JPH05345789A - Production of silylbiphenyl compound - Google Patents

Abstract

PURPOSE:To obtain a silylbiphenyl compound simply, inexpensively and in high yield by reacting an organomonohalosilane with a 4-halophenyl metal halide, then introducing zinc, etc., and reacting the resulting reaction product with 1,4-dihalobenzene, etc. CONSTITUTION:A compound of formula I (R<1> and R<2> are 1-10C chain organo; X<1> is halogen) is subjected to first coupling reaction with a compound of formula II (M is magnesium or zinc)(preferably Grignard reagent) in a solvent such as THF preferably at 0-80 deg.C to synthesize a compound of formula III, to which magnesium or zinc is introduced to synthesize an organosilylphenyl metal halide of formula IV. This compound is subjected to second coupling reaction with a 1,4-dihalobenzene of formula V (X<2> is halogen or cyano; n is 0-4) or 4- cyanobenzene in the presence of nickel or palladium catalyst in a solvent such as THF preferably at 0 deg.C to room temperature to give the objective compound of formula VI such as 4'-organosilyl-4-halobiphenyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a liquid crystalline silylbiphenyl compound used as a display material for electro-optical switching or a display device.

[0002]

Liquid crystal compounds are often used in electro-optical switching or display devices. As such a liquid crystal compound, for example, 4'-cyano-4-alkylbiphenyl is known.

For the synthesis of 4'-cyano-4-alkylbiphenyl, there has been known a method which is carried out, for example, through the following linear route. That is, using biphenyl as a starting material, an acyl group is introduced into the 4-position by Friedel-Crafts reaction, and the carbonyl group of the acyl group is reduced by Wolff-Kishner to synthesize 4-alkylbiphenyl. Then, 4'of the 4-alkylbiphenyl
An acetyl group is introduced into the position by Friedel-Crafts reaction, and this acetyl group is converted into a cyano group through functional group conversion of several steps.

[0004]

In the method of synthesizing the display compound starting from biphenyl, there are problems that many steps of a long linear route are required, the production is complicated and the yield is low. In addition, there is a drawback that a compound such as diimide which is industrially difficult to handle must be used as a reaction reagent.

In order to solve these problems, the present invention provides a method capable of easily producing a liquid crystalline biphenyl compound in a high yield from a readily available starting material through a convergent route. To aim.

[0006]

In order to achieve the above object, the method for producing a silylbiphenyl compound of the present invention comprises:
General formula 1

[0007]

[Chemical 13]

Organomonohalosilane represented by the general formula 2

[0009]

[Chemical 14]

A first coupling reaction with a dehalogenated metal is carried out with a 4-halophenyl metal halide represented by the general formula 3

[0011]

[Chemical 15]

A 4-organosilylhalobenzene represented by the following formula is synthesized, and magnesium or zinc is introduced into the obtained 4-organosilylhalobenzene to give a compound represented by the general formula 4

[0013]

[Chemical 16]

A 4-organosilylphenyl metal halide represented by the following formula was synthesized, and the obtained 4-organosilylphenyl metal halide and the general formula 5

[0015]

[Chemical 17]

1,4-dihalobenzene or 4 represented by
A second coupling reaction with a dehalogenated metal with cyanohalobenzene to give a compound of the general formula 6

[0017]

[Chemical 18]

4'-organosilyl-4-halobiphenyl or 4'-organosilyl-4-cyanobiphenyl represented by

In the above formula, R ¹ and R ² have 1 to 1 carbon atoms.
A chain organo group of 0, X ¹ is halogen, M is magnesium or zinc, X ² is a halogen or cyano group, and n is 0 to
It is 4.

The partner of the second coupling reaction with the 4-organosilylphenyl metal halide is not limited to 4'-organosilyl-4-halobiphenyl or 4'-organosilyl-4-cyanobiphenyl.

