JP3765046B2 - Photobissilylation of unsaturated compounds using fullerenes as photosensitizers, organosilicon compounds obtained by the reactions - Google Patents
Photobissilylation of unsaturated compounds using fullerenes as photosensitizers, organosilicon compounds obtained by the reactions Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims description 26
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 20
- 229910003472 fullerene Inorganic materials 0.000 title claims description 19
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 title description 15
- 239000003504 photosensitizing agent Substances 0.000 title description 3
- OHJXHDSSJBWWAI-UHFFFAOYSA-N disilirane Chemical compound C1[SiH2][SiH2]1 OHJXHDSSJBWWAI-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 37
- -1 Cation radical Chemical class 0.000 description 10
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 0 C1CC*CC1 Chemical compound C1CC*CC1 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- ZUKOXCIXRUTONV-UHFFFAOYSA-N O1[SiH2][SiH2]1 Chemical compound O1[SiH2][SiH2]1 ZUKOXCIXRUTONV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003473 flash photolysis reaction Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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
- HGCIXCUEYOPUTN-UHFFFAOYSA-N C1CC=CCC1 Chemical compound C1CC=CCC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- BIOPPFDHKHWJIA-UHFFFAOYSA-N anthracene-9,10-dinitrile Chemical compound C1=CC=C2C(C#N)=C(C=CC=C3)C3=C(C#N)C2=C1 BIOPPFDHKHWJIA-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、ジシリラン骨格を有するケイ素化合物と不飽和有機化合物、例えばＣ≡Ｎ結合を有する化合物やＣ＝Ｏ結合を持つアルデヒド類、ケトン類等とを触媒量のフラーレン類の存在する極性溶媒中で光照射（波長４００ｎｍ以上）してビスシリル化反応させて、前記不飽和有機化合物に前記ケイ素化合物が付加した有機ケイ素化合物を製造する方法、及び前記ビシリル化反応によって得られる新規な有機ケイ素化合物に関する。
特に、電気・電子材料分野において利用される機能性有機ケイ素化合物の製造に関する。
【０００２】
【従来技術】
従来から不飽和有機化合物のビシリル化反応による有機ケイ素化合物の合成は、２つのケイ素−炭素結合が一度に形成されることから多くの関心が寄せられてきた。
そしてそのような反応を促進する触媒化合物として、パラジュウム錯体のような金属化合物を使用したビシリル化反応方法が開発されてきた（M.Murakami,M.Suginome,and Y.Ito,J.Synth.Org.Chem.53,47(1995)）（特公平７−２１０５９号公報）。
