JPH02247190A - Novel organosilicic compound - Google Patents
Novel organosilicic compoundInfo
- Publication number
- JPH02247190A JPH02247190A JP1066663A JP6666389A JPH02247190A JP H02247190 A JPH02247190 A JP H02247190A JP 1066663 A JP1066663 A JP 1066663A JP 6666389 A JP6666389 A JP 6666389A JP H02247190 A JPH02247190 A JP H02247190A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- methylindolyl
- examples
- expressed
- silane
- 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
- 150000001875 compounds Chemical class 0.000 title abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 125000004188 dichlorophenyl group Chemical group 0.000 claims description 5
- -1 N-substituted indole Chemical class 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000548 poly(silane) polymer Polymers 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
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000005055 methyl trichlorosilane Substances 0.000 abstract description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002642 lithium compounds Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000001979 organolithium group Chemical group 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- 239000005054 phenyltrichlorosilane Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 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
- 125000003944 tolyl group Chemical group 0.000 description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000004020 conductor 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
- 239000000706 filtrate Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 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
- 239000003921 oil Substances 0.000 description 2
- 239000000725 suspension Substances 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000004210 ether based solvent Substances 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 229910052757 nitrogen Inorganic materials 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
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
主策上色朴朋分顆
本発明は、新規な有機ケイ素化合物に関し、詳しくは、
インドリル置換二官能性有機ケイ素化合物に関する。か
かる有機ケイ素化合物は、例えば、ナトリウムによる重
合によって、重合体を得ることができ、このようにして
得られるポリシランは、フォトレジスト材や導電材とし
て有用である。即ち、本発明による有機ケイ素化合物は
、フォトレジスト材や導電材となるポリシランの合成中
間体として有用である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organosilicon compound.
This invention relates to indolyl-substituted difunctional organosilicon compounds. Such an organosilicon compound can be obtained as a polymer by, for example, polymerization with sodium, and the polysilane thus obtained is useful as a photoresist material or a conductive material. That is, the organosilicon compound according to the present invention is useful as a synthetic intermediate for polysilane, which is used as a photoresist material or a conductive material.
狐米■肢街
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、ケイ素原子がへテロ環にて置換されている二官能性
有機ケイ素化合物は、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。Kitsunemi ■Ojigai Various organosilicon compounds have been known, but compared to organic carbon compounds, their research has not yet 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 the silicon atom have been known, but bifunctional compounds in which the silicon atom is substituted with a heterocycle are known. Very little is known about organic silicon compounds, and, of course, no method has been established for their production.
が じようとする
本発明は、ケイ素原子上にヘテロ環を置換基として有す
る新規な有機ケイ素化合物、特に、インドリル置換二官
能性有機ケイ素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 organosilicon compound having a heterocycle as a substituent on a silicon atom, particularly an indolyl-substituted bifunctional organosilicon compound.
ｉ を”するための
本発明によるポリシラン化合物は、−数式ビ
（式中、Ｒ１及びＲ２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、Ｘはハロゲン原子
を示す。）
表わされることを特徴とする。The polysilane compound according to the present invention for "i" has the formula -bi (wherein R1 and R2 are each independently an alkyl group,
It represents an aryl group or an aralkyl group, and X represents a halogen atom. ) is characterized by being expressed.
上記−数式（１）において、Ｒ１は、好ましくは、炭素
数１〜６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、ヘン
シル、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。Ｒ２は、好ましくは、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), R1 preferably represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, and specific examples include an alkyl group. For example, methyl, ethyl, n
-propyl, isopropyl, n-butyl, 5ec-butyl, t-butyl, amyl, hexyl groups, etc., aryl groups include phenyl, tolyl, methoxyphenyl groups, etc., and aralkyl groups include, for example, Examples include hensyl, phenethyl, p-methylbenzyl groups, and the like. R2 is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 7 to 12 carbon atoms.
13 aralkyl groups, and specific examples include methyl, ethyl, n-propyl,
Examples of aryl groups include isopropyl, n-butyl, 5ec-butyl, t-butyl, amyl, hexyl, octyl, and dodecyl groups; examples of aryl groups include phenyl, tolyl, and methoxyphenyl groups; and examples of aralkyl groups, such as , benzyl, phenethyl, p-methylhensyl group and the like.
また、Ｘは、好ましくは、塩素、臭素又はヨウ素を示し
、好ましくは、塩素である。Moreover, X preferably represents chlorine, bromine or iodine, and is preferably chlorine.
