JPH07173176A - Silacyclohexane compound, its production and liquid crystal composition containing the compound - Google Patents

Abstract

PURPOSE:To obtain a new silacyclohexane compound giving a nematic liquid crystal having an increased refractive index anisotropy expanded to a low temperature side and, accordingly, having improved response and compatibility at low temperature and useful as a base material for a liquid crystal phase. CONSTITUTION:This silacyclohexane compound is expressed by formula I (R is a 1-10C straight-chain alkyl, a 2-8C alkenyl, etc.; the ring A is a trans-1- sila-1,4-cyclohexylene or a trans-4-sila-1,4-cyclohexylene having substituent such as H and F on the Si at 1 or 4-site; X is CN, F, etc.; Y2 and Z each is H or F; Y1 is F, Cl, etc.), e.g. 4'-(trans-4-n-propyl-4-silacyclohexyl)-4-fluorobiphenyl. The compound can be produced by reacting a silacyclohexane compound of formula II (W is Cl, CH3, etc.; Q is a halogen or an alkoxy) with an organometallic reagent of formula R-M [M is MgP, ZnP (P is a halogen) or Li].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silacyclohexane compound, a method for producing the same, a liquid crystal composition containing the same, and a liquid crystal display device containing the liquid crystal composition.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal substance, and depending on its display mode, TN type (twisted nematic type), STN type (super twisted nematic type), SBE type (super birefringence type), DS
There are various types such as a type (dynamic scattering type), a guest-host type, a DAP type (deformation of aligned phase), and an OMI type (optically mode interference type). The most common display device is based on the Schut-Helfrich effect and has a twisted nematic structure.

The properties required for the liquid crystal substances used for these liquid crystal displays are slightly different depending on the display system, but they are stable against a wide range of liquid crystal temperature, moisture, air, light, heat, electric field and the like. Things are commonly requested in any display method. Furthermore, it is desired that the liquid crystal material has a low viscosity and provides a short addressing time, a low threshold voltage and a high contrast in the cell.

At present, there is no substance that satisfies all of these requirements with a single compound, and actually, a liquid crystal mixture obtained by mixing several to several dozen liquid crystal compounds / latent liquid crystal compounds is used. . Therefore, it is an important property that the constituent components of the liquid crystal composition can be easily mixed with each other.

Among the liquid crystal compounds that can be these constituent components, the following so-called cyclohexyl ring-phenyl ring-phenyl ring structure (BCH structure) has been conventionally used as one of the basic components that control the electro-optical performance. The compound that they have is known.

[Chemical 12] (Japanese Patent Publication No. 63-55496)

[Chemical 13] (Japanese Patent Publication No. 63-7169)

[Chemical 14] (Japanese Patent Publication No. 64-4496)

[0006]

With the recent widespread use of liquid crystal displays, the properties required of liquid crystal materials are becoming more and more severe. In particular, it has been desired that the characteristics of conventional liquid crystal substances, such as higher driving voltage, wider temperature range corresponding to vehicle needs, and improvement of low temperature performance, are further exceeded.

From this point of view, the present invention is a liquid crystal material newly developed for the purpose of improving the characteristics of the liquid crystal material, and the above-mentioned conventional cyclohexyl ring-phenyl ring-phenyl ring structure (BCH). An object of the present invention is to provide a liquid crystal compound having a silacyclohexane ring which is completely different from the liquid crystal compound having a structure).

[0008]

That is, the present invention is a silacyclohexane compound represented by the following general formula (I).

[Chemical 15] In the formula, R is a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, and an alkoxy group having 2 to 7 carbon atoms. It represents an alkyl group or an alkenyl group having 2 to 8 carbon atoms.

[Chemical 16] Represents a trans-1-sila-1,4-cyclohexylene or trans-4-sila-1,4-cyclohexylene group in which silicon at the 1- or 4-position has a substituent of H, F, Cl or CH _3. . X is CN, F, Cl, CF ₃ , CF ₂ C
1, CHFCl, OCF ₃ , OCHF ₂ , OCF ₂ Cl,
It represents an OCHFCl, R or OR group (R is the same as defined in formula (I)). Y ₂ and Z each independently represent H or F. Y ₁ represents H, F or Cl.

The present invention is also a method for producing a silacyclohexane compound represented by the general formula (I) characterized by carbon-carbon bond formation or carbon-silicon bond formation using a specific organometallic reagent. The manufacturing methods are listed below.

Organometallic reagent RM (M is MgP or Zn
Represents P (P is a halogen atom) or Li. ) And a silacyclohexane compound

[Chemical 17] (W represents H, F, Cl or CH ₃ group, Q represents a halogen atom or an alkoxy group, and X, Y ₁ , Y ₂ and Z are the same as defined in the general formula (I)). A method for producing a silacyclohexane compound represented by the above general formula (I) by a reaction.

Organometallic reagent

[Chemical 18] (R and Z are the same as defined in formula (I), M ′ is M or B (OR ′) ₂ (R ′ represents a Me group or an H atom),

[Chemical 19] Represents a trans-1-sila-1,4-cyclohexylene or trans-4-sila-1,4-cyclohexylene group in which the silicon at the 1- or 4-position has a H or CH ₃ substituent. ) And an aromatic compound

[Chemical 20] (P ¹ represents Cl, Br or I, and X, Y ₁ and Y ₂ are the same as defined in the general formula (I).) Silacyclohexane represented by the general formula (I) Method for producing compound.

