JPH02247188A - Novel polysilane compound - Google Patents
Novel polysilane compoundInfo
- Publication number
- JPH02247188A JPH02247188A JP1066661A JP6666189A JPH02247188A JP H02247188 A JPH02247188 A JP H02247188A JP 1066661 A JP1066661 A JP 1066661A JP 6666189 A JP6666189 A JP 6666189A JP H02247188 A JPH02247188 A JP H02247188A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- substituted indole
- tetramethyldisilane
- methylindolyl
- examples
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 229920000548 poly(silane) polymer Polymers 0.000 title claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- -1 N-substituted indole Chemical class 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract description 2
- SFAZXBAPWCPIER-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]-dimethylsilane Chemical compound C[Si](C)(Cl)[Si](C)(C)Cl SFAZXBAPWCPIER-UHFFFAOYSA-N 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 238000012685 gas phase polymerization Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000001979 organolithium group Chemical group 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MHBOFSJQAKACCM-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octakis-phenyltetrasiletane Chemical compound C1=CC=CC=C1[Si]1(C=2C=CC=CC=2)[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 MHBOFSJQAKACCM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YBFCBQMICVOSRW-UHFFFAOYSA-N 1-phenylindole Chemical compound C1=CC2=CC=CC=C2N1C1=CC=CC=C1 YBFCBQMICVOSRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YLFSKHFWQGRUCI-UHFFFAOYSA-N [Li]CCc1ccccc1 Chemical compound [Li]CCc1ccccc1 YLFSKHFWQGRUCI-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
意１」ぼり月」矩顆
本発明は、新規なポリシラン化合物に関し、詳しくは、
インドリル置換ポリシラン化合物に関する。かかるポリ
シラン化合物は、例えば、気相重合法によるシリコン薄
膜の製造原料や、或いは光デイスク用色素材料の原料と
して有用である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polysilane compound.
This invention relates to indolyl-substituted polysilane compounds. Such polysilane compounds are useful, for example, as raw materials for producing silicon thin films by vapor phase polymerization or as raw materials for dye materials for optical disks.
従米夏狡森
従来、種々の有機ケイ素化合物が知られているが、しか
し、有機炭素化合物に比べれば、その研究は未だ十分に
は進んでいない。例えば、従来、ケイ素原子上にアルキ
ル基、フェニル基、アルコキシ基、ハロゲン原子等の置
換基を有する有機ケイ素化合物は種々知られているもの
の、ケイ素原子かへテロ環にて置換されているポリシラ
ン化合物は、殆ど、知られておらず、勿論、その製造に
ついては、何らその手法が確立されていない。A variety of organosilicon compounds have been known in the past, but compared to organic carbon compounds, their research has not progressed as far as they have. For example, various organosilicon compounds having substituents such as alkyl groups, phenyl groups, alkoxy groups, and halogen atoms on silicon atoms have been known, but polysilane compounds in which silicon atoms are substituted with heterocycles is little known, and of course, no method has been established for its production.
が しようとする
本発明は、ケイ素原子上にペテロ環を置換基として有す
る新規なポリシラン化合物、特に、インドリル置換ポリ
シラン化合物を提供することを目的とする。An object of the present invention is to provide a novel polysilane compound having a petero ring as a substituent on a silicon atom, particularly an indolyl-substituted polysilane compound.
扉ｌ］」靴七【支（へｑ手段
本発明によるポリシラン化合物は、−数式（式中、Ｒ１
、Ｒ２及びＲ３は、それぞれ独立にアルキル基、アリー
ル基又はアラルキル基を示し、ｎは２以上の整数を示す
。）
表わされることを特徴とする。The polysilane compound according to the present invention has -formula (in the formula, R1
, R2 and R3 each independently represent an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 2 or more. ) is characterized by being expressed.