従って、本発明による好ましい有機ケイ素化合物の具体
例として、例えば、ジクロロメチル〔２（１−メチルイ
ンドリル）〕シランや、ジクロロフェニル（２−（１−
メチルインドリル）〕シラン等を挙げることができる。Therefore, specific examples of preferred organosilicon compounds according to the present invention include dichloromethyl[2(1-methylindolyl)]silane and dichlorophenyl(2-(1-methylindolyl)).
Examples include methylindolyl)]silane, and the like.
本発明によるかかる新規な有機ケイ素化合物は、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及びＸは、前記と同じである。）で表わさ
れるトリハロ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 organosilicon compound according to the present invention is prepared under an inert atmosphere by N
- Obtained by reacting a substituted indole with an alkyllithium, aryllithium or aralkyllithium, and then reacting a trihalosilane represented by the formula % (wherein R2 and X are the same as above) be able to.
上記−数式（ＩＩ）で表わされるＮ−置換インドールに
おいて、Ｒ１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), R1 is the same as above, and therefore, examples of the N-substituted indole include N-methylindole and N-substituted indole.
-phenylindole, etc. Furthermore,
The N-substituted indole may have the above-mentioned 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−メチルヘンシルリ
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-methylhensillithium, 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、−数式（ＩＶ）（ＩＶ）
（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（Ｉ）
で表わされるトリハロン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二官能性有機ケイ素化合
物を得ることができる。By reacting the N-substituted indole with an organolithium as described above, a lithiated N-substituted indole compound represented by the formula (IV) (IV) (wherein R1 is the same as above) is obtained. . However, usually such a lithiated N-substituted indole compound is not isolated and is added to a reaction mixture containing the above-mentioned formula (I).
The indolyl-substituted bifunctional organosilicon compound according to the present invention can be obtained by reacting trihalonrane represented by:
前記−数式（ＩＩＩ）で表わされるトリハロシランにお
いて、Ｒ２は、好ましくは、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、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、Ｌ−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、
ヘンシル、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 trihalosilane represented by formula (III), R2 preferably represents 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, and Similarly, examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-butyl, L-butyl,
Examples of aryl groups include amyl, hexyl, octyl, and dodecyl groups; examples of aryl groups include phenyl, tolyl, and methoxyphenyl groups; examples of aralkyl groups include;
Examples include hensyl, phenethyl, p-methylbenzyl groups, 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.
従って、本発明の方法においては、Ｉ−リハロシランと
して、例えば、メチルトリクロロシラン、フェニルトリ
クロロシラン等が好ましく用いられる。Therefore, in the method of the present invention, as the I-rehalosilane, for example, methyltrichlorosilane, phenyltrichlorosilane, etc. are preferably used.
本発明においては、前記Ｎ−置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
ドール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、トリハロシランも、Ｎ〜置換インド
ール１モルに対して、通常、１．０〜１．２モルの範囲
で用いられる。In the present invention, 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. Further, trihalosilane is also generally used in an amount of 1.0 to 1.2 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、Ｎｉ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°Ｃ３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
ｉ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 organolithium solution is added to the Ni-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
Generate i-converted indole.
次いで、このリチウム化Ｎ置換インドールとトリハロシ
ランとの反応においては、トリハロシランを含む反応混
合物にリチウム化Ｎ置換インドールを、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、３
０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。Then, in the reaction of this lithiated N-substituted indole with a trihalosilane, the lithiated N-substituted indole is added to the reaction mixture containing the trihalosilane, usually at -100
°C to 80°C1 preferably = 80°C to 30°
After addition at a temperature in the range of 30°C to 80°C1
Preferably at a temperature in the range of 0 to 50°C, usually 3
The reaction is allowed to proceed with stirring for 0 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二官能性有機ケイ素
化合物を得ることができる。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 bifunctional organosilicon compound. can.
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。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−置換インドールやトリ
ハロシランに対応して、例えば、ジクロロメチル［２−
（１−メチルインドリル）〕シランや、ジクロロフェニ
ル（２−（１−メチルインドリル）〕シラン等を得るこ
とができる。According to the method of the present invention, for example, dichloromethyl[2-
(1-methylindolyl)]silane, dichlorophenyl(2-(1-methylindolyl))]silane, etc. can be obtained.
光肌■跋果
本発明によれば、新規なインドリル置換二官能性有機ケ
イ素化合物が提供される。かかる有機ケイ素化合物は、
Ｎ−置換インドールに有機リチウムを反応させ、次いで
、トリハロシランを反応させることによって得ることが
できる。According to the present invention, a novel indolyl-substituted bifunctional organosilicon compound is provided. Such organosilicon compounds are
It can be obtained by reacting an N-substituted indole with an organolithium and then reacting with a trihalosilane.
実施法
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
（ジクロロフェニル［１−（１−メチルインドリル）］
シランの合成）
１−メチルインドール６．３０ｇ（４８ミリモル）のテ
トラヒドロフラン溶液１００ｍ１を一７８゛Ｃに冷却し
、これに濃度１．７モル／βのｔ−ブチルリチウムのヘ
キサン溶液２８．２ｍｌを加えた。２５°Ｃまで昇温さ
せ、この温度にて２時間攪拌したところ、懸濁液を得た
。Example 1 (dichlorophenyl[1-(1-methylindolyl)]
Synthesis of silane) 100 ml of a solution of 6.30 g (48 mmol) of 1-methylindole in tetrahydrofuran was cooled to -78°C, and 28.2 ml of a hexane solution of t-butyllithium with a concentration of 1.7 mol/β was added thereto. Ta. When the temperature was raised to 25°C and stirred at this temperature for 2 hours, a suspension was obtained.
この懸濁液を再度、−７８”Ｃまで冷却し、これをフェ
ニルトリクロロシラン１０．２ｇ（４８ミリモル）のテ
トラヒドロフラン溶液（４０ｍｌ）に加え、２５°Ｃま
で昇温し、２０時間攪拌した。This suspension was again cooled to -78''C, added to a solution of 10.2g (48 mmol) of phenyltrichlorosilane in tetrahydrofuran (40ml), heated to 25°C, and stirred for 20 hours.
この後、反応混合物を濾過して、不溶物を除去した後、
濾液を濃縮した。得られた油状物を減圧蒸留（０，４ｍ
ｍ１ｇ） シて、ジクロロフェニル〔２（ｌ−メチルイ
ンドリル）〕シラン９．５ｇを得た。After this, the reaction mixture was filtered to remove insoluble materials, and then
The filtrate was concentrated. The obtained oil was distilled under reduced pressure (0.4 m
m1g) to obtain 9.5g of dichlorophenyl[2(l-methylindolyl)]silane.
収率６５％。Yield 65%.
沸点 １４６〜１４８°Ｃ／ ０．４ ｍｍＨｇ赤外線
吸収スペクトル（Ｎｅａｔ法、ｃｍ−’ ）３０４５、
２９２５．１６０２．１５８２．１４９０．１４６０．
１．４２２１３５５、１３００．１１１０．１０７５．
８００．７３０．６９０．５８０５５５゜
Ｈ−核磁気共鳴吸収スペクトル（ＣＤＣｈ溶液、δ（ｐ
ｐｍ））
３．８７ （３１１，ｓ、 ＮＣＩ＋３）、 ６．８９
（Ｉｌｌ、 ｓ、 Ｃ＝ＣＨ）。Boiling point 146-148°C/0.4 mmHg Infrared absorption spectrum (Neat method, cm-') 3045,
2925.1602.1582.1490.1460.
1.4221355, 1300.1110.1075.
800.730.690.580555°H-nuclear magnetic resonance absorption spectrum (CDCh solution, δ(p
pm)) 3.87 (311,s, NCI+3), 6.89
(Ill, s, C=CH).
６．９−７．９ （９Ｈ，ｍ、 ａｒｏｍａｔｉｃ Ｈ
）。6.9-7.9 (9H, m, aromatic H
).
マススペクトル（ｍ／ｅ）
３０５ （Ｍ＋）
実施例２
（ジクロロメチル［２−（１−メチルインドリル）〕シ
ランの合成）
実施例１において、フェニルトリクロロシランに代えて
、メチルトリクロロ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。Mass spectrum (m/e) 305 (M+) Example 2 (Synthesis of dichloromethyl[2-(1-methylindolyl)]silane) In Example 1, methyltrichlorosilane was used instead of phenyltrichlorosilane. The reaction was carried out in the same manner as in Example 1 except for this.
反応終了後、反応混合物を濾過して、不溶物を除去した
後、濾液を濃縮した。得られた油状物を減圧蒸留（０，
４ｍｍＨｇ） シて、ジクロロメチル（２（１−メチル
インドリル）〕シラン５．７ｇを得た。収率４９％。After the reaction was completed, the reaction mixture was filtered to remove insoluble matter, and the filtrate was concentrated. The obtained oil was distilled under reduced pressure (0,
4 mmHg) to obtain 5.7 g of dichloromethyl(2(1-methylindolyl))silane. Yield: 49%.
沸点 ９３〜９５°Ｃ／ ０．４ ｍｍ１ｇ赤外線吸収
スペクトル（ＫＢｒ錠剤法、ｃｍ−’ ）３０５０、２
９２０．１５４５．１４６０．１３３８．１２７０．１
０００１１６０．７４０−７８０゜
１Ｈ−核磁気共鳴吸収スペクトル（ＣＤＣｈ ｆＩ液、
δ（ｐｐｍ））
１．１７ （３Ｈ，ｓ、 ５ｉＣＨｓ）、３．９７ （
３Ｈ，ｓ、 ＮＣ１＋３）６．９４ （ＬＨ，ｓ、
Ｃ＝ＣＨ）ｔｉｃ Ｈ）。Boiling point 93-95°C/0.4 mm1g Infrared absorption spectrum (KBr tablet method, cm-') 3050,2
920.1545.1460.1338.1270.1
0001160.740-780°1H-nuclear magnetic resonance absorption spectrum (CDCh fI liquid,
δ (ppm)) 1.17 (3H,s, 5iCHs), 3.97 (
3H,s, NC1+3)6.94 (LH,s,
C=CH)tic H).
マススペクトル（ｍ／ｅ） ２４３ （Ｍａ。Mass spectrum (m/e) 243 (Ma.
６．９−７．７ （４Ｈ，ｍ、ａｒｏｍａ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
手続補正書く自発）
２゜
３゜
４゜
平成０１年特許願第０６６６６３号
発明の名称
新規な有機ケイ素化合物
補正をする者
事件との関係 特許出願人
住 所 東京都千代田区霞が関三丁目２番５号名 称
三井石油化学工業株式会社6.9-7.7 (4H, m, aroma patent applicant Mitsui Petrochemical Industries Co., Ltd. agent, patent attorney Ittsu Makino, volunteer to write the procedural amendment) 2゜3゜4゜1999 Patent Application No. 066663 Invention Relationship to the case of a person making a new organosilicon compound amendment Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name Name
Mitsui Petrochemical Industries Co., Ltd.
Claims (3)
基、アリール基又はアラルキル基を示し、Ｘはハロゲン
原子を示す。） 表わされることを特徴とする有機ケイ素化合物。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 and R^2 each independently represent an alkyl group, aryl group, or aralkyl group, and X represents a halogen atom. ) An organosilicon compound characterized by the following:
〕シラン。(2) Dichloromethyl [2-(1-methylindolyl)
] Silane.
）〕シラン。(3) Dichlorophenyl[2-(1-methylindolyl)]silane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066663A JP2676109B2 (en) | 1989-03-17 | 1989-03-17 | New organosilicon compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066663A JP2676109B2 (en) | 1989-03-17 | 1989-03-17 | New organosilicon compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02247190A true JPH02247190A (en) | 1990-10-02 |
| JP2676109B2 JP2676109B2 (en) | 1997-11-12 |
Family
ID=13322365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1066663A Expired - Lifetime JP2676109B2 (en) | 1989-03-17 | 1989-03-17 | New organosilicon compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2676109B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100372759B1 (en) * | 2000-08-29 | 2003-02-19 | 한국과학기술원 | Novel Chiral Ligand and Process for Preparing (2R,3R)-2,3-dialkyltartaric Acid Employing the Same |
| KR100372758B1 (en) * | 2000-08-29 | 2003-02-19 | 한국과학기술원 | Novel Chiral Ligand and Process for Preparing (2S,3S)-2,3-dialkyltartaric Acid Employing the Same |
-
1989
- 1989-03-17 JP JP1066663A patent/JP2676109B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100372759B1 (en) * | 2000-08-29 | 2003-02-19 | 한국과학기술원 | Novel Chiral Ligand and Process for Preparing (2R,3R)-2,3-dialkyltartaric Acid Employing the Same |
| KR100372758B1 (en) * | 2000-08-29 | 2003-02-19 | 한국과학기술원 | Novel Chiral Ligand and Process for Preparing (2S,3S)-2,3-dialkyltartaric Acid Employing the Same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2676109B2 (en) | 1997-11-12 |
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