これに対して、ケイ素などの１４族グループの有機金属化合物は、電子豊富な化合物群であり、光化学的に、電子欠損型の分子へ電子を供与しやすく、イオンラジカルを形成した後、種々の付加体を生成したり、あるいは伝導性を向上させたりするなどの特性を有することから、近年前記１４族グループの有機金属化合物の光誘起電子移動反応が、前記ビシリル化反応に関連して注目されている（Y.Nakadaira,S.Kyushin,and M.Ohashi,J.Synth.Org.Chem.48,331(1990)）。
Ｓｉ−Ｓｉシグマ結合は、光励起９，１０−ジシアノアントラセン（ＤＣＡ）のような電子受容体の存在下において優れた電子供与体として機能することが良く知られている。
ジシランやポリシランの光誘起電子移動反応において生成するカチオンラジカル中間体は、アルコール及び四塩化炭素に効率的に捕らえられ、種々の有機ケイ素化合物が合成されている。
【０００３】
一方、Ｃ60は、その低い最低空軌道により優れた電子受容体としてふるまうが、光励起Ｃ60は基底状態のＣ60よりさらに強い電子受容体である。このような状況の中で、本発明者は、トルエン中におけるジシリラン１とＣ60との光化学的付加反応についてすでに報告している（T.Akasaka,W.Ando,K.Kobayashi,andS.Nagase,J.Am.Chem.Soc.,115,10366(1993)）。
また、金属内包フラーレンの誘導体として、金属内包フラーレンの二重結合にジシリランが付加した有機ケイ素誘導体の合成方法に関する報告もある（Nature 1995,374,600、J.Chem.Soc.Commun.1995,1343、特開平９−８７２８６号公報第４欄）（図Ａ参照、但し、Ｍｅｓは、メシチル基、すなわち２，４，６−トリメチルフェニル基を表す。）。
ところで、有機ケイ素化合物は、シリコーンをはじめとして、半導体レジストの中間体等の電子材料やニューセラミックスとして使用されている。新規な有機ケイ素化合物の合成やその物性に関する研究も盛んであり、これらの成果は、新規機能材料設計の宝庫ともなっている。
【０００４】
【発明が解決しようとする課題】
このような技術的な展開の中で、電子材料としての有機ケイ素化合物としては、金属元素が含まれると不都合な場合がある、また、金属元素を有機ケイ素化合物から完全に取り除くのは難しいし、金属類が環境に排出された場合は色々な不都合を引き起こす原因ともなるなどの問題があった。
従って、金属を含まない光誘起触媒を用いた有機ケイ素化合物類の合成法が望まれている。よって、本発明の課題は、前記問題のない有機ケイ素化合物類の合成法を見出すことにある。
【０００５】
【課題を解決するための手段】
本発明の要旨の第１は、一般式（１）ジシリラン
【化４】
【化５】
Ｒ１Ｃ≡Ｎ （２）
（式中Ｒ１は、アリール基、アルキル基である。）
、更に具体的にはフラーレン類がＣ60、Ｃ70、高次フラーレン類、及び金属内包フラーレンから選択されることを特徴とする前記付加化合物を製造する方法である。
また、本発明の要旨の第２は、前記ビスシリル化で得られる一般式（３）で表される有機ケイ素化合物
【化６】
本発明者は、紫外領域の光を含まないという比較的温和な条件において、有機ケイ素化合物類の合成反応を進行させることができることを見出すことにより、前記課題を解決したものである。
【０００６】
【本発明の態様】
本発明において、光誘起触媒として使用されるフラーレン類としては、Ｃ60、Ｃ70、高次フラーレン類、及び金属内包フラーレンなどを挙げることができる。
また、極性溶媒としては、ベンゾニトリル、アルデヒド、ケトン類などを挙げることができる。
前記フラーレン類の光増感剤の反応系への配合量は、触媒量である。
この反応は、ジシリラン化合物（Ｄ．Ｓ）が、光照射（ｈｖ）により励起状態になったフラーレン類（Ｃ60）に電子を渡して反応中間体となり、これと不飽和化合物が反応することにより、付加化合物（Ａ．Ｄ）が生成される（図１参照）。
本発明のビスシリル化反応は、遷移金属等による金属触媒を用いることなく、フラーレン類を光増感剤として用いて自然光下の温和な条件で進行させることができる。
従って、本発明のビシリル化反応は、簡便かつクリーンに有機ケイ素化合物を合成できる技術として、新機能材料の創出に資するものと期待される。
【０００７】
【実施例】
実施例１
ジシリラン１（式中Ｍｅｓは、メシチル基を表す。）及びＣ60フラーレンをベンゾニトリル（ＢＮ＝ＰｈＣＮ／トルエン＝ＰｈＭｅ）に溶解し、該溶液をハロゲンランプを使用して光照射する。その際、波長４００ｎｍより短い波長をカットして光照射する。
その結果、ＢＮと前記ジシりランとが１：１の付加化合物３と１：２の付加化合物４とが生成していた。付加化合物３の生成率は５１％であり、付加化合物４の生成率は１８％であった。
その反応を図２に示す。
付加化合物３の分析値。
