JPH06306087A - Optically active organosilicon compound - Google Patents

Abstract

PURPOSE:To obtain the compound consisting of organic mono-, di- or tri- chlorosilanes, etc., having one or more optically active organic substituent groups and useful as an enantiomer recognizing material, a raw material, etc., for high molecular standard substance, etc., for one-dimensional semiconductor and quantum microline structure. CONSTITUTION:The interior of a reacting vessel is dehydrated and degassed and substituted with argon gas and magnesium, molecular sieve and tetrahydrofuran are added thereto and optically active halogenated hydrocarbons [e.g (S)-(+)-1-bromo-2-methylbutane] are added thereto and the halogenated hydrocarbons react with magnesium to afford a Grignard reagent. Then, the Grignard reagent reacts with tetrachlorosilane, methyltrichlorosilane, dimethyl- dichlorosilane, etc., to provide the objective optically active organosilicon compound expressed by formula I (R is lower alkyl or aryl; R* is chiral alkyl) or formula II to formula VI and introducing one or more optically active organic substituent groups therein, e.g. organic monochlorosilanes, organic dichlorosilanes or organic trichlorosilanes.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optically active organosilicon compound expected as a new type of enantiomer recognition material and an organopolysilane expected as a polymer standard substance having a one-dimensional semiconductor / quantum wire structure.

[0002]

BACKGROUND OF THE INVENTION Many organic silicon compounds are industrially useful, including surface treatment agents, water repellent and oil repellent agents, electrical insulators,
Both the heat medium and the precursor of the ceramic material are polymers containing silicon in a part of the skeleton. In recent years, solvent-soluble organic polysilanes whose main chain skeleton is composed of only silicon have been attracting attention as a new type of functional material. Photoresists, optical waveguide materials, precursors of silicon carbide, and electrophotography. Many research examples directed to applications such as photoconductors, nonlinear optical materials, and light emitting materials have been reported. Generally, organic polysilane has an ultraviolet absorption band around 300 to 400 nm based on the main chain skeleton peculiar to Si-Si chains. The absorption of the main chain in a room temperature solution usually has a molecular absorption coefficient of about 5000 to 8000 (monomer unit) ^-1 (liter) ^-1 and a half width of 0.5 to 0.6 eV (about 40 to 60 nm). On the other hand, the half-width of the main chain emission in a room temperature solution is 0.1 to 0.2 eV (about 10 to 20 nm), which is considerably narrower than the main chain absorption. That is, the emission spectrum shape and the absorption spectrum shape of the organic polysilane are not in a mirror image relationship, which is usually seen in the absorption / light emission phenomenon of organic substances. Many studies have already explained that one of the main chains of the organopolysilane behaves as an aggregate in which trans-zigzag or segments with a gentle helix structure close to it are connected via a conformational defect. It has been revealed that there is. That is, the main chain absorption width of the organic polysilane is a superposition of absorption of these segments having various absorption maxima,
Photoexcitation of main chain absorption causes energy transfer to the lowest excitation energy segment, and the light is emitted from there. Therefore, the optical and electrical properties such as hole mobility and non-linear optical properties reported in conventional organic polysilanes are substantially dominated by many defects in the main chain. It is expected that it was far from the true physical properties that it possesses. Since the organic polysilane is a polymer whose main chain itself is composed of only silicon, the main chain is easily decomposed by irradiation of ultraviolet rays, and the molecular weight reduction or siloxane formation easily proceeds. An application example as a photoresist that actually uses this has been reported. Therefore, organic polysilanes are not suitable for application as functional materials related to light such as electrophotographic photoreceptors, nonlinear optical materials, and light emitting materials. However,
In terms of absorption and emission of ultraviolet rays and the fact that a polymer soluble in a solvent can be easily obtained by a relatively simple chemical synthesis,
It is important as a valuable model material for basic research on optical and electrical properties of one-dimensional semiconductor materials, and can be expected to be marketable as a polymer standard material. On the other hand, as a polymer material that recognizes enantiomers, the main chain such as poly (triphenylmethylmethacrylate) and poly (diphenylpyridylmethylmethacrylate) synthesized with sparteine-butyllithium as a polymerization initiator has one-way helicity. Carbon skeleton polymers having are known [eg, Y. Y. Okamoto et al., Journal of American Chemical Society (J. Am. Chem. Soc.), 103, 6971 (1981)]. These one-way helicity organic polymers are actually supported on silica gel surface and are marketed as column materials for high performance liquid chromatography that separates and separates enantiomers [Chiralpak-OT, Chiralpak, Daicel Chemical Co., Ltd.]. -O
P]. However, in these poly (triarylmethylmethacrylate) materials, the side chain triaryl ester moiety that fixes the main chain helicity gradually loses its main chain helicity due to hydrolysis or solvolysis, and at the same time loses its enantiomer recognition ability. It has the fatal drawback of being exposed. If the silicon main chain skeleton and the hydrocarbon side chains of organic polysilane can be used to the advantage that they are resistant to hydrolysis and solvolysis, they will usually be used in high-performance liquid chromatography under dark and deoxygenated conditions. Graphography (HPL
It can be used as a column material for gas chromatography (abbreviated as C) and gas chromatography (abbreviated as GC). Further, it is expected that the optically active organic polysiloxane structure will further improve the resistance to oxygen as compared with the organic polysilane. For example, when a thermodynamically unstable organopolysilane skeleton is oxidized,
Although it is believed that they will eventually be converted into thermodynamically stable optically active organopolysiloxanes, nonetheless, the enantiomer recognition ability derived from the chirality of the main chain is still retained, and therefore, it is suitable for long-term repeated use. On the other hand, it can be fully expected to have the characteristics that can be practically used. Currently HPLC
There is particularly strong potential demand for an enantiomer-recognizing column material (abbreviated as CSP) that can be used even under reversed-phase conditions as a separation and analysis means according to. Many of the CSP materials for reverse phase are derived from biological materials, and most of them are alkyl derivatives having an amide bond, so that the problem of column deterioration due to hydrolysis still remains. Here, either a monomeric siloxane or a polymeric siloxane derived from a chlorosilane-based material having an optically active substituent is loaded on the column carrier, or an optically active organic polysilane having the helicity of the main chain skeleton is loaded on the carrier. If possible, CSP or GC for HPLC
The application as a CSP for use can be opened. At present, such organic polysilanes or organic polysiloxanes are not known.

[0003]

The object of the present invention is to provide an organic compound containing a chiral center as an enantiomer recognition material, particularly as a material for CSP for HPLC and GC, and as a model reference material for studying physical properties of one-dimensional semiconductor / quantum wire structure. It is an object of the present invention to provide a group of optically active organosilicon compounds having a structure in which a substituent is directly bonded to a silicon atom, in which unidirectional helix is stably retained even in a room temperature solution.