Organometallic reagent

[Chemical 21] (X, Y ₁ and Y ₂ are the same as defined in the general formula (I), M ′
Is the same as the definition in [Chemical Formula 18]. ) And silacyclone hexane compound

[Chemical formula 22] (R and Z are the same as the definition in the general formula (I), P ¹ is the same as the definition in [Chemical Formula 20],

[Chemical formula 23] Is the same as the definition in [Chemical 19]. ), And the manufacturing method of the silacyclohexane compound represented by the said General formula (I).

Silacyclohexane compound

[Chemical formula 24] (R is the same as the definition in the general formula (I), and W and Q are [Chemical Formula 1
7] is the same as the definition in [7]. ) And an organometallic reagent

[Chemical 25] (X, Y ₁ and Y ₂ are the same as defined in the general formula (I), M is MgP or ZnP (P is a halogen atom) or Li) and is represented by the general formula (I). Method for producing silacyclohexane compound.

Further, the present invention is a liquid crystal composition containing the silacyclohexane compound represented by the general formula (I) and a liquid crystal display device using the same.

The novel compound represented by the general formula (I) is specifically a silacyclohexane compound represented by the ring structure shown in [Chemical formula 26] or [Chemical formula 27] below.

[Chemical formula 26]

[Chemical 27]

In the formula, R is a linear alkyl group having 1 to 10 carbon atoms, that is, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n.
-Octyl, n-nonyl or n-decyl group; carbon number 1 to
10 mono- or difluoroalkyl groups, that is, fluoromethyl, 1-fluoroethyl, 1-fluoropropyl, 1-fluorobutyl, 1-fluoropentyl, 1-fluorohexyl,
1-Fluoroheptyl, 1-Fluorooctyl, 1-Fluorononyl, 1-Fluorodecyl, 2-Fluoroethyl, 2-Fluoropropyl, 2-Fluorobutyl, 2-Fluoropentyl, 2-Fluorohexyl, 2-Fluoroheptyl, 2-Fluorooctyl , 2-fluorononyl, 2-fluorodecyl,
3-fluoropropyl, 3-fluorobutyl, 3-fluoropentyl, 3-fluorohexyl, 3-fluoroheptyl, 3
-Fluorooctyl, 3-fluorononyl, 3-fluorodecyl, 4-fluorobutyl, 4-fluoropentyl, 4-fluorohexyl, 4-fluoroheptyl, 4-fluorooctyl, 4-fluorononyl, 4-fluorodecyl, 5-fluoropentyl, 5 -Fluorohexyl, 5-fluoroheptyl,
5-fluorooctyl, 5-fluorononyl, 5-fluorodecyl, 6-fluorohexyl, 6-fluoroheptyl, 6-
Fluorooctyl, 6-fluorononyl, 6-fluorodecyl, 7-fluoroheptyl, 7-fluorooctyl, 7-fluorononyl, 7-fluorodecyl, 8-fluorooctyl,
8-fluorononyl, 8-fluorodecyl, 9-fluorononyl, 9-fluorodecyl, 10-fluorodecyl, difluoromethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1-difluoropentyl, 1,1-difluoropentyl, 1,1-difluorohexyl, 1,1-difluoroheptyl, 1,1-difluorooctyl, 1,1-difluorononyl, 1,1-difluorodecyl, 2,2-difluoroethyl, 2,2-difluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 2,2-difluorooctyl, 2,2-difluorononyl, 2,2-difluorodecyl, 3,3-difluoropropyl, 3,3-difluorobutyl, 3,3-difluoropentyl, 3,3-difluorohexyl, 3, -Difluoroheptyl, 3,3-difluorooctyl, 3,3-difluorononyl, 3,3-difluorodecyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-difluorohexyl, 4,4 -Difluoroheptyl, 4,4-difluorooctyl, 4,4-difluororonyl, 4,4-difluorodecyl, 5,5-difluoropentyl, 5,5-difluorohexyl, 5,5-difluoroheptyl, 5 , 5-Difluorooctyl, 5,5-
Difluorononyl, 5,5-difluorodecyl, 6,6-difluorohexyl, 6,6-difluoroheptyl, 6,6-
Difluorooctyl, 6,6-difluorononyl, 6,6-
Difluorodecyl, 7,7-difluoroheptyl, 7,7-
Difluorooctyl, 7,7-difluorononyl, 7,7-
Difluorodecyl, 8,8-difluorooctyl, 8,8-
Difluorononyl, 8,8-difluorodecyl, 9,9-difluorononyl, 9,9-difluorodecyl or 10,10
-Difluorodecyl; a branched chain alkyl group having 3 to 8 carbon atoms, that is, isopropyl, sec-butyl, isobutyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3
-Methylpentyl, 1-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 2
-Ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl or 3-methylheptyl group; an alkoxyalkyl group having 2 to 7 carbon atoms, that is, methoxymethyl, ethoxymethyl, propoxylmethyl, butoxymethyl, pentoxy. Methyl, methoxyethyl, ethoxyethyl, proxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, methoxybutyl, ethoxybutyl, methoxypentyl or ethoxypentyl groups; or alkenyl groups having 2 to 8 carbon atoms, that is, vinyl, 1-propenyl, allyl, 1-
Butenyl, 3-butenyl, isoprenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl or 7-octenyl. Group: represents.

W represents H, F, Cl or CH ₃ . X
Is CN, F, Cl, CF ₃ , CF ₂ Cl, CHFCl, O
Represents CF ₃ , OCF ₂ Cl, OCHFCl, OCHF ₂ , R or OR. Y ₂ and Z are each independently H
Or F. Y ₁ represents H, F or Cl.

[0018]

[Chemical 28] As specifically

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44]

[Chemical formula 45]

[Chemical formula 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

[Chemical 53]

[Chemical 54]

[Chemical 55]

[Chemical 56]

[Chemical 57]

[Chemical 58]

[Chemical 59]

[Chemical 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

[Chemical 64]

[Chemical 65]

[Chemical formula 66]

[Chemical formula 67]

[Chemical 68]

[Chemical 69]

[Chemical 70]

[Chemical 71]

[Chemical 72]

[Chemical formula 73]

[Chemical 74]

[Chemical 75]

[Chemical 76]

[Chemical 77]

[Chemical 78]

[Chemical 79]

[Chemical 80]

[Chemical 81]

[Chemical formula 82]

[Chemical 83]

[Chemical 84]

[Chemical 85]

[Chemical 86] And so on.

R is a linear alkyl group having 3 to 7 carbon atoms, that is, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl group; 1 to 10 carbon atoms.
2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2-fluoropentyl, 2-fluorohexyl, 2-fluoroheptyl, 4-fluorobutyl, 4-fluoropentyl, 4-fluoro, among the mono- or difluoroalkyl groups of Hexyl, 4-fluoroheptyl, 5-fluoropentyl, 5-fluorohexyl, 5-fluoroheptyl, 6-fluorohexyl, 6-fluoroheptyl, 7-fluoroheptyl, 2,2-difluoropropyl, 2,2-difluoropropyl 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-di Fluorohexyl, 4,4-difluoroheptyl, 5,5-difluoropentyl, 5,5-difluorohexyl, 5,5-di Rorohepuchiru, 6,6-difluorobenzyl hexyl, 6,6-difluorobenzyl heptyl or 7,7-difluorobenzyl heptyl; of branched alkyl group, isopropyl, 1-methylpropyl, 2-methylpropyl, 1-
Methylbutyl, 2-methylbutyl, 3-methylbutyl,
1-methylpentyl, 2-methylpentyl or 2-ethylhexyl group; alkoxyalkyl group having 2 to 6 carbon atoms,
That is, a methoxymethyl, methoxyethyl, methoxypropyl, methoxypentyl, ethoxymethyl, ethoxyethyl, propoxymethyl or pentoxymethyl group; or among alkenyl groups, vinyl, 1-propenyl, 3-butenyl, 1-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 6-heptenyl or 7-octenyl groups are practically desirable.

As for W, H, F and CH ₃ groups are practically desirable. As for Q, F, Cl, Br, I,
OCH ₃ and OC ₂ H ₅ are preferable.

[0021]

[Chemical 87] about

[Chemical 88]

[Chemical 89]

[Chemical 90]

[Chemical Formula 91]

[Chemical Formula 92]

[Chemical formula 93]

[Chemical 94]

[Chemical 95]

[Chemical 96]

[Chemical 97]

[Chemical 98]

[Chemical 99]

[Chemical 100]

[Chemical 101]

[Chemical 102]

[Chemical 103]

[Chemical 104]

[Chemical 105]

[Chemical formula 106]

[Chemical formula 107]

[Chemical 108]

[Chemical 109]

[Chemical 110]

[Chemical 111]

[Chemical 112]

[Chemical 113]

[Chemical 114]

[Chemical 115]

[Chemical formula 116]

[Chemical 117]

[Chemical 118]

[Chemical formula 119]

[Chemical 120]

[Chemical 121]

[Chemical formula 122]

[Chemical 123]

[Chemical formula 124]

[Chemical 125]

[Chemical formula 126]

[Chemical 127]

[Chemical 128]

[Chemical formula 129]

[Chemical 130] Is practically preferable.

Next, a method for producing these compounds will be described. Although the reaction substrates differ slightly depending on the ring structure, they are commonly produced by the coupling reaction of the following organometallic reagents.

[Chemical 131]

[Chemical 132]

[Chemical 133]

[Chemical 134]

In the above production method, the R-halide, aromatic halide or silacyclohexyl halide is reacted with a metal in a solvent to obtain an organometallic reagent. For example, in the reaction shown in [Chemical Formula 133], an organometallic reagent is used.

[Chemical 135] Is the corresponding halide

[Chemical 136] It can be easily prepared from (P is a halogen atom). For example,
You can follow the route below.

[Chemical 137] (P and P'represent a halogen atom.)

In addition,

[Chemical 138] And alkyllithium are reacted to directly ortho-thiolate to give a compound

[Chemical 139] After synthesizing, it is also possible to follow the synthetic route described above.

For the reaction shown in [Chemical 134],

[Chemical 140] To

[Chemical 141] And replace it with

[Chemical 142] Can be obtained.