上記−数式（１）において、Ｒ′、Ｒ２及びＲ３は、好
ましくは、それぞれ独立に、炭素数１〜１２のアルキル
基、炭素数６〜１２のアリール基又は炭素数７〜１３の
アラルキル基を示し、具体例としては、アルキル基とし
ては、例えば、メチル、エチル、ｎ−プロピル、イソプ
ロピル、ｎ−ブチル、５ｅｃ−ブチル、ｔ−ブチル、ア
ミル、ヘキシル、オクチル、ドデシル基等を、アリール
基としては、例えば、フェニル、トリル、メトキシフェ
ニル基等を、また、アラルキル基としては、例えば、ベ
ンジル、フェネチル、ｐ−メチルヘンシル基等を挙げる
ことができる。In the above formula (1), R', R2 and R3 preferably each independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-butyl, t-butyl, amyl, hexyl, octyl, dodecyl groups, etc. Examples of the aralkyl group include phenyl, tolyl, and methoxyphenyl groups, and examples of the aralkyl group include benzyl, phenethyl, and p-methylhensyl groups.
従って、本発明による好ましいポリシラン化合物の具体
例として、例えば、１，２−ジ［２−（１メチルインド
リル））−ＬＬ２．２−テトラメチルジシランや、１．
４−ジ（２−（１−メチルインドリル） ） −ＬＬ２
，２，３．３．４．４−オクタフェニルテトラシラン等
を挙げることができる。Therefore, specific examples of preferred polysilane compounds according to the present invention include, for example, 1,2-di[2-(1methylindolyl))-LL2.2-tetramethyldisilane, 1.
4-di(2-(1-methylindolyl)) -LL2
, 2,3.3.4.4-octaphenyltetrasilane and the like.
本発明によるかかる新規なポリシラン化合物は、不活性
雰囲気下に一般式
（式中、Ｒ１は前記と同じである。）
で表わされるＮ−置換インドールにアルキルリチウム、
アリールリチウム又はアラルキルリチウムを反応させ、
次いで、−数式
％式％）
（式中、Ｒ２、Ｒ３及びｎは、前記と同じであり、Ｘは
ハロゲン原子を示す。）
で表わされるα、ω−ジハロポリシランを反応させるこ
とによって得ることができる。Such a novel polysilane compound according to the present invention is prepared by adding alkyl lithium to an N-substituted indole represented by the general formula (wherein R1 is the same as above) under an inert atmosphere.
Reacting aryllithium or aralkyllithium,
Then, it can be obtained by reacting an α,ω-dihalopolysilane represented by the formula %) (wherein R2, R3 and n are the same as above, and X represents a halogen atom) I can do it.
上記−数式（ＩＩ）で表わされるＮ−置換インドールに
おいて、１１７１は前記と同じであり、従って、Ｎ−置
換インドールとしては、例えば、Ｎ−メチルインドール
やＮ−フェニルインドール等を挙げることができる。更
に、Ｎ−置換インドールは、ベンゼン環上に前記したよ
うなアルキル基、アリール基又はアラルキル基等を置換
基として有していてもよい。In the N-substituted indole represented by the above-mentioned formula (II), 1171 is the same as above, and therefore, examples of the N-substituted indole include N-methylindole and N-phenylindole. Furthermore, the N-substituted indole may have the above-described alkyl group, aryl group, aralkyl group, or the like as a substituent on the benzene ring.
また、前記アルキルリチウムとしては、例えば、メチル
リチウム、エチルリチウム、ｎ−プロピルリチウム、イ
ソプロピルリチウム、ｎ−ブチルリチウム、５ｅｃ−ブ
チルリチウム、ｔ−ブチルリチウム、アミルリチウム、
ヘキシルリチウム等を挙げることができる。アリールリ
チウムとしては、例えば、フェニルリチウム、トリルリ
チウム、メトキシフェニルリチウム等を挙げることがで
きる。In addition, examples of the alkyllithium include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ec-butyllithium, t-butyllithium, amyllithium,
Examples include hexyllithium. Examples of the aryllithium include phenyllithium, tolyllithium, and methoxyphenyllithium.
また、アラルキルリチウムとしては、例えば、ベンジル
リチウム、フェネチルリチウム、ｐ−メチルベンジルリ
チウム等を挙げることができる。かかる有機リチウムの
なかでは、特に、ｔ−ブチルリチウムが好ましく用いら
れる。Furthermore, examples of the aralkyllithium include benzyllithium, phenethyllithium, p-methylbenzyllithium, and the like. Among such organolithiums, t-butyllithium is particularly preferably used.