General formula 7

[0022]

[Chemical 19]

A second coupling reaction with a dehalogenated metal is carried out with 4-organohalobenzene represented by the formula and having an organo group having 1 to 10 carbon atoms to give a compound represented by the general formula 8

[0024]

[Chemical 20]

4'-organosilyl-4-organobiphenyl represented by may be synthesized.

As described above, in the present invention, the first coupling reaction with the dehalogenated metal is carried out between the organomonohalosilane and the 4-halophenyl metal halide,
4-Organosilylhalobenzene is synthesized.

The other 4-halophenyl metal halide which undergoes the first coupling reaction with the organomonohalosilane is preferably 4-halophenyl magnesium halide which is a Grignard reagent.

4-Halophenyl magnesium halide can be easily synthesized by adding equimolar amounts of 1,4-dihalobenzene and magnesium to an anhydrous organic solvent.
The two substituted halogens of 1,4-dihalobenzene may be the same or different from each other. The reaction formula is shown.

[0029]

[Chemical 21]

Preferred examples of 1,4-dihalobenzene to be reacted with magnesium include 1,4-dichlorobenzene, 4-bromochlorobenzene and 1,4-dibromobenzene.

Examples of the synthetic solvent for the Grignard reagent include ethers such as tetrahydrofuran, diethyl ether and dibutyl ether, and hydrocarbons such as benzene, toluene and xylene.
These may be used alone or in a mixture with each other.

In the first coupling reaction, when an active functional group which causes a side reaction with the Grignard reagent is bonded to the organomonohalosilane, 4-
It is recommended that the halophenylmagnesium halide is once changed to 4-halophenylzinc halide, and the 4-halophenylzinc halide and organomonohalosilane are subjected to a coupling reaction.

The 4-halophenyl zinc halide is a 4-halophenyl magnesium halide and a zinc (II) halide.
It can be synthesized by mixing and in an anhydrous organic solvent. The reaction formula is shown.

[0034]

[Chemical formula 22]

In the above formula, the halogen element in the 4-halophenyl magnesium halide represented by X ¹ and the halogen element in the zinc (II) halide may be the same or different. Examples of the zinc (II) halide include zinc chloride, zinc bromide and zinc iodide. From 4-halophenyl magnesium halide 4-
Examples of the organic solvent for synthesizing the halophenyl zinc halide include the same organic solvents as those exemplified for the synthesis of the Grignard reagent.

The above 4-halophenyl magnesium halide or 4-halophenyl zinc halide is used for the first coupling reaction with the organomonohalosilane.

R in Formula 1 representing an organomonohalosilane
Examples of the silicon-bonded organo group represented by ¹ and R ² include chain hydrocarbon groups such as an alkyl group, an alkenyl group and an alkynyl group. In addition, an ether group (-O
-) Included, for example, an alkoxyalkyl group, sulfide group (-S-) included, for example, alkylthioalkyl group, carbonyl group (-CO-) included, for example, acylalkyl group, carbonyloxy group (- COO
Examples thereof include an acyloxyalkyl group containing-). Even between two of R ¹ each other Formula 1, even among themselves, including R ² in the R ^1, it may be the same group together, or may be different groups.

Among them, it is preferable that both R ¹ are methyl groups, both are ethyl groups, or one is a methyl group and the other is an ethyl group. R ² is preferably a chain alkyl group having 1 to 10 carbon atoms.

The first coupling reaction is preferably carried out in an organic solvent. Examples of the organic solvent in this case include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether and the like. In addition to these, hydrocarbons such as benzene, toluene and xylene can be mentioned, and aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoric triamide can also be mentioned. These may be used alone or in a mixture with each other. The reaction temperature is preferably 0 ° C to 80 ° C. The reaction formula is shown.

[0040]

[Chemical formula 23]

The metal halide produced as a by-product can be recovered by washing the reaction mixture with water, cooling the obtained wash water and filtering. In the case of zinc halide, it can be used repeatedly.
4-Organosilylhalobenzene can be isolated by removing the metal halide from the reaction mixture and then concentrating under reduced pressure.