As the solvent used at this time, ether solvents such as diethyl ether and THF (tetrahydrofuran) and hydrocarbon solvents such as toluene and xylene can be used alone or in combination. At this time, an appropriate metal species is selected depending on the types of the substituents X, Y, P and P ¹ . Cl, Br and l are preferable as P and P ¹ .

The produced organometallic reagent is a silacyclohexane compound in which silicon is substituted with W and Q
1] or [Chemical 132], or with an aromatic halide such as [Chemical 133] or [Chemical 134].

At this time, the coupling reaction of [Chemical Formula 133] and [Chemical Formula 134] requires a heavy metal solvent. Particularly, palladium and nickel catalysts are preferable. For example, as a nickel catalyst, (1,3-bis (diphenylphosphino) propane) nickel chloride (II), (1,2
-Bis (diphenylphosphino) ethane) nickel chloride (II), bis (triphenylphosphine) nickel chloride (II), as a palladium catalyst, tetrakis (triphenylphosphine) palladium (0), di (1,2-bis ( Examples thereof include diphenylphosphino) ethane) palladium (0) and bis (dibenzylideneacetone) palladium (0).

Since the compound produced here is a mixture of the trans form and the cis form in the configuration of the silacyclohexane ring, the trans form is separated and purified by a conventional purification means such as chromatography or recrystallization. A silacyclohexane compound represented by the general formula (I) of the present invention is obtained.

The silacyclohexane compound of the present invention can be mixed with a known compound to obtain a liquid crystal composition.
The compound specifically mixed for producing the liquid crystal composition can be selected from the known compounds shown below.

[0031]

[Chemical 143]

[Chemical 144]

In addition, in [Chemical formula 143] and [Chemical formula 144], (M) and (N) are one or more F, C which are unsubstituted or substituted.
1, Br, CN, trans-1,4 having an alkyl group
-Cyclohexylene group, a ring in which one or two non-adjacent CH ₂ groups in a cyclohexane ring are replaced by O and S, 1,4-cyclohexenylene group, unsubstituted or one as a substituent Or two F, Cl, C
A 1,4-phenylene group having a H ₃ or CN group, or a ring in which one or two CH groups in the ring of the 1,4-phenylene group are replaced by N atoms.

A ¹ and A ² are --CH ₂ CH _2- , --CH = C
H -, - C≡C -, - CO 2 -, - OCO -, - CH 2 O
-, - represents a single bond or - OCH _2.

L (ell), m = 0, 1, 2 (provided that l +
m = 1, 2, 3, n = 0, 1, 2).

R is a linear alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms in which one or two hydrogen atoms are substituted with fluorine atoms, and a group having 3 to 8 carbon atoms. It is a branched alkyl group, an alkoxyalkyl group having 2 to 7 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.

X, Y and Z have the same definitions as in formula (I).

In the above, l (ell) and n = 2
In the case of, a heterocyclic ring may be contained in (M), and in the case of m = 2, a heterocyclic ring may be contained in (N).

The proportion of the silacyclohexane compound of the present invention in the liquid crystal composition is 1 to 2 inclusive,
50% by weight, preferably 5 to 30% by weight. In addition, the liquid crystal composition may include a pleochroic dye for forming a colored guest-host system or an additive for changing the dielectric anisotropy, the viscosity and the orientation of the nematic phase.

Using the liquid crystal composition thus formed, various liquid crystal display devices can be manufactured by a usual method. That is, the liquid crystal composition containing the silacyclohexane compound of the present invention is used as a liquid crystal display device by enclosing it between transparent substrates having electrodes of a desired shape. This element may have various undercoats, alignment control overcoats, polarizing plates, filters, reflective layers, etc., if necessary, and can be used as a multilayer cell, in combination with other display elements, or using a semiconductor substrate, Alternatively, various things such as using a light source can be used.

The driving method of the liquid crystal display device is a dynamic scattering (DSM) method, a twisted nematic (TN) method, a guest host (GH) method, a super twisted nematic (STN) method, a polymer dispersed liquid crystal (PDLC) method. For example, a method known in the liquid crystal display element industry can be adopted.

[0041]

EXAMPLES The present invention will be described in more detail with reference to specific examples.

"Example 1" 4 '-(trans-4-n
-Propyl-4-silacyclohexyl) -4-fluorobiphenyl 2.5 g (20 mmol) of n-propyl bromide was added to a mixture of 0.5 g (21 mmol) of magnesium and 50 ml of tetrahydrofuran (hereinafter abbreviated as "THF").
Was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added to 4 '-(4-chloro-4-silacyclohexyl) -4-.
Fluorobiphenyl 6.1 g (20 mmol) THF
4 '-(trans-4-n- was added dropwise to a 50 ml solution.
Propyl-4-silacyclohexyl) -4-fluorobiphenyl was obtained. This is a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, which was separated by chromatography to give 5.7 g of trans isomer (yield 91
%) Was obtained. The analysis results are shown below. IR (liquid film) νmax: 2918, 2854, 208
7, 1604, 1497, 1238, 987, 889,
816 cm ^-1 C-N transition temperature: 80.2 ° C NI transition temperature: 119.3 ° C

"Example 2" 4 '-(trans-4-
(1-Propenyl) -4-silacyclohexyl) -4-
Preparation of n-propylbiphenyl In Example 1, allyl chloride was replaced with n-propyl bromide, and 4 '-(4- was replaced with 4'-(4-chloro-4-silacyclohexyl) -4-fluorobiphenyl.
It was prepared in the same manner as in Example 1 except that chloro-4-silacyclohexyl) -4-n-propylbiphenyl was used.