Ｃ44Ｈ51ＮＳｉ2
1Ｈ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ 7.24(m.H),7.15(brs,2H),7.14(brs,2H),6.55(s,4H),6.50(s,4H),2.23(s,12H),2.17(s,6H),2.16(s,6H),2.05(s,12H),1.61(s,2H),
13Ｃ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ 201.18,143.60,143.46,143,03,138.45,137.33,134.73,131.51,129.14*,128.65,127.64,125.89,24.70,23.37,20.31,20.29.11.12
*２つのピークが重なっており、ghmqcにより検出した。
29Ｓｉ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ -0.21,-8.25
ＦＴ−ＩＲ(neat) 1604cm-1
ＵＶ−Ｖｉｓ(λｍａｘ,hexane) 215,219,225,272nm
ＦＡＢ ＭＳ,m/z 648-654
付加化合物４の分析値
Ｃ51Ｈ56Ｎ2Ｓｉ2
ｍｐ 266℃
1Ｈ−ＮＭＲ（Ｃ6Ｄ6）
δ 7.69(d,J=7.0Hz,4H),6.86(s,4H)6.84(d,J=7.0Hz,2H),6.76(t.J=7.0Hz,4H),6.21(s.4H),2.96(s.12H),2.53(s.12H),2,75(s.6H),2.13(s.6H),2.12(s.2H)
13Ｃ−ＮＭＲ（Ｃ6Ｄ6）
δ 178.78,144.74,144.26,139.09,138.70,138.64,135.28,133.56,130.88,130.27,129.88,129,04,127.99,25.30,24.72,21.46,21.18,14,94
１つのピークは,Ｃ6Ｄ6と重なっており、ghmqcにより検出した。
29Ｓｉ−ＮＭＲ（Ｃ6Ｄ6）
δ -15.98
ＦＴ−ＩＲ(neat) 1604cm-1
ＵＶ−Ｖｉｓ(λｍａｘ,hexane) 222,261,416nm
ＦＡＢ ＭＳ,m/z 751-755
得られた化合物は、含ケイ素高分子などの原材料としてとして有用である。
【０００８】
実施例２
オキサジシリラン５（Ｄｅｐは、ジエチルフェニル基を表す。）及びＣ60フラーレンを実施例１と同様にベンゾニトリル（ＢＮ）に溶解し、実施例１と同様な条件下で反応させてると、オキサジシリラン５：ＢＮが１：１の付加物７が得られた。収率は６２％である。
その反応を図３に示す。
付加化合物５の分析値。
Ｃ51Ｈ56Ｎ2Ｓｉ2
mp 211℃
1Ｈ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ 7.60(d,J=6.5Hz,2H),7.36(t,J=7.5Hz,H)7.30(t,J=7.5Hz,2H), 7.26(t,J=7.8Hz,2H),7.25(t,J=7.8Hz,2H),7.00(d,J=8.0Hz,4H), 6.99(d,J=7.5Hz,4H),3.07(q,J=7.3Hz,4H),2.68(q,J=7.0Hz,4H), 2.62(q,J=7.3Hz,4H),2.43(q,J=7.3Hz,4H),0.77(t,J=7.3Hz,12H), 0.61(q,J=7.5Hz,12H)
13Ｃ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ 201.71,150.08,149.13,145.13,135.45,133,08,129.62,129.61,129.03, 127.47,127.15,125.93,125.72,29.93,28.32,15.13,14.31
29Ｓｉ−ＮＭＲ（ＣＤ2Ｃｌ2）
δ -6.38,-19.47
ＦＴ−ＩＲ(neat) 1587cm-1
ＵＶ−Ｖｉｓ(λｍａｘ,hexane) 213,239,253nm
得られた化合物は、含ケイ素高分子などの原材料として有用である。
【０００９】
実施例１及び２で得られた付加化合物２、３及び５の化学構造の吸収スペクトルによるデータは上記したとおりである。付加化合物２及び３に対しては最終的にはＸ線結晶解析により決定した。その結果らの分子構造を図４に示す。
ジシラン１は３５０ｎｍより長波長光を吸収しない、従って、４００ｎｍ以上の波長域の照射はＣ60だけを励起することができる。ジシラン１からＣ60の三重項状態への電子転移の自由エネルギー変化（ΔＧ）は−８．３ｋｃａｌ／ｍｏｌ．である。
Ｃ60の消滅速度は、ジアザビシクロ〔２．２．２．〕オクタン及び１，２，４，５−テトラメトキシベンゼン（これらはＣ60よりも低い酸化電位を有しており、かつＣ60に対して非反応性である）の付加によって抑制される。
これらの結果から、付加化合物２及び３は、基底状態のジシラン１と3Ｃ60 *（三重項励起状態）との間での光誘起電子移動の反応を経由して形成される。
その反応の想像図を図５に示す。
【００１０】
反応メカニズムを明らかにするために、５３２ｎｍのレーザー光分解反応において近赤外領域における遷移吸収帯を観察した。
非極性溶媒（ベンゼン）中では、Ｃ60 -・の遷移吸収帯は１０７０ｎｍでは現れなかった、しかしながら、励起錯体の形成によるものと思われるかなり早い７４０ｎｍでの3Ｃ60 *の減衰が観察された（図６）。
非極性溶媒中では、ジシラン１とＣ60の付加物は、励起錯体を経由して形成される。
【００１１】
極性溶媒（ベンジルニトリル）中では、７４０ｎｍでの3Ｃ60 *の吸収帯はレーザー照射直後に現れ、ジシラン１の存在中で減衰が開始された（図７）。3Ｃ60 *の減衰に伴って、１０７０ｎｍでのＣ60 -・の吸収強度は増大し、約５００ｎｓ後に飽和強度に達する。これからＣ60 -・は3Ｃ60 *が１から電子を受け取ることにより生成することは明らかである。
この新規な光化学ビシリル化システムを発展させて、ベンゾニトリル中で触媒量のＣ60の存在中で１の光照射を行なった。２及び３もまた高収率で得られた。この結果は、Ｃ60は光誘起電子移動触媒としての作用をしていることを示唆している。
同様の結果は、Ｃ70、ＤＣＡ及び２，４，６−トリフェニルピリリュウムテトラフルオロ硼酸塩を増感剤とした場合にも得られた。
【００１２】
【発明の効果】
以上述べたように、本発明は、フラーレン化合物が光化学ビシリル化反応の触媒として有用であること見出すことにより、金属原子を含まなで、温和な条件において、電子材料、高分子などの原材料などの用途に用いられる有機ケイ素化合物を製造することができる方法を提供する、という優れた効果をもたしたものである。
【図面の簡単な説明】
【図１】 ジシランの不飽和化合物への付加反応
【図２】 ジシラン１とベンゾニトリルとの付加反応
【図３】 オキサジシリラン５とベンゾニトリルとの付加反応
【図４】 付加化合物２及び３のＸ線結晶構造解析による分子構造
【図５】 ジシラン１とベンゾニトリルとの付加反応の想像図
【図６】 脱空気ベンゼン中のジシリラン（５ｍＭ）の存在下でのＣ60（０．１ｍＭ）の５３２ｎｍレーザーフラシュ光分解による遷移吸収スペクトル５０ｎｓ（○）、５００ｎｓ（●）
【図７】 脱空気ベンゾニトリル中のジシリラン（５ｍＭ）の存在下でのＣ60（０．１ｍＭ）の５３２ｎｍレーザーフラシュ光分解による遷移吸収スペクトル１００ｎｓ（○）、１μｓ（●）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silicon compound having a disilirane skeleton and an unsaturated organic compound, for example, a compound having a C≡N bond, an aldehyde having a C═O bond, a ketone, etc. in a polar solvent having a catalytic amount of fullerenes. The present invention relates to a method for producing an organosilicon compound in which the silicon compound is added to the unsaturated organic compound by irradiating with light (wavelength of 400 nm or more) and a novel organosilicon compound obtained by the bisilylation reaction .
In particular, it relates to the production of functional organosilicon compounds used in the field of electrical and electronic materials.
[0002]
[Prior art]
Conventionally, the synthesis of organosilicon compounds by bisilylation reaction of unsaturated organic compounds has attracted much interest because two silicon-carbon bonds are formed at once.
As a catalyst compound for promoting such a reaction, a bisilylation reaction method using a metal compound such as a palladium complex has been developed (M. Murakami, M. Suginome, and Y. Ito, J. Synth. Org). Chem. 53, 47 (1995)) (Japanese Patent Publication No. 7-21059).
On the other hand, group 14 group organometallic compounds such as silicon are a group of compounds rich in electrons, and are easy to donate electrons to an electron-deficient molecule photochemically. In recent years, the photoinduced electron transfer reaction of the organometallic compounds of the group 14 group has attracted attention in connection with the bisilylation reaction because it has properties such as the formation of an adduct or improved conductivity. (Y. Nakadaira, S. Kyushin, and M. Ohashi, J. Synth. Org. Chem. 48, 331 (1990)).
It is well known that the Si—Si sigma bond functions as an excellent electron donor in the presence of an electron acceptor such as photoexcited 9,10-dicyanoanthracene (DCA).
Cation radical intermediates generated in the photoinduced electron transfer reaction of disilane or polysilane are efficiently captured by alcohol and carbon tetrachloride, and various organosilicon compounds have been synthesized.
[0003]
On the other hand, C 60 behaves as an excellent electron acceptor due to its low lowest unoccupied orbital, but photoexcited C 60 is a stronger electron acceptor than ground state C 60 . Under such circumstances, the present inventor has already reported on the photochemical addition reaction between
In addition, as a derivative of metal-encapsulated fullerene, there is also a report on a synthesis method of an organosilicon derivative in which disilirane is added to the double bond of metal-encapsulated fullerene (Nature 1995, 374,600, J. Chem. Soc. Commun. 1995, 1343, special feature). No. 9-87286, column 4) (see FIG. A, where Mes represents a mesityl group, that is, a 2,4,6-trimethylphenyl group).
By the way, organosilicon compounds are used as electronic materials such as intermediates of semiconductor resists and new ceramics including silicone. Studies on the synthesis of new organosilicon compounds and their physical properties are also active, and these results are a treasure trove for designing new functional materials.
[0004]
[Problems to be solved by the invention]
In such technical development, as an organosilicon compound as an electronic material, it may be inconvenient if a metal element is included, and it is difficult to completely remove the metal element from the organosilicon compound, When metals are discharged into the environment, there are problems such as causing various inconveniences.
Therefore, a method for synthesizing organosilicon compounds using a photo-inducing catalyst containing no metal is desired. Therefore, an object of the present invention is to find a method for synthesizing organosilicon compounds without the above-mentioned problems.
[0005]
[Means for Solving the Problems]
The first of the gist of the present invention is the general formula (1) disilirane
R1C≡N (2)
(Wherein R1 is an aryl group or an alkyl group.)
More specifically, the fullerenes are selected from C 60 , C 70 , higher-order fullerenes, and metal-encapsulated fullerenes.
The second gist of the present invention is an organosilicon compound represented by the general formula (3) obtained by the bissilylation:
The present inventor has solved the above-mentioned problems by finding that the synthesis reaction of organosilicon compounds can proceed under a relatively mild condition of not containing light in the ultraviolet region.
[0006]
[Aspect of the present invention]
In the present invention, examples of the fullerenes used as the photo-induced catalyst include C 60 , C 70 , higher-order fullerenes, and metal-encapsulated fullerenes.
Examples of polar solvents include benzonitrile, aldehydes, ketones and the like.
The blending amount of the fullerenes in the reaction system of the photosensitizer is a catalytic amount.
In this reaction, the disilirane compound (DS) passes an electron to fullerenes (C 60 ) excited by light irradiation (hv) to become a reaction intermediate, which reacts with the unsaturated compound. The addition compound (AD) is produced (see FIG. 1).
The bissilylation reaction of the present invention can proceed under mild conditions under natural light using fullerenes as a photosensitizer without using a metal catalyst such as a transition metal.
Therefore, the bisilylation reaction of the present invention is expected to contribute to the creation of a new functional material as a technique for synthesizing an organosilicon compound easily and cleanly.
[0007]
【Example】
Example 1
Disilirane 1 (wherein Mes represents a mesityl group) and C 60 fullerene are dissolved in benzonitrile (BN = PhCN / toluene = PhMe), and the solution is irradiated with a halogen lamp. At that time, light having a wavelength shorter than 400 nm is cut and irradiated.
As a result, 1: 1
The reaction is shown in FIG.
Analytical value of
C 44 H 51 NSi 2
1 H-NMR (CD 2 Cl 2 )
δ 7.24 (mH), 7.15 (brs, 2H), 7.14 (brs, 2H), 6.55 (s, 4H), 6.50 (s, 4H), 2.23 (s, 12H), 2.17 (s, 6H), 2.16 ( s, 6H), 2.05 (s, 12H), 1.61 (s, 2H),
13 C-NMR (CD 2 Cl 2 )
δ 201.18,143.60,143.46,143,03,138.45,137.33,134.73,131.51,129.14 *, 128.65,127.64,125.89,24.70,23.37,20.31,20.29.11.12
* The two peaks overlap and were detected by ghmqc.
29 Si-NMR (CD 2 Cl 2 )
δ -0.21, -8.25
FT-IR (neat) 1604cm -1
UV-Vis (λmax, hexane) 215,219,225,272nm
FAB MS, m / z 648-654
Analytical value of addition compound 4 C 51 H 56 N 2 Si 2
mp 266 ℃
1 H-NMR (C 6 D 6 )
δ 7.69 (d, J = 7.0Hz, 4H), 6.86 (s, 4H) 6.84 (d, J = 7.0Hz, 2H), 6.76 (tJ = 7.0Hz, 4H), 6.21 (s.4H), 2.96 ( s.12H), 2.53 (s.12H), 2,75 (s.6H), 2.13 (s.6H), 2.12 (s.2H)
13 C-NMR (C 6 D 6 )
δ 178.78,144.74,144.26,139.09,138.70,138.64,135.28,133.56,130.88,130.27,129.88,129,04,127.99,25.30,24.72,21.46,21.18,14,94
One peak overlapped with C 6 D 6 and was detected by ghmqc.
29 Si-NMR (C 6 D 6 )
δ -15.98
FT-IR (neat) 1604cm -1
UV-Vis (λmax, hexane) 222,261,416nm
FAB MS, m / z 751-755
The obtained compound is useful as a raw material for silicon-containing polymers and the like.
[0008]
Example 2
When oxadisilirane 5 (Dep represents a diethylphenyl group) and C 60 fullerene were dissolved in benzonitrile (BN) in the same manner as in Example 1 and reacted under the same conditions as in Example 1, oxadisilirane 5:
The reaction is shown in FIG.
Analytical value of Addition Compound 5.
C 51 H 56 N 2 Si 2
mp 211 ℃
1 H-NMR (CD 2 Cl 2 )
δ 7.60 (d, J = 6.5Hz, 2H), 7.36 (t, J = 7.5Hz, H) 7.30 (t, J = 7.5Hz, 2H), 7.26 (t, J = 7.8Hz, 2H), 7.25 ( t, J = 7.8Hz, 2H), 7.00 (d, J = 8.0Hz, 4H), 6.99 (d, J = 7.5Hz, 4H), 3.07 (q, J = 7.3Hz, 4H), 2.68 (q, J = 7.0Hz, 4H), 2.62 (q, J = 7.3Hz, 4H), 2.43 (q, J = 7.3Hz, 4H), 0.77 (t, J = 7.3Hz, 12H), 0.61 (q, J = (7.5Hz, 12H)
13 C-NMR (CD 2 Cl 2 )
δ 201.71,150.08,149.13,145.13,135.45,133,08,129.62,129.61,129.03, 127.47,127.15,125.93,125.72,29.93,28.32,15.13,14.31
29 Si-NMR (CD 2 Cl 2 )
δ -6.38, -19.47
FT-IR (neat) 1587cm -1
UV-Vis (λmax, hexane) 213, 239, 253 nm
The obtained compound is useful as a raw material for silicon-containing polymers.
[0009]
The data by the absorption spectrum of the chemical structures of the addition compounds 2, 3 and 5 obtained in Examples 1 and 2 are as described above. The addition compounds 2 and 3 were finally determined by X-ray crystallography. The resulting molecular structure is shown in FIG.
The disappearance rate of C 60 is diazabicyclo [2.2.2. ] Octane and 1,2,4,5-methoxybenzene (these are C 60 has a lower oxidation potential than, and is non-reactive to C 60) is inhibited by the addition of.
From these results, adducts 2 and 3 are formed via a photoinduced electron transfer reaction between
An imaginary view of the reaction is shown in FIG.
[0010]
In order to clarify the reaction mechanism, a transition absorption band in the near infrared region was observed in a laser photolysis reaction at 532 nm.
In a non-polar solvent (benzene) , the transition absorption band for C 60 − · did not appear at 1070 nm, however, a much faster decay of 3 C 60 * at 740 nm was observed, which was probably due to the formation of an exciplex. (FIG. 6).
In nonpolar solvents, the adduct of
[0011]
In a polar solvent (benzylnitrile), the 3 C 60 * absorption band at 740 nm appeared immediately after laser irradiation, and attenuation began in the presence of disilane 1 (FIG. 7). 3 With the decay of C 60 * , the absorption intensity of C 60 − at 1070 nm increases and reaches a saturation intensity after about 500 ns. From this, it is clear that C 60 − · is generated when 3 C 60 * receives electrons from 1.
This novel photochemical bisilylation system was developed to perform 1 light irradiation in the presence of catalytic amounts of C 60 in benzonitrile. 2 and 3 were also obtained in high yield. This result suggests that C 60 acts as a photoinduced electron transfer catalyst.
Similar results were obtained when C 70 , DCA and 2,4,6-triphenylpyrylium tetrafluoroborate were used as sensitizers.
[0012]
【The invention's effect】
As described above, the present invention finds that a fullerene compound is useful as a catalyst for a photochemical bisilylation reaction, so that it does not contain metal atoms and can be used for raw materials such as electronic materials and polymers under mild conditions. This has an excellent effect of providing a method capable of producing an organosilicon compound used for a use.
[Brief description of the drawings]
[Fig. 1] Addition reaction of disilane to unsaturated compound [Fig. 2] Addition reaction of
FIG. 7 Transition absorption spectrum by 532 nm laser flash photolysis of C 60 (0.1 mM) in the presence of disilirane (5 mM) in deaired benzonitrile 100 ns (◯), 1 μs (●)
Claims (4)
と不飽和有機化合物とを触媒量のフラーレン類の存在する極性溶媒中で波長４００ｎｍ以上の光を照射してビスシリル化して前記ケイ素化合物と不飽和化合物との付加化合物を製造する方法。General formula (1) disilirane
And an unsaturated organic compound are irradiated with light having a wavelength of 400 nm or more in a polar solvent containing a catalytic amount of fullerenes to bissilylate to produce an addition compound of the silicon compound and the unsaturated compound.
【化２】
Ｒ１Ｃ≡Ｎ （２）
（式中Ｒ１は、アリール基、アルキル基である。）The method for producing an addition compound according to claim 1, wherein the unsaturated compound is a compound represented by the general formula (2).
[Chemical 2]
R1C≡N (2)
(Wherein R1 is an aryl group or an alkyl group.)
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| US7531209B2 (en) | 2005-02-24 | 2009-05-12 | Michael Raymond Ayers | Porous films and bodies with enhanced mechanical strength |
| WO2007143026A2 (en) | 2006-05-31 | 2007-12-13 | Roskilde Semiconductor Llc | Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials |
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| WO2007143029A1 (en) | 2006-05-31 | 2007-12-13 | Roskilde Semiconductor Llc | Porous materials derived from polymer composites |
| US7790234B2 (en) | 2006-05-31 | 2010-09-07 | Michael Raymond Ayers | Low dielectric constant materials prepared from soluble fullerene clusters |
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