上記反応は、不活性雰囲気下に、通常、溶剤中にて行な
われる。溶剤としては、前記したような有機リチウム化
合物に不活性な溶剤であれば、特に、限定されるもので
はないが、例えば、ジエチルエーテル、ジメトキシエタ
ン、ジオキサン、テトラヒドロフラン等のエーテル系溶
剤、ペンタン、ヘキサン等の脂肪族炭化水素、ベンゼン
、トルエン、キシレン等の芳香族炭化水素、又はこれら
の混合溶剤が好ましく用いられる。また、前記有機リチ
ウムも、通常、これらと同じ不活性溶剤中にて調製され
、かかる溶液として用いられる。不活性雰囲気としては
、通常、窒素、アルゴン等が好適である。The above reaction is carried out under an inert atmosphere, usually in a solvent. The solvent is not particularly limited as long as it is inert to the organolithium compounds mentioned above, but examples include ether solvents such as diethyl ether, dimethoxyethane, dioxane, and tetrahydrofuran, pentane, and hexane. Aromatic hydrocarbons such as benzene, toluene, xylene, etc., or mixed solvents thereof are preferably used. Moreover, the organolithium is also usually prepared in the same inert solvent as these and used as such a solution. Generally, nitrogen, argon, etc. are suitable as the inert atmosphere.
前記Ｎ置換インドールに前記したような有機リチウムを
反応させることによって、−ｉ式（■）（ＴＶ）
（式中、Ｒ１は前記と同じである。）
で表わされるリチウム化Ｎ置換インドール化合物を得る
。しかし、通常は、かかるリチウム化Ｎ置換インドール
化合物を単離することなく、これを含む反応混合物に前
記−数式（ＩＩＩ）で表わされるα、ω〜ジハロポリシ
ランを反応させることによって、本発明によるインドリ
ル置換ポリシラン化合物を得ることができる。By reacting the N-substituted indole with an organic lithium as described above, a lithiated N-substituted indole compound represented by the formula -i (■) (TV) (wherein R1 is the same as above) is obtained. . However, usually, without isolating such a lithiated N-substituted indole compound, the method according to the present invention is carried out by reacting a reaction mixture containing the lithiated N-substituted indole compound with the α, ω-dihalopolysilane represented by the formula (III). Indolyl-substituted polysilane compounds can be obtained.
前記−数式（ＩＩＩ）で表わされるα、ω−ジハロポリ
シランにおいて、Ｒ２及びＲ３は、好ましくは、それぞ
れ独立に、炭素数１〜１２のアルキル基、炭素数６〜１
２のアリール基又は炭素数７〜１３のアラルキル基を示
し、前述したと同様に、アルキル基としては、例えば、
メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブ
チル、５ｅｃ−ブチル、ｔ−ブチル、アミル、ヘキシル
、オクチル、ドデシル基等を、アリール基としては、例
えば、フェニル、トリル、メトキシフェニル基等を、ま
た、アラルキル基としては、例えば、ベンジル、フェネ
チル、ｐ−メチルベンジル基等を挙げることができる。In the α,ω-dihalopolysilane represented by formula (III), R2 and R3 are preferably each independently an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 1 carbon atoms.
2 represents an aryl group or an aralkyl group having 7 to 13 carbon atoms, and as mentioned above, as the alkyl group, for example,
Examples of aryl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-butyl, t-butyl, amyl, hexyl, octyl, and dodecyl groups; examples of aryl groups include phenyl, tolyl, and methoxyphenyl groups; Further, examples of the aralkyl group include benzyl, phenethyl, p-methylbenzyl group, and the like.
また、Ｘはハロゲン原子を示し、例えば、塩素、臭素又
はヨウ素であり、特に、塩素が好ましい。Further, X represents a halogen atom, such as chlorine, bromine or iodine, with chlorine being particularly preferred.
ｎは、２以上の整数を示し、好まし７くは、２〜６の整
数である。n represents an integer of 2 or more, preferably an integer of 2 to 6.