Example 3 Preparation of 4 '-(trans-4-isobutyl-4-silacyclohexyl) -4-difluoromethoxybiphenyl Isobutyl bromide, 4'-(in place of n-propyl bromide in Example 1 4-chloro-4-silacyclohexyl) -4-fluorobiphenyl instead of 4'-
It was produced in the same manner as in Example 1 except that (4-chloro-4-silacyclohexyl) -4-difluoromethoxybiphenyl was used.

"Example 4" 4 '-(trans-4-n
-Propyl-4-silacyclohexyl) -3,4,5-
Preparation of trifluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
2.5 ml of n-propyl bromide (20 ml) in a mixture of ml.
(mmol) was added dropwise to obtain a Grignard reagent. continue,
6.5 g of this solution was added to 4 '-(4-fluoro-4-silacyclohexyl) -3,4,5-trifluorobiphenyl.
(20 mmol) was added dropwise to a solution of 50 ml of THF to obtain 4 '.
-(Trans-4-n-propyl-4-silacyclohexyl) -3,4,5-trifluorobiphenyl was obtained. This was a mixture of a trans isomer and a cis isomer with respect to the silacyclohexane ring and was separated by chromatography to obtain 5.9 g of the trans isomer (yield 91%).

[Example 5] 4 '-(trans-4-n
-Pentyl-4-fluoro-4-silacyclohexyl)
Preparation of 4-trifluoromethylbiphenyl 0.5 g (21 mmol) of magnesium and THF50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was dropped into a solution of 7.1 g (20 mmol) of 4 '-(4,4-difluoro-4-silacyclohexyl) -4-trifluoromethylbiphenyl in 50 ml of THF to add 4'-(trans-4-. n-Pentyl-4-fluoro-4-silacyclohexyl) -4-trifluoromethylbiphenyl was obtained. This product was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, and was separated by chromatography to obtain 6.4 g of trans isomer (yield 78%).

"Example 6" 4 '-(trans-4-n
-Butyl-4-methyl-4-silacyclohexyl) -4
-Preparation of chloro-3,5-difluorobiphenyl 12.5 ml of 1.6M butyl lithium solution in hexane
Was added dropwise to a solution of 7.3 g (20 mmol) of 4 '-(4-chloro-4-methyl-4-silacyclohexyl) -4-chloro-3,5-difluorobiphenyl in 50 ml of THF, and 4'-(trans-4 -N-butyl-4-methyl-4-silacyclohexyl) -4-chloro-3,5-
Difluorobiphenyl was obtained. This is a mixture of trans-form and cis-form with respect to the silacyclohexane ring,
6.6 g of trans form separated by chromatography
(Yield 87%) was obtained.

"Example 7" 4 '-(trans-4-n
Preparation of -pentyl-4-silacyclohexyl) -2,2'-difluoro-4-propoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a solution of 7.5 g (20 mmol) of 4 '-(4-methoxy-4-silacyclohexyl) -2,2'-difluoro-4-propoxybiphenyl in 50 ml of THF to prepare 4'-(trans- 4-n-pentyl-
4-silacyclohexyl) -2,2'-difluoro-4
-Propoxybiphenyl was obtained. This is a mixture of a trans isomer and a cis isomer with respect to the silacyclohexane ring, and the trans isomer 7.
1 g (yield 86%) was obtained.

"Embodiment 8" 4 '-(trans-4-n
-Pentyl-4-silacyclohexyl) -2 ', 5'-
Preparation of difluoro-4-trifluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 4 '-(4-ethoxy-4-silacyclohexyl) -2', 5'-difluoro-4-trifluoromethoxybiphenyl 8.3 g (20 mmol) of TH.
F50 ml solution was added dropwise to 4 ′-(trans-4-n
-Pentyl-4-silacyclohexyl) -2 ', 5'-
Difluoro-4-trifluoromethoxybiphenyl was obtained. This product was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, and was separated by chromatography to obtain 7.5 g of the trans isomer (yield 85%).

"Example 9" 4 '-(trans-4-n
-Pentyl-4-methyl-4-silacyclohexyl)-
Preparation of 2'-fluoro-4-propylbiphenyl 0.5 g (21 mmol) magnesium and THF 50
7.1 g (20 mmol) of 4- (trans-4-n-pentyl-4-methyl-4-silacyclohexyl) -1-bromo-2-fluorobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. Then, p-
Propyl bromobenzene (4.0 g, 20 mmol) and tetrakis (triphenylphosphine) palladium (0) were added dropwise to a solution of 50 ml of THF to which a catalytic amount was added, and 4 '-(trans-4-n-pentyl-4-methyl-4-methyl-4- Silacyclohexyl) -2'-fluoro-4-
Propyl biphenyl was obtained. This was purified by chromatography to obtain 7.2 g of the desired product (yield 91%).

"Example 10" 4 '-(trans-4-
(1-Propenyl) -4-silacyclohexyl) -3-
Preparation of fluoro-4-trifluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
To a mixture of ml, p- (trans-4- (1-propenyl) -4-silacyclohexyl) chlorobenzene 5.
6 g (20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, 4.3 g (20 mmo) of 1-chloro-4-trifluoromethoxy-3-fluorobenzene was added to this solution.
l) and (1,3-bis (diphenylphosphino) propane) nickel chloride (II) in catalytic amounts
4 '-(trans-4
-(1-Propenyl) -4-silacyclohexyl) -3
-Fluoro-4-trifluoromethoxybiphenyl was obtained. This is purified by chromatography to obtain the desired product 7.
4 g (yield 94%) was obtained.

"Embodiment 11" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -4-trifluoromethoxybiphenyl 0.5 g magnesium (21 mmol) and THF 50
In a mixture of ml, 6.5 g of p- (trans-4-n-pentyl-4-silacyclohexyl) bromobenzene
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a THF solution of 2.1 g of trimethyl borate and then hydrolyzed with an acid to obtain a boric acid derivative. Next, 4.8 g (20 mmol) of p-trifluoromethoxybromobenzene and tetrakis (triphenylphosphine) palladium (0) were added dropwise to a 50 ml solution of THF to which a catalytic amount was added, and 4 ′-(trans-
4-n-pentyl-4-silacyclohexyl) -4-trifluoromethoxybiphenyl was obtained. This was purified by chromatography to give 7.4 g of the desired product (yield 91%).
Got The analysis results are shown below. C-S transition temperature: 68.3 ° C S-N transition temperature: 103.1 ° C NI transition temperature: 113.9 ° C

"Example 12" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -2-fluoro-4-methoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 6.5 g of p- (trans-4-n-pentyl-4-silacyclohexyl) bromobenzene
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a solution of 2-fluoro-1-iodo-4-methoxybenzene (5.0 g, 20 mmol) and tetrakis (triphenylphosphine) palladium (0) in a catalytic amount of 50 ml of THF to obtain 4'-. (T
rans-4-n-pentyl-4-silacyclohexyl) -2-fluoro-4-methoxybiphenyl was obtained.
This is purified by chromatography to give 6.8 g of the desired product.
(Yield 92%) was obtained.

"Example 13" 4 '-(trans-4-
(3-methoxypropyl) -4-silacyclohexyl)
Preparation of 4-cyanobiphenyl 0.5 g (21 mmol) magnesium and THF 30
6.5 g (20 mmol) of p- (trans-4- (3-methoxypropyl) -4-silacyclohexyl) bromobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. This is treated with 2.8 g (20 mmol) of zinc chloride in T
It was added dropwise to a 20 ml HF solution to obtain an organozinc reagent. Subsequently, 4.6 g of this solution was added to p-iodobenzonitrile.
(20 mmol) and tetrakis (triphenylphosphine) palladium (0) in a catalytic amount added to THF50
4 '-(trans-4- (3-
Methoxypropyl) -4-silacyclohexyl) -4-
Cyanobiphenyl was obtained. This was purified by chromatography to obtain 6.8 g of the desired product (yield 98%).

"Example 14" 4 '-(trans-4-
Preparation of n-propyl-4-silacyclohexyl) -3,4-difluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
3.0 g (20 mmol) of 1-chloro-3,4-difluorobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. Then, this solution was added to p- (trans-4-
6.9 g (20 mmol) of n-propyl-4-silacyclohexyl) iodobenzene and tetrakis (triphenylphosphine) palladium (0) were added dropwise to a solution of 50 ml of THF to which a catalytic amount was added, and 4 '-(trans-
4-n-propyl-4-silacyclohexyl) -3,4
-Difluorobiphenyl was obtained. This was purified by chromatography to obtain 6.4 g of the desired product (yield 97%). The analysis results are shown below. IR (liquid film) νmax: 2918, 2873, 210
0,1605,1504,1311,1119,98
5,889,812 cm ^-1 C-N transition temperature: 25.4 ° C NI transition temperature: 44.0 ° C

"Example 15" 4 '-(trans-4-
n-pentyl-4-silacyclohexyl) -4,2 ',
Preparation of 6'-trifluorobiphenyl 0.5 g (21 mmol) magnesium and ether 5
P-iodofluorobenzene 4.4 was added to 0 ml of the mixture.
g (20 mmol) was added dropwise to obtain a Grignard reagent.
Subsequently, the solution was treated with 4- (trans-4-n-pentyl-4-silacyclohexyl) -1-chloro-2,6-.
THF 50 m to which 6.3 g (20 mmol) of difluorobenzene and (1,3-bis (diphenylphosphino) propane) nickel chloride (II) were added in catalytic amounts
The resulting solution was added dropwise to the 1 solution to obtain 4 '-(trans-4-n-pentyl-4-silacyclohexyl) -4,2', 6'-trifluorobiphenyl. This was purified by chromatography to obtain 7.3 g of the desired product (yield 97%).

"Example 16" 4 '-(trans-4-
n-pentyl-1-silacyclohexyl) -2,2'-
Preparation of difluoro-4-propylbiphenyl 0.5 g (21 mmol) magnesium and THF 50
4-Bromo-2,2'-difluoro- was added to a mixture of ml.
6.2 g (20 mmol) of 4'-propylbiphenyl was added dropwise to obtain a Grignard reagent. Then add this solution to 4
-N-Pentyl-1-methoxy-1-silacyclohexane 4.0 g (20 mmol) was added dropwise to a solution of 50 ml of THF to obtain 4 '-(trans-4-n-pentyl-1-.
Silacyclohexyl) -2,2'-difluoro-4-propylbiphenyl was obtained. This was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, which was separated by chromatography to obtain 6.4 g of the trans isomer (yield 80%).

"Example 17" 4 '-(trans-4-
(3-methoxypropyl) -1-silacyclohexyl)
Preparation of 4-ethoxy-2-fluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
5.9 g (20 mmol) of 4, -bromo-2-fluoro-4-ethoxybiphenyl was added dropwise to the mixture of ml to obtain a Grignard reagent. Subsequently, this solution is 4- (3-
Methoxypropyl) -1-chloro-1-silacyclohexane 4.1 g (20 mmol) in a solution of 50 ml of THF was added dropwise to 4 '-(trans-4- (3-methoxypropyl) -1-silacyclohexyl) -4-ethoxy-. Two
-Fluorobiphenyl was obtained. This is a mixture of trans-form and cis-form with respect to the silacyclohexane ring,
6.7 g of trans form after separation by chromatography
(Yield 87%) was obtained.

"Example 18" 4 '-(trans-4-
Preparation of n-pentyl-1-silacyclohexyl) -2′-fluoro-4-propylbiphenyl 0.5 g (21 mmol) magnesium and ether 5
To 0 ml of the mixture, p-propyl bromobenzene 4.0
g (20 mmol) was added dropwise to obtain a Grignard reagent.
Subsequently, this solution was added to 1-chloro-2-fluoro-4-
(Trans-4-n-pentyl-1-silacyclohexyl) benzene 6.0 g (20 mmol) and (1,
3-bis (diphenylphosphino) propane) nickel chloride (II) was added dropwise to a solution of 50 ml of THF to which a catalytic amount was added, and 4 '-(trans-4-n-pentyl-
1-Silacyclohexyl) -2'-fluorobiphenyl was obtained. This was purified by chromatography to obtain 7.3 g of the desired product (yield 95%).

"Example 19" 4 '-(trans-4-
Preparation of isobutyl-1-silacyclohexyl) -4-difluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
To the mixture of ml, 3.6 g (20 mmol) of p-difluoromethoxychlorobenzene was added dropwise to obtain a Grignard reagent. Then, to this solution was added 6.2 g (20 mmol) of p- (trans-4-isobutyl-1-silacyclohexyl) bromobenzene and tetrakis (triphenylphosphino) palladium (0) in a catalytic amount.
4 '-(trans-4
-Isobutyl-1-silacyclohexyl) -4-difluoromethoxybiphenyl was obtained. This was purified by chromatography to obtain 7.0 g of the target product (yield 94%).

"Example 20" 4 '-(trans-4-
n-pentyl-1-methyl-1-silacyclohexyl)
Preparation of -4-pentoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
7.8 g (20 mmol) of p- (trans-4-n-pentyl-1-methyl-1-silacyclohexyl) iodobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a THF 50 ml solution in which 4.9 g (20 mmol) of p-pentoxybromobenzene and a catalytic amount of tetrakis (triphenylphosphine) palladium (0) were added, and 4′- ′ (trans).
-4-n-Pentyl-1-methyl-1-silacyclohexyl) -4-pentoxybiphenyl was obtained. This was purified by chromatography to obtain 7.7 g of the desired product (yield 91
%) Was obtained.

"Example 21" 4 '-(trans-4-
Preparation of n-pentyl-1-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl p- (trans-4-n was added to a mixture of 0.5 g (21 mmol) magnesium and 50 ml diethyl ether.
7.4 g (20 mmol) of -pentyl-1-silacyclohexyl) iodobenzene was added dropwise to obtain a Grignard reagent. Subsequently, 6.1 g (20 g) of 3,5-difluoro-1-iodo-4-difluoromethoxybenzene was added to this solution.
mmol) and tetrakis (triphenylphosphine) palladium (0) in a catalytic amount of THF 50 ml
4 '-(trans-4-n-pentyl-1-silacyclohexyl) -3,5-difluoro-4 was added dropwise to the solution.
-Difluoromethoxybiphenyl was obtained. This was purified by chromatography to obtain 7.9 g of the desired product (yield 93
%) Was obtained.

"Example 22" 4 '-(trans-4-
Preparation of n-pentyl-1-silacyclohexyl) -3-fluoro-4-cyanobiphenyl 0.5 g (21 mmol) magnesium and THF 30
4- (trans-4-n-pentyl-1-silacyclohexyl) -1-bromobenzene 6.
5 g (20 mmol) was added dropwise to obtain a Grignard reagent. This is zinc chloride 2.8 g (20 mmol) in THF
It was added dropwise to 20 ml to obtain an organozinc reagent. Subsequently, this solution was treated with 4-bromo-2-fluorobenzonitrile 4.
THF with catalytic amounts of 0 g (20 mmol) and tetrakis (triphenylphosphine) palladium (0)
The solution was added dropwise to a 50 ml solution, and 4 '-(trans-4-n
-Pentyl-1-silacyclohexyl) -3-fluoro-4-cyanobiphenyl was obtained. This was purified by chromatography to obtain 6.9 g of the desired product (yield 95%).

"Example 23" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -4-chloro-3-fluorobiphenyl 0.5 g (21 mmol) magnesium and THF 30
In a mixture of ml, 6.5 g of p- (trans-4-n-pentyl-4-silacyclohexyl) bromobenzene
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a solution of 4-chloro-3-fluoro-1-bromobenzene (4.2 g, 20 mmol) and tetrakis (triphenylphosphine) palladium (0) in a catalytic amount of 50 ml of THF to give 4'-. (Tr
ans-4-n-pentyl-4-silacyclohexyl)
-4-Chloro-3-fluorobiphenyl was obtained. This was purified by chromatography to obtain 6.8 g of the desired product (yield 98%). IR (liquid film) νmax: 2953, 2916, 287
0,2108,1479,1396,1200,98
5,879,812 cm ^-1 C-N transition temperature: 86.3 ° C NI transition temperature: 103.5 ° C

"Example 24" 4 '-(trans-4-
n-propyl-1-methyl-1-silacyclohexyl)
Preparation of 4-cyanobiphenyl 0.5 g (21 mmol) magnesium and THF 30
To a mixture of ml, 6.2 g (20 mmol) of 4- (trans-4-n-propyl-1-methyl-1-silacyclohexyl) -1-bromobenzene was added dropwise to obtain a Grignard reagent. This is 2.8 g of zinc chloride (20 mmo
l) was dropped into 20 ml of THF to obtain an organozinc reagent. Subsequently, this solution was treated with 4-bromobenzonitrile 3.
THF5 to which 7 g (20 mmol) and tetrakis (triphenylphosphine) palladium (0) were added in catalytic amounts
The solution was added dropwise to a 0 ml solution, and 4 '-(trans-4-n-
Propyl-1-methyl-1-silacyclohexyl) -4
-Cyanobiphenyl was obtained. This was purified by chromatography to obtain 6.1 g of the desired product (yield 91%). IR (liquid film) νmax: 2956, 2912, 283
9, 2224, 1606, 1254, 1113, 98
4,854,806 cm ^-1 C-I transition temperature: 87.0 ° C

"Example 25" 4 '-(trans-4-
n-butyl-1-methyl-1-silacyclohexyl)-
Preparation of 4-cyanobiphenyl 4- (trans-4-n-propyl-1 of Example 24
-Methyl-1-silacyclohexyl) -1-bromobenzene instead of 4- (trans-4-n-butyl-1)
-Methyl-1-silacyclohexyl) -1-bromobenzene was used and carried out as in Example 24 to give 4 '.
-(Trans-4-n-butyl-1-methyl-1-silacyclohexyl) -4-cyanobiphenyl was obtained. This was purified by chromatography to give 6.4 g of the desired product.
(Yield 92%) was obtained. IR (liquid film) νmax: 2956, 2918, 285
8, 2839, 2229, 1608, 1242, 111
5,978,850,812 cm ^-1 C-I transition temperature: 78.2 ° C

"Example 26" 4 '-(trans-4-
Preparation of n-pentyl-1-silacyclohexyl) -4-cyanobiphenyl 4- (trans-4-n-propyl-1 of Example 24
-Methyl-1-silacyclohexyl) -1-bromobenzene instead of 4- (trans-4-n-pentyl-
The procedure was the same as in Example 24 except that 1-silacyclohexyl) -1-bromobenzene was used, and 4 '-(tra
ns-4-n-pentyl-1-silacyclohexyl)-
4-Cyanobiphenyl was obtained. This was purified by chromatography to obtain 6.0 g of the desired product (yield 86%). IR (liquid film) νmax: 2954, 2924, 285
2,2229,2100,1608,1115,98
5,887,850,816,814,808 cm ^-1 C-S transition temperature: 79.1 ° C SN transition temperature: 78.5 ° C (monotropic) NI transition temperature: 114.3 ° C

"Example 27" 4 '-(trans-4-
Preparation of ethyl-4-silacyclohexyl) -4-fluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
3.5 g of p-fluorobromobenzene in a mixture of ml
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, the solution is treated with 4- (trans-4-ethyl-4-).
Silacyclohexyl) bromobenzene 5.7 g (20 m
mol) and tetrakis (triphenylphosphine) palladium (0) were added dropwise to a solution of 50 ml of THF to which a catalytic amount was added to obtain 4 ′-(trans-4-ethyl-4-silacyclohexyl) -4-fluorobiphenyl. This was purified by chromatography to give 5.6 g of the desired product.
(Yield 94%) was obtained. IR (liquid film) νmax: 2956, 2916, 287
3,2096,1495,1238,966,887,
881,814 cm ^-1 C-N transition temperature: 94.5 ° C NI transition temperature: 95.8 ° C

"Example 28" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -4-fluorobiphenyl 4- (tra-4-ethyl-4-silacyclohexyl) bromobenzene was replaced by 4- (tra).
ns-4-n-pentyl-4-silacyclohexyl) bromobenzene was used and carried out in the same manner as in Example 27 to obtain 4 '-(trans-4-n-pentyl-4-silacyclohexyl) -4-. Fluorobiphenyl was obtained. