JPH07300489A - 2,5-Reactive Substituent-Containing Silole and Silole Polycondensation Product, and Their Production Process - Google Patents

Abstract

(57) [Summary] [Structure] A polycondensation product of silole represented by the following formula (2) is provided. [Chemical 1] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group or aryl group, and A and B are the same or different from each other,
A hydrogen atom, a halogen atom or an alkali metal atom is shown.
n is an integer of 2 or more. ) [Effect] The silole polycondensation product is useful as an optical functional material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silole polycondensation product which is a new π-electron conjugated organic compound having a light absorption band from the ultraviolet region to the visible light region, an intermediate thereof and a method for producing them.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As examples of the π-electron conjugated organic polymer, polyacetylene, polythiophene, polypyrrole, and other highly stable polymers have been reported, and their application to organic conductive substances is being investigated. In recent years, in addition to homopolymers, various copolymers have been synthesized, such as by combining thiophene and pyrrole, and due to the contribution of electron intramolecular donor / acceptor structures, etc., they have become new functional materials from their unique optical absorption spectra. It's being watched as a gain.

On the other hand, the development of the silole skeleton from a structure capable of functioning as both an electron donor and an electron acceptor to polymerization has been studied, and the inventors of the present invention have previously investigated the copolymer of the silole skeleton and the thiophene skeleton. As filed (Japanese Patent Application Nos. 4-196609 and 5-82620), a polymer having extremely unique light absorption properties and expected to be applied to an optical functional material can be synthesized. In this case, the polysilole bonded at the 2,5-position may be a polymer having excellent nonlinear optical characteristics according to theoretical calculation.
Et al., And Frapper et al., Reported that the bandgap is extremely small and that it is highly possible as a conductive material. However, it is difficult to introduce a highly reactive group into the 2,5-position of a silole compound by a conventionally known method, and thus far, it is not enough to synthesize a 2,5-reactive substituent-containing silole. No studies have been done. Slightly by Wracmeyer et al.
hem, Comm. , 86,397) Bis (2-stannylethynyl) silane and borane have only been reported to synthesize siloles having a boron substituent at the 3-position.

In view of the above point, the present applicant previously proposed a novel 2,5-reactive substituent-containing silole and a method for producing the same in Japanese Patent Application No. 5-345214. This will be described in detail below. (1) The following general formula (I)

[0005]

[Chemical 8] (In the formula, R ^{11 to} R ¹⁴ are the same or different and have 1 to 12 carbon atoms.
Represents a monovalent hydrocarbon group or a hydrogen atom of R ¹⁵ and R
¹⁶ is a group selected from sulfur, selenium, silicon, germanium, tin or phosphorus substituted with a monovalent hydrocarbon,
Or R ¹⁵ and R ¹⁶ may be the same or different from each other. ) 2,5-
A silole containing a reactive substituent. (2) The following general formula (II)

[0006]

[Chemical 9] (In the formula, R ^{11 to} R ¹⁴ are the same or different and have 1 to 12 carbon atoms.
Represents a monovalent hydrocarbon group or a hydrogen atom, and M ′ is an alkali metal or an alkali metal complex. ) 2,5
A reactive substituent-containing silole. (3) R ^{15 is} added to the 2,5-reactive substituted silole of formula (II)
X, R ¹⁶ X (provided that R ¹⁵ and R ¹⁶ are a monovalent hydrocarbon-substituted group selected from sulfur, selenium, silicon, germanium, tin or phosphorus, or a halogen atom,
R ¹⁵ and R ¹⁶ may be the same as or different from each other. X is a halogen atom. ) 2,5- of formula (I) characterized by reacting a halide represented by
A process for producing a reactive substituent-containing silole. (4) The following general formula (III)

[0007]

[Chemical 10] (In the formula, R ^{11 to} R ¹⁴ are the same or different and have 1 to 12 carbon atoms.
Represents a monovalent hydrocarbon group or a hydrogen atom. The reaction mixture obtained by reacting the silane compound represented by the formula (4) with an alkali metal or an alkali metal complex has R ¹⁵ X, R ¹⁶ X (provided that R
¹⁵ and R ¹⁶ are a monovalent hydrocarbon-substituted group selected from sulfur, selenium, silicon, germanium, tin or phosphorus, or a halogen atom, and R ¹⁵ and R ¹⁶ are the same as each other. , May be different. X is a halogen atom. ) A method for producing a 2,5-reactive substituent-containing silole of the formula (I), which comprises reacting a halide represented by the formula (1). (5) The following general formula (III)

[0008]

[Chemical 11] (In the formula, R ^{11 to} R ¹⁴ are the same or different and have 1 to 12 carbon atoms.
Represents a monovalent hydrocarbon group or a hydrogen atom. ) The silane compound represented by the formula (2) is reacted with an alkali metal or an alkali metal complex to prepare a 2,5-reactive substituent-containing silole of the formula (II).