In the present invention, a metal is introduced into the 4-organosilylhalobenzene obtained above, and dehalogenation is performed between the 4-organosilylphenyl metal halide and 1,4-dihalobenzene or 4-cyanohalobenzene. A second coupling reaction with a metal oxide is performed.

The 4-organosilylphenyl metal halide is preferably 4-organosilylphenyl magnesium halide which is a Grignard reagent.

The synthesis of 4-organosilylphenylmagnesium halide is carried out in the same manner as in the above-mentioned synthesis of 4-halophenylmagnesium halide, in a dry organic solvent.
It suffices to mix the organosilyl-halobenzene and magnesium.

When a partner such as a cyano group of 4-cyanohalobenzene for a coupling reaction with 4-organosilylphenyl metal halide has a functional group other than halogen and reactive with a Grignard reagent, 4- As the organosilylphenyl metal halide, 4-organosilylphenyl zinc halide may be used. 4-Organosilylphenyl zinc halide is synthesized by mixing 4-organosilylphenyl magnesium halide and zinc halide in an organic solvent. The reaction formula for introducing a metal is shown.

[0046]

[Chemical formula 24]

The 4-organosilylphenyl metal halide undergoes a second coupling reaction with 1,4-dihalobenzene or 4-cyanohalobenzene. The 1,4-dihalobenzene or 4-cyanohalobenzene which undergoes the second coupling reaction may be further substituted with 1 to 4 halogens or cyano groups at the 2,3,5,6 position, and is not substituted. May be. Specific examples include the following substances.

As 1,4-dihalobenzene, 4-fluorobromobenzene, 4-fluoroiodobenzene,
3,4-difluorobromobenzene and the like can be mentioned.
Examples of 4-cyanohalobenzene include 4-bromobenzonitrile and 4-iodobenzonitrile. All of these are easily available.

In carrying out the method for producing a silylbiphenyl-based compound of the present invention, 4-organohalobenzene is used without using 1,4-dihalobenzene or the like, and is used in combination with 4-organosilylphenyl metal halide. Two
The coupling reaction may be performed.

In this case, the organo group of 4-organohalobenzene may be an alkoxy group having 1 to 10 carbon atoms or an alkoxycarbonyl group. In addition, those derivative groups partially substituted with halogen or a cyano group can be mentioned. Further, the 4-organohalobenzene may or may not be substituted with 1 to 4 halogens or cyano groups at the 2,3,5,6 positions of the benzene ring. Specific examples include the following substances.

4-alkoxycarbonyl bromobenzene, 4-alkoxy bromobenzene, 4-alkoxy iodobenzene, 4-monofluoromethoxy bromobenzene, 4-difluoromethoxy bromobenzene, 4-trifluoromethoxy bromobenzene, 4-perfluoroalkoxy Preferred examples include bromobenzene.

The second coupling reaction is preferably carried out in the presence of a nickel or palladium catalyst. Examples of the nickel catalyst in that case include [1,3-bis (diphenylphosphino) propane] nickel (II) chloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) chloride, and bis (triphenylphosphine). ) Nickel (I
I) Examples include chloride. Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), di [1,2-bis (diphenylphosphino) ethane] palladium (0), bis (dibenzylideneacetone) palladium (0) and the like. Can be mentioned.

The amount of the catalyst is 0.1 to 50 mol% with respect to the amount including the reactant and the catalyst. From the viewpoint of price and post-treatment,
0.2 mol% -5 mol% are preferable.

Examples of the reaction solvent include ethers such as tetrahydrofuran, diethyl ether and dibutyl ether, hydrocarbons such as benzene, toluene and xylene, N, N-dimethylformamide, dimethyl sulfoxide and hexamethylphosphoric triamide. Aprotic polar solvent of. These may be used alone or in combination.

The reaction temperature is −78 ° C. to +80.
C, preferably 0 C to room temperature is desirable. When the reaction progresses slowly, the temperature may be raised to the reflux condition. The reaction formula is shown.

