｄ（ＰＰｈ3 ）4 ，Ｐｄ
（ＰＯ3 Ｃ6 Ｈ11）4 ，ＰｄＣｌ2 ，Ｐｄ（ＣＨ3 ＣＯ
Ｏ）2 ，Ｒｕ触媒として、ＲｕＣｌ2 （ＰＰｈ3 ）3 ，
ＲｕＣｌ2 （ＰＯ3 Ｃ6 Ｈ11）3 ，ＲｕＣｌ2 （ＣＯ）
3 ，Ｒｕ3 （ＣＯ）12等が挙げられる。特に好ましく
は、Ｐｔ（ｄｂａ）2 ，Ｐｔ（ＣＨ2 ＝ＣＨ2 ）（ＰＰ
ｈ3 ）2 である。またこれらの触媒は助触媒として触媒
の１〜１０等量のＮＥｔ3 ，ＰＰｈ 3 等の配位子を加え
て用いてもよい。例を挙げれば、ＰｔＣｌ2 （ＰＰｈ
3 ）2にＮＥｔ3 を２等量加えて用いる、Ｐｄ（ｄｂ
ａ）2 にＰＰｈ3 を２等量加えて用いる等である。Catalyst used in synthesizing the compound of the present invention
As a specific example of Pt (dba)2
(Dba: dibenzylideneacetone), Pt (CH2 =
CH2) (PPh3 )2 , PtCl2 (PPh3 )2 ，
PtCl2 (PO3 C6 H11) 2 , Pt (PPh3 )
Four , Pt (PO3 C6 H11)Four , Pt (CO2 (PPh
3)2 , Pt (PhCCPh) (PPh3 )2 , Pt
(C8 H12)2 , H2 PtCl6 , Pd as a catalyst
d (dba)2 , Pd (CH2 = CH2 ) (PPh3)2
, Pd (PO3 C6 H11)2 , Pd (CH2 = CH
2 ) (PO3 C6 H11)2 , Pd (PPh3 )Four , Pd
(PO3 C6 H11)Four , PdCl2 , Pd (CH3 CO
O)2 , RuCl as RuCl2 (PPh3 )3 ，
RuCl2 (PO3 C6 H11)3 , RuCl2 (CO)
3 , Ru3 (CO)12Etc. Particularly preferred
Is Pt (dba)2 , Pt (CH2 = CH2 ) (PP
h3 )2 Is. In addition, these catalysts are used as promoters
1 to 10 equivalents of NEt3 , PPh 3 Add ligands such as
You may use it. For example, PtCl2 (PPh
3 )2To NEt3 Of Pd (db
a)2 To PPh3 Is used by adding 2 equivalents thereof.
【００１１】化学子式（１）に示す化学物の製造法を以
下に説明する。反応容器内に化学式（２）で示されたテ
トラキス（ヒドロシリル）ベンゼン化合物、化学式
（３）で示されたアセチレン化合物、触媒を仕込む。必
要に応じて溶媒も仕込む。これらの反応容器への仕込み
の順序は特に限定するものではない。これらを同時に混
合してもよいし、原料の一方ないし両方を反応中に連続
して、もしくは断続的に反応容器内に供給してもよい。
反応容器内は反応前には高純度窒素、高純度アルゴン等
の不活性ガスで置換しておくことが好ましい。反応容器
を所定の反応温度に制御しつつ、攪拌しながら所定の時
間、反応させる。目的の化合物は反応液からデカンテー
ション、濾過、溶媒による抽出、蒸留、クロマトグラフ
ィー等通常の方法で容易に分離精製することができる。A method for producing the chemical substance represented by the chemical formula (1) will be described below. A tetrakis (hydrosilyl) benzene compound represented by the chemical formula (2), an acetylene compound represented by the chemical formula (3), and a catalyst are charged in a reaction vessel. A solvent is also added if necessary. The order of charging these reaction vessels is not particularly limited. These may be mixed simultaneously, or one or both of the raw materials may be continuously or intermittently fed into the reaction vessel during the reaction.
Before the reaction, the inside of the reaction vessel is preferably replaced with an inert gas such as high-purity nitrogen or high-purity argon. The reaction is performed for a predetermined time while stirring while controlling the reaction container to a predetermined reaction temperature. The target compound can be easily separated and purified from the reaction solution by a conventional method such as decantation, filtration, extraction with a solvent, distillation, and chromatography.
【００１２】反応に用いるアセチレン化合物の量はテト
ラキス（ヒドロシリル）ベンゼン化合物１ｍｏｌに対し
て０．０２〜２００ｍｏｌ、さらに好ましくは０２．〜
２０ｍｏｌ、特に好ましくは２〜４ｍｏｌが適当であ
る。The amount of the acetylene compound used in the reaction is 0.02 to 200 mol, more preferably 02.200 mol, per 1 mol of the tetrakis (hydrosilyl) benzene compound. ~
20 mol, particularly preferably 2 to 4 mol is suitable.
【００１３】テトラキス（ヒドロシリル）ベンゼン化合
物に対する触媒の量は化合物１ｍｏｌに対して０．００
０１〜０．１ｍｏｌ、さらに好ましくは０．００１〜
０．０１ｍｏｌである。The amount of the catalyst for the tetrakis (hydrosilyl) benzene compound is 0.00 based on 1 mol of the compound.
01-0.1 mol, more preferably 0.001-
It is 0.01 mol.
【００１４】溶媒はベンゼンやトルエン等の芳香族系溶
剤やシクロヘキサンや正ヘプタン等の飽和炭化水素系溶
剤等が有効に用いられる。テトラキス（ヒドロシリル）
ベンゼン化合物に対する溶媒の量は、テトラキス（ヒド
ロシリル）ベンゼン化合物１ｍｍｏｌに対して０．１〜
１００ｍｌ、さらに好ましくは１〜１０ｍｌが適当であ
る。As the solvent, aromatic solvents such as benzene and toluene and saturated hydrocarbon solvents such as cyclohexane and normal heptane are effectively used. Tetrakis (hydrosilyl)
The amount of the solvent for the benzene compound is 0.1 to 1 mmol of the tetrakis (hydrosilyl) benzene compound.
100 ml, more preferably 1 to 10 ml is suitable.
【００１５】反応温度は０〜２００℃、より好ましくは
５０〜１００℃が適当である。The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 100 ° C.
【００１６】反応時間は原料の化合物の量等にもよる
が、１０分〜２４時間、さらに好ましくは３０分〜１０
時間が適当である。The reaction time depends on the amount of the raw material compound, etc., but is 10 minutes to 24 hours, more preferably 30 minutes to 10 hours.
Time is appropriate.
【００１７】[0017]
【実施例】以下に実施例に基づいて具体的に説明する。
実施例１
化学式（１）においてＲ1 およびＲ2 がメチル基である
環状の有機ケイ素化合物の製造方法について述べる。ま
ず５００ｍｌのガラス製反応容器に滴下ロートを付け、
反応容器の内部に磁気攪拌子を設置した。反応容器内を
高純度窒素ガスで置換した。続いて反応容器内に化学式
（２）で示されたテトラキス（ジメチルヒドロシリル）
ベンゼン２０．２ｇ（６５．０ｍｍｏｌ）とビス（ジベ
ンジリデンアセトン）白金（Ｏ）触媒２４５ｍｇ（０．
３６９ｍｍｏｌ）およびベンゼン溶媒２５０ｍｌを仕込
んだ。EXAMPLES Specific examples will be described below. Example 1 A method for producing a cyclic organosilicon compound in which R 1 and R 2 in the chemical formula (1) are methyl groups will be described. First, attach a dropping funnel to a 500 ml glass reaction container,
A magnetic stir bar was installed inside the reaction vessel. The inside of the reaction vessel was replaced with high-purity nitrogen gas. Then, tetrakis (dimethylhydrosilyl) represented by the chemical formula (2) was placed in the reaction vessel.
Benzene 20.2 g (65.0 mmol) and bis (dibenzylideneacetone) platinum (O) catalyst 245 mg (0.
369 mmol) and 250 ml of benzene solvent were charged.
【００１８】続いて滴下ロートにビス（ジメチルフロロ
シリル）アセチレン３６．５ｇ（２０４ｍｍｏｌ）を仕
込んだ。Subsequently, 36.5 g (204 mmol) of bis (dimethylfluorosilyl) acetylene was charged into the dropping funnel.
【００１９】反応容器を８０℃に設定した油浴に浸し、
反応温度を制御しつつ、磁気攪拌子で攪拌しながら滴下
ロートからアセチレン化合物を２時間かけて滴下した。Immerse the reaction vessel in an oil bath set at 80 ° C.,
While controlling the reaction temperature, the acetylene compound was added dropwise from the dropping funnel over 2 hours while stirring with a magnetic stirrer.
【００２０】ガスクロマトグラフィーで原料がほぼ消失
したことを確認後、反応容器を油浴から外し、室温に戻
し反応液を取り出した。シリカゲルの分離カラムに反応
液を担持し、ベンゼンで溶出させ、ヘキサン中で再結晶
させることにより生成物を分離精製した。目的化合物が
２０．０ｇ（３０．１ｍｍｏｌ）得られた。収率はテト
ラキス（ジメチルヒドロシリル）ベンゼンに対して４
６．３％であった。After confirming almost disappearance of the raw materials by gas chromatography, the reaction vessel was removed from the oil bath, returned to room temperature, and the reaction solution was taken out. The reaction solution was loaded on a silica gel separation column, eluted with benzene, and recrystallized in hexane to separate and purify the product. 20.0 g (30.1 mmol) of the target compound was obtained. The yield is 4 based on tetrakis (dimethylhydrosilyl) benzene.
It was 6.3%.
【００２１】化合物の形態は無色の結晶で、融点は２４
４℃である。The compound is in the form of colorless crystals and has a melting point of 24.
4 ° C.
【００２２】元素分析の測定値は、炭素４７．３０％
（理論値４７．０８％）、水素７．４２％（理論値７．
６０％）、フッ素１１．２０％（理論値１１．４６％）
であり、測定値は、測定誤差の範囲で理論値とよく一致
している。The measured value of elemental analysis is carbon 47.30%
(Theoretical value 47.08%), hydrogen 7.42% (theoretical value 7.
60%), fluorine 11.20% (theoretical value 11.46%)
The measured value is in good agreement with the theoretical value within the range of measurement error.
【００２３】マススペクトル（ＥＩ；７０ｅＶ）の主な
ピークは、ｍ／ｅ値が６６２（４８％）、５８５（５５
％）、７３（１００％）であった。ｍ／ｅ値の最大値で
ある６６２は、Ｍ+の理論値（６６２）と一致してい
る。The main peaks of the mass spectrum (EI; 70 eV) have m / e values of 662 (48%), 585 (55).
%), 73 (100%). 662, which is the maximum value of the m / e value, matches the theoretical value of M + (662).
【００２４】赤外吸収スペクトルをＫＢｒ錠剤法により
測定した。主な吸収ピーク波数（単位はｃｍ-1）は２９
５０，２９００，１４１０，１２６０，１１５０，１１
００であった。The infrared absorption spectrum was measured by the KBr tablet method. The main absorption peak wave number (unit: cm -1 ) is 29
50, 2900, 1410, 1260, 1150, 11
It was 00.
【００２５】1 Ｈ−ＮＭＲを重ベンゼン溶液で測定し
た。化学シフト（δ値）はＴＭＳを基準として、０．３
８６ｐｐｍ（１２Ｈ、２重項、ＪJ-F ＝８．０Ｈｚ）、
０．３９３ｐｐｍ（１２Ｈ、２重項、ＪH-F ＝８．０Ｈ
ｚ）、０．５３６ｐｐｍ（１２Ｈ、１重項）、０．５３
９ｐｐｍ（１２Ｈ、１重項）、７．９４ｐｐｍ（２Ｈ、
１重項）であった。０．３８ｐｐｍから０．５４ｐｐｍ
の合計４８個の水素は、ケイ素上の１６個のメチル基の
合計４８個の水素に、７．９４ｐｐｍの２個の水素は、
ベンゼン環上の２個の水素に同定でき、理論値と一致し
ている。 1 H-NMR was measured with a heavy benzene solution. Chemical shift (δ value) is 0.3 based on TMS.
86 ppm (12H, doublet, J JF = 8.0 Hz),
0.393 ppm (12H, doublet, J HF = 8.0H
z), 0.536 ppm (12H, singlet), 0.53
9ppm (12H, singlet), 7.94ppm (2H,
It was a singlet). 0.38ppm to 0.54ppm
The total of 48 hydrogens of 16 is the total of 48 hydrogens of 16 methyl groups on silicon, and the two hydrogens of 7.94ppm are
It can be identified as two hydrogens on the benzene ring, which is in agreement with the theoretical value.
【００２６】13Ｃ−ＮＭＲを重ベンゼン溶液で測定し
た。化学シフト（δ値）はＴＭＳを基準として、１．１
０ｐｐｍ、１．１３ｐｐｍ、１．３０ｐｐｍ（ＪC-F ＝
１３Ｈｚ）、１．３６ｐｐｍ（ＪC-F ＝１３Ｈｚ），１
２８．３０ｐｐｍ、１３６．５４ｐｐｍ、１４４．５５
ｐｐｍ、１８７．５０ｐｐｍ（ＪC-F ＝１６Ｈｚ）であ
った。 13 C-NMR was measured with a heavy benzene solution. Chemical shift (δ value) is 1.1 based on TMS.
0 ppm, 1.13 ppm, 1.30 ppm (J CF =
13 Hz), 1.36 ppm (J CF = 13 Hz), 1
28.30 ppm, 136.54 ppm, 144.55
ppm and 187.50 ppm (J CF = 16 Hz).
【００２７】29Ｓｉ＝ＮＭＲを重ベンゼン溶液で測定し
た。化学シフト（δ値）はＴＭＳを基準として、−２
５．９２ｐｐｍ、１８．６１ｐｐｍ（ＪS1-F＝２７８Ｈ
ｚ）であった。 29 Si = NMR was measured with a heavy benzene solution. Chemical shift (δ value) is -2 based on TMS
5.92 ppm, 18.61 ppm (J S1-F = 278H
z).
【００２８】[0028]
【発明の効果】本発明は、新しい環状の有機ケイ素化合
物を提供するものである。この化合物は耐熱性、耐燃焼
性の含ケイ素高分子材料の原料等として産業上有用であ
る。INDUSTRIAL APPLICABILITY The present invention provides a new cyclic organosilicon compound. This compound is industrially useful as a raw material for heat-resistant and flammable silicon-containing polymer materials.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内海 哲良 神奈川県横浜市栄区笠間町1190番地 三 井東圧化学株式会社内 (72)発明者 岩田 健二 神奈川県横浜市栄区笠間町1190番地 三 井東圧化学株式会社内 (72)発明者 三塚 雅彦 神奈川県横浜市栄区笠間町1190番地 三 井東圧化学株式会社内 (72)発明者 田中 正人 茨城県つくば市東１丁目１番地 工業技 術院物質工学工業技術研究所内 (72)発明者 内丸 祐子 茨城県つくば市東１丁目１番地 工業技 術院物質工学工業技術研究所内 (56)参考文献 特開 平５−310752（ＪＰ，Ａ) 特開 平６−247983（ＪＰ，Ａ) 特開 平６−247984（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuyoshi Utsumi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Kenji Iwata 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Kagaku (72) Inventor Masahiko Mitsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. Masato Tanaka 1-1, Higashi 1-1 Tsukuba-shi, Ibaraki Industrial Technology Institute In-house (72) Inventor Yuko Uchimaru 1-1, Higashi, Tsukuba-shi, Ibaraki Inside Institute of Materials Engineering, Industrial Technology Institute (56) References JP-A-5-310752 (JP, A) JP-A-6-247983 (JP , a) JP flat 6-247984 (JP, a) (58 ) investigated the field (Int.Cl. 7, DB name) CA (STN) CAOLD (STN ) R GISTRY (STN)
Claims (3)
アルケニル基または低級アルキル基、低級アルケニル
基、低級アルコキシ基もしくはハロゲンで置換されてい
てもよいフェニル基である。）で示されるフロロシリル
基を有する環状有機ケイ素化合物。1. A chemical formula (1): (In the above formula, R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms,
It is an alkenyl group or a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen. ) A cyclic organosilicon compound having a fluorosilyl group.
ニル基または低級アルキル基、低級アルケニル基、低級
アルコキシ基もしくはハロゲンで置換されていてもよい
フェニル基である。）で示される化合物と化学式（３） 【化３】 （上式中、Ｒ2 は炭素数１〜１０のアルキル基、アルケ
ニル基または低級アルキル基、低級アルケニル基、低級
アルコキシ基もしくはハロゲンで置換されていてもよい
フェニル基である。）で示される化合物とを触媒の存在
下に、反応させることを特徴とする請求項１記載のフロ
ロシリル基を有する環状有機ケイ素化合物の製造方法。2. A chemical formula (2): (In the above formula, R 1 is an alkyl group, an alkenyl group or a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with a halogen, each having 1 to 10 carbon atoms.) And chemical formula (3) (In the above formula, R 2 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group optionally substituted with halogen.) The method for producing a cyclic organosilicon compound having a fluorosilyl group according to claim 1, wherein the reaction is carried out in the presence of a catalyst.
ウムいずれかの錯体である請求項２記載の製造方法。3. The method according to claim 2, wherein the catalyst is a complex of platinum, palladium or ruthenium.
Priority Applications (1)
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