JPH05310752A - Bis@(3754/24)1,2-bissilylethylene)compound, silicon-containing stepladder polymer, its production and materials using the same - Google Patents

Abstract

PURPOSE:To obtain a bis(1,2-bissilylethylene) compound which is useful as a synthetic intermediate for medicines, agrochemicals and fine chemicals by allowing 1,2-bis(dimethylsilyl)benzene to react with bis(acetylene) in the presence of a platinum compound. CONSTITUTION:The reaction of 1,2-bis(dimethylsilyl)benzene with bis(acetylene) of the formula: R<1>-CidenticalC-A-CidenticalC-R<1> (R<1> is monovalent and A is divalent group) is carried out in the presence of a platinum compound such as tetrakis(diphenylphosphine)platinum in the absence of solvent at 0 to 150 deg.C to give a compound of the formula (Me is methyl). The molar ratio of the benzene to the acetylene is 1/50 to 10/1 and the amount of the catalyst used is 0.00001 to 0.5 mole per mole of the benzene. The dehydrogenative reaction between 1,2,4,5-tetrakis(dimethylsilyl)benzene and bis(acetylene) gives polycarbosilanes which are useful as heat-resistant materials, electrically conductive materials, or preceramics.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the production of bis (1,2-bissilylethylene) s by reacting 1,2-bis (dimethylsilyl) benzene with bis (acetylene) s in a dehydrogenative manner. The present invention relates to a production method and novel bis (1,2-bissilylethylene) s obtained thereby. The present invention also provides a method for producing bis (1,2-bissilylethylene) s by reacting 1,2,4,5-tetrakis (dimethylsilyl) benzene with acetylenes in a dehydrogenative manner, and The present invention relates to novel bis (1,2-bissilylethylene) s obtained by Furthermore, the present invention provides a method for producing polycarbosilanes having a step ladder structure by reacting 1,2,4,5-tetrakis (dimethylsilyl) benzene with bis (acetylene) s in a dehydrogenative manner, The present invention relates to a novel polycarbosilane obtained by the above, a heat resistant material containing the same, a preceramic (ceramic precursor), and a conductive material.

The bis (1,
2-Bissilylethylene) has a vinylsilane structure and is useful as a synthetic intermediate for fine chemicals such as medical and agricultural chemicals. In addition, the polycarbosilanes produced by the method of the present invention have a step ladder structure containing a rigid skeleton and thus exhibit high heat resistance, and are expected to be used as engineering plastics. Among the polycarbosilanes produced by the method of the present invention, those having a high residual rate during thermal decomposition at high temperatures are expected to be used as preceramics. In addition, this polycarbosilane has a bond between an organic π electron system and silicon.
It is a one-dimensional polymer related to conductive polycarbosilanes and is expected to be used as a conductive material.

[0003]

2. Description of the Related Art Conventionally, many attempts have been made to use polycarbosilanes as preceramics. Further, in recent years, polycarbosilanes have been found to have heat resistance and conductivity, and attempts have been made to use such compounds as heat resistance and conductive materials (for example, Chem. Mater., 2 , 351 (199
0), Macromolecules, 23 , 4485.
(1990)). However, such polycarbosilanes are limited to those having a linear main chain and a one-dimensional structure, and in a conductive and heat resistant material containing such polycarbosilanes, However, there are still many points left to be improved in the characteristics and the manufacturing method. on the other hand,
By introducing a ladder structure into such polycarbosilanes, stability such as heat resistance of the polymer is expected to be improved, and conductivity is expected to be improved by spreading the conjugated chain due to the two-dimensional structure. .. However, up to now, polycarbosilanes having a regular step ladder structure and a method for producing the same have not been known.

[0004]

DISCLOSURE OF THE INVENTION According to the present invention, 1,2-bis (dimethylsilyl) benzene and bis (acetylene) s, which are easily available raw materials, are dehydrogenatively reacted under mild conditions. It is an object of the present invention to provide a method for producing bis (1,2-bissilylethylene) s, and a novel bis (1,2-bissilylethylene) s obtained thereby. In addition, the present invention provides a bis (1,2,4) compound obtained by reacting easily available raw materials 1,2,4,5-tetrakis (dimethylsilyl) benzene with acetylenes in a dehydrogenative manner under mild conditions. -Bissilylethylene) production method and a novel bis (1,2-bissilylethylene) obtained thereby. Furthermore, the present invention provides a step of dehydrogenatively reacting easily available raw materials 1,2,4,5-tetrakis (dimethylsilyl) benzene with bis (acetylene) s under mild conditions. To provide a method for producing a polycarbosilane having a ladder structure, a novel polycarbosilane obtained thereby, a heat-resistant material containing the same, a preceramic containing the same, and a conductive material containing the same Is its purpose.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that 1,2-bis (dimethylsilyl) benzene and specific bis (acetylene) s are platinum compounds. Was found to react rapidly under mild conditions in the presence of to give bis (1,2-bissilylethylene) derivatives. Further, 1,2,4,5-tetrakis (dimethylsilyl) benzene and specific acetylenes react rapidly in the presence of a platinum compound under mild conditions to give a bis (1,2-bissilylethylene) derivative. I found the fact of giving. Furthermore, 1, 2, 4, 5-
It has been found that tetrakis (dimethylsilyl) benzene and specific bis (acetylene) s react rapidly in the presence of platinum compounds under mild conditions to give polycarbosilanes. The present invention has been completed based on these facts.

That is, the present invention includes (1) (a) 1,2-bis (dimethylsilyl) benzene and (b) general formula (I) R ¹ -C≡CAC ≡CR ¹ (I) (wherein R ¹ And A are monovalent and divalent groups, respectively.) The bis (acetylene) s represented by the formula (c) are reacted in the presence of (c) a platinum compound.

[Chemical 9] (In the formula, R ¹ and A have the same meanings as described above.) A method for producing bis (1,2-bissilylethylene) s (referred to as a first invention). (2) (a) 1,2,4,5-tetrakis (dimethylsilyl)
Benzene and (b) an acetylene compound represented by the general formula (III) R ² -C≡CR ³ (III) (wherein R ² and R ³ are monovalent groups) (c) a platinum compound Of the general formula (IV) characterized by reacting in the presence of

[Chemical 10] (In the formula, R ² and R ³ have the same meanings as described above.) Or the general formula (V)

[Chemical 11] (In the formula, R ² and R ³ have the same meanings as described above.) A method for producing bis (1,2-bissilylethylene) s (referred to as a second invention). (3) (a) 1,2,4,5-tetrakis (dimethylsilyl)
Benzene and (b) bis (acetylene) represented by the general formula (I) R ¹ -C≡CAC ≡CR ¹ (I) (wherein R ¹ and A are monovalent and divalent groups, respectively). With a general formula (VI), characterized in that (c) is reacted in the presence of a platinum compound.

[Chemical formula 12] (Wherein R ¹ and A have the same meanings as described above,
m and n are each 0 or a positive integer, and m + n
≧ 1. ) A method for producing polycarbosilanes represented by () (referred to as a third invention). It is about. The present invention also relates to the compound represented by the general formula (II), (IV), (V) or (VI). Further, the present invention relates to a heat resistant material, a preceramic or a conductive material containing the polycarbosilane represented by the general formula (VI). In the production method of the present invention (first invention to third invention) described above, the reaction is considered to proceed according to the following equation.

[Chemical 13] (Wherein R ¹ and A have the same meanings as described above), or

[0007]

[Chemical 14] (In the formula, R ² and R ³ have the same meanings as described above.), Or

[0008]

[Chemical 15] (In the formulae, R ¹ , A, m and n have the same meanings as described above.).

The bis (acetylene) s used in the first and third inventions of the present invention are represented by the general formula (I) R ¹ -C≡CAC≡CR ¹ (I). Where R ¹ and A are monovalent and 2 respectively
A valent group, examples of R ¹ include an alkyl group, an aryl group, an aralkyl group, a thienyl group, a pyridyl group, and a furyl group, and examples of A include an alkylene group, an arylene group, an aralkylene group, and oligosilanylene. _{group, -R 2 Si-O-SiR} 2 -, -C 6 H 4 -OC 6 H 4 -, 1,1'- ferrocenylene group, 2,5-furylene group, 3,4-thienylene group, 2,5 Examples include -thienylene group and 2,6-pyridylene group. Examples of the bis (acetylene) s having these substituents and represented by the general formula (I) include 1,4-
Bis (2-phenylethynyl) benzene, 1,4-bis (1-octynyl) benzene, 1,1′-bis (2-phenylethynyl) ferrocene, bis {4- (2-phenylethynyl) phenyl} ether , 2,2-bis {4-
(2-phenylethynyl) phenyl} propane, bis (2-phenylethynyl) dimethylsilane, 1,3-bis (2-phenylethynyl) -1,1,3,3-tetramethylsiloxane, 1,2-bis { 4- (2-phenylethynyl) phenyl} -1,2-dimethyldisilane,
1,2-bis (2-phenylethynyl) -1,2-diisopropyl-1,2-dimethyldisilane, 2,5-bis (2-phenylethynyl) thiophene, 1,3-bis (2-phenylethynyl) benzene , 2,5-bis (2
-Phenylethynyl) furan, 2,6-bis (2-phenylethynyl) pyridine, 4,4'-bis (2-phenylethynyl) benzophenone, 2,7-bis (2-phenylethynyl) -9-fluorenone, 1 , 4-bis {2
-(2-thienyl) ethynyl} benzene, 1,4-bis (3-phenyl-1,1-dimethyl-2-propynyl)
Benzene, 1,6-bis (2-naphthylethynyl)-
1,1,2,2,3,3,4,4,5,5,6,6-dodecamethylhexasilane, 1,4-bis {2- (4-pyridyl) ethynyl} benzene, 1,4- Screw {2- (2
-Furyl) ethynyl} benzene and the like.

The acetylenes used in the second invention of the present invention are represented by the general formula (III) R ² -C≡CR ³ (III). In the formula, R ² and R ³ are monovalent groups, and examples thereof include an alkyl group, an aryl group, an aralkyl group,
Examples thereof include an alkoxy group, an alkoxymethyl group, an acyloxymethyl group, an alkoxycarbonyl group, a thienyl group, a pyridyl group, a furyl group and a ferrocenyl group. Examples of the acetylenes having these substituents and represented by the general formula (III) include 3-hexyne, 1-phenyl-1-propyne, diphenylacetylene and bis (2-thienyl).
Acetylene, bis (4-pyridyl) acetylene, bis (2-furyl) acetylene, 1-ferrocenyl-2-phenylacetylene, methyl (3-phenyl-2-propyl) ether, 1,4-diacetoxy-2-butyne , Phenyl (cyclohexyl) acetylene, phenylethynyl (ethyl) ether, methyl phenylpropionate, and the like.

In the production methods of the first to third inventions of the present invention, the ratio of the reaction raw materials 1,2-bis (dimethylsilyl) benzene and bis (acetylene) s is 1,2,4,5-
The ratio of tetrakis (dimethylsilyl) benzene to acetylenes and the ratio of 1,2,4,5-tetrakis (dimethylsilyl) benzene to bis (acetylene) s are usually 1,2-bis (dimethylsilyl) benzene to bis. (Acetylene) s, 1,2,4,5-tetrakis (dimethylsilyl) benzene and acetylenes, and 1,2,4,5
-The molar ratio of tetrakis (dimethylsilyl) benzene and bis (acetylene) s is 1:50 to 100: respectively.
1, 1: 100 to 200: 1, and 1: 100 to 10
It is carried out in the range of 0: 1, preferably 2: 5 to 5 respectively.
The ranges are 5: 1, 1: 5 to 10: 1, and 1: 5 to 5: 1.

As the platinum compound used as a catalyst in the production method of the present invention, various conventionally known compounds can be used, but it is kinetic to use a compound at least partially soluble in the reaction system. Is preferred. As these compounds, a complex containing an organic ligand is particularly preferably used. Examples of the ligand used in the present invention include:
Examples thereof include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β-diketonato ligand, conjugated ketone, amine and carbon monoxide.
Specific examples of these include trimethylphosphine,
Chain phosphines such as tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p-tolyl) phosphine, tri (p-anisyl) phosphine, diphenylmethylphosphine and phenyldimethylphosphine, p-methylphosphorene, p Cyclic phosphines such as -methylphosphole, 9-methyl-9-phosphabicyclo [4.2.1] nonane,
1,2-bis (dimethylphosphino) ethane, 1,3-
Bis (dimethylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis ( Diphenylphosphino) butane, 1,1'-bis (dimethylphosphino)
Ferrocene, 1,1'-bis (diphenylphosphino)
Ferrocene, α, α'-bis (dimethylphosphino)-
Bisphosphines such as o-xylene and 1,2-bis (dimethylphosphino) benzene, phosphonites such as dimethyl methylphosphonite and dimethyl phenylphosphonite, phosphinites such as methyl dimethylphosphinite and phenyldiphenylphosphinite, and triethyl. Phosphite, triphenylphosphite, 1-
Phosphite such as phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane, ethylene, propene, cyclooctene, maleic anhydride, 1,
5-hexadiene, 1,5-cyclooctadiene, 1,
3-cyclopentadiene, 2,5-norbornadiene,
Olefins such as 1,3,5,7-cyclooctatetraene and dienes, β-diketonato ligands such as acetylacetonato, conjugated ketones such as dibenzylideneacetone, amines such as ethylenediamine and 2,2′-bipyridyl, And carbon monoxide. Therefore, specific examples of the platinum compound used in this reaction include (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum, and chlorohydridobis (tributylphosphine). ) Platinum, dichloro (tetramethylethylenediamine) platinum, dibromobis (triethylphosphite) platinum, bis (η-1,5-cyclooctadiene) platinum, dichloro (η-1,5-cyclooctadiene) platinum, dicarbonylbis (Tributylphosphine)
Examples thereof include platinum, carbonatobis (tricyclohexylphosphine) platinum, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum, and bis (dibenzylideneacetone) platinum, but are not limited thereto.

In addition, these platinum compounds are not used alone but in 2
It may be carried out in the presence of one or more species, and it is also included in an advantageous embodiment of the present invention that the same or different organic ligands from those contained in the platinum compound are added together with the platinum compound. ..

The amount of these platinum compounds used may be a so-called catalytic amount, such as 1,2-bis (dimethylsilyl) benzene or 1,2,4,5-tetrakis (dimethylsilyl).
It is used in the range of 0.00001 to 0.5 mol with respect to 1 mol of benzene. The ligand is used in an amount of 1 to 20 mol, preferably 1 to 4 mol, per 1 mol of platinum atom.

In the reaction of the present invention, a mixture of 1,2-bis (dimethylsilyl) benzene and bis (acetylene) s to be subjected to the reaction, or 1,1, without using a solvent.
Mixture of 2,4,5-tetrakis (dimethylsilyl) benzene and acetylenes, or 1,2,4,5-tetrakis (dimethylsilyl) benzene and bis (acetylene)
It is easily carried out by using a mixture of classes. However, the use of a solvent does not hinder the occurrence of this reaction, and it is carried out in a solvent if necessary. These solvents are selected such that the reactivity and boiling point of 1,2-bis (dimethylsilyl) benzene or 1,2,4,5-tetrakis (dimethylsilyl) benzene to be reacted, and bis (acetylene) s or acetylenes. In consideration of the boiling point and the like, it is preferable to select from commonly used solvents, for example, hydrocarbon-based or ether-based solvents.

In each of the production methods of the present invention, the reaction proceeds even at 0 ° C. or lower, but in order to reach a preferable rate, it is 25
It is also possible to heat up to a temperature of 0 ° C. Although it depends on the structure of the raw material, a generally preferable temperature range is 0 to 150.
℃.

Separation of the product after the reaction is easily carried out by a commonly used means of organic chemistry such as ordinary distillation, recrystallization, chromatography, extraction with a solvent, or reprecipitation.

The molecular weight of the polycarbosilane represented by the general formula (VI) of the present invention is usually 500 to 10,000.
50,000, preferably 1000 to 1,000,000
However, the present invention is not limited to this.

According to the production method of the third invention, the temperature at which the weight loss is 5% is 3 in thermogravimetric analysis in a helium atmosphere.
It is possible to produce polycarbosilanes having a temperature of 00 ° C. or higher, or polycarbosilanes having a residual rate of 20% or higher when heated to 900 ° C. Such polycarbosilanes themselves can be used as heat resistant materials or preceramics.

The polycarbosilanes usually have an electric conductivity of 10 ^-8 S / cm or less. However, by conducting doping on these polycarbosilanes, the conductivity is 10 ^-7 ~
It is in the range of 10 ³ S / cm. Therefore, this polycarbosilane can be used as a conductive material.

As the dopant in this doping, various known dopants can be used. For example, I ₂ , SbF ₅ , AsF ₅ , S
O ₃ , FeCl _{3 and the} like can be mentioned. These dopants can be used alone or in combination of two or more.

The method of doping the polycarbosilanes is not particularly limited. For example, after forming a thin film of polycarbosilanes obtained by the present invention, a method of exposing this to a vapor of a dopant and a method of immersing it in a liquid of a dopant, or a method of previously depositing a polycarbosilane and a dopant. Various methods can be used, such as a method of forming a doped film using a solution containing the compound, or a method of forming a doped pellet using a mixture of polycarbosilanes and dopant. ..

[0023]

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

Example 1 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
Benzene solution containing 0.25 mmol of 1,2-bis (dimethylsilyl) benzene and 0.125 mmol of 1,4-bis (1-octynyl) benzene
1 was reacted at 30 ° C. for 12 hours. After concentration, it was purified by preparative thin layer chromatography (silica gel, hexane-benzene = 3: 1) to give 1,4-bis {2-
(5-Benzo-1,1,4,4-tetramethyl-3-hexyl-1,4-disilacyclohexa-2,5-dienyl)} benzene was obtained with a yield of 78%. This compound is
It could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0025]

[Chemical 16] Melting point: 130-132 ° C. ¹ H-NMR (CDCl ₃ ): δ 7.65-7.5
5 (m, 4H), 7.4-7.35 (m, 4H), 6.
90 (s, 4H), 2.18 (t, J = 7Hz, 4
H), 1.4-1.1 (br, 16H), 0.83
(T, J = 7Hz, 6H), 0.41 (s, 12H),
0.18 (s, 12H) IR (KBr): 1258, 1241 cm ^-1 Elemental analysis C ₄₂ H ₆₂ Si ₄ (theoretical value) C 74.26%; H 9.20%: (actual value) C 73.94 %; H 9.59%

Example 2 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
4 ml of a benzene solution containing 0.125 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of diphenylacetylene,
When the reaction was carried out at 30 ° C. for 8 hours, it was confirmed by gas chromatography analysis that the starting compound had completely disappeared, and the yield was 91%, and the white sparingly soluble 1,4,5,5
8-tetrahydro-1,4,5,8-tetrasila-1,
1,4,4,5,5,8,8-octamethyl-2,3
6,7-Tetraphenylanthracene was obtained. This compound could be crystallized from a large amount of benzene. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0027]

[Chemical 17] Melting point: 310 ° C. (DSC) ¹ H-NMR (C ₆ D ₆ ): δ 8.1 (s, 2
H), 7.1-6.8 (m, 20H), 0.5 (s, 1
2H), 0.4 (s, 12H) IR (KBr): 1259 cm ^-1 Elemental analysis C ₄₂ H ₄₆ Si ₄ (theoretical value) C 76.07%; H 6.99%: (actual value) C 76. 24%; H 7.04%

Example 3 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
4 ml of a benzene solution containing 0.25 mmol of 1,2-bis (dimethylsilyl) benzene and 0.125 mmol of 1,1′-bis (2-phenylethynyl) ferrocene at 30 ° C. for 18 hours. Allowed to react. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 3: 1) gave 1,1 ′.
-Bis {2- (5-benzo-1,1,4,4-tetramethyl-3-phenyl-1,4-disilacyclohexa-
2,5-dienyl)} ferrocene was obtained with a yield of 83%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0029]

[Chemical 18] Melting point: 229-230.5 ° C ¹ H-NMR (CDCl ₃ ): δ 7.7-7.15
(M, 14H), 7.0-6.81 (m, 4H), 3.
89 (br s, 4H), 3.70 (br s, 4)
H), 0.5 (s, 12H), 0.12 (s, 12H) IR (KBr): 1245 cm ^-1 Elemental analysis C ₄₆ H ₅₀ Si ₄ Fe (theoretical value) C 71.65%; H 6. 54% (actual value) C 71.99%; H 6.89%

Example 4 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
6 ml of a benzene solution containing 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of 1,4-bis (2-phenylethynyl) benzene was added to 30 ° C. After reacting for 18 hours, an insoluble white polymer, poly (1,4,4)
5,8-Tetrahydro-1,4,5,8-tetrasila-
1,1,4,4,5,5,8,8-octamethyl-3,
7-diphenylanthracene-2,6-diyl-1,4
-Phenylene) poly (1,4,5,8-tetrahydro-
1,4,5,8-Tetrasila-1,1,4,4,5,5
5,8,8-octamethyl-3,6-diphenylanthracene-2,7-diyl-1,4-phenylene) is 91
% Yield. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0031]

[Chemical 19] Melting point: 280 ° C. or higher IR (KBr): 1244 cm ⁻¹ Elemental analysis (C ₃₆ H ₄₀ Si ₄ ) _n (theoretical value) C 73.91%; H 6.89% (actual value) C 72.68%; H 7.11% Thermogravimetric analysis (heated to 900 ° C at a heating rate of 10 ° C / min in a helium atmosphere) 496 ° C residual rate 95% 520 ° C residual rate 90% 900 ° C residual rate 62%

Example 5 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
6 ml of a benzene solution containing 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of 1,4-bis (1-octynyl) benzene at 60 ° C. After reacting for 20 hours, a sparingly soluble yellow-white polymer, poly (1,4,5,8-)
Tetrahydro-1,4,5,8-tetrasila-1,1,
4,4,5,5,8,8-Octamethyl-3,7-dihexylanthracene-2,6-diyl-1,4-phenylene) poly (1,4,5,8-tetrahydro-1,4
5,8-Tetrasila-1,1,4,4,5,5,8,8
-Octamethyl-3,6-dihexylanthracene-
2,7-diyl-1,4-phenylene) was obtained. This is a benzene soluble part (yield 25%) and an insoluble part (yield 50%
%). This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0033]

[Chemical 20] Benzene soluble part Melting point: 300 ° C or higher Weight average molecular weight (standard polystyrene standard, 135 ° C):
4500 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
1.5 ¹ H-NMR (CDCl ₃ ): δ 7.8-7.7
(M, 2H), 6.8 (s, 4H), 2.2-2.0
(Br s, 4H), 1.3-1.1 (br s, 16
H), 0.7 (br s, 6H), 0.37 (s, 6
H), 0.35 (s, 6H), 0.15 (s, 6H),
0.12 (s, 6H) IR (KBr): 1241 cm ⁻¹ Benzene insoluble part Melting point: 300 ° C. or higher Weight average molecular weight (standard polystyrene standard, 135 ° C.):
11100 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
1.9 IR (KBr): 1241 cm ⁻¹ Elemental analysis (C ₃₆ H ₅₆ Si ₄ ) _n (theoretical value) C 71.92%; H 9.39% (measured value) C 71.60%; H 9. 62% Thermogravimetric analysis (in a helium atmosphere, heated to 900 ° C at a heating rate of 10 ° C / min) 424 ° C residual rate 95% 440 ° C residual rate 90% 900 ° C residual rate 24%

Example 6 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
6 ml of a benzene solution containing 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of 1,1′-bis (2-phenylethynyl) ferrocene was added at 30 ° C. After reacting for 18 hours, the soluble red-brown polymer, poly (1,
4,5,8-Tetrahydro-1,4,5,8-tetrasila-1,1,4,4,5,5,8,8-octamethyl-
3,7-Diphenylanthracene-2,6-diyl-
1,1′-ferrocenylene) poly (1,4,5,8-tetrahydro-1,4,5,8-tetrasila-1,1,
4,4,5,5,8,8-octamethyl-3,6-diphenylanthracene-2,7-diyl-1,1'-ferrocenylene) was obtained in 94% yield. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0035]

[Chemical 21] Melting point: 300 ° C or higher Weight average molecular weight (standard polystyrene standard, 135 ° C):
22600 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
2.9 ¹ H-NMR (CDCl ₃ ): δ 7.8-7.7
(M, 2H), 7.25 (br s, 6H), 6.9
(Br s, 4H), 3.8 (s, 4H), 3.7
(S, 4H), 0.57 (s, 6H), 0.52 (s,
6H), 0.12 (s, 6H), 0.07 (s, 6H) IR (KBr): 1246 cm ^-1 elemental analysis (C ₄₀ H ₄₄ Si ₄ Fe) _n (theoretical value) C 69.33%; H 6.40% (actual value) C 68.62%; H 6.66% Thermogravimetric analysis (heated to 900 ° C. at a temperature rising rate of 10 ° C./min in a helium atmosphere); 454 ° C. residual rate 95% 472 ℃ 90% residual rate 900 ℃ 49% residual rate

Example 7 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
4 ml of a benzene solution containing 0.25 mmol of 1,2-bis (dimethylsilyl) benzene and 0.125 mmol of 2,6-bis (2-phenylethynyl) pyridine was reacted at 30 ° C. for 18 hours. I went. After concentration,
Preparative thin layer chromatography (silica gel, hexane-
When purified with benzene = 2: 1), 2,6-bis {2- (5-benzo-1,1,4,4-tetramethyl-
3-phenyl-1,4-disilacyclohexa-2,5-
Dienyl)} pyridine was obtained with a yield of 76%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0037]

[Chemical formula 22] ^{Mp: 230-232 ℃ 1 H-NMR (} CDCl 3): δ 7.67-7.6
2 (m, 4H), 7.47-7.39 (m, 5H),
7.15-7.00 (m, 6H), 6.87-6.79
(M, 4H), 6.21 (d, J = 7.7Hz, 2
H), 0.34 (s, 12H), 0.31 (s, 12
H) IR (KBr): 1253, 1235 cm ^-1 Elemental analysis C ₄₁ H ₄₅ NSi ₄ (theoretical value) C 74.14%; H 6.83%; N
2.11%: (Actual value) C 73.91%; H 6.82%; N
2.08%

Example 8 The reaction was carried out in the same manner as in Example 5 except that the reaction conditions were 30 ° C. and 18 hours, and a yellow-white polymer and poly {2,7- were used.
(1,4,5,8-Tetrahydro-1,4,5,8-tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,7-dihexyl-2,6-anthracenylene )} (1,4-phenylene) {2,7- (1,4)
5,8-Tetrahydro-1,4,5,8-tetrasila-
1,1,4,4,5,5,8,8-octamethyl-2,
6-dihexyl-3,7-anthracenylene)} (1,
4-phenylene) was obtained. This was separated into a benzene-soluble part (yield 72%) and an insoluble part (yield 25%). The physical properties were as follows. Benzene soluble part Melting point: 300 ° C or higher Weight average molecular weight (standard polystyrene standard, 135 ° C):
12000 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
2.1 Benzene-insoluble part Melting point: 300 ° C or higher Weight average molecular weight (standard polystyrene standard, 135 ° C):
21000 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
2.8

Example 9 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
4 ml of a benzene solution containing 0.25 mmol of 1,2-bis (dimethylsilyl) benzene and 0.125 mmol of 2,5-bis (2-phenylethynyl) thiophene was reacted at 30 ° C. for 18 hours. I went. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 10: 1) gave 2,5.
-Bis {2- (5-benzo-1,1,4,4-tetramethyl-3-phenyl-1,4-disilacyclohexa-
2,5-dienyl)} thiophene was obtained with a yield of 78%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0040]

[Chemical formula 23] Melting point: 158-160 ° C ¹ H-NMR (CDCl ₃ ): δ 7.61-7.5
4 (m, 4H), 7.42-7.35 (m, 4H),
7.22-7.00 (m, 6H), 6.86-6.80
(M, 4H), 6.15 (s, 2H), 0.24 (s,
12H), 0.18 (s, 12H) IR (KBr): 1247 cm ⁻¹ Elemental analysis C ₄₀ H ₄₄ SSi ₄ (theoretical value) C 71.79%; H 6.62%; S
4.79%: (actual value) C 71.81%; H 6.61%; S
4.76%

Example 10 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 m.
And 0.25 mmol of 1,2-bis (dimethylsilyl) benzene and 0.125 mmol of 1,1,3,3-tetramethyl-1,3-bis (1-propynyl) -disiloxane. 4 ml of benzene solution was reacted at 50 ° C. for 18 hours. After concentration, preparative thin-layer chromatography (silica gel, hexane-benzene = 4: 1)
, 1,1,3,3-tetramethyl-
The yield of 1,3-bis {2- (5-benzo-1,1,4,4-tetramethyl-3-methyl-1,4-disilacyclohexa-2,5-dienyl)} disiloxane was 75. Obtained in%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0042]

[Chemical formula 24] Melting point: 76 ° C. ¹ H-NMR (CDCl ₃ ): δ 7.55-7.4
5 (m, 4H), 7.4 0-7.30 (m, 4H), 2.23 (s, 6H),
0.35 (s, 24H), 0.28 (s, 12H) IR (KBr): 1254 cm ^-1 Elemental analysis C ₃₀ H ₅₀ OSi ₆ (theoretical value) C 60.53%; H 8.46%: ( Measured value) C 60.66%; H 8.50%

Example 11 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
6 ml of a benzene solution containing 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of 2,5-bis (2-phenylethynyl) thiophene at 30 ° C. After reacting for 18 hours, the insoluble yellow polymer, poly {2,5-
Thiophenediyl- (1,4,5,8-tetrahydro-
1,4,5,8-Tetrasila-1,1,4,4,5,5
5,8,8-Octamethyl-3,7-diphenylanthracene-2,6-diyl)} poly {2,5-thiophenediyl- (1,4,5,8-tetrahydro-1,4
5,8-Tetrasila-1,1,4,4,5,5,8,8
-Octamethyl-3,6-diphenylanthracene-
2,7-diyl)} was obtained in 85% yield. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0044]

[Chemical 25] Melting point: 300 ° C or higher Weight average molecular weight (standard polystyrene standard, 135 ° C):
6100 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
1.8 ¹ H-NMR (CDCl ₃ ): δ 7.85-7.7
5 (m, 2H), 7.35-7.05 (m, 6H),
6.95-6.8 (brs, 4H), 6.2-6.1
(Br s, 2H), 0.27 (s, 12H), 0.2
0 (s, 12H) IR (KBr): 1246 cm ^-1 Elemental analysis (C ₃₄ H ₃₈ SSi ₄ ) _n (theoretical value) C 69.08%; H 6.48%; S
5.42%: (actual value) C 68.71%; H 6.48%; S
5.13% Thermogravimetric analysis (in a helium atmosphere, heated to 900 ° C at a heating rate of 10 ° C / min) 426 ° C residual rate 95% 900 ° C residual rate 49%

Example 12 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
6 ml of a benzene solution containing 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 0.25 mmol of 2,6-bis (2-phenylethynyl) pyridine was added to 30 ° C. After reacting for 18 hours, the soluble pale yellow polymer, poly {2,6-
Pyridinediyl- (1,4,5,8-tetrahydro-
1,4,5,8-Tetrasila-1,1,4,4,5,5
5,8,8-Octamethyl-3,7-diphenylanthracene-2,6-diyl)} poly {2,6-pyridinediyl- (1,4,5,8-tetrahydro-1,4,5,5
8-Tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,6-diphenylanthracene-2,7
-Diyl)} was obtained in 71% yield. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0046]

[Chemical formula 26] Melting point: 230-235 ° C (softening point) Weight average molecular weight (standard polystyrene standard, 135 ° C):
3500 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
1.4 ¹ H-NMR (CDCl ₃ ): δ 7.84-7.7
4 (m, 2H), 7.2-6.9 (m, 7H), 6.7
8-6.74 (m, 4H), 6.13 (d, J = 7.7)
Hz, 2H), 0.32 (s, 6H), 0.30 (s,
6H), 0.28 (s, 12H) IR (KBr): 1239 cm ^-1 Elemental analysis (C ₃₅ H ₃₉ NSi ₄ ) _n (theoretical value) C 71.73%; H 6.71%; N
2.39%: (actual value) C 70.83%; H 6.73%; N
2.33% Thermogravimetric analysis (in a helium atmosphere, heated to 900 ° C at a heating rate of 10 ° C / min) 470 ° C residual rate 95% 900 ° C residual rate 70%

Example 13 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.010 m.
And 0.25 mmol of 1,2,4,5-tetrakis (dimethylsilyl) benzene and 1,1,3,3
6 ml of a benzene solution containing 0.25 mmol of tetramethyl-1,3-bis (1-propynyl) -disiloxane
Was reacted at 50 ° C. for 18 hours. As a result, soluble pale yellow polymer, poly {(1,4,5,8-tetrahydro-1,4,5,8-tetrasila-1,1,4, 4,
5,5,8,8-Octamethyl-3,7-dimethylanthracene-2,6-diyl) 1,1,3,3-tetramethyl-1,3-disiloxanediyl} poly {(1,4,
5,8-Tetrahydro-1,4,5,8-tetrasila-
1,1,4,4,5,5,8,8-octamethyl-3,
6-dimethylanthracene-2,7-diyl) 1,1,
3,3-Tetramethyl-1,3-disiloxanediyl}
Was obtained in 70% yield. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0048]

[Chemical 27] Melting point: 120-125 ° C (softening point) Weight average molecular weight (standard polystyrene standard, 135 ° C):
5410 Molecular weight distribution index (weight average molecular weight / number average molecular weight):
1.6 ¹ H-NMR (CDCl ₃ ): δ 7.71-7.6
2 (m, 2H), 2.23 (s, 6H), 0.38
(S, 12H), 0.35 (s, 12H), 0.30
(S, 12H) IR (KBr): 1252 cm ⁻¹ Elemental analysis (C ₂₄ H ₄₄ OSi ₆ ) _n (theoretical value) C 55.74%; H 8.58%: (actual value) C 55.02%; H 8.56% Thermogravimetric analysis (in a helium atmosphere, heated to 900 ° C at a heating rate of 10 ° C / min) 425 ° C residual rate 95% 900 ° C residual rate 21%

Example 14 Poly (1,4,5,8-tetrahydro-1,4,5,8-tetrasila-1,1,4,4, obtained in Example 4
5,5,8,8-Octamethyl-3,7-diphenylanthracene-2,6-diyl-1,4-phenylene) poly (1,4,5,8-tetrahydro-1,4,5,8-
Tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,6-diphenylanthracene-2,7-diyl-1,4-phenylene) 0.015 mmol (monomer unit), 1 ml of nitromethane was added and stirred for 30 minutes, but the polymer did not dissolve at all. To this mixture was added 0.2 ml of a nitromethane solution containing anhydrous FeCl ₃ (0.03 mmol) at room temperature, and the polymer was doped. Immediately, the color of the polymer changed from white to brown and dissolved. did. After further stirring at room temperature for 30 minutes, the mixture was concentrated under reduced pressure. The obtained brown powder was molded into pellets, and the electrical conductivity was measured by the two-terminal method to find that it was 6 × 10 ⁻⁴ S / cm. The above operations were all performed under nitrogen from the preparation of a nitromethane solution of polymer and anhydrous FeCl _{3 to} the measurement of electric conductivity. Comparative Example Only the polymer obtained in Example 4 was molded into pellets,
When the electric conductivity was measured by the two-terminal method, it was 10 ^-10 S / cm or less.

Example 15 Poly (1,4,5,8-tetrahydro-1,4,5,8-tetrasila-1,1,4,4, obtained in Example 5
5,5,8,8-Octamethyl-3,7-dihexylanthracene-2,6-diyl-1,4-phenylene) poly (1,4,5,8-tetrahydro-1,4,5,8-
Tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,6-dihexylanthracene-2,7-diyl-1,4-phenylene) in the same manner as in Example 14, anhydrous FeCl ₃ The conductivity was measured to be 1 × 10 ⁻⁴ S / cm.

Example 16 Poly (1,4,5,8-tetrahydro-1,4,5,8-tetrasila-1,1,4,4, obtained in Example 6
5,5,8,8-Octamethyl-3,7-diphenylanthracene-2,6-diyl-1,1'-ferrocenediyl) poly (1,4,5,8-tetrahydro-1,4
5,8-Tetrasila-1,1,4,4,5,5,8,8
-Octamethyl-3,6-diphenylanthracene-
2,7-diyl-1,1′-ferrocenediyl) was doped with anhydrous FeCl _{3 in the same} manner as in Example 14 to measure the electric conductivity, which was 7 × 10 ⁻³ S / cm.
Met.

Example 17 The poly {2,5-thiophenediyl- (1,4,5,8-tetrahydro-1,4,5,8-obtained in Example 11)
Tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,7-diphenylanthracene-2,6-diyl)} poly {2,5-thiophenediyl- (1,4,
5,8-Tetrahydro-1,4,5,8-tetrasila-
1,1,4,4,5,5,8,8-octamethyl-3,
6-diphenylanthracene-2,7-diyl)} was subjected to ^doping with anhydrous FeCl _{3 in the same} manner as in Example 14 and the electric conductivity was measured to be 1 × 10 ⁻³ S / c.
It was m.

Example 18 Poly {2,6-pyridinediyl-obtained in Example 12
(1,4,5,8-Tetrahydro-1,4,5,8-tetrasila-1,1,4,4,5,5,8,8-octamethyl-3,7-diphenylanthracene-2,6- Diyl)} poly {2,6-pyridinediyl- (1,4,5,5
8-tetrahydro-1,4,5,8-tetrasila-1,
1,4,4,5,5,8,8-octamethyl-3,6-
Diphenylanthracene-2,7-diyl)} was subjected to ^doping with anhydrous FeCl _{3 in the same} manner as in Example 14, and the electric conductivity was measured to be 7 × 10 ⁻³ S / cm.
Met.

[0054]

According to the present invention, easily available 1,2-bis (dimethylsilyl) benzene and bis (acetylene) s or easily available 1,2,4,5-tetrakis (dimethylsilyl) benzene. Bis (1,2-bissilylethylene) s can be obtained from acetylene and acetylene by a one-step reaction, and their separation and purification are easy. Further, according to the present invention, polycarbosilanes having a step ladder structure can be obtained from 1,2,4,5-tetrakis (dimethylsilyl) benzene and bis (acetylene) s by a single step reaction, and separation and purification thereof can be carried out. Is also easy. Further, according to the present invention, there are provided preceramics, heat resistant materials and electrically conductive materials, which are composed of the above polycarbosilanes.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C07B 61/00 300

Claims (9)

[Claims] (A) 1,2-bis (dimethylsilyl) benzene (b) General formula R ¹ -C≡CAC ≡CR ¹ (I) (wherein R ¹ and A are monovalent and 2 respectively) And a bis (acetylene) compound represented by the formula (1) are reacted in the presence of (c) a platinum compound. (In the formula, R ¹ and A have the same meanings as described above.) A method for producing bis (1,2-bissilylethylene) s. 2. (a) 1,2,4,5-tetrakis (dimethylsilyl) benzene and (b) the general formula R ² -C≡CR ³ (III) (wherein R ² and R ³ are monovalent). And a acetylene group represented by the formula (3) in the presence of (c) a platinum compound. (Wherein R ² and R ³ have the same meanings as described above), or the general formula: (In the formula, R ² and R ³ have the same meanings as described above.) A method for producing bis (1,2-bissilylethylene) s. (A) 1,2,4,5-tetrakis (dimethylsilyl) benzene and (b) the general formula R ¹ -C≡CAC ≡CR ¹ (I) (wherein R ¹ and A are respectively Bis (acetylene) s represented by a monovalent or divalent group) in the presence of (c) a platinum compound. (Wherein R ¹ and A have the same meanings as described above,
m and n are each 0 or a positive integer, and m + n
≧ 1. The manufacturing method of the polycarbosilanes represented by these. 4. A general formula: (In the formula, R ¹ and A are monovalent and divalent groups, respectively.) Bis (1,2-bissilylethylene) s. 5. A general formula: (In the formula, R ² and R ³ are monovalent groups.) Or the general formula: (In the formula, R ² and R ³ are monovalent groups.) Bis (1,2-bissilylethylene)
Kind. 6. A general formula: (In the formula, R ¹ and A are monovalent and divalent groups, respectively, and m and n are 0 or a positive integer.
+ N ≧ 1. ) Is represented by the polycarbosilanes. 7. A heat-resistant material containing the polycarbosilane according to claim 6. 8. A preceramic containing the polycarbosilane according to claim 6. 9. A conductive material containing the polycarbosilane according to claim 6.