[0056]

[Chemical 25]

Or

[0058]

[Chemical formula 26]

The metal halide produced as a by-product can be recovered by washing the reaction mixture with water, cooling the wash water and filtering. The metal halide is removed from the reaction mixture and then concentrated under reduced pressure to produce a silylbiphenyl compound, that is,
4'-Organosilyl-4-halobiphenyl, 4'-organosilyl-4-cyanobiphenyl or 4'-organosilyl-4-organobiphenyl are obtained. If necessary, it may be further purified by recrystallization, distillation under reduced pressure, column chromatography and the like.

[0060]

In the method for producing a silylbiphenyl compound of the present invention, 4-organosilylphenyl metal halide and 4
Performing a second coupling reaction with a dehalogenated metal with an organohalobenzene. One of 4-organosilylphenyl metal halide and 4-organohalobenzene can be independently synthesized in parallel without waiting for the synthesis of the other.

Generally, organomonohalosilanes, 1,4
-Dihalobenzene etc. are very easy to obtain. In addition, no industrially difficult reagent such as diimide is used.

[0062]

INDUSTRIAL APPLICABILITY As described above in detail, the method for producing a silylbiphenyl compound of the present invention reaches a target product from a readily available starting material through a convergent route, so that the target product can be easily collected with high yield. Can be manufactured at a rate. It is safe to operate because it does not use industrially difficult reagents.

[0063]

EXAMPLES Examples of the present invention will be shown below.

Example 1 4- (n-hexyldimethylsilyl) chlorobenzene was produced and magnesium was added to obtain a Grignard reagent to produce 4- (n-hexyldimethylsilyl) -4'-trifluoromethoxybiphenyl. ..

I 4- (n-hexyldimethylsilyl)
Production of chlorobenzene p-Dichlorobenzene (147 g, 1.00 mol) and metallic magnesium (26.7 g, 1.10 g atom) were mixed in tetrahydrofuran (800 ml) to give 4-chlorophenylmagnesium chloride (Grignard reagent).
Was prepared.

N-Hexyldimethylchlorosilane 178
g (1.00 mol) was dissolved in 300 ml of tetrahydrofuran, and the above 4 was mixed with stirring under a nitrogen stream.
-Chlorophenylmagnesium chloride was added dropwise at room temperature to synthesize a crude product of 4- (n-hexyldimethylsilyl) chlorobenzene in the reaction mixture.

The above reaction mixture was stirred at room temperature for 2 hours and further refluxed for 1 hour, then poured into a saturated aqueous solution of ammonium chloride, and the synthesized 4- (n-hexyldimethylsilyl) chlorobenzene was extracted with ether. The ether organic layer was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated saline to remove unreacted substances and by-produced magnesium chloride, and the ether organic layer was dried over magnesium sulfate,
It was concentrated under reduced pressure. The obtained residue was distilled under reduced pressure to obtain 223.3 g of a highly pure target product. The yield was 88%. The inspection results are shown below.

Boiling point (however, pressure 2.0 Torr): 10
3 ° C. to 104 ° C. ¹ H-NMR (CCl ₄ ) δ (ppm) 0.22 (6H, S) 0.64-0.98
(5H, m) 1.04-1.50 (8H, m) 7.26-
7.38 (4H, m) Infrared absorption analysis (ν _max ) Wave number (cm ^-1 ) 2957, 2922, 2872, 157
8, 1485, 1381, 1251, 10
86, 839, 808, 783, 7
39 From the above results, the existence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0069]

[Chemical 27]

Ii 4- (n-obtained in this way
Hexyldimethylsilyl) chlorobenzene 44.0 g
(0.173 mol) and magnesium 5.00 g (0.2
(06 g atom) was put into 250 ml of tetrahydrofuran to prepare 4- (n-hexyldimethylsilyl) phenylmagnesium chloride (Grignard reagent).

4-1.7 g (0.173 mol) of 4- (trifluoromethoxy) bromobenzene and 1.0 g of tetrakis (triphenylphosphine) palladium (0) (0.
(5 mol%) and 250 ml of tetrahydrofuran were refluxed, and the Grignard reagent was added dropwise to the refluxed liquid while stirring.

After stirring the mixture for 2 hours while refluxing, the reaction mixture was poured into an ice-cooled aqueous ammonium chloride solution to prepare 4- (n-hexyldimethylsilyl) phenylmagnesium chloride and 4-trifluoromethoxybromobenzene. The reaction crude product was extracted with methylene chloride.
A methylene chloride organic layer was added to a saturated sodium hydrogen carbonate aqueous solution,
Wash with water and saturated saline to remove unreacted substances and by-products,
It was dried over magnesium sulfate and concentrated under reduced pressure. The residue was distilled under reduced pressure to obtain 47.4 g of a highly pure target product. Yield 7
It was 2%. The inspection results are shown below.

Boiling point (however, pressure 5.0 Torr): 18
2 ° C. to 185 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 0.37 (6H, S) 0.82-0.90
(2H, t) 0.91-0.99 (3H, t) 1.30-
1.36 (8H, m) 7.25-7.44 (2H, m) 7.56-
7.72 (6H, m) Infrared absorption analysis (ν _max ) Wave number (cm ^-1 ) 2956, 2922, 2856, 151
8, 1491, 1259, 1221, 11
67, 1113, 839, 808, mass spectrometry (EI) m / z 114, 142, 165, 27 by gas chromatography
9, 295, 380. From the above results, the presence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0074]

[Chemical 28]

The phase transition temperature was confirmed. Crystal phase-nematic phase-21.1 ° C Nematic phase-isotropic liquid phase-12.7 ° C Example 2 Preparation of 4- (n-hexyldimethylsilyl) -4'-cyanobiphenyl In the same manner as in Example 1. 4- (n-Hexyldimethylsilyl) phenyl magnesium chloride (Grignard reagent) was prepared. 0.4 mol of the obtained 4- (n-hexyldimethylsilyl) phenyl magnesium chloride was dissolved in tetrahydrofuran.

54.4 g (0.400 mol) of zinc chloride was dissolved in 200 ml of tetrahydrofuran and ice-cooled, and the tetrahydrofuran solution of phenylmagnesium chloride was added dropwise to the ice-cooled liquid while stirring.
-(N-Hexyldimethylsilyl) phenyl magnesium chloride was reacted with zinc chloride. Stirring temperature 0 ℃ ~
The mixture was stirred at 5 ° C. for 30 minutes to obtain a suspension of 4- (n-hexyldimethylsilyl) phenylzinc chloride.

65.2 g of 4-bromobenzonitrile
(0.358 mol), tetrakis (triphenylphosphine) palladium (0) 1.10 g (5.3 mol%) and tetrahydrofuran 400 ml were prepared, and the above suspension was stirred while stirring the mixture. It was added dropwise at room temperature.

The mixture was stirred for 12 hours to cause 4- (n-hexyldimethylsilyl) phenylzinc chloride to react with 4-bromo-benzenezonitrile, and the reaction mixture was placed in an ice-cooled saturated aqueous ammonium chloride solution. After that, the crude product was extracted with methylene chloride. The methylene chloride organic layer is washed with water and saturated saline to remove unreacted substances and by-products,
The extract was dried over magnesium sulfate and concentrated under reduced pressure.

The residue was purified by silica gel column chromatography using a mixed solution of hexane and ether with a mixing ratio of 20: 1 as the effluent to obtain 85.9 g of the desired product. The yield was 75%. The inspection results are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.34 (6H, S) 0.78-0.86
(2H, t) 0.87-0.94 (3H, t) 1.26-
1.44 (8H, m) 7.30-7.38 (2H, m) 7.56-
7.77 (6H, m) Infrared absorption analysis (ν _max ) Wave number (cm ^-1 ) 2954, 2854, 2227, 160
8, 1587, 1490, 1388, 12
49, 1112, 1005, 810, mass spectrometry by gas chromatography (EI) m / z 118, 142, 206, 22
2, 236, 251, 306, 3
21. From the above results, the existence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0081]

[Chemical 29]

Example 3 4- (n-decyldimethylsilyl) chlorobenzene was produced and magnesium was introduced to obtain a Grignard reagent.
4- (n-decyldimethylsilyl) -4'-trifluoromethoxybiphenyl was prepared.

200 g of 4-bromochlorobenzene
(1.04 mol) and 25.39 g of magnesium metal
(1.04 g atom) was put into 1000 ml of tetrahydrofuran to obtain 4-chlorophenylmagnesium bromide (Grignard reagent).

N-decyldimethylchlorosilane 240.
0 g (1.02 mol) was dissolved in 300 ml of tetrahydrofuran, and the Grignard reagent was added dropwise at room temperature while stirring the n-decyldimethylchlorosilane solution under a nitrogen stream.

Thereafter, in the same manner as in Example 1, 4- (n-
Decyldimethylsilyl) chlorobenzene 248 g. 4 g
Got The yield was 78%. The inspection results are shown below.

Boiling point (however, pressure 2.0 Torr): 17
3 ° C. to 179 ° C. ¹ H-NMR (CCl ₄ ) δ (ppm) 0.20 (6H, S) 0.60-1.46
(21H, m) 7.06-7.40 (4H, m) Infrared absorption analysis (ν _max ) Wave number (cm ⁻¹ ) 2957, 2924, 2854, 157
8, 1485, 1379, 1252, 10
86, 1016, 839, 808, 7
39 From the above results, the existence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0087]

[Chemical 30]

Ii 4- (n-obtained in this way
Decyldimethylsilyl) chlorobenzene 45.4g
4- (n-decyldimethylsilyl) phenylmagnesium chloride (Grignard reagent) was synthesized from (0.146 mol) and magnesium in the same manner as in Example 1.

4- (n-decyldimethylsilyl) phenylmagnesium chloride thus obtained and 4- (n-decyldimethylsilyl) phenylmagnesium chloride
35.2 g of trifluoromethoxybromobenzene (0.
146 mol) was subjected to a coupling reaction. The reaction was carried out in the presence of 1.60 g (2.0 mol%) of [1,3-bis (diphenylphosphino) propane] nickel (II) chloride. The reaction mixture was purified by silica gel column chromatography to obtain 45.2 g of a highly pure target product. The yield was 71%. The inspection results are shown below.

¹ H-NMR (CDCl ₃ ) δ (ppm) 0.35 (6H, S) 0.84-0.97
(5H, m) 1.32-1.38 (18H, m) 7.31-
7.67 (8H, m) Infrared absorption analysis (ν _max ) Wave number (cm ^-1 ) 2957, 2924, 2855, 126
0, 1223, 1169, 1115, 10
05, 837, 806, 773, mass spectrometry by gas chromatography (EI) m / z 43, 127, 152, 198,
279, 295, 436 From the above results, the presence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0091]

[Chemical 31]

Example 4 Preparation of 4- (n-decyldimethylsilyl) -4'-difluoromethoxybiphenyl In the same manner as in Example 3, 52.3 g (0.168 mol) of 4- (n-decyldimethylsilyl) chlorobenzene was prepared. ) Was synthesized and magnesium was added to prepare 4- (n-decyldimethylsilyl) phenylmagnesium chloride (Grignard reagent).

The obtained 4- (n-decyldimethylsilyl) phenylmagnesium chloride and 37.5 g (0.168 mol) of 4-difluoromethoxybromobenzene.
And were subjected to a coupling reaction. This reaction is performed by [1,3-bis (diphenylphosphino) propane] nickel (I
I) Carried out in the presence of 1.57 g (2.0 mol%) of chloride. The reaction mixture was purified by silica gel column chromatography to obtain 41.6 g of the desired product. The yield was 68%. The inspection results are shown below.

Infrared absorption analysis (ν _max ) Wave number (c
m ^-1 ) 2957, 2922, 2854, 159
9, 1520, 1491, 1466, 13
81, 1250, 1223, 1176, 1
172, 1053, 1005, 837 812, 774, mass spectrometry (EI) m / z 43, 127, 141, 170 by gas chromatography.
201, 220, 263, 27
7, 418 From the above results, the presence of the compound having the following structure was confirmed. It was also found that the yield was very high.

[0095]

[Chemical 32]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshinobu Ishihara Niigata Prefecture Nakakubiki-gun Kubiki-mura Large number 28 Nishifukushima 1 Shinsei Chemical Industry Co., Ltd. Synthetic Technology Research Laboratory (72) Inventor Tatsushi Kaneko Nakakubiki-gun Niigata Prefecture 1 at 28, Nishi-Fukushima, Kubiki-mura, Shin-Etsu Chemical Co., Ltd. within the Synthetic Technology Laboratory (72) Inventor Tsutomu Ogihara, 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture 1 within Shin-Etsu Chemical Co., Ltd. (72) Inventor Yamato Miura 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. General formula 1 (Wherein R ¹ and R ² are chain organo groups having 1 to 10 carbon atoms and are the same or different from each other, and X ¹ is halogen), and an organomonohalosilane represented by the general formula 2 (Wherein M is magnesium or zinc, X ¹ is halogen, and they are the same or different from each other, including X ¹ in formula 1)
A first coupling reaction with a dehalogenated metal is carried out with a halophenyl metal halide to give a compound represented by the general formula 3 The 4-organosilylhalobenzene represented by
Magnesium or zinc is introduced into the obtained 4-organosilylhalobenzene to give a compound represented by the general formula 4 A 4-organosilylphenyl metal halide represented by the following formula was synthesized, and the obtained 4-organosilylphenyl metal halide was represented by the following general formula 5: (Wherein X ² is a halogen or a cyano group, which are the same or different from each other, n is 0 to 4) and a 1,4-dihalobenzene or 4-cyanohalobenzene represented by A coupling reaction is carried out to give a compound of the general formula 6 A method for producing a silylbiphenyl-based compound, which comprises synthesizing 4'-organosilyl-4-halobiphenyl or 4'-organosilyl-4-cyanobiphenyl represented by 2. General formula 1 (Wherein R ¹ and R ² are chain organo groups having 1 to 10 carbon atoms and are the same or different from each other, and X ¹ is halogen), and an organomonohalosilane represented by the general formula 2 (Wherein M is magnesium or zinc, X ¹ is a halogen and is the same or different including X ¹ of the formula 1) and the first coupling reaction with a dehalogenated metal with a 4-halophenyl metal halide Then, the general formula 3 The 4-organosilylhalobenzene represented by
Magnesium or zinc is introduced into the obtained 4-organosilylhalobenzene to give a compound represented by the general formula 4 A 4-organosilylphenyl metal halide represented by the following formula was synthesized, and the obtained 4-organosilylphenyl metal halide and the compound represented by the general formula 7: (Wherein X ² is a halogen or cyano group, the same or different from each other, n is 0 to 4 and R ³ is a chain organo group having 1 to 10 carbon atoms) and 4-organohalobenzene , A second coupling reaction with a dehalogenated metal is carried out to give a compound of the general formula 8: A method for producing a silylbiphenyl-based compound, which comprises synthesizing 4′-organosilyl-4-organobiphenyl represented by 3. The method for producing a silylbiphenyl compound according to claim 1, wherein the second coupling reaction is carried out in the presence of a nickel catalyst or a palladium catalyst. 4. The method for producing a silylbiphenyl compound according to claim 1, wherein R ¹ 's are methyl groups and / or ethyl groups. 5. The method for producing a silylbiphenyl compound according to claim 4, wherein R ² is an alkyl group having 1 to 10 carbon atoms.