JPH0753740B2 - Five-coordinate silicon compound and method for producing the same - Google Patents
Five-coordinate silicon compound and method for producing the sameInfo
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- JPH0753740B2 JPH0753740B2 JP2065290A JP2065290A JPH0753740B2 JP H0753740 B2 JPH0753740 B2 JP H0753740B2 JP 2065290 A JP2065290 A JP 2065290A JP 2065290 A JP2065290 A JP 2065290A JP H0753740 B2 JPH0753740 B2 JP H0753740B2
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- compound
- silicon compound
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- phenylaminosilane
- reaction
- Prior art date
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Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は、新規な五配位ケイ素化合物及びその製造方法
に関する。TECHNICAL FIELD The present invention relates to a novel pentacoordinate silicon compound and a method for producing the same.
(従来技術) 最近になって、エレクトロニクス、ホトニクス材料とし
て、五配位ケイ素化合物が注目されている。(Prior Art) Recently, a pentacoordinate silicon compound has been attracting attention as an electronic material and a photonics material.
従来公知の五配位ケイ素化合物の構造及び反応機構につ
いては、Tandaura,St.N.;Alekseev,N.V.;Voronkov,M.G.
Topics Curr.Chem.1986,131,99-189で報告されており、
また五配位結合の性質については、Sini,G;Hiberty,P.
C.;Shaik,S.S.J.Chem.Commun.1989,772等で報告されて
いる。For the structure and reaction mechanism of conventionally known five-coordinate silicon compounds, see Tandaura, St.N .; Alekseev, NV; Voronkov, MG.
Topics Curr. Chem. 1986, 131, 99-189,
For the properties of the five-coordinate bond, Sini, G; Hiberty, P.
C.; Shaik, SSJ Chem.Commun. 1989, 772, etc.
(発明の目的) 本発明は、文献未載の新規構造の五配位ケイ素化合物及
びその製造方法を提供することを目的とするものであ
る。(Object of the Invention) It is an object of the present invention to provide a pentacoordinate silicon compound having a novel structure, which has not been described in any literature, and a method for producing the same.
(発明の構成) 即ち本発明によれば、下記一般式〔I〕: 式中、R1及びR2は、それぞれフッ素原子または炭素数1
〜15の非置換又は置換の1価炭化水素基を表し、各3個
のR1及びR2はそれぞれ同一でも互いに異なる基であって
もよく、Xは、炭素数1〜15の非置換1価炭化水素基を
示し、 nは0〜4の整数である、 で表される五配位ケイ素化合物が提供される。(Structure of the Invention) That is, according to the present invention, the following general formula [I]: In the formula, R 1 and R 2 are each a fluorine atom or a carbon number 1
To 15 unsubstituted or substituted monovalent hydrocarbon groups, each three R 1 and R 2 may be the same or different from each other, and X is an unsubstituted 1 to 15 carbon atom A pentacoordinated silicon compound represented by the following formula is shown, wherein: n is an integer of 0 to 4;
本発明によれば更に、 フェニルアミノシラン化合物にアルキルリチウムを反応
させた後に、更にクロロシラン化合物を反応させて該フ
ェニルアミノシラン化合物のベンゼン環のo−位にケイ
素原子を導入し、 次いで上記合成化合物についてイソプロポキシ化をおこ
なってイソプロポキシシランを合成し、 該イソプロポキシシランのフルオロ化を行ってフルオロ
シラン化合物を合成し、 更に該フルオロシラン化合物にふっ化カリウム及び18−
クラウン−6を反応させることにより上記五配位ケイ素
化合物を製造する方法が提供される。According to the present invention, further, a phenylaminosilane compound is reacted with alkyllithium, and then a chlorosilane compound is further reacted to introduce a silicon atom into the o-position of the benzene ring of the phenylaminosilane compound. Propoxylation is carried out to synthesize isopropoxysilane, and fluorination of the isopropoxysilane is carried out to synthesize a fluorosilane compound. Further, potassium fluoride and 18-
A method for producing the above pentacoordinate silicon compound by reacting crown-6 is provided.
以下本発明を詳細に説明する。The present invention will be described in detail below.
五配位ケイ素化合物 本発明の五配位ケイ素化合物は、前述した一般式
[I]、即ち、 で表されるものであり、フッ素陰イオンが橋かけ結合に
より2つのケイ素原子間を結んだ新規な五配位構造を有
している。Five-coordinate silicon compound The five-coordinate silicon compound of the present invention has the above-mentioned general formula [I], that is, And has a novel pentacoordinate structure in which a fluorine anion connects two silicon atoms by a bridge bond.
上記一般式において、ケイ素原子に結合している基R1及
びR2は、フッ素原子或いは炭素数1〜15の非置換又は置
換の1価炭化水素基を表し、各R1及びR2は全て同一の基
であってもよいし互いに異なる基であってもよいが、配
位化合物の安定性の面からは、R1及びR2の各々のうち少
なくとも1個はフッ素原子であることが好ましい。In the above general formula, groups R 1 and R 2 bonded to a silicon atom represent a fluorine atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 15 carbon atoms, and each R 1 and R 2 are all The groups may be the same or different from each other, but from the viewpoint of stability of the coordination compound, at least one of R 1 and R 2 is preferably a fluorine atom. .
また前記1価の炭化水素基の例としては、例えばメチ
ル、エチル、プロピル、ブチル、ペンチル、ヘキシル、
ヘプチル、オクチル、ノニル、デシル、ウンデシル、ド
デシル、トリデシル、テトラデシル、ペンタデシル等の
アルキル基、ビニル、アリル等のアルケニル基、シクロ
ペンチル、シクロヘキシル、シクロオクチル、シクロド
デシル等のシクロアルキル基、3,3,3−トリフルオロプ
ロピル、2−パーフルオロブチルエチル、2−パーフル
オロヘキシルエチル、2−パーフルオロオクチルエチ
ル、2−パーフルオロイソプロピルエチル、3−クロロ
プロピル等のハロゲン置換アルキル基、フェニル、o−
メチルフエニル、m−メチルフェニル、p−メチルフェ
ニル、o−エチルフェニル、m−エチルフェニル、p−
エチルフェニル、2,3−ジメチルフェニル、2,4−ジメチ
ルフェニル、3,4−ジメチルフェニル、ナフチル等のア
リール基等を挙げることができるが、後述する様なアミ
ノフェニルシラン化合物をアルキルリチウムとの反応に
おいて安定である点で、これらのうちではアルケニル基
を除く非置換の1価炭化水素基であることが好ましい。Examples of the monovalent hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc., alkenyl groups such as vinyl, allyl, etc., cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 3,3,3 -Halogen-substituted alkyl groups such as trifluoropropyl, 2-perfluorobutylethyl, 2-perfluorohexylethyl, 2-perfluorooctylethyl, 2-perfluoroisopropylethyl, 3-chloropropyl, phenyl, o-
Methylphenyl, m-methylphenyl, p-methylphenyl, o-ethylphenyl, m-ethylphenyl, p-
Examples thereof include aryl groups such as ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, and naphthyl. Of these, unsubstituted monovalent hydrocarbon groups other than alkenyl groups are preferable from the viewpoint of stability in the reaction.
更に2個のケイ素原子が結合しているベンゼン環には、
少なくとも1ヶ所のo−位を除く位置に置換した、炭素
数1〜15の非置換1価炭化水素基、例えば後述する製造
例において使用される各種の試剤に対して安定な置換基
を有していることができる。このような置換基としては
前記R1、R2として例示したもののうち非置換の炭化水素
基と同様のものが挙げられ、具体的には、メチル、エチ
ル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチ
ル、オクチル、ノニル、デシル、ウンデシル、ドデシ
ル、トリデシル、テトラデシル、ペンタデシル等のアル
キル基、ビニル、アリル等のアルケニル基、シクロペン
チル、シクロヘキシル、シクロオクチル、シクロドデシ
ル等のシクロアルキル基、フェニル、o−メチルフェニ
ル、m−メチルフェニル、p−メチルフェニル、o−エ
チルフェニル、m−エチルフェニル、p−エチルフェニ
ル、2,3−ジメチルフェニル、2,4−ジメチルフェニル、
3,4−ジメチルフェニル、ナフチル等のアリール基等を
挙げることができるが、前記したR1、R2と同様の理由
で、これらのうちではアルケニル基を除く、非置換の1
価炭化水素基であることが好ましい。In the benzene ring where two more silicon atoms are bonded,
It has an unsubstituted monovalent hydrocarbon group having 1 to 15 carbon atoms, which is substituted in at least one position except the o-position, for example, has a substituent stable to various reagents used in the production examples described later. Can be Examples of such a substituent include those similar to the unsubstituted hydrocarbon groups among those exemplified as R 1 and R 2 , and specifically include methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc., alkyl groups, vinyl, allyl, etc., alkenyl groups, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, etc., cycloalkyl groups, phenyl, o-methylphenyl , M-methylphenyl, p-methylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,
Examples thereof include aryl groups such as 3,4-dimethylphenyl and naphthyl. Of these, for the same reason as described above for R 1 and R 2 , an unsubstituted 1 group excluding an alkenyl group is used.
It is preferably a valent hydrocarbon group.
五配位ケイ素化合物の合成 本発明の五配位ケイ素化合物を合成するにあたっては、
出発物質として、フェニルアミノシラン化合物、例え
ば、下記式〔II〕、 式中、RAは、前記一般式〔I)における基R1のうちの非
置換又は置換の1価炭化水素基に相当する基であり、 RNは、アミノ基含有有機基であり、 aは、0〜2の整数であり、bは1〜3の整数であっ
て、且つa+b=3である、X及びnは、前述した意味
を示すが、Xはアミノシリル基に対して少なくとも1ヶ
所のo−位を除く位置に置換したものてある、 で表されるフェニルアミノシラン化合物が使用される。Synthesis of pentacoordinate silicon compound In synthesizing the pentacoordinate silicon compound of the present invention,
As a starting material, a phenylaminosilane compound, for example, the following formula [II], In the formula, R A is a group corresponding to an unsubstituted or substituted monovalent hydrocarbon group of the group R 1 in the general formula [I], R N is an amino group-containing organic group, and a Is an integer of 0 to 2, b is an integer of 1 to 3, and a + b = 3. X and n have the above-mentioned meanings, but X is at least one position relative to the aminosilyl group. A phenylaminosilane compound represented by the following is used, which is substituted at the position except the o-position.
ここで、上記アミノ基含有有機基としては、例えば次の
様なエチレンジアミン型の基を挙げることができる。Here, examples of the amino group-containing organic group include the following ethylenediamine type groups.
(ここでR3,R4,R5はそれぞれ独立に炭素数1〜4のア
ルキル基又はアルコキシ置換アルキル基を示す。) ここで、このフェニルアミノシラン化合物は、例えばt
ーブチルリチウム等のアルキルリチウムと下記反応式の
様に反応して、フェニル基のo−位をリチオ化するた
め、R3,R4,R5のアルキル基としては立体障害の小さい
メチル基であることが好ましい。 (Here, R 3 , R 4 , and R 5 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy-substituted alkyl group.) Here, this phenylaminosilane compound is, for example, t
-Since it reacts with alkyl lithium such as butyl lithium as shown in the reaction formula below to lithiate the o-position of the phenyl group, the alkyl group of R 3 , R 4 and R 5 must be a methyl group with little steric hindrance. Is preferred.
上記のフェニルアミノシラン化合物を出発物質として、
五配位ケイ素化合物を合成する時の合成経路の一例を以
下に示す。 Starting from the above phenylaminosilane compound,
An example of a synthetic route for synthesizing a pentacoordinate silicon compound is shown below.
合成経路: 尚、上記において、基RBは前記一般式[I]における基
R2のうちの非置換又は置換の1価炭化水素基に相当する
基であり、i−Prは、イソプロピル基を表すものとす
る。Synthetic route: In the above, the group R B is the group in the above general formula [I].
It is a group corresponding to an unsubstituted or substituted monovalent hydrocarbon group of R 2 , and i-Pr represents an isopropyl group.
工程(a); この工程(a)においては、フェニルアミノシラン
(イ)をt−ブチルリチウム(t−BuLi)等のアルキル
リチウムで処理し、フェニル基のo−位をリチオ化し、
次いでフェニルトリクロロシラン等のクロロシランを反
応させて、前記フェニル基のo−位にケイ素原子を導入
し、更に2−プロパノールと、トリエチルアミン及び水
等の縮合触媒で処理することによってイソプロポキシ化
を行い、イソプロポキシシラン(ロ)を得る。Step (a): In this step (a), phenylaminosilane (a) is treated with alkyllithium such as t-butyllithium (t-BuLi) to lithiate the o-position of the phenyl group,
Then, chlorosilane such as phenyltrichlorosilane is reacted to introduce a silicon atom at the o-position of the phenyl group, and further treated with 2-propanol and a condensation catalyst such as triethylamine and water for isopropoxylation, Isopropoxysilane (II) is obtained.
ここで使用したフェニルアミノシランが有している有機
基RAが、前記一般式〔I〕における基R1のうちの1価炭
化水素基として五配位ケイ素化合物中に導入される。ま
た使用したクロロシランのケイ素原子に結合した有機基
(RB)が、前記一般式〔I〕における基R2のうちの1価
炭化水素基として五配位ケイ素化合物中に導入されるこ
とになる。The organic group R A possessed by the phenylaminosilane used here is introduced into the pentacoordinated silicon compound as a monovalent hydrocarbon group among the groups R 1 in the above formula [I]. Further, the organic group (R B ) bonded to the silicon atom of the chlorosilane used is introduced into the pentacoordinated silicon compound as a monovalent hydrocarbon group among the groups R 2 in the above formula [I]. .
上記の反応工程において、t−BuLiを用いてのリチオ化
は、t−BuLiに対して不活性な溶媒、例えばベンゼン、
ヘキサン、テトラヒドロフラン等を用いて、フェニルア
ミノシラン(イ)にt−BuLiを滴下し、滴下後2〜3時
間攪拌を続けることによって行われる。この際の反応温
度は、−20〜20℃の範囲とし、t−BuLiの滴下量は、モ
ル比で、t−BuLi/フェニルアミノシラン=1〜5.0、好
ましくは1.5〜3.0の範囲とするのがよい。In the above reaction step, lithiation with t-BuLi is carried out in a solvent inert to t-BuLi, such as benzene,
T-BuLi is added dropwise to phenylaminosilane (ii) using hexane, tetrahydrofuran or the like, and stirring is continued for 2 to 3 hours after the addition. The reaction temperature at this time is in the range of −20 to 20 ° C., and the dropping amount of t-BuLi is in a molar ratio of t-BuLi / phenylaminosilane = 1 to 5.0, preferably 1.5 to 3.0. Good.
o−位がリチオ化されたフェニルアミノシランに対する
クロロシランの反応は、−10〜20℃、好ましくは0〜5
℃の温度において、該クロロシランを滴下し、滴下後、
反応系を40〜60℃の温度に保持しながら2〜3時間攪拌
を続けることによって行われる。この場合、浴媒は特に
必要ではないが、必要に応じて、前記リチオ化工程で用
いた溶媒を使用することができる。クロロシランの滴下
量は、クロロシランとしてフェニルトリクロロシランを
使用した場合において、t−BuLiとのモル比で、t−Bu
Li/フェニルトリクロロシラン=1〜5.0、好ましくは3.
0〜4.0の範囲とするのがよい。The reaction of chlorosilane with phenylaminosilane which is lithiated at the o-position is -10 to 20 ° C, preferably 0 to 5 ° C.
The chlorosilane was added dropwise at a temperature of ° C, and after the addition,
It is carried out by keeping the reaction system at a temperature of 40 to 60 ° C. and continuing stirring for 2 to 3 hours. In this case, the bath medium is not particularly necessary, but the solvent used in the lithiation step can be used if necessary. When phenyltrichlorosilane was used as chlorosilane, the dropping amount of chlorosilane was t-BuLi in a molar ratio with t-BuLi.
Li / phenyltrichlorosilane = 1 to 5.0, preferably 3.
It is recommended that the range is 0 to 4.0.
上記によって、o−位にケイ素原子が導入されたフェニ
ルアミノシランのイソプロポキシ化は、0〜10℃の温度
で2−プロパノールを反応系に滴下し、次いで室温下で
12〜24時間攪拌を行った後に、室温条件でトリエチルア
ミン及び水を滴下し、更に0.5〜2時間、攪拌を行うこ
とによって完了する。用いる2−プロパノール、トリエ
チルアミン及び水の量は、フェニルアミノシランのSi−
N結合及びSi-Cl結合の全てをSi−O結合に変換するに
十分な量とする。According to the above, isopropoxylation of phenylaminosilane having a silicon atom introduced at the o-position is carried out by adding 2-propanol dropwise to the reaction system at a temperature of 0 to 10 ° C and then at room temperature.
After stirring for 12 to 24 hours, triethylamine and water are added dropwise at room temperature, and the stirring is continued for 0.5 to 2 hours. The amounts of 2-propanol, triethylamine and water used were the same as those of phenylaminosilane, Si-
Sufficient to convert all N-bonds and Si-Cl bonds to Si-O bonds.
かくしてイソプロポキシシラン(ロ)が合成される。Thus, isopropoxysilane (II) is synthesized.
工程(b); この工程(b)においては、HBF4・OEt2等のフルオロ化
剤を用いて、前記イソプロポキシシラン(ロ)のフルオ
ロ化を行い、フルオロシラン(ハ)を誘導する。Step (b); In this step (b), the isopropoxysilane (b) is fluorinated using a fluorinating agent such as HBF 4 · OEt 2 to induce fluorosilane (c).
フルオロ化は、イソプロポキシシラン(ロ)を、塩化メ
チレン、クロロホルム等のフルオロシランやフルオロ化
剤に不活性な溶媒中に溶解させ、0〜−20℃の範囲に冷
却したのち、HBF4・OEt2等のフルオロ化剤を滴下し、滴
下終了後、反応系を10〜40℃の範囲に保持させながら5
〜10時間攪拌を行うことによって、フルオロシラン
(ハ)が得られる。Fluorination is carried out by dissolving isopropoxysilane (b) in a solvent inert to fluorosilane and a fluorinating agent such as methylene chloride and chloroform, and cooling to a range of 0 to -20 ° C, followed by HBF 4 · OEt. Fluorinating agent such as 2 is added dropwise, and after completion of the addition, while maintaining the reaction system in the range of 10-40 ℃,
The fluorosilane (c) is obtained by stirring for about 10 hours.
工程(c); この工程(c)においては、フルオロシラン(ハ)をフ
ッ化カリウム及び18−クラウン−6と反応させることに
よって、目的とする五配位ケイ素化合物(ニ)が合成さ
れる。Step (c); In this step (c), the target pentacoordinate silicon compound (d) is synthesized by reacting the fluorosilane (c) with potassium fluoride and 18-crown-6.
これら各成分の反応は、ベンゼン、トルエン、キシレン
等のフルオロシラン及びえられる五配位ケイ素化合物に
対して不活性な溶媒中で行われ、反応温度は10〜40℃、
及び反応時間は10〜30時間である。The reaction of each of these components is carried out in a solvent inert to fluorosilane such as benzene, toluene, xylene and the obtained pentacoordinate silicon compound, and the reaction temperature is 10 to 40 ° C.
And the reaction time is 10 to 30 hours.
(実施例) 実施例1 [o−C6H4(SiPhF2)2F](-)K(+)・18−クラウン−6の
合成: 合成経路; (ここでMe,Phはそれぞれメチル基、フェニル基を示
す。以下同じ。) 工程(a); Ph2Si(NMeCH2CH2NMe2)21.91g(5.25mmol)に、窒素雰囲
気下、0℃でt−BuLiのペンタン溶液(1.4モル濃度)
8.6ml(12.0mmol)を滴下する。滴下終了後、0℃と室
温で各1時間攪拌を行い、リチオ化を行った。尚、Phは
フェニル基を表し、Meはメチル基を表す。EXAMPLES Example 1 [o-C 6 H 4 (SiPhF 2) 2 F] (-) K (+) · 18- Synthesis of crown-6: synthesis pathway; (Here, Me and Ph respectively represent a methyl group and a phenyl group. The same applies to the following.) Step (a); Ph 2 Si (NMeCH 2 CH 2 NMe 2 ) 2 1.91 g (5.25 mmol) in a nitrogen atmosphere at 0 T-BuLi pentane solution (1.4 molar) at ℃
8.6 ml (12.0 mmol) is added dropwise. After completion of the dropping, stirring was carried out at 0 ° C. and room temperature for 1 hour each to carry out lithiation. In addition, Ph represents a phenyl group and Me represents a methyl group.
次いで、上記反応系に、フェニルトリクロロシラン6.45
ml(40.5mmol)を0℃で加え、その後50℃で3時間攪拌
して反応を行った。Then, to the above reaction system, phenyltrichlorosilane 6.45
ml (40.5 mmol) was added at 0 ° C., and then the reaction was carried out by stirring at 50 ° C. for 3 hours.
得られた反応混合物に、室温でイソプロピルアルコール
10mlを滴下し、12時間反応を行った。更にトリエチルア
ミン7.5ml,水95μlを加えた。反応混合物を濾過し、Mg
SO4で乾燥を行い、減圧下にフェニルトリ(イソプロポ
キシ)シランを除いた後、シリカゲルカラムクロマトで
精製したところ、 が53%の収率で得られた。The resulting reaction mixture was added with isopropyl alcohol at room temperature.
10 ml was added dropwise and the reaction was performed for 12 hours. Further, 7.5 ml of triethylamine and 95 μl of water were added. The reaction mixture was filtered, Mg
After drying with SO 4 , removing phenyltri (isopropoxy) silane under reduced pressure, and then purifying with silica gel column chromatography, Was obtained in a yield of 53%.
工程(b); 工程(a)で得られたイソプロポキシシラン414mg(0.9
8mmol)を塩化メチレンに溶解し、HBF4・OEt2981mg(6.
06mmol)を加えて、窒素雰囲気下で12時間反応させた。Step (b); 414 mg (0.9 of isopropoxysilane obtained in step (a)
8 mmol) was dissolved in methylene chloride, and HBF 4 OEt 2 981 mg (6.
06 mmol) was added and the mixture was reacted for 12 hours under a nitrogen atmosphere.
反応混合物を減圧蒸留したところ、207〜211℃/1.6mmHg
(油浴温度)の留分として、 が88%の収率で得られた。When the reaction mixture was distilled under reduced pressure, 207 ~ 211 ℃ / 1.6mmHg
As a fraction of (oil bath temperature), Was obtained in a yield of 88%.
工程(c); 工程(b)で得られたフルオロシラン384mg(1.06mmo
l)と、スプレー乾操したフッ化カリウム67.9mg(1.17m
mol)及び18−クラウン−6 308mg(1.17mmol)をトルエ
ン(2.5ml)中、室温で20時間反応させた。Step (c); 384 mg (1.06 mmo) of fluorosilane obtained in step (b)
l) and spray dried potassium fluoride 67.9mg (1.17m
mol) and 308 mg (1.17 mmol) of 18-crown-6 were reacted in toluene (2.5 ml) at room temperature for 20 hours.
得られた白色の固体を濾別し、エーテル(30ml)で洗浄
し、THFで再結晶したところ、 が、462mg(収率64%)得られた。The white solid obtained was filtered off, washed with ether (30 ml) and recrystallized from THF, Was obtained (462 mg, yield 64%).
この五配位ケイ素化合物の融点、NMR分析、元素分析の
結果を以下に示す。The melting point, NMR analysis and elemental analysis results of this pentacoordinated silicon compound are shown below.
融点:149.5〜150.5℃(分解)1 H NMR:(アセトン−d6,200μHz;内部標準アセトン−
d5)δ(ppm)3.554(s,24H)7.137〜7.256(m,6H)7.4
09(dd,5.6,3.4Hz,2H)7.868〜7.951(m,4H)8.208(d
d,5.6,3.4Hz,2H) この1H NMRの分析チヤート、及び13C,19F,29SiのNMRの
分折チャートをそれぞれ第1図〜第4図に示す。Melting point: 149.5 to 150.5 ° C. (decomposition) 1 H NMR: (acetone-d 6 , 200 μHz; internal standard acetone-
d 5 ) δ (ppm) 3.554 (s, 24H) 7.137 to 7.256 (m, 6H) 7.4
09 (dd, 5.6,3.4Hz, 2H) 7.868-7.951 (m, 4H) 8.208 (d
d, 5.6, 3.4 Hz, 2H) The analytical chart of 1 H NMR and the NMR analysis chart of 13 C, 19 F, 29 Si are shown in FIGS. 1 to 4, respectively.
元素分析: C30H38O6F5Si2Kとして、 C H F 計算値; 52.61% 5.59% 13.87% 実測値; 52.35% 5.55% 14.06% 実施例2 [o−C6H4(SiPh2F)(SiF3)F](-)K(+)・18−クラ
ウン−6の合成: 合成経路; 工程(a); PhSi(NMeCH2CH2NMe2)32.94g(7.19mmol)を、ヘキサン
14mlに溶かし、窒素雰囲気下、−20℃に冷却した。この
溶液にt−BuLiのペンタン溶液(1.4モル濃度)12.3ml
(17.26mmol)を滴下し、−20℃で1時間、更に室温で
2時間攪拌を行い、リチオ化を行った。Elemental analysis: C 30 H 38 O 6 F 5 Si 2 K, C H F calculated value; 52.61% 5.59% 13.87% measured value; 52.35% 5.55% 14.06% Example 2 [o-C 6 H 4 (SiPh 2 F) (SiF 3 ) F] (−) K (+) · 18-crown-6 synthesis: synthetic route; Step (a); PhSi (NMeCH 2 CH 2 NMe 2 ) 3 2.94 g (7.19 mmol) was added to hexane.
It was dissolved in 14 ml and cooled to -20 ° C under a nitrogen atmosphere. To this solution, 12.3 ml of a t-BuLi pentane solution (1.4 molar concentration)
(17.26 mmol) was added dropwise, and the mixture was stirred at -20 ° C for 1 hour and further at room temperature for 2 hours for lithiation.
次いで、上記反応溶液を0℃に冷却し、ジフェニルジク
ロロシラン11.9ml(57.4mmol)を加え、室温で1時間、
更に50℃で2時聞攪拌して反応を行った。Then, the above reaction solution was cooled to 0 ° C., 11.9 ml (57.4 mmol) of diphenyldichlorosilane was added, and the mixture was stirred at room temperature for 1 hour.
Further, the reaction was carried out by stirring at 50 ° C. for 2 hours.
得られた反応溶液を再び0℃に冷却し、イソプロピルア
ルコール12mlを滴下し、次いで室温で12時間攪拌を行っ
た。更にトリエチルアミン11.5ml,水128μlを加え、30
分攪拌後、反応混合物を濾過し、濾液をエバポレータで
留去したのち、減圧下にジフェニルジ(イソプロポキ
シ)シランを除いた後、シリカゲルカラムクロマトで精
製したところ、 が27%の収率で得られた。The obtained reaction solution was cooled to 0 ° C. again, 12 ml of isopropyl alcohol was added dropwise, and then the mixture was stirred at room temperature for 12 hours. Further, add 11.5 ml of triethylamine and 128 μl of water, and add 30
After stirring for minutes, the reaction mixture was filtered, the filtrate was distilled off with an evaporator, diphenyldi (isopropoxy) silane was removed under reduced pressure, and the residue was purified by silica gel column chromatography. Was obtained in a yield of 27%.
工程(b); 工程(a)で得られたイソプロポキシシラン544.5mg
(1.294mmol)を塩化メチレン7mlに溶解し、窒素雰囲気
下−10℃に冷却した。Step (b); 544.5 mg of isopropoxysilane obtained in step (a)
(1.294 mmol) was dissolved in 7 ml of methylene chloride and cooled to -10 ° C under a nitrogen atmosphere.
これにHBF4・OEt21.391g(8.145mmo1)を加えて室温で
6時間反応させた。To this, 1.391 g (8.145 mmo1) of HBF 4 .OEt 2 was added and reacted at room temperature for 6 hours.
溶媒をエバポレータで留去し、残液を減圧蒸留したとこ
ろ、196〜201℃/1.5mmHgの留分として、 が72%の収率で得られた。The solvent was distilled off with an evaporator, and the residual liquid was distilled under reduced pressure to obtain a fraction of 196 to 201 ° C / 1.5 mmHg. Was obtained in a yield of 72%.
工程(c); 工程(b)で得られたフルオロシラン220mg(0.607mmo
l)と、スプレー乾燥したフッ化カリウム36.2mg(0.623
mmol)及び18−クラウン−6 168.2mg(0.636mmol)をト
ルエン(2ml)に加え、室温で攪拌を行った。Step (c); 220 mg (0.607 mmo) of fluorosilane obtained in step (b)
l) and spray-dried potassium fluoride 36.2 mg (0.623
mmol) and 168.2 mg (0.636 mmol) of 18-crown-6 were added to toluene (2 ml), and the mixture was stirred at room temperature.
反応混合物を濾過し、得られた白色粉末をエーテル(30
ml)で洗浄し、THFで再結晶し、得られた白色結晶を6
時間かけて真空乾燥したところ、 が、291mg(収率70%)得られた。The reaction mixture was filtered and the resulting white powder was washed with ether (30
ml) and recrystallized from THF to give 6 white crystals.
After vacuum drying over time, Was obtained in an amount of 291 mg (yield 70%).
この五配位ケイ素化合物の融点、NMR分析、元素分析の
結果を以下に示す。The melting point, NMR analysis and elemental analysis results of this pentacoordinated silicon compound are shown below.
融点:146.5〜147.0℃(分解)1 H NMR:(アセトン−d6,400MHz)δ(ppm)3.638(s,24
H)7.175〜7.246(m,6H)7.336(Broad triplet.J=6.4
7Hz,1H)7.394(dt,J=7.30Hz,J=1.63Hz,1H)7.816〜
7.877(m,4H)8.195(Broad doublet.J=7.66Hz,1H)8.
217(ddd,J=7.39Hz,1.04Hz,0.65Hz,1H)19 NMR:(400MHz,アセトン−d6)δ(ppm)−117.187
(s,JFSi=209.79Hz) 元素分析: C30H38O6F5Si2Kとして、 C H F 計算値; 52.61% 5.59% 13.87% 実測値; 52.36% 5.60% 14.02% 実施例3 [o−C6H4(SiPh2F)(SiPhF2)F](-)K(+)・18−ク
ラウン−6の合成: 合成経路; 工程(a); Ph2Si(NMeCH2CH2NMe2)22.73g(7.10mmol)を、ヘキサン
15mlに溶かし、窒素雰囲気下、−30℃に冷却した。この
溶液にt−BuLiのペンタン溶液(1.4モル濃度)12.2ml
(17.0mmol)を滴下し、−30℃で1時間、更に室温で2
時間攪拌を行い、リチオ化を行った。Melting point: 146.5-147.0 ° C. (decomposition) 1 H NMR: (acetone-d 6 , 400 MHz) δ (ppm) 3.638 (s, 24
H) 7.175 to 7.246 (m, 6H) 7.336 (Broad triplet.J = 6.4
7Hz, 1H) 7.394 (dt, J = 7.30Hz, J = 1.63Hz, 1H) 7.816〜
7.877 (m, 4H) 8.195 (Broad doublet.J = 7.66Hz, 1H) 8.
217 (ddd, J = 7.39Hz, 1.04Hz, 0.65Hz, 1H) 19 NMR: (400MHz, acetone-d 6 ) δ (ppm) -117.187
(S, J FSi = 209.79 Hz) Elemental analysis: C 30 H 38 O 6 F 5 Si 2 K, C H F calculated value: 52.61% 5.59% 13.87% Measured value; 52.36% 5.60% 14.02% Example 3 [ o-C 6 H 4 (SiPh 2 F) (SiPhF 2) F] (-) K (+) · 18- synthesis of crown-6: synthesis pathway; Step (a); Ph 2 Si (NMeCH 2 CH 2 NMe 2 ) 2 2.73 g (7.10 mmol) was added to hexane.
It was dissolved in 15 ml and cooled to -30 ° C under a nitrogen atmosphere. To this solution, t-BuLi pentane solution (1.4 molar concentration) 12.2 ml
(17.0 mmol) was added dropwise at -30 ° C for 1 hour, then at room temperature for 2 hours.
Stirring was carried out for a time to effect lithiation.
次いで、上記反応溶液を−10℃に冷却し、ジフェニルジ
クロロシラン11.8ml(56.8mmol)を加え、室温で1時間
攪拌し、更に50℃で2時聞攪拌して反応を行った。Then, the above reaction solution was cooled to -10 ° C, 11.8 ml (56.8 mmol) of diphenyldichlorosilane was added, and the mixture was stirred at room temperature for 1 hour and further stirred at 50 ° C for 2 hours to carry out the reaction.
得られた反応溶液を再び0℃に冷却し、イソプロピルア
ルコール8mlを滴下し、次いで室温で12時間攪拌を行っ
た。更にトリエチルアミン11mlを加え、1時間攪拌後、
反応混合物を濾過し、濾液をエバポレータで留去したの
ち、減圧下にジフェニルジ(イソプロポキシ)シランを
除いた後、シリカゲルカラムクロマトで精製したとこ
ろ、 が76.7%の収率で得られた。The obtained reaction solution was cooled to 0 ° C. again, 8 ml of isopropyl alcohol was added dropwise, and then the mixture was stirred at room temperature for 12 hours. Add 11 ml of triethylamine and stir for 1 hour.
The reaction mixture was filtered, the filtrate was distilled off with an evaporator, diphenyldi (isopropoxy) silane was removed under reduced pressure, and the residue was purified by silica gel column chromatography. Was obtained in a yield of 76.7%.
工程(b); 工程(a)で得られたイソプロポキシシラン564.2mg
(1.286mmol)を塩化メチレン7mlに溶解し、窒素雰囲気
下−20℃に冷却した。Step (b); 564.2 mg of isopropoxysilane obtained in step (a)
(1.286 mmol) was dissolved in 7 ml of methylene chloride and cooled to -20 ° C under a nitrogen atmosphere.
これにHBF4・OEt21.208g(7.461mmo1)を加えて室温で
6時間反応させた。To this was added 1.208 g (7.461 mmo1) of HBF 4 .OEt 2 and the mixture was reacted at room temperature for 6 hours.
溶媒をエバポレータで留去し、残液を減圧蒸留したとこ
ろ、259〜265℃/1.5mmHgの留分として、 が87.2%の収率で得られた。The solvent was distilled off with an evaporator, and the residual liquid was distilled under reduced pressure. As a fraction at 259 to 265 ° C / 1.5 mmHg, Was obtained in a yield of 87.2%.
工程(c); 工程(b)で得られたフルオロシラン440mg(1.046mmo
l)と、スプレー乾燥したフッ化カリウム63.3mg(1.090
mmol)及び18−クラウン−6 296.1mg(1.120mmol)をト
ルエン(2ml)に加え、室温で2日間攪拌を行った。Step (c); 440 mg (1.046 mmo of fluorosilane obtained in step (b)
l) and spray-dried potassium fluoride 63.3 mg (1.090
mmol) and 296.1 mg (1.120 mmol) of 18-crown-6 were added to toluene (2 ml), and the mixture was stirred at room temperature for 2 days.
反応混合物を濾過し、得られた白色粉末をエーテル(30
ml)で洗浄し、THFで再結晶し、得られた白色結晶を6
時間かけて真空乾燥したところ、 が、444mg(収率57.1%)得られた。The reaction mixture was filtered and the resulting white powder was washed with ether (30
ml) and recrystallized from THF to give 6 white crystals.
After vacuum drying over time, Was obtained (444 mg, yield 57.1%).
この五配位ケイ素化合物の融点及びNMR分析の結果を以
下に示す。The melting point and the result of NMR analysis of this pentacoordinate silicon compound are shown below.
融点:153.5〜155.0℃(分解)1 H NMR:(アセトン−d6,200MHz)δ(ppm)3.603(s,24
H),6.867〜7.248(m,8H)7.273〜7.419(m,3H)7.440
〜7.540(m,2H)7.764〜7.874(m,4H)8.253〜8.356
(m,2H)19 NMR:(188.15MHz,アセトン−d6;−90℃)δ(ppm)
−70.399(broad,1F)−108.485(broad,1F)−126.617
(t,J=14.30Hz,JFSi=259.08Hz)−136.154(s,JFSi=
220.32Hz)Melting point: 153.5 to 155.0 ° C. (decomposition) 1 H NMR: (acetone-d 6 , 200 MHz) δ (ppm) 3.603 (s, 24
H), 6.867 ~ 7.248 (m, 8H) 7.273 ~ 7.419 (m, 3H) 7.440
~ 7.540 (m, 2H) 7.764 ~ 7.874 (m, 4H) 8.253 ~ 8.356
(M, 2H) 19 NMR: (188.15MHz, acetone-d 6 ; -90 ° C) δ (ppm)
-70.399 (broad, 1F) -108.485 (broad, 1F) -126.617
(T, J = 14.30Hz, J FSi = 259.08Hz) -136.154 (s, J FSi =
220.32Hz)
第1図乃至第4図は、実施例1で得られた五配位ケイ素
化合物の1H,13C,19F及び29SのNMR分析の結果を示すチ
ャートである。1 to 4 are charts showing the results of 1 H, 13 C, 19 F and 29 S NMR analysis of the pentacoordinate silicon compound obtained in Example 1.
Claims (2)
〜15の非置換又は置換の1価炭化水素基を表し、各3個
のR1及びR2はそれぞれ同一でも互いに異なる基であって
もよく、 Xは、炭索数1〜15の非置換1価炭化水素基を示し、 nは0〜4の整数である、 で表される五配位ケイ素化合物。1. The following general formula: In the formula, R 1 and R 2 are each a fluorine atom or a carbon number 1
~ 15 represents an unsubstituted or substituted monovalent hydrocarbon group, and each of the three R 1 and R 2 may be the same or different from each other, X is an unsubstituted group having 1 to 15 carbon atoms. A pentacoordinate silicon compound represented by: which represents a monovalent hydrocarbon group, and n is an integer of 0 to 4.
チウムを反応させた後に、更にクロロシラン化合物を反
応させて該フェニルアミノシラン化合物のベンゼン環の
o−位にケイ素原子を導入し、 次いで上記合成化合物についてイソプロポキシ化をおこ
なってイソプロポキシシランを合成し、 該イソプロポキシシランのフルオロ化を行ってフルオロ
シラン化合物を合成し、 更に該フルオロシラン化合物にふっ化カリウム及び18−
クラウン−6を反応させることにより請求項1に記載の
五配位ケイ素化合物を製造する方法。2. A phenylaminosilane compound is reacted with an alkyllithium, and then a chlorosilane compound is further reacted to introduce a silicon atom into the o-position of the benzene ring of the phenylaminosilane compound. Then, the synthetic compound is isopropoxylated. To synthesize isopropoxysilane, fluorinating the isopropoxysilane to synthesize a fluorosilane compound, and further adding potassium fluoride and 18-
The method for producing the pentacoordinate silicon compound according to claim 1, by reacting Crown-6.
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