従って、本発明の方法においては、α、ω−ジハロポリ
シランとして、例えば、１，２−ジクロロＬＬ２．２−
テトラメチルジシラン、■、４−ジクロロー１．１，２
，２，３，３，４．４−オクタフェニルテトラシラン等
が好ましく用いられる。Therefore, in the method of the present invention, as the α,ω-dihalopolysilane, for example, 1,2-dichloroLL2.2-
Tetramethyldisilane, ■,4-dichloro1.1,2
, 2,3,3,4,4-octaphenyltetrasilane and the like are preferably used.
前記Ｎ−［換インドールと有機リチウムとの反応におい
て、有機リチウムは、Ｎ−置換インド−ル１モルに対し
て、通常、１〜１．２モルの範囲で用いられる。また、
α、ω−ジハロポリシランは、Ｎ−置換インドール１モ
ルに対して、通常、０．５〜０．６モルの範囲で用いら
れる。In the reaction between the N-substituted indole and the organolithium, the organolithium is usually used in an amount of 1 to 1.2 mol per 1 mol of the N-substituted indole. Also,
α,ω-dihalopolysilane is generally used in an amount of 0.5 to 0.6 mol per 1 mol of N-substituted indole.
反応温度や反応時間等は、特に、限定されるものではな
いが、例えば、Ｎ置換インドールと有機リチウムとの反
応においては、Ｎ置換インドール溶液に有機リチウム溶
液を、通常、−１００°Ｃから２５“Ｃ１好ましくは、
−８０°Ｃから一３０°Ｃの範囲の温度にて加えた後、
−３０°Ｃから８０°Ｃ１好ましくは、０〜４０°Ｃの
範囲の温度にて、通常、数分乃至約１０時間、好ましく
は３０分間乃至２時間攪拌し、かくして、リチウム化Ｎ
置換インドールを生成させる。Although the reaction temperature and reaction time are not particularly limited, for example, in the reaction between N-substituted indole and organolithium, the organic lithium solution is added to the N-substituted indole solution at a temperature of -100°C to 25°C. “C1 Preferably,
After adding at a temperature ranging from -80°C to -30°C,
The lithiated N
Generates a substituted indole.
次いで、このリチウム化Ｎ置換インドールとα。Then this lithiated N-substituted indole and α.
ω−ジハロポリシランとの反応においては、リチウム化
Ｎ置換インドールを含む反応混合物にαω−ジハロポリ
シランを、通常、−１００°Ｃから８０”Ｃ１好ましく
は、−８０”Ｃから３０°Ｃの範囲の温度にて加えた後
、−３０°Ｃから８０°Ｃ１好ましくは、０〜５０°Ｃ
の範囲の温度にて、通常、３０分間乃至約４０時間、好
ましくは１時間乃至２０時間攪拌下に反応させる。In the reaction with the ω-dihalopolysilane, the αω-dihalopolysilane is added to the reaction mixture containing the lithiated N-substituted indole, usually at a temperature of -100°C to 80"C, preferably -80"C to 30°C. After addition at a temperature in the range -30°C to 80°C1, preferably 0 to 50°C
The reaction is carried out under stirring at a temperature in the range of 30 minutes to about 40 hours, preferably 1 hour to 20 hours.
反応終了後、反応混合物から溶剤を減圧下に留去し、得
られた残渣を適宜の溶剤から再結晶し、或いは減圧蒸留
すれば、目的とするインドリル置換ポリシラン化合物を
得ることができる。再結晶溶剤としては、例えば、芳香
族炭化水素、脂肪族炭化水素又はこれらの混合溶剤が好
適である。After the reaction is completed, the solvent is distilled off from the reaction mixture under reduced pressure, and the resulting residue is recrystallized from an appropriate solvent or distilled under reduced pressure to obtain the desired indolyl-substituted polysilane compound. As the recrystallization solvent, aromatic hydrocarbons, aliphatic hydrocarbons, or mixed solvents thereof are suitable, for example.
本発明の方法によれば、前記Ｎ−置換インドールやα、
ω−ジハロポリシランに対応して、例えば、１．２−ジ
［’２−（１−メチルインドリル） ） −ＬＬ２．２
−テトラメチルジシランや、１，４−ジ〔２（１−メチ
ルインドリル） Ｅ −ＬＬ２，２，３，３，４Ａ−オ
クタフェニルテトラシラン等を得ることができる。According to the method of the present invention, the N-substituted indole, α,
Corresponding to ω-dihalopolysilane, for example, 1,2-di['2-(1-methylindolyl) ) -LL2.2
-Tetramethyldisilane, 1,4-di[2(1-methylindolyl)E-LL2,2,3,3,4A-octaphenyltetrasilane, etc. can be obtained.
光尻■殊来
本発明によれば、新規なポリシラン化合物であるインド
リル置換ポリシラン化合物が提供される。According to the present invention, an indolyl-substituted polysilane compound, which is a novel polysilane compound, is provided.
かかるポリシラン化合物は、Ｎ−置換インドールに有機
リチウムを反応させ、次いで、α、ω−ジハロポリシラ
ンを反応させることによって得ることができる。Such a polysilane compound can be obtained by reacting an N-substituted indole with an organolithium and then reacting an α,ω-dihalopolysilane.
実施用
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
（１，２−ジ（２−（１−メチルインドリル）〕ＬＬ、
２．２−テトラメチルジシランの合成）■−メチルイン
ドール１．３１ｇ（１０ミリモル）のテトラヒドロフラ
ン溶液７ｍｌを一７８°Ｃに冷却し、これに濃度１．７
モル／ｌのｔ−ブチルリチウムのヘキサン溶液７．１ｍ
ｌを加えた。２５°Ｃまで昇温させ、この温度にて１．
５時間攪拌した。この後、反応混合物を再度、−７８°
Ｃまで冷却し、これに１．２−ジクロロ−１，１，２，
２−テトラメチルジシラン０．９４ｇ（５，０ミリモル
）を加え、次いで、室温まで昇温させて、−晩、放置し
た。Example 1 (1,2-di(2-(1-methylindolyl))LL,
2. Synthesis of 2-Tetramethyldisilane) 7 ml of a solution of 1.31 g (10 mmol) of -methylindole in tetrahydrofuran was cooled to -78°C, and added to it at a concentration of 1.7
7.1 mol/l of t-butyllithium in hexane solution
Added l. Raise the temperature to 25°C, and at this temperature 1.
Stirred for 5 hours. After this time, the reaction mixture was again heated at −78°
1,2-dichloro-1,1,2,
0.94 g (5.0 mmol) of 2-tetramethyldisilane was added, then the temperature was raised to room temperature and left overnight.
反応混合物を濾過して、無機塩を除去した後、濾液を濃
縮した。得られた残渣にヘキサンを加えて、−晩、放置
したところ、結晶が析出した。この結晶を濾取し、ヘキ
サンから再結晶して、１，２−ジ［２−（１−メチルイ
ンドリル） ） −１，１，２゜２−テトラメチルジシ
ラン０．５０ｇ（収率２７％）を得た。After filtering the reaction mixture to remove inorganic salts, the filtrate was concentrated. Hexane was added to the obtained residue, and when it was left to stand overnight, crystals were precipitated. The crystals were collected by filtration and recrystallized from hexane to give 0.50 g of 1,2-di[2-(1-methylindolyl))-1,1,2°2-tetramethyldisilane (yield 27%). ) was obtained.
融点 １１９〜１２０°Ｃ
赤外線吸収スペクトル（ＫＢｒ錠剤法、ｃｍ−’ ）１
４９０、 １４４２． １４０２．１３５０．１３２０
．１３００． １２５０１０６０、８３５．７９５．７
３０．６５０゜ＩＨ−核磁気共鳴吸収スペクトル（ＣＤ
ＣＩ３溶液、δ（ｐｐｍ））
０．５０ （１２Ｈ，ｓ、 ５ｉＣＨ３）、 ３．３６
（６Ｈ，ｓ、 ＮＣＨ３）。Melting point 119-120°C Infrared absorption spectrum (KBr tablet method, cm-') 1
490, 1442. 1402.1350.1320
．． 1300. 12501060, 835.795.7
30.650° IH-Nuclear Magnetic Resonance Absorption Spectrum (CD
CI3 solution, δ (ppm)) 0.50 (12H,s, 5iCH3), 3.36
(6H,s, NCH3).
６．６５ （２Ｈ，ｓ、 ＮＣ＝ＣＨ）、 ６．９−７
．７ （８Ｈ，ｍ。6.65 (2H,s, NC=CH), 6.9-7
．． 7 (8H, m.
ａｒｏｍａｔｉｃ Ｈ）。aromatic H).
マススペクトル（ｍ／ｅ）
３７６ （Ｍ”）、 ３６Ｌ １８８．１４４．５９゜
参考例１
（オクタフェニルシクロテトラシランの合成）窒素雰囲
気下に粉末状金属リチウムにジクロロジフェニルシラン
７６．３ｇ（０，３モル）の乾燥テトラヒドロフラン溶
液１１５ｍ１を速やかに加え、撹拌した。室温で５時間
、攪拌した後、固形物を濾取し、温ベンゼン各５０ｍ１
にて３回、エタノール各３５ｍ１にて２回及び温水各７
０ｍ１にて３回、洗浄した。Mass spectrum (m/e) 376 (M"), 36L 188.144.59° Reference Example 1 (Synthesis of octaphenylcyclotetrasilane) 76.3 g (0, 115 ml of a dry tetrahydrofuran solution of 3 mol) was quickly added and stirred. After stirring at room temperature for 5 hours, the solid matter was filtered, and 50 ml each of hot benzene was added.
3 times with ethanol, 2 times with 35 ml each of ethanol, and 7 times each with hot water
Washed 3 times at 0ml.
窒素ガス流通下、−晩、乾燥させた後、ソックスレー抽
出器を用いて２７時間、トルエン抽出した。得られたト
ルエン溶液を濃縮し、晶出させ、得られた結晶を濾取、
乾燥して、オクタフェニルシクロテトラシランを白色結
晶として得た。収率５％、融点３２１〜３２３”Ｃ。After drying overnight under nitrogen gas flow, toluene extraction was performed using a Soxhlet extractor for 27 hours. The obtained toluene solution was concentrated and crystallized, and the obtained crystals were collected by filtration.
After drying, octaphenylcyclotetrasilane was obtained as white crystals. Yield 5%, melting point 321-323''C.
参考例２
（１，１−ジクロロ−ＬＬ２，２，３，３，４．４−オ
クタフェニルテトラシランの合成）
窒素雰囲気下にオクタフェニルシクロテトラシラン３．
４５ｇ（４，７ミリモル）に１．Ｌ２．２−テトラクロ
ロエタン５０ｍ１を加え、攪拌した。次いで、１６０°
Ｃにて１時間攪拌し、不溶物を濾過にて除去した後、濃
縮した。得られた油状物にヘキサンを加え、析出した結
晶を濾取し、ヘキサン３０ｍ１にて３回洗浄した後、乾
燥して、１，１−ジクロロＬＬ２，２，３，３，４．４
−オクタフェニルテトラシランを白色結晶として得た。Reference Example 2 (Synthesis of 1,1-dichloro-LL2,2,3,3,4.4-octaphenyltetrasilane) Octaphenylcyclotetrasilane 3.
1.45 g (4.7 mmol). 50 ml of L2.2-tetrachloroethane was added and stirred. Then 160°
The mixture was stirred at C for 1 hour, insoluble materials were removed by filtration, and then concentrated. Hexane was added to the obtained oil, and the precipitated crystals were collected by filtration, washed three times with 30 ml of hexane, and dried to give 1,1-dichloroLL2,2,3,3,4.4
-Octaphenyltetrasilane was obtained as white crystals.
収率９０％。融点１７８〜１８０°Ｃ０
実施例２
〔１，４−ジ（２−（１−メチルインドリル）〕＝１、
Ｌ２，２，３，３，４．４−オクタフェニルテトラシラ
ンの合成）
実施例１において、■、２−ジクロローＬＬ２．２テト
ラメチルジシランに代えて、１．４−ジクロロ−ＬＬ２
２，３，３．４４−オクタフェニルテトラシランを用い
た以外は、実施例１と同様にして反応を行なった。Yield 90%. Melting point 178-180°C0 Example 2 [1,4-di(2-(1-methylindolyl)] = 1,
Synthesis of L2,2,3,3,4.4-octaphenyltetrasilane) In Example 1, 1,4-dichloro-LL2 was substituted for 2-dichloro-LL2.2tetramethyldisilane.
The reaction was carried out in the same manner as in Example 1 except that 2,3,3.44-octaphenyltetrasilane was used.
反応終了後、反応混合物を濾過して、無機塩を除去した
後、濾液を濃縮し、得られた残渣にトルエン／ヘキサン
（容量比１１５）を加えて、更に、沈殿物を除去した。After the reaction was completed, the reaction mixture was filtered to remove inorganic salts, the filtrate was concentrated, and toluene/hexane (volume ratio 115) was added to the resulting residue to further remove the precipitate.
濾液を濃縮し、得られた粗結晶からクーゲルロール（２
００°Ｃ／ ０．５ ｍｍＨｇ ）にて不純物の１−メ
チルインドールを除去し、残渣をヘキサンから再結晶し
て、１，４−ジＣ２−（１−メチルインドリルＬ） −
ＬＬ２，２，３，３，４．４−オクタフェニルテトラシ
ランを得た。The filtrate was concentrated, and Kugelrohr (2
The impurity 1-methylindole was removed at 00°C/0.5 mmHg), and the residue was recrystallized from hexane to give 1,4-diC2-(1-methylindolyl L)-
LL2,2,3,3,4.4-octaphenyltetrasilane was obtained.
＋Ｈ−核磁気共鳴吸収スペクトル（ＣＤＣＩ：ｌ溶液、
δ（ｐｐｍ））
３．５６ （６Ｈ，ｓ、 ＮＣＨ３）、 ６．７２ （
２１（、ｓ、 ＮＣ＝ＣＨ）６．５−７．８ （４８Ｈ
ｍ、 ａｒｏｍａｔｉｃ １＋）。+H- nuclear magnetic resonance absorption spectrum (CDCI: l solution,
δ (ppm)) 3.56 (6H,s, NCH3), 6.72 (
21(,s, NC=CH)6.5-7.8 (48H
m, aromatic 1+).
マススペクトル（ｍ／ｅ） ９８８ （Ｍ”）。Mass spectrum (m/e) 988 (M”).
特許出願人 三井石油化学工業株式会社代理人 弁理士
牧 野 逸 部Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent attorney Itsube Makino
Claims (3)
アルキル基、アリール基又はアラルキル基を示し、ｎは
２以上の整数を示す。） 表わされることを特徴とするポリシラン化合物。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1, R^2 and R^3 each independently represent an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 2 or more.) A polysilane compound characterized by the following:
１，１，２，２−テトラメチルジシラン。(2) 1,2-di[2-(1-methylindolyl)]-
1,1,2,2-tetramethyldisilane.
１，１，２，２，３，３，４，４−オクタフェニルテト
ラシラン。(3) 1,4-di[2-(1-methylindolyl)]-
1,1,2,2,3,3,4,4-octaphenyltetrasilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066661A JPH02247188A (en) | 1989-03-17 | 1989-03-17 | Novel polysilane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066661A JPH02247188A (en) | 1989-03-17 | 1989-03-17 | Novel polysilane compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02247188A true JPH02247188A (en) | 1990-10-02 |
Family
ID=13322308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1066661A Pending JPH02247188A (en) | 1989-03-17 | 1989-03-17 | Novel polysilane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02247188A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170069857A1 (en) * | 2015-09-08 | 2017-03-09 | Universal Display Corporation | Organic Electroluminescent Materials and Devices |
-
1989
- 1989-03-17 JP JP1066661A patent/JPH02247188A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170069857A1 (en) * | 2015-09-08 | 2017-03-09 | Universal Display Corporation | Organic Electroluminescent Materials and Devices |
| US11706972B2 (en) * | 2015-09-08 | 2023-07-18 | Universal Display Corporation | Organic electroluminescent materials and devices |
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