[0004]

The present invention will be described in brief. The first invention of the present invention relates to an optically active organosilicon compound, which is represented by the following general formula (Formula 1):

[0005]

[Chemical 1]

(Wherein R represents a lower alkyl group or an aryl group, and R ^* represents a chiral alkyl group), organic monochlorosilanes and organic dichlorosilanes into which at least one optically active organic substituent is introduced. Or organic trichlorosilanes. A second invention of the present invention relates to another optically active organosilicon compound, which is represented by the following general formula (Formula 2):

[0007]

[Chemical 2]

At least 1 per silicon repeating unit represented by the formula: wherein R and R ^* have the same ^{meanings as} in the formula (Formula 1).
An organic polysilane having a repeating unit containing one optically active organic substituent. Furthermore, the third invention of the present invention relates to still another optically active organosilicon compound, which is represented by the following general formula (Formula 3):

[0009]

[Chemical 3]

(Wherein R ₁ , R ₂ and R ₃ are lower alkyl groups or aryl groups, R ^* is a chiral alkyl group, and 0.
01 ≦ n ≦ 0.5), which is characterized in that the main chain skeleton contains a silicon unit into which an optically active organic substituent is introduced. The present invention is a weight average molecular weight,
If n ≧ 10, it can be used.

The present invention will be described in detail below. First, the first invention of the present invention will be described more specifically with reference to a synthesis example. The chlorosilanes containing an asymmetrically substituted optically active organic substituent having 1 or 2 Si—Cl bonds of the present invention are synthesized based on the following general reaction formula (Formula 4).

[0012]

[Chemical 4]

Et ₂ O is diethyl ether, and THF is tetrahydrofuran. Examples of the group R are CH ₃ ,
_{C 2 H 5, n-C} 3 H 7, n-C 4 H 9, n-C 5
_{H 11, n-C 6 H} 13, n-C 7 H 15, n-C 8 H 17, n
_{-C 9 H 19, n-C} 10 H 21, n-C 11 H 23, n-C 12 H
_{25, i-C 4 H 9} , 3-CH 3 -C 4 H 9, phenyl,
Examples thereof include p-tolyl, benzyl, β-phenylethyl, and the like. Examples of R ^* include groups represented by the following formula (Formula 5).

[0014]

[Chemical 5]

Further, the symmetrically substituted optically active organic-substituted dichlorosilane having two Si-Cl bonds or the optically active organic-substituted trichlorosilane having three Si-Cl bonds is based on the following general reaction formula (Formula 6). Are synthesized.

[0016]

[Chemical 6]

The chiral organic substituent is (S)-(+)-1-halo-2 in view of availability and price.
-Methylbutane is convenient. Using the Grignard reagent derived from this alkyl halide, the corresponding chiral alkylsilane chloride compound can be easily prepared. The chiral alkyl halide includes (S)-(+)
Not only substances represented by -1-halo-2-methylbutane having a chiral center at the β-position as viewed from the silicon side, but also 1
It is also possible to use substances with the chiral center in the α-position, such as menthyl chloride. However, since a substance having a chiral center at the α-position is likely to racemize, in this case, a chiral alkyl halide having a plurality of chiral centers such that the chiral center exists not only at the α-position but also at another position is preferable. . Through these reactions, the optically active organic chlorosilanes represented by the above general formula (Formula 1) can be obtained.

The optically active organic polysilanes obtained by desalting and condensing dichlorosilanes containing an optically active organic substituent together with metallic Na in the second invention of the present invention are represented by the following general reaction formula (Formula 7). And (Chem. 8).

[0019]

[Chemical 7]

[0020]

[Chemical 8]

The groups R and R in the formulas (7) and (8)
The example of ^* is the same as the formula (Formula 4). As the dichlorosilanes containing an optically active organic substituent used here, CH ₃ , C ₂ H ₅ , and n-C ₃ are used as the group R because of easy synthesis.
_{H 7, n-C 4 H} 9, n-C 5 H 11, n-C 6 H 13, n
_{-C 7 H 15, n-C} 8 H 17, n-C 9 H 19, n-C 10 H
₂₁ , n-C ₁₁ H ₂₃ , n-C ₁₂ H ₂₅ , i-C ₄ H ₉ , β-
A combination of a structure selected from phenylethyl and the like and a (S) -2-methylbutyl structure of the formula (Formula 5) as the group R ^* is suitable. The dichlorosilanes containing this optically active organic substituent do not have the risk of racemization during the Na desalting condensation reaction process because the chiral center is at the β-position, and also cause steric hindrance between silicon monomers during the condensation reaction. Since the degree is relatively small, a high molecular weight optically active chain organic polysilane is produced. According to the knowledge of the present inventor, the methyl group and the ethyl group, which are relatively compact alkyl groups, are asymmetrically arranged on the β-position chiral carbon. The main chain of the organic polysilane having a chain skeleton obtained in (1) has a unidirectional and fixed pitch spiral fixing effect.

In the second invention of the present invention, the network-like optically active organic polysilane obtained by desalting and condensing trichlorosilanes containing an optically active organic substituent together with metallic Na is represented by the following reaction formula ).

[0023]

[Chemical 9]

The trichlorosilanes containing an optically active organic substituent used here are easy to synthesize,
[(S) -2-Methylbutyl] trichlorosilane is convenient. Trichlorosilane containing this optically active organic substituent has no chiral center at the β-position, so there is no fear of racemization in the Na desalting condensation reaction process, and the degree of steric hindrance between silicon monomers during the condensation reaction. Is not so large, an optically active network-like organic polysilane having a relatively high molecular weight is produced.

In Examples 8 and 9 below, synthesis examples of corresponding optically active organic polysilanes by Na condensation of chlorosilane single monomers containing optically active organic substituents having relatively small steric hindrance were shown, however, larger phenyl, In the case of benzyl, (S) -2-methylbutyl group, etc., the homopolymerization by Na condensation does not produce the corresponding optically active organic polysilane or has a low degree of polymerization.
In such a case, the third aspect of the present invention, the co-condensation of dichlorosilanes into which at least one optically active organic substituent is introduced, and chlorosilanes containing an optically inactive organic substituent with less steric hindrance. Thus, an optically active organic polysilane copolymer can be synthesized. At this time, the proportion of the dichlorosilanes is suitably 0.01 to 0.50 parts (molar fraction), whereby the organic polysilane represented by the general formula (Formula 3) can be obtained. Specific examples 8 and 9 described later show the case where n is 0 or 1.

[0026]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Methyl [(S) -2-methylbutyl] dichlorosilane was prepared by the following method. Magnesium 9.5g
(0.41 mol) and molecular sieve 4A were placed, dehydrated and degassed, and 125 ml of dehydrated tetrahydrofuran was placed in a reaction vessel in which the atmosphere was replaced with argon gas, and an extremely small amount of iodine was gently added. While gently stirring, (S)
4.5 g of-(+)-1-bromo-2-methylbutane
(0.03 mol) was gradually added dropwise. To the extent that the reaction solution is gently refluxed, (S)-(+)-1-chloro-
36 g (0.34 mol) of 2-methylbutane was gradually added dropwise. After the reaction was completed, this Grignard reagent was transferred to a dropping funnel. Dehydration Degassed and charged with argon gas, put 80 g (0.54 mol) of methyltrichlorosilane and 150 ml of dehydrated diethyl ether in another reaction vessel, and slowly stir the above-mentioned Grignard reagent at a reaction temperature of 2 to 5 ° C. Dropped. After the dropping was completed, the reaction was further continued at room temperature for one day. Hexane (500 ml) was added to the reaction mixture, the hexane-soluble component was filtered under pressure, and the filtrate was then fractionally distilled to obtain the desired component. Main distillation: Boiling point 78-79 ° C
/ 20 mmHg, yield 20.5 g (30%). ²⁹ Si-NM
R (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method) 32.5 ppm, ¹³
C-NMR (deuterated chloroform, tetramethylsilane internal standard, WALTZ proton noise decoupling method) 3
2.2, 30.3, 29.4, 21.7, 11.1,
6.4 ppm.

Example 2 [(S) -2-Methylbutyl] phenyldichlorosilane was prepared by the following method. Magnesium 5.7g
(0.24 mol) and molecular sieves 4A were put therein, and 125 ml of dehydrated tetrahydrofuran was put into a reaction vessel which was dehydrated and degassed and replaced with argon gas, and an extremely small amount of iodine was gently added. While gently stirring the reaction solution so that the reaction solution is gently refluxed, (S)-(+)-
30 g (0.20 mol) of 1-bromo-2-methylbutane
Was gradually added dropwise. After the reaction was completed, this Grignard reagent was transferred to a dropping funnel. 50 g of phenyltrichlorosilane was placed in another reaction vessel that had been dehydrated, degassed, and purged with argon gas.
(0.24 mol) and 50 ml of dehydrated tetrahydrofuran were added, and the above Grignard reagent was slowly added dropwise at a reaction temperature of 40 to 50 ° C. with stirring. After the dropping was completed, the reaction was further continued at room temperature for one day. Hexane 500 in the reaction mixture
ml was added, and the target component was obtained by pressure filtration of the hexane-soluble component and fractional distillation of the filtrate. Main distillation: Boiling point 77-78 ° C / 0.8 mmHg, Yield 19.8 g (Yield 3
4%). ²⁹ Si-NMR (heavy chloroform, tetramethylsilane internal standard, gated proton decoupling method) 18.9 ppm, ¹³ C-NMR (heavy chloroform, tetramethylsilane internal standard, WALTZ proton noise decoupling method) 133.4, 133.3, 131.
5, 128.3, 32.3, 30.4, 28.4, 2
1.8, 11.2 ppm.

Example 3 [(S) -2-Methylbutyl] trichlorosilane and bis [(S) -2-methylbutyl] dichlorosilane were prepared by the following method. 7.4 g (0.31 mol) of magnesium and molecular sieves 4A were put, and 125 ml of dehydrated diethyl ether was put into a reaction vessel which was dehydrated and degassed and replaced with argon gas, and an extremely small amount of iodine was gently added. While gently stirring this, (S)-
2.5 g of (+)-1-bromo-2-methylbutane (0.
02 mol) was gradually added dropwise. 27 g (0.25 mol) of (S)-(+)-1-chloro-2-methylbutane was gradually added dropwise until the reaction solution was gently refluxed. Dehydration Deaeration and 15 g (0.088 mol) of tetrachlorosilane and 50 ml of dehydrated diethyl ether were placed in another reaction vessel which had been replaced with argon gas, and the Grignard reagent described above was slowly added dropwise at a reaction temperature of 40 to 50 ° C while stirring. did. After the dropping was completed, the reaction was further continued at room temperature for one day. Hexane (500 ml) was added to the reaction mixture, and the desired component was obtained by pressure filtration of the hexane-soluble component and fractional distillation of the filtrate. Main distillation: Boiling point 45-46 ° C / 7mmHg, yield 1
2.1 g (yield 22%). ²⁹ Si-NMR (heavy chloroform, tetramethylsilane internal standard, gated proton decoupling method) 12.6 ppm, ¹³ C-NMR (heavy chloroform, tetramethylsilane internal standard, WALT
Z proton noise decoupling method) 32.0, 30.
5, 21.5, 11.2 ppm. Second fraction: Boiling point 77 to 7
8 ° C./2.5 mmHg, Yield 6.5 g (Yield 20%). ²⁹ S
i-NMR (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method) 32.7
ppm, ¹³ C-NMR (deuterated chloroform, tetramethylsilane internal standard, WALTZ proton noise decoupling method) 32.3, 30.2, 28.9, 21.8, 1
1.2 ppm. ^{From the 29} Si-NMR and the boiling point, the first fraction and the second fraction were identified as [(S) -2-methylbutyl] trichlorosilane and bis [(S) -2-methylbutyl] dichlorosilane, respectively.

The boiling points and chemical shifts of ²⁹ Si-NMR (deuterated chloroform, internal standard of tetramethylsilane, gated protons) for a total of 14 kinds of dichlorosilanes containing other (S) -2-methylbutyl groups synthesized in the same manner. Decoupling method), ¹³ C-NMR chemical shift (deuterated chloroform, tetramethylsilane internal standard, WALTZ
(Proton noise decoupling method) is summarized in Tables 1 to 3. In the ¹³ C-NMR data, x2 and x3 indicate that the peak intensities are 2 times and 3 times, respectively. Moreover, in ¹³ C-NMR data, R ^* means
It is identified by 5 carbon peaks of each of the (S) -2-methylbutyl groups. The synthesis yields of these dichlorosilanes are about 45-based on the raw material (S)-(+)-1-bromo-2-methylbutane or (S)-(+)-1-chloro-2-methylbutane. It was about 55%.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

In the following Examples 4 to 6, specific synthesis examples of optically active chain organic polysilanes will be shown taking alkyl [(S) -2-methylbutyl] dichlorosilane as an example. The present invention has revealed that the fine molecular structure, material properties, and optical properties of the optically active chain organic polysilane greatly differ depending on the achiral structure.

Example 4 First, a specific synthesis example of methyl [(S) -2-methylbutyl] polysilane will be shown. The inside of the reaction vessel was thoroughly dehydrated and degassed, and the atmosphere was replaced with argon gas. Then, 1.9 g of a sodium metal dispersion liquid (toluene 30%), 0.05 g of 18-crown ether-6 and 50 ml of dehydrated diethyl ether were placed in the flask. . Methyl [(S) -2-methylbutyl] dichlorosilane 2.05 at an oil bath temperature of 40 ° C.
g (0.011 mol) was added and reacted for 12 hours.
The reaction mixed solution was filtered under pressure, and ethyl alcohol was added to the filtrate. The resulting white viscous precipitate was collected by a centrifuge and vacuum dried at 60 ° C. The yield was 0.45g. A unimodal polymer having a weight average molecular weight of 51,000 and a dispersity (= weight average degree of polymerization / number average degree of polymerization) of 3.1 by gel permeation chromatography (hereinafter abbreviated as GPC) method based on monodisperse polystyrene. was gotten. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method) of the obtained chain organic polysilane is shown in FIG. Almost one rather broad peak appeared at around -31.5 ppm. If the resolution is improved by further processing mathematically,
It was found that this peak is represented by an overlap of at least 7 peaks. ¹³ C of the obtained chain organic polysilane
-NMR (deuterated chloroform, tetramethylsilane internal standard, proton noise decoupling method) is shown in FIG.
Broad peaks were observed around 34, 23, 11, and -2 ppm. The UV-visible absorption spectrum and the circular dichroism spectrum of the obtained optically active chain organic polysilane are shown in FIG. 3, and the emission spectrum (each in i-octane solution, 20 ° C.)
Is shown in FIG. From the comparison of these three spectra, the lowest excited state of the main chain skeleton near 4.2 eV of the obtained chain organic polysilane is composed of a strong Cotton positive signal near 4.0 eV and a weak Cotton negative signal near 4.5 eV. It was shown that it was done. In addition, the emission spectrum has no mirror image relationship with the ultraviolet absorption spectrum and the circular dichroism spectrum,
Rather, it appears to be a mirror image of the negative Cotton peak in the circular dichroic spectrum. For comparison, no such cotton signal was observed with the poly (methylpropylsilane) homopolymer. From these, in the obtained optically active chain organic polysilane, the right-handed helix structure and the left-handed helix structure having different excitation energy values coexist in one main chain, and the fraction thereof is This can be explained by a model in which the latter and the latter are contained in approximately the same amount.In terms of electron quantity, the silicon-bonded electrons do not spread throughout the polymer chain, but the right-handed helix with different energy eigenvalues. It can be considered to be localized in the segment and the left-handed spiral segment.

Example 5 Next, a specific synthesis example of n-butyl [(S) -2-methylbutyl] polysilane will be shown. After thoroughly dewatering and degassing the inside of the reaction vessel and substituting with argon gas, 3.8 g of a sodium metal dispersion liquid (toluene 30%), 0.05 g of 15-crown ether-5 and 50 ml of dehydrated toluene were placed in the flask. N-Butyl [(S) at an oil bath temperature of 120 ° C.
2-Methylbutyl] dichlorosilane 5.0 g (0.0
(22 mol) was added and reacted for 8 hours. The reaction mixed solution was filtered under pressure, and ethyl alcohol was added to the filtrate. The resulting white precipitate was collected by a centrifuge and vacuum dried at 60 ° C. The yield was 0.27 g. The yield was n-butyl [(S) -2-methylbutyl] dichlorosilane,
It was 7.9%. Weight average molecular weight of 3 by GPC method
A monodisperse polymer having a polydispersity of 140 and a dispersity of 1.14 was obtained.
²⁹ Si-NMR (heavy toluene, tetramethylsilane internal standard, gated proton decoupling method, measurement temperature 60 ° C.) of the obtained chain organic polysilane is shown in FIG.
Broad peak due to the main chain skeleton is -19.7 ppm ~
It appeared at -21.0 ppm. ¹³ C-NMR (heavy toluene, tetramethylsilane internal standard, proton noise decoupling method, measurement temperature 6) of the obtained chain organic polysilane.
0 ° C.) is shown in FIG. 35, 31, 28, 23, 17,
Peaks were observed around 14 and 12 ppm (however, 2
7 peaks around 0 ppm are peaks based on the methyl group of heavy toluene). The ultraviolet absorption spectrum and circular dichroism spectrum of the obtained optically active chain organic polysilane are shown in FIG. 7, and the emission spectrum thereof (in an i-octane solution, 20 ° C.) is shown in FIG. From the mutual comparison of these three kinds of spectra, it is found that the cotton absorption at 3.93 eV is a perfect analog of the main chain absorption at 3.93 eV and the absorption maxima match, and the emission spectrum shape at 3.83 eV is Since there is a mirror image relationship between the main chain absorption of 3.93 eV and the cotton absorption, one main chain of the obtained optically active chain organic polysilane has a single spiral structure with a constant spiral structure in the right-handed spiral direction. You can see that it is composed of structures. The main chain skeleton absorption of this n-butyl [(S) -2-methylbutyl] polysilane is due to the conventionally known optically inactive organic polysilane such as methyl (n-
The absorption intensity is about 3 times that of propyl) polysilane,
Its half-width is about 1/3, and it has the characteristics that the polymer has a very narrow molecular weight distribution and is substantially monodisperse. Further, in i-octane, at least -1
In the temperature range of 0 ° C to 80 ° C, the main chain absorption at -10 ° C and its cotton absorption strength are only about 10% higher than those at 80 ° C, and these unidirectional helical structures are present. It has been revealed that can exist in a solution very stably even near room temperature.

N-Butyl [(S) -2-methylbutyl]
Such properties of polysilane (monodispersion of molecular weight, increase and sharpening of main chain absorption intensity, mirror image of absorption spectrum and emission spectrum, agreement between absorption spectrum and circular dichroism spectrum) are described in n-butyl [( S) -2-methylbutyl] polysilane has an n-butyl moiety of ethyl group, n-propyl group,
It also appears in the case of i-butyl group, n-pentyl group, (S) -2-methylbutyl group and β-phenylethyl group. Obtained under the same polymerization conditions as in Example 5, here ethyl [(S) -2-methylbutyl] polysilane, n-propyl [(S) -2-methylbutyl] polysilane, i-butyl [(S) -2 -Methylbutyl] polysilane, n-pentyl [(S) -2-methylbutyl] polysilane, bis [(S) -2-methylbutyl] polysilane, β-phenylethyl [(S) -2-methylbutyl] polysilane with ultraviolet absorption spectra The circular dichroism spectra (in an i-octane solution, 20 ° C.) are shown in FIGS. 9 to 14, respectively.

Example 6 Next, a specific synthesis example of n-hexyl [(S) -2-methylbutyl) polysilane will be shown. After thoroughly dewatering and degassing the inside of the reaction vessel and substituting with argon gas, 3.8 g of a sodium metal dispersion liquid (toluene 30%), 0.05 g of 15-crown ether-5 and 50 ml of dehydrated toluene were placed in the flask. 5.2 g of n-hexyl [(S) -2-ethylbutyl] dichlorosilane at an oil bath temperature of 120 ° C.
Was added and reacted for 3 hours. The reaction mixture solution was subjected to pressure filtration, and ethyl alcohol was added to the filtrate to cause fractional precipitation. The resulting white precipitate first component and second component were collected by a centrifuge and vacuum dried at 60 ° C., respectively. First
The yield of the component was 0.19 g (5.1% yield), and the yield of the second component was 0.44 g (12.0% yield). GPC
By the method, the weight average molecular weight of the first component was 5160, the polydispersity was 1.38, the weight average molecular weight of the second component was 19200, and the polydispersity was 1.66. n-hexyl [(S)-
2-Ethylbutyl] polysilane First component ²⁹ Si-NM
R (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method, measurement temperature 60 ° C)
Is shown in FIG. One rather broad peak based on the main chain skeleton appeared at -22 to -23 ppm. n-hexyl [(S) -2-methylbutyl] polysilane First component
FIG. 16 shows ¹³ C-NMR (deuterated chloroform, tetramethylsilane internal standard, proton noise decoupling method). 35, 34, 32, 29, 23, 22, 16, 1
Peaks were observed around 4, 11, and 10 ppm. UV absorption spectrum of the obtained optically active chain organic polysilane,
The circular dichroism spectrum is shown in FIG. 17 and the emission spectrum (in an i-octane solution, 20 ° C.) is shown in FIG. From the mutual comparison of these three kinds of spectra, the cotton absorption at 3.83 eV is almost similar to the main chain absorption at 3.85 eV, and the absorption maximum photon energy values also agree well.
Since the shape of the emission spectrum at 3.78 eV is almost a mirror image of the main chain absorption at 3.85 eV and the cotton absorption at 3.83 eV, the main chain of one obtained optically active chain organic polysilane is right-handed. It can be seen that it is composed of a substantially single spiral structure having a constant spiral structure in the spiral direction. This n-
The main chain skeleton absorption of hexyl [(S) -2-methylbutyl] polysilane is about 5 times higher than that of conventionally known optically inactive organic polysilane, for example, methyl (n-propyl) polysilane, It exhibits a very characteristic optical characteristic that its half-value width is about 1/5. Furthermore, in i-octane, the main chain absorption at -10 ° C and its cotton absorption strength are only about 10% higher than those at 80 ° C in the temperature range of at least -10 ° C to 80 ° C. , It was revealed that these unidirectional helical structures can exist extremely stably even in a solution. However, unlike the n-butyl [(S) -2-methylbutyl] polysilane shown in Example 5, the polymer has a molecular weight distribution of about 2 or more, and often tends to be bimodal. Such features are
In addition to n-hexyl [(S) -2-methylbutyl] polysilane, the n-hexyl group is an n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group. Also appears in the case of.

N was obtained under the same polymerization conditions as in Example 6.
-Heptyl [(S) -2-methylbutyl] polysilane,
n-octyl [(S) -2-methylbutyl] polysilane, n-nonyl [(S) -2-methylbutyl] polysilane, n-decyl [(S) -2-methylbutyl] polysilane, n-undecyl [(S)- Ultraviolet absorption spectrum and circular dichroism spectrum (i of 2-methylbutyl] polysilane and n-dodecyl [(S) -2-methylbutyl] polysilane (i
-Octane solution at 20 ° C) is shown in Figs.
Shown in.

However, the ultraviolet absorption spectrum and the circular dichroism spectrum are very similar for the second fractional precipitation component of FIG. 19 with respect to the weight average molecular weight of 18180 and the polydispersity of 2.14. In addition, the ultraviolet absorption spectrum and circular dichroism spectrum are very similar for the weight-average molecular weight 21670 and the dispersity of 2.50 in the second fractional precipitation component in FIG. In addition, the ultraviolet absorption spectrum and the circular dichroism spectrum are very similar for the weight-average molecular weight of 37840 and the dispersity of 1.88 in the second fractional precipitation component in FIG. In addition, the ultraviolet absorption spectrum and the circular dichroism spectrum are very similar for the weight average molecular weight of 5550 and the dispersity of 1.44 in the second fractional precipitation component in FIG. The ultraviolet absorption spectrum and circular dichroism spectrum of the second fractional precipitation component of FIG. 24 are very similar for the weight average molecular weight of 6360 and the dispersity of 1.25.

Example 7 Here, a specific synthesis example of an optically active network-like organic polysilane will be described by taking [(S) -2-methylbutyl] trichlorosilane as an example. After thoroughly dewatering and degassing the inside of the reaction vessel and replacing with argon gas, 3.7 g of a sodium metal dispersion liquid (toluene 30%), 0.05 g of 15-crown ether-5, and 50 ml of toluene were placed in the flask. At an oil bath temperature of 60 ° C., 3.05 g (0.015 mol) of [(S) -2-methylbutyl) trichlorosilane
Was added and reacted for 15 minutes. The reaction mixture was pressure filtered and the filtrate was added to degassed cold ethyl alcohol. The resulting yellow precipitate was collected by a centrifuge and vacuum dried at 60 ° C. The yield was 0.4 g. By the GPC method, a monomodal poly [(S) -2-methylbutylsilane] having a weight average molecular weight of 4,200 and a dispersity of 1.8 was obtained. ²⁹ Si-NMR of poly [(S) -2-methylbutylsilane]
(Deuterated chloroform, tetramethylsilane internal standard, gated proton dicoupling method) is shown in FIG. −
A broad signal was observed from 20 to -70 ppm. Such a broad signal is characteristic of the network-like organic polysilane obtained by the condensation reaction of n-alkyltrichlorosilane with an alkali metal, which has been reported so far. This is because the structure of poly [(S) -2-methylbutylsilane] formed by desalting condensation of [(S) -2-methylbutyl] trichlorosilane is microscopically different from that of silicon having different magnetic environments. It is suggested that there are distributions of bond states, that is, bond distance, bond angle, and dihedral angle. Further, while the main peak of the network-shaped organic polysilane obtained from the n-alkyltrichlorosilane reported so far appeared around -60 ppm, poly [(S) -2-methylbutylsilane] The main peak appears around -45 to -50 ppm.
Cyclic permethyl oligosilane (silicon units 4, 5,
6) ²⁹ Si-NMR, it is known that permethylcyclotetrasilane exhibits a low magnetic field shift of about 15 ppm as compared with permethylcyclopentasilane and permethylcyclohexasilane. From this, it is speculated that poly [(S) -2-methylbutylsilane] is a condensed ring structure mainly called a ladder-type polysilane and having a 4-membered ring silicon skeleton. ¹³ C-NMR of the obtained poly [(S) -2-methylbutylsilane]
(Deuterated chloroform, tetramethylsilane internal standard, proton noise decoupling method) is shown in FIG. 34,
Broad peaks are observed around 30, 23 and 12 ppm. FIG. 27 shows an ultraviolet-visible absorption spectrum and a circular dichroism spectrum of poly [(S) -2-methylbutylsilane], and FIG. 28 shows an emission spectrum thereof (each in an i-octane solution, 20 ° C.). A broad absorption hem that does not have the absorption maximum characteristic of network-like organic polysilane appeared from 5 to 3 eV. On the other hand, the circular polarization spectrum is 2 to 6
At eV, the cotton band should be positive and negative at least 4
Individually recognized. This means that a right-handed helix (ladder) structure and a left-handed helix (ladder) structure, which have different energy eigenvalues, coexist in one polymer, and electronically speaking, they are distributed throughout the polymer chain. This can be explained by a model in which silicon-bonded electrons are not spread but localized as segments.

Example 8 Here, a specific synthesis example of an optically active chain organic polysilane copolymer by copolymerization of an asymmetrically substituted optically active dichlorosilane and an asymmetrically substituted optically inactive dichlorosilane will be shown. After thoroughly dehydrating and degassing the inside of the reaction vessel and replacing with argon gas, metallic sodium dispersion (toluene 30%)
A flask was charged with 5.7 g and 50 ml of toluene. Methylphenyldichlorosilane at an oil bath temperature of 70 ° C. 6.
0 g and [(S) -2-methylbutyl] phenyldichlorosilane 0.75 g mixed monomer (molar charge ratio = 90
/ 10) was added and reacted for 1 hour. The reaction mixed solution was filtered under pressure and separated into a high molecular weight component and a low molecular weight component by fractional precipitation from toluene / isopropyl alcohol. The produced white precipitate was collected by a centrifuge for each component and vacuum dried at 60 ° C. The yields of the first separated precipitation component and the second separated precipitation component were 0.17 g and 1.3 g, respectively. According to the GPC method, the first fractional precipitation component had a weight average molecular weight of 154000 and a dispersity of 3.0, and the second fractional precipitation component had a weight average molecular weight of 5,300 and a dispersity of 2.0. ²⁹ Si-NMR (deuterated chloroform, deuterated chloroform, of the first fractional precipitation component of the obtained poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} phenylsilane] ₁₀ was obtained.
FIG. 29 shows an internal standard of tetramethylsilane and a proton decoupling method with a gate. Multiple peaks were observed around -40 ppm. Poly (methylphenylsilane)
FIG. 30 shows the ¹³ C-NMR (deuterated chloroform, tetramethylsilane internal standard, proton noise decoupling method) of the first fractional precipitation component of ₉₀ -co-poly [{(S) -2-methylbutyl} phenylsilane] ₁₀ . Show. Based on Si-methyl group of poly (methylphenylsilane) homopolymer-
In addition to multiple peaks around 3 ppm, 33, 22, 10,
A plurality of peaks based on the (S) -2-methylbutyl group were observed around 0 ppm.

From these results, it was found that [(S) -2-methylbutyl] phenylsilane units were introduced into the main chain skeleton of this organic polysilane, and the ratio thereof was almost the same as the monomer charging ratio. Poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl}
Phenylsilane] FIG. 31 shows an ultraviolet-visible absorption spectrum and a circular dichroism spectrum of a high molecular weight component of ₁₀ and an emission spectrum (each in a tetrahydrofuran solution at 20 ° C.).
2 shows. From the comparison of these spectra, the lowest excited state of the main chain skeleton of poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} phenylsilane] ₁₀ is a strong cotton positive signal around 3.6 eV. And 4.3 eV
It was shown to consist of a weak cotton negative signal component in the vicinity. For comparison, no cotton signal was observed with the poly (methylphenylsilane) homopolymer. From these facts, the main chain absorption becomes optically active and the excitation energy characteristic value is obtained only by introducing a small amount (about 10 mol%) of [(S) -2-methylbutyl] phenylsilane moiety into the poly (methylphenylsilane) skeleton. Different right-handed and left-handed helical structures can be formed in one main chain, and the fraction can be explained by a model in which the former is considerably higher than the latter. Electronically, it corresponds to the fact that the silicon-bonded electrons do not spread over the entire polymer chain but are localized in the right-handed helical segment and the left-handed helical segment with different energy eigenvalues. To do.

Example 9 Here, a specific synthesis example of an optically active chain organic polysilane copolymer by a copolymerization ratio of symmetrically substituted optically active dichlorosilane and symmetrically substituted optically inactive dichlorosilane will be shown. 3. After thoroughly dehydrating and degassing the inside of the reaction vessel and replacing with argon gas, metallic sodium dispersion liquid (toluene 30%) 4.
A flask was charged with 8 g, 0.12 g of 15-crown ether-5 and 50 ml of toluene. At an oil bath temperature of 100 ° C., 4.7 g of di (n-butyl) dichlorosilane and 0.62 of bis [(S) -2-methylbutyl] dichlorosilane.
g of mixed monomer (molar ratio charged = 90/10) was added, and the mixture was further reacted for 3 hours. The reaction mixture solution was filtered under pressure, and the filtrate was separately precipitated with degassed cold isopropyl alcohol. The resulting white precipitate is collected by a centrifuge and the temperature is 60 ° C.
It was dried in vacuum. The GPC method determined that the first fractionated component had a weight average molecular weight of 517,000 and a polydispersity of 1.8, and the second fractionated component had a weight average molecular weight of 13,000 and a polydispersity of 2.1. The yield is 0.1 for each of the first and second fractionated components.
It was 2 g and 0.78 g. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard, gate) of the first fractionated component of poly [di (n-butyl) silane] ₉₀ -co-poly [bis {(S) -2-methylbutyl} silane] ₁₀ . FIG. 33 shows the attached proton decoupling method). Found in poly [di (n-butyl) silane] homopolymers-2
In addition to the peak around 3.0 ppm, -22.5 and 2
Two peaks were observed at 2.7 ppm. Since the intensity ratio of these is approximately 70:20:10, it is 22.5.
ppm is bis [(S) -2-methylbutyl] silane unit,
22.7 ppm is identified as the di (n-butyl) silane unit adjacent to the bis [(S) -2-methylbutyl] silane unit. Poly [di (n-butyl) silane] ₉₀ -co-poly [bis {(S) -2-methylbutyl} silane] 1st ₁₀
¹³ C-NMR of fractionated components (deuterated chloroform, tetramethylsilane internal standard, proton noise decoupling method)
Is shown in FIG. Poly [di (n-butyl) silane] homopolymers based on Si-butyl groups 30, 27, 15, 1
In addition to multiple peaks around 4ppm, 34, 29, 25,
A plurality of peaks, which are considered to be derived from the (S) -2-methylbutyl group, were weakly observed around 23, 16, and 11 ppm. From these results, it was found that bis [(S) -2-methylbutyl] silane units were introduced into the main chain skeleton of this organic polysilane, and the ratio thereof was almost the same as the monomer charging ratio. Poly [di (n-butyl) silane] ₉₀
-Co-poly [bis {(S) -2-methylbutyl} silane] ₁₀ The UV-visible absorption spectrum and circular dichroism spectrum of the high molecular weight component are shown in Fig. 35, and the emission spectrum (i-
FIG. 36 shows the temperature in an octane solution at 20 ° C.). From the comparison of these spectra, in the obtained chain organic polysilane copolymer, the lowest excited state of the silicon main chain skeleton near 4.0 eV was a strong cotton positive signal near 3.8 eV.
It was shown to consist of a weak cotton negative signal around 2 eV. For comparison, such a cotton single was not observed in the poly [di (n-butyl) silane] homopolymer. From these facts, main chain absorption becomes optically active simply by introducing a small amount (about 10 mol%) of a bis [(S) -2-methylbutyl] silane moiety into a poly [di (n-butyl) silane] skeleton. A right-handed helix structure and a left-handed helix structure having different excitation energy eigenvalues can be formed in one main chain, and the fraction can be explained by a model in which the former is considerably higher than the latter. Stoichiometrically, the silicon bond electrons do not spread over the entire polymer chain but are localized in the right-handed helical segment and the left-handed helical segment with different energy eigenvalues. Correspond.

[0045]

INDUSTRIAL APPLICABILITY As shown in the present invention, by including a chiral organic substituent as a side chain, it becomes possible to synthesize an organic polysilane exhibiting circular dichroism in main chain skeleton absorption. Such an optically active organic polysilane is expected to be used as a new type of enantiomer recognition material and as a polymer standard substance having a one-dimensional semiconductor / quantum wire structure. In addition, chlorosilicones having a chiral organic substituent can be directly supported on porous silica (spherical or pulverized as a form) to give HP.
Application as CSP for LC and GC is also expected. Also,
By appropriately selecting the side chain substituents, compared to conventional organic polysilanes, the main chain absorption strength is dramatically stronger and has an extremely narrow optical characteristic, and in some cases the molecular weight is monodisperse. It is possible to provide an organic polysilane having a single helical structure having substantially complete primary structure, secondary structure and chain length. These single helical organic polysilanes are
It is extremely useful as a basic model substance for studying the ideal optical and electrical properties of ideal one-dimensional semiconductors without interchain interactions and atomic quantum limit quantum wire structures that will become reality in the near future. It becomes possible to provide it as a polymer standard substance.

[Brief description of drawings]

FIG. 1 Methyl [(S) -2-methylbutyl] polysilane obtained in Example 4 (weight average molecular weight 5100
0 is a diagram showing the ²⁹ Si-NMR (heavy chloroform, tetramethylsilane internal standard, gated proton decoupling method) of dispersity 3.1).

FIG. 2 Methyl [(S) -2-methylbutyl] polysilane obtained in Example 4 (weight average molecular weight 5100
0, dispersion degree 3.1) ¹³ C-NMR (deuterated chloroform,
It is a figure which shows a tetramethylsilane internal standard and a proton noise decoupling method.

FIG. 3 shows methyl [(S) -2-methylbutyl] polysilane obtained in Example 4 (weight average molecular weight: 5100).
It is a figure which shows the ultraviolet absorption spectrum of 0, and dispersion degree 3.1) and a circular dichroism spectrum (in an i-octane solution, 20 degreeC).

FIG. 4 Methyl [(S) -2-methylbutyl] polysilane obtained in Example 4 (weight average molecular weight 5100
It is a figure which shows the emission spectrum (in an i-octane solution, 20 degreeC) of 0, and dispersion degree 3.1).

FIG. 5: n-butyl [(S) -2 obtained in Example 5]
-Methylbutyl] polysilane (weight average molecular weight 314
0, dispersion degree 1.14) ²⁹ Si-NMR (heavy toluene,
It is a figure which shows the tetramethylsilane internal standard and the proton decoupling method with a gate.

6] n-butyl [(S) -2 obtained in Example 5]
-Methylbutyl] polysilane (weight average molecular weight 314
It is a figure which shows < ¹³ > C-NMR (heavy toluene, tetramethylsilane internal standard, proton noise decoupling method) of 0, and dispersion degree 1.14).

FIG. 7 shows n-butyl [(S) -2 obtained in Example 5]
-Methylbutyl] polysilane (weight average molecular weight 314
It is a figure which shows the ultraviolet absorption spectrum of 0, and the dispersion degree of 1.14) and a circular dichroism spectrum (in an i-octane solution, 20 degreeC).

8] n-butyl [(S) -2 obtained in Example 5]
-Methylbutyl] polysilane (weight average molecular weight 314
It is a figure which shows the emission spectrum (in i-octane solution, 20 degreeC) of 0, and dispersion degree 1.14).

9: Ethyl [(S) -obtained by the method of Example 5]
2-methylbutyl] polysilane (weight average molecular weight 82
FIG. 4 is a diagram showing an ultraviolet absorption spectrum of 40 and a dispersity of 1.40) and a circular dichroism spectrum (in an i-octane solution, 20 ° C.).

FIG. 10: UV absorption spectrum and circular dichroism spectrum of n-propyl [(S) -2-methylbutyl] polysilane (weight average molecular weight 2950, dispersity 1.11) obtained by the method of Example 5 ( 20 ° C in i-octane solution)
FIG.

FIG. 11: UV absorption spectrum and circular dichroism spectrum of n-pentyl [(S) -2-methylbutyl] polysilane (weight average molecular weight 5960, dispersity 1.19) obtained by the method of Example 5 ( 20 ° C in i-octane solution)
FIG.

FIG. 12 shows an ultraviolet absorption spectrum and a circular dichroism spectrum of i-butyl [(S) -2-methylbutyl] polysilane (weight average average molecular weight: 2140, dispersity: 1.11) obtained by the method of Example 5 ( 20 ° C in i-octane solution)
FIG.

13 is an ultraviolet absorption spectrum and circular dichroism spectrum of β-phenylethyl [(S) -2-methylbutyl] polysilane (weight average molecular weight 5810, dispersity 1.27) obtained by the method of Example 5. FIG. (20 in i-octane solution
FIG.

FIG. 14 is a diagram showing the bis [(S) -obtained by the method of Example 5.
2-methylbutyl] polysilane (weight average molecular weight 26
It is a figure which shows the ultraviolet absorption spectrum of 80, and the degree of dispersion of 1.13) and a circular dichroism spectrum (in an i-octane solution, 20 degreeC).

FIG. 15: ²⁹ Si of the first component (weight average molecular weight 5160, dispersity 1.38) of n-hexyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6.
It is a figure which shows -NMR (deuterated chloroform, the tetramethylsilane internal standard, the proton decoupling method with a gate).

16 shows the ¹³ C- of the first component (weight average molecular weight 5160, dispersity 1.38) of n-hexyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6.
It is a figure which shows NMR (deuterated chloroform, an internal standard of tetramethylsilane, a proton noise decoupling method).

FIG. 17: UV absorption spectrum of the first component (weight average molecular weight 5160, dispersity 1.38) of n-hexyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6, It is a figure which shows a color spectrum (in an i-octane solution, 20 degreeC).

FIG. 18: Emission spectrum (i-octane) of the first component (weight average molecular weight 5160, dispersity 1.38) of n-hexyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6. It is a figure which shows 20 degreeC in a solution.

19 is a first fractional precipitation component of n-heptyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6 (weight average molecular weight 91270, dispersity 1.42).
FIG. 3 is a diagram showing an ultraviolet absorption spectrum and a circular dichroism spectrum (in an i-octane solution, 20 ° C.) of the above.

FIG. 20: First fractional precipitation component of n-octyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6 (weight average molecular weight 50650, dispersity 1.85).
FIG. 3 is a diagram showing an ultraviolet absorption spectrum and a circular dichroism spectrum (in an i-octane solution, 20 ° C.) of the above.

21] An ultraviolet absorption spectrum and a circular dichroism spectrum (i) of n-nonyl [(S) -2-methylbutyl] polysilane (weight average molecular weight 40110, dispersity 2.28) obtained by the method of Example 6. -In octane solution, 20 ° C)
FIG.

22 is a first fractional precipitation component of n-decyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6 (weight average molecular weight 415300, dispersity 5.6).
FIG. 3 is a diagram showing an ultraviolet absorption spectrum and a circular dichroism spectrum (in an i-octane solution, 20 ° C.) of the above.

23 is a first fractional precipitation component of n-undecyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6 (weight average molecular weight 45600, dispersity 2.55).
FIG. 3 is a diagram showing an ultraviolet absorption spectrum and a circular dichroism spectrum (in an i-octane solution, 20 ° C.) of the above.

24 is a first fractional precipitation component of n-dodecyl [(S) -2-methylbutyl] polysilane obtained by the method of Example 6 (weight average molecular weight 36400, dispersity 2.08).
FIG. 3 is a diagram showing an ultraviolet absorption spectrum and a circular dichroism spectrum (in an i-octane solution, 20 ° C.) of the above.

FIG. 25 shows the poly [(S) -obtained by the method of Example 7.
2-methylbutylsilane] (weight average molecular weight 420
It is a figure which shows ²⁹ Si-NMR (deuterated chloroform, an internal standard of tetramethylsilane, a proton decoupling method with a gate) of 0, and dispersity 1.8.

FIG. 26 shows ¹³ C-NMR (heavy chloroform, tetramethylsilane internal) of poly [(S) -2-methylbutylsilane] (weight average molecular weight 4200, dispersity 1.8) obtained in Example 7. It is a figure showing a standard and a proton noise decoupling method.

27] An ultraviolet absorption spectrum and a circular dichroism spectrum (i-octane) of poly [(S) -2-methylbutylsilane] (weight average molecular weight: 4200, dispersity: 1.8) obtained in Example 7. It is a figure which shows 20 degreeC in a solution.

FIG. 28: Emission spectrum of poly [(S) -2-methylbutylsilane] (weight average molecular weight: 4,200, dispersity: 1.8) obtained in Example 7 (2 in i-octane solution)
It is a figure which shows (0 degreeC).

FIG. 29: Poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} obtained in Example 8
Phenylsilane] ²⁹ Si-NMR of the first fractional precipitation component of ₁₀ (weight average molecular weight 154000, dispersity 3.0)
FIG. 3 is a diagram showing (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method).

FIG. 30: Poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} obtained in Example 8
Phenylsilane] ¹³ C-NMR of the first fractional precipitation component of ₁₀
It is a figure which shows (deuterated chloroform, tetramethylsilane internal standard, a proton noise decoupling method).

FIG. 31: Poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} obtained in Example 8
Phenylsilane] UV absorption spectrum and circular dichroism spectrum of high molecular weight component of ₁₀ (in tetrahydrofuran solution, 2
It is a figure which shows (0 degreeC).

FIG. 32: Poly (methylphenylsilane) ₉₀ -co-poly [{(S) -2-methylbutyl} obtained in Example 8
[Phenylsilane] ₁₀ is a view showing an emission spectrum of a high molecular weight component of ₁₀ (in tetrahydrofuran solution, 20 ° C.).

FIG. 33 shows the first fractionated component ²⁹ Si— of poly [di (n-butyl) silane] ₉₀ -co-poly [{bis (S) -2-methylbutyl} silane] ₁₀ obtained in Example 9. NMR
FIG. 3 is a diagram showing (deuterated chloroform, tetramethylsilane internal standard, gated proton decoupling method).

FIG. 34: ¹³ C- of the first fractionated component of poly [di (n-butyl) silane] ₉₀ -co-poly [bis {(S) -2-methylbutyl} silane] ₁₀ obtained in Example 9. It is a figure which shows NMR (deuterated chloroform, an internal standard of tetramethylsilane, a proton noise decoupling method).

FIG. 35 is an ultraviolet absorption spectrum of the first fractionated component of poly [di (n-butyl) silane] ₉₀ -co-poly [bis {(S) -2-methylbutyl} silane] ₁₀ obtained in Example 9. , Circular dichroism spectrum (in i-octane solution, 20 ° C)
FIG.

36 is an emission spectrum of the first fractional component of poly [di (n-butyl) silane] ₉₀ -co-poly [bis {(S) -2-methylbutyl} silane] ₁₀ obtained in Example 9 ( It is a figure which shows 20 degreeC in an i-octane solution.

Claims (3)

[Claims] 1. The following general formula (Formula 1): (Wherein R represents a lower alkyl group or an aryl group, and R ^* represents a chiral alkyl group), organic monochlorosilanes, organic dichlorosilanes, in which at least one optically active organic substituent is introduced, or An optically active organosilicon compound, which is an organic trichlorosilane. 2. The following general formula (Formula 2): (Wherein R represents a lower alkyl group or an aryl group, R ^* represents a chiral alkyl group), and is an organic polysilane having a repeating unit containing at least one optically active organic substituent per silicon repeating unit. An optically active organosilicon compound characterized by the above. 3. The following general formula (Formula 3): (Wherein R ₁ , R ₂ , and R ₃ are lower alkyl groups or aryl groups, R ^* is a chiral alkyl group, and 0.01 ≦ n ≦
0.5) An optically active organosilicon compound comprising a silicon unit having an optically active organic substituent introduced therein, which is part of the main chain skeleton.