However, the polycondensation product of the above silole has not been known.

[0010]

Means and Actions for Solving the Problems As a result of further studies on the above-mentioned polycondensation product of silole, the present inventor reacts a dihalogenosilole represented by the following formula (3) with an alkyl compound of an alkali metal. As a result, a silole containing a 2,5-reactive substituent represented by the formula (1) is obtained, and the silole of the formula (1) is polycondensed under oxidizing conditions in the presence of a monovalent copper compound. Or by carrying out a similar reaction using the silole polycondensation product of the formula (4) obtained by using the silole of the formula (1) as a starting material, it is possible to obtain the silole polycondensation product of the formula (2). I found it.

[0011]

[Chemical 12] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X represents a halogen atom, and M represents an alkali metal atom. A and B are the same or different from each other and represent a hydrogen atom, a halogen atom or an alkali metal atom, n is an integer of 2 or more, m is an integer of 1 or more, and n> m.)

Further, a reactive halogen-containing compound is allowed to act on a dialkali silole represented by the following formula (5), and then iron (III) acetylacetonate is condensed as a catalyst to obtain the following formula (6). It has been found that a silole polycondensation product is obtained.

[0013]

[Chemical 13] (In the formula, R ^{1 to} R ⁴ and M have the same meanings as described above.
p represents an integer of 2 or more. )

Further, AX is added to the silole of the above formula (1) (wherein A represents sulfur, selenium, silicon, germane, tin or phosphorus substituted with a monovalent hydrocarbon group, and X represents a halogen atom). By reacting a compound represented by
It was found that a 2,5-hetero-reactive substituent-containing silole compound represented by the following formula (7) was obtained, and that the silole polycondensation product as described above was obtained by using a palladium catalyst.

[0015]

[Chemical 14] (In the formula, R ^{1 to} R ⁴ and A and X have the same meanings as described above.)

The polycondensation product of silole obtained here is an optical functional material such as a conductive organic material, a non-linear optical material or a photoresponsive material, or another π-conjugated polymer for obtaining such an optical functional material. Alternatively, they have found that they are useful as a raw material for a copolymer with the monomer, and have completed the present invention.

Therefore, according to the present invention, (i) the formula (1)
5-reactive substituent-containing silole, (ii) silole polycondensation product of formula (2), (iii) dihalogenosylol of formula (3) is reacted with an alkyl compound of an alkali metal 2,5 of formula (1) A method for producing a reactive substituent-containing silole, (iv) a silole polycondensation of the formula (2) in which a silole of the formula (4) or a silole polycondensation product is polycondensed under oxidizing conditions in the presence of a monovalent copper compound. Manufacturing method (v) formula (5)
(Vi) Formula (7) 2, wherein the reactive halogen-containing compound is allowed to act on the dialkali silole, and then condensed with iron (III) acetylacetonate as a catalyst. (5) A method for producing a silole of the formula (7), which comprises reacting a silole of the formula (1) with a heterologous reactive substituent-containing silole (vii).

The present invention will be described in more detail below.
The 2,5-reactive substituent-containing silole according to the present invention is represented by the following formula (1).

[0019]

[Chemical 15] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X represents a halogen atom, and M represents an alkali metal atom. )

Examples of the alkyl group include methyl, ethyl, n-propyl and isopropyl, examples of the cycloalkyl group include cyclohexyl, and examples of the aryl group include phenyl, tolyl, and Xylyl etc. can be illustrated. In this case, R
It is preferable that ¹ and R ² are alkyl groups, and R ³ and R ⁴ are aryl groups. Further, examples of the halogen atom include chlorine, bromine and iodine, and examples of the alkali metal include lithium, sodium and potassium.

The silole of the above formula (1) has the following formula (3)
It can be obtained by reacting the dihalogenosylol of the above with an alkyl compound of an alkali metal.

[0022]

[Chemical 16] (In the formula, R ^{1 to} R ⁴ and X have the same meanings as described above.)

The silole of the formula (3) is obtained from Japanese Patent Application No. 5-3.
It can be obtained by the method described in Japanese Patent No. 45214. That is, in the above description of Japanese Patent Application No. 5-345214, the silole of the above formula (3) corresponds to the case where R ¹⁵ and R ¹⁶ are halogen atoms in the formula (I),
Formula (II) obtained by the method (4) or the method (5)
It can be obtained by applying the method of (3) to the silole of.

As the alkali metal alkylated product which reacts with the silole of the above formula (3), methyllithium, n-butyllithium, tert-butyllithium and the like can be used, and the amount thereof is represented by the formula (1) It is preferable that the amount is 0.5 to 2 mol with respect to 1 mol of silole.

This reaction can be carried out at a temperature of -110 ° C to 0 ° C using a solvent such as diethyl ether. For example, at -78 ° C, an alkali metal alkyl compound is added and the temperature is gradually raised. The reaction can be completed at around 0 ° C. The reaction time is usually 5 to 60 minutes.

Next, the silole polycondensation product according to the present invention is
It is represented by the following formula (2).

[0027]

[Chemical 17] (In the formula, R ^{1 to} R ⁴ have the same meanings as above.
A and B are the same or different from each other and represent a hydrogen atom, a halogen atom or an alkali metal atom. n is an integer of 2 or more. )

The silole polycondensation product of the above formula (2) is obtained by polycondensing the silole or silole polycondensation product of the following formula (4) under oxidizing conditions in the presence of a monovalent copper compound (oxidative coupling reaction). Can be obtained by

[0029]

[Chemical 18] (In the formula, R ^{1 to} R ⁴ and M and X have the same meanings as described above. M is an integer of 1 or more, and n> m.)

More specifically, the silole or polycondensation product of the formula (4) is polycondensed under oxidizing conditions in the presence of a monovalent copper compound to give a polycondensation product of the silole of formula (2a) ( In the formula (2), both A and B are halogen atoms).

[0031]

[Chemical 19]

By subjecting the compound of formula (4) to the oxidative coupling reaction as described above, a silole polycondensation product is obtained for the first time. Here, as the monovalent copper compound used in this oxidative coupling reaction, copper bromide C can be used.
uBr, copper iodide CuI, cuprous cyanide CuCN, etc. may be used, and the amount thereof is preferably 0.5 to 2 mol per 1 mol of the compound of the formula (4). In addition, the oxidative coupling reaction includes p-dinitrobenzene, o-dinitrobenzene, tetracyanoquinodimethane (TCNQ),
It can be carried out by using an oxidizing agent such as CuCl _{2 in} an amount of 0.5 to 10 mol with respect to 1 mol of the compound of the formula (4), or by bubbling air or oxygen.

As a reaction solvent, tetrahydrofuran,
2-Methylhydrofuran, diethylene glycol dimethyl ether, hexamethylphosphoamide and the like can be used. The reaction atmosphere is preferably an inert atmosphere such as dry nitrogen or argon, and the reaction temperature is preferably -130 to 0 ° C. The reaction time is usually 30 minutes to 3 hours.

The silole polycondensation product of the formula (2a) obtained by the above method can be obtained by reacting an alkylated product of an alkali metal in the same manner as in the case of the method for producing the silole of the above formula (1). A compound in which one X in the formula (2a) is substituted with an alkali metal M (a silole condensate having m ≧ 2 in the formula (4), that is, a silole condensate in which A is a halogen atom and B is an alkali metal in the formula (2). ) Can be obtained, which can also be used as a raw material for producing a silole polycondensation product of the formula (2).

Further, in the formula (2), the polycondensation product in which both A and B are alkali metals can be obtained by reacting an alkali metal alkylated product in an amount of at least 2 times the above molar amount, Further, the polycondensation product in which one or both of A and B are hydrogen atoms can be obtained by causing water or the like to act on the above-mentioned alkali metal adduct.

In this case, in the formula (2), the polycondensation product in which both A and B are hydrogen atoms is caused by reacting the reactive halogen-containing compound with the dialkali silole represented by the following formula (5). It can also be obtained by condensation using iron (III) acetylacetonate as a catalyst.

[0037]

[Chemical 20] (In the formula, R ^{1 to} R ⁴ and M have the same meanings as described above.
p represents an integer of 2 or more. )

The silole of the formula (5) corresponds to the above formula (II) and can be obtained by the method described in Japanese Patent Application No. 5-345214 (the method of the above (5)). Further, the reactive halogen-containing compound excludes excess alkali metal or alkali metal complex, and may be any one having such action, and triarylhalosilane such as triphenylsilyl chloride should be used. However, the amount used is preferably 2 to 3 mol per 1 mol of the silole of the formula (5). Further, the amount of iron (III) acetylacetonate used can be usually 0.5 to 2 mol per 1 mol of the silole of the formula (5).

The above reactive halogen-containing compound and formula (5)
The reaction with the silole is preferably carried out in a solvent such as tetrahydrofuran, and the reaction temperature is preferably 0 to 60 ° C. The reaction time is usually 10 to 60 minutes. Further, the subsequent reaction with iron (III) acetylacetonate can be carried out in the same solvent, the reaction temperature is preferably 0 to 60 ° C., and the reaction time is usually 30 minutes to 24 hours.

Further, the present invention provides a 2,5-hetero-reactive substituent-containing silole represented by the following formula (7). This silole can be obtained by reacting the silole of the above formula (1) with a compound represented by AX.

[0041]

[Chemical 21] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X is a halogen atom, and A is a monovalent hydrocarbon group. Indicates substituted sulfur, selenium, silicon, germane, tin or phosphorus.)

Here, R ^{1 to} R ⁴ and X are the same as above, and A is specifically R ⁵ R ⁶ R such as trimethylsilyl group, tributylsilyl group and phenyldimethylsilyl group.
Substituted silyl group represented by ⁷ Si, substituted germyl group represented by R ⁵ R ⁶ R ⁷ Ge such as triethyl germyl group, trimethylstannyl group, tributylstannyl group, R ⁵ R ^6, such as phenyl dimethyl stannyl group A substituted stannyl group represented by R ⁷ Sn, an ethyl selenenyl group, a butyl selenenyl group, a phenyl selenenyl group and the like, a substituted selenenyl group represented by R ⁵ Se, a R ⁵ R ⁶ such as a diphenylphosphino group
The substituted phosphino group shown by P is mentioned. In addition, R
⁵ , R ⁶ and R ⁷ are the same or different monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms or phenyl groups.

When the silole of the formula (1) is reacted with the compound of AX, the compound AX can be used in an amount of 1 to 3 mol per mol of the silole of the formula (1), and the reaction temperature is 0 to 60. ℃ is preferred, the reaction time is usually 10 to 60
Minutes.

The silole of the formula (7) can be obtained as a silole polycondensation product by using a palladium catalyst such as palladium metal or a palladium compound.

The silole or silole polycondensation product of the present invention can form a copolymer with another π-conjugated polymer known as a functional material or its raw material, and the silole polycondensation product of the present invention is unique. To show a simple π-electron system,
It is useful as a raw material for synthesizing optoelectronic functional materials. In particular, conductive organic materials with excellent processability, nonlinear optical materials,
It is suitable as a raw material for synthesizing an optical functional material such as a photoresponsive material.

[0046]

INDUSTRIAL APPLICABILITY The silole of the formula (1) of the present invention is useful as a raw material for synthesizing a silole condensation polymer, and the silole of the formula (2) is useful as an optical functional material. The manufacturing method of the present invention uses the formulas (1) and (2)
It is possible to reliably produce the silole and polycondensation product of silole.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following examples, Me is a methyl group, Et is an ethyl group,
Ph represents a phenyl group and ⁱ Pr represents an isopropyl group.

[Example 1] 2,5-dibromo-1,1-
Diethyl-3,4-diphenylsilole 427 mg
(0.95 mmol) was added with 10 ml of dried diethyl ether, cooled to −78 ° C., and 0.7 ml of 1.64 M n-butyllithium was added dropwise thereto. The temperature was gradually raised and the reaction was carried out at 0 ° C. for 3 hours to obtain the following formula (1a ′).

[0049]

[Chemical formula 22] The following reaction was performed on the reaction mixture (1a ′), and it was confirmed that the product was the formula (1a).

[0050]

[Chemical formula 23]

2-bromo-1,1-diethyl-3,4
-Synthesis of diphenylsilole The reaction mixture of the formula (1a ') was deactivated by adding 100 µl of water, about 1 g of sodium sulfate was added, dehydrated, and filtered through a filter paper.
The solvent was removed from the filtrate under reduced pressure. The residue was subjected to silica gel column chromatography (hexane, Rf = 0.
35) However, 2-bromo-1,1-diethyl-3,4
289 mg of diphenylsilole colorless liquid were obtained (yield 82%).

[0052]

[Chemical formula 24]

The physical property values are shown below. ¹ H NMR δ: 0.83 to 0.98 (m, 4H),
1.02 to 1.12 (m, 6H), 6.09 (s, 1
H), 6.92 to 7.14 (m, 7H), 7.16 to
7.22 (m, 3H).

Example 2 2-Bromo-1,1-diethyl-3,4-diphenyl-
Synthesis of 5-trimethylsilylsilole The same operation as in Example 1 was performed except that 450 mg (1 mmol) of 2-bromo-1,1-diethyl-3,4-diphenylsilole was used. Then, instead of the water of Example 1, 0.19 ml of trimethylchlorosilane (1.5
(mmol) was added to inactivate. Perform the same operation as in Example 1 to give 2-bromo-1,1-diethyl-3,4-
351 mg of a colorless liquid of diphenyl-5-trimethylsilylsilole was obtained (yield 79%).

[0055]

[Chemical 25]

The physical property values are shown below. ¹ H NMR δ: −0.16 (s, 9H), 0.86
~ 1.18 (m, 10H), 6.83-6.93 (m,
4H), 7.02 to 7.14 (m, 6H). Rf = 0.23 (hexane)

Example 3 2-Bromo-1,1-diethyl-3,4-diphenyl-
Synthesis of 5-tributylstannylsilole Instead of the trimethylchlorosilane of Example 2, tri (n
-Butyl) chlorostannane 0.42 ml (1.50 mm
was carried out in the same manner as above except that 640 mg (0.84 mmol) of a colorless liquid compound shown below was obtained (84% yield).

[0058]

[Chemical formula 26]

The physical property values are shown below. ¹ H NMR δ: 0.53 to 0.63 (m, 6H),
0.78-0.97 (m, 19H), 1.10-1.5
0 (m, 28H), 6.80 to 6.88 (m, 2H),
6.88-6.96 (m, 2H), 7.02-7.16
(M, 6H). Rf = 0.50 (hexane)

Example 4 5,5'-Dibromo-1,1,1 ', 1'-tetraethyl-3,3,3', 3'-tetraphenyl-2,2'-
Synthesis of Bisylol 186 mg (0.415 mmol) of 2,5-dibromo-1,1-diethyl-3,4-diphenylsilole was dissolved in 1 ml of diethyl ether, cooled to −78 ° C., and 290 μl of n-butyllithium ( 1.59 M hexane solution) (0.437 mmol) was added. The temperature of the reaction vessel was gradually raised and kept at -10 ° C for 3 hours for reaction. After completion of the reaction, butyl bromide and diethyl ether as a by-product were removed under reduced pressure at a temperature of 0 to 10 ° C, and the atmosphere was replaced with an argon atmosphere. Copper cyanide (CuC) while introducing argon
N) 18 mg (0.2 mmol) was added as a solid,
Mixed. The mixture was again cooled to −78 ° C., 1 ml of tetrahydrofuran was added in a sealed state, the mixture was heated with stirring, and the mixture was reacted at 0 ° C. for 2 minutes, whereupon a dark green homogeneous solution was obtained. Immediately cool to −78 ° C. and hold for 13 minutes, then 90 μl of tetramethylethylenediamine (0.6 m
mol) was added and kept for 35 minutes. Then, a solution of 336 mg (2 mmol) of p-dinitrobenzene dissolved in 2 ml of tetrahydrofuran was added and oxidized. The reaction solution turned into a yellowish brown suspension. The reaction was carried out at -78 ° C for 1 hour. Then, 2 ml of a mixed solution of an equal amount of (saturated aqueous solution of sodium hydrogen sulfite) / (methanol) was added,
Reduced. The reaction solution became a yellow suspension. 1 at room temperature
The mixture was acidified with 20 ml of an aqueous N hydrochloric acid solution, extracted with diethyl ether, and the organic layer was washed with a saturated calcium chloride solution. After dehydration over anhydrous sodium sulfate and filtration, the solvent was removed under reduced pressure. The residue is Florisil
Subjected to column chromatography (hexane, Rf =
0.22), 1 as a yellow crystal compound of the following structural formula
06 mg (yield 69%) was obtained.

[0061]

[Chemical 27]

The physical property values are shown below. Melting point: 157-159 ° C (decomposition) ¹ H NMR δ: -0.14 (m, 4H), 0.41
(M, 4H), 0.77 (t, J = 7.8Hz, 12
H), 6.87-6.95 (m, 4H), 6.96-
7.06 (m, 4H), 7.07 to 7.18 (m, 12
H). ¹³ C NMR δ: 2.43, 7.47, 124.7
1,126.81, 127.35, 127.85, 12
9.04, 130.81, 137.97, 139.4
6,141.40,156.39,157.89. Calcd; C = 65.21%, H = 5.47% (C 40 H 40 Si 2 Br 2) Found; C = 65.43%, H = 5.52%

[Example 5] 5,5 'synthesized in Example 2
-Dibromo-1,1,1 ', 1'-tetraethyl-3,
To a yellow solution prepared by dissolving 113 mg (0.154 mmol) of 3,3 ′, 3′-tetraphenyl-2,2′-bisylol in 4 ml of diethyl ether was added t- at −78 ° C.
BuLi (1.61M, 210 μl, 0.34 mmo
The pentane solution of l) was added. The solution immediately turned deep red and was stirred for 1 hour under similar temperature conditions. After the temperature was raised to 0 ° C using an ice water bath, the solvent was reduced under reduced pressure to 1 ° C at 1 ° C.
Removed for 0 minutes. The flask was purged with argon and the solid reaction mixture was charged with 6.9 mg of copper cyanide under a stream of argon.
(0.0077 mmol) was added. The reaction mixture
Cooled to 78 ° C. and introduced 3 ml of dry THF. Warm the resulting dark red suspension to -40 ° C and
The reaction mixture turned into a dark red solution upon stirring for a minute. 70 μl of TMEDA (0.4
6 mmol) was added to the reaction mixture. The reaction mixture
The mixture was stirred at 40 ° C to -20 ° C for another hour, and cooled to -78 ° C. 134 mg of p-nitrobenzene (0.8 mm
ol) in THF (3 ml) using a transfer tube (Transfer)
-Tube) to the solution. The resulting yellow-brown suspension was stirred under similar temperature conditions for 1 hour,
2 ml of saturated NaHSO ₃ / MeOH 1/1 mixed solution was introduced into the mixture using a syringe under −78 ° C. condition.
Return the obtained yellow-orange suspension to room temperature and
Diluted with Cl solution. Extracted with Et ₂ O,
The organic layer was washed with brine, dried over anhydrous Na ₂ SO ₄ and then concentrated under reduced pressure. Addition of 5 ml of 1,2-dichloroethane to the concentrate gave an orange precipitate. After filtration and washing with Et ₂ O, the precipitate was dissolved in about 3 ml of a mixed solution of hexane / CH ₂ Cl ₂ (= 1/1) and subjected to column chromatography using Florisil to give a compound of the formula 16 0.7 mg (yield 1
6%) as an orange solid.

The physical property values are shown below. Melting point: 287 to 289 ° C. (decomposition) ¹ H NMR δ: −1.20 to −0.34 (br
m, 8H), -0.05 to 0.25 (br m, 2
H), 0.25 to 0.70 (m, 24H), 0.82
1.10 (m, 6H), 6.60 to 7.55 (br
m, 40H). UV-vis (CHCl ₃ ) λ max nm (log
ε): 243 (4.75), 282 (4.62), 37
8 (sh, 3.97), 443 (4.21). FABMS: 1310 (M ⁺ ), 1312, 1314. Rf = 0.58 (hexane _{/ CH 2 Cl 2 = 2/} 1). Calcd; C = 73.14%, H = 6.14% (C 80 H 80 Br 2 Si 4) Found; C = 72.89%, H = 6.16%

[0065]

[Chemical 28]

[0066]

[Chemical 29]

A solution of triphenylsilyl chloride (590 mg, 2 mmol) in dry THF (4 ml) was added to a THF solution of 1,1-diisopropyl-2,5-dilithiosilole (1 mmol), and the mixture was stirred for 30 minutes. Iron (III) acetylacetonate (494 mg, 1.4 mmol) in THF (6
ml) solution was added at room temperature. The resulting yellow-orange suspension was stirred at room temperature for 12 hours and then filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (hexane Rf = 0.13) to obtain 77 mg of a crude product as a yellow solid. When this was recrystallized using a hexane / ethyl ether mixed solvent, 1,
1,1 ', 1'-tetraisopropyl-3,3', 4
30 mg of yellow crystals of 4'-tetraphenyl-2,2'-bisylol were obtained (yield 9%).

The physical property values are shown below. The ultraviolet absorption spectrum of this compound is shown in FIG. mp: 202 ° C. ¹ H NMR δ: 0.2 to 0.4 (m, 2H), 0.
84 (d, J = 7.4Hz, 6H), 0.90 (d, J
= 7.4 Hz, 6H), 5.95 (s, 2H), 6.8
7 to 6.96 (m, 4H), 7.02 to 7.14 (m,
6H). ¹³ C NMR δ: 11.49, 19.16, 20.0
3,126.17, 126.51, 127.21, 12
7.36, 127.82, 128.39, 130.7
4,140.24,142.30,145.58,15
3.11, 162.96. UV-vis: 242 nm (log ε = 4.51),
266 nm (sh., Log ε = 4.43), 398
nm (log ε = 3.71). MS: m / e 634 (M ⁺ , 100), 591 (4
1). Elemental analysis: calculated value; C = 83.22%, H = 7.94%
(C ₄₄ H ₅₀ Si ₂ ) measured value; C = 82.95%, H = 8.01%

[Brief description of drawings]

1 is an ultraviolet absorption spectrum of the compound of Example 6. FIG.

Claims (7)

[Claims] 1. A 2,5-reactive substituent-containing silole represented by the following formula (1): [Chemical 1] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X represents a halogen atom, and M represents an alkali metal atom. ) 2. A silole polycondensation product represented by the following formula (2). [Chemical 2] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group or aryl group, and A and B are the same or different from each other,
A hydrogen atom, a halogen atom or an alkali metal atom is shown.
n is an integer of 2 or more. ) 3. The following formula (3): (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group or aryl group, and X represents a halogen atom). The method for producing a 2,5-reactive substituent-containing silole according to claim 1, wherein the silole is reacted with an alkali metal alkyl compound. 4. The following formula (4): (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X represents a halogen atom, and M represents an alkali metal atom. m is an integer of 1 or more, and n> m.) The silole or silole polycondensation product represented by the formula) is polycondensed under oxidizing conditions in the presence of a monovalent copper compound. 2. The method for producing a polycondensation product of silole according to 2. 5. The following formula (5): (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, and M represents an alkali metal atom). A compound represented by the following formula (6), which comprises reacting an alkali silole with a reactive halogen-containing compound and then condensing it with iron (III) acetylacetonate as a catalyst. (In the formula, R ^{1 to} R ⁴ have the same meanings as described above. P is 2
It is an integer above the above. ) The method for producing a silole polycondensation product represented by: 6. A 2,5-hetero-reactive substituent-containing silole represented by the following formula (7). [Chemical 7] (In the formula, R ^{1 to} R ⁴ represent the same or different substituted or unsubstituted C 1-10 alkyl group, cycloalkyl group or aryl group, X is a halogen atom, and A is a monovalent hydrocarbon group. Indicates substituted sulfur, selenium, silicon, germane, tin or phosphorus.) 7. The silole represented by the formula (1) according to claim 1 has AX (wherein A represents sulfur, selenium, silicon, germane, tin or phosphorus substituted with a monovalent hydrocarbon group. X
Represents a halogen atom. 7. The method for producing a 2,5-hetero-reactive substituent-containing silole according to claim 6, which comprises reacting a compound represented by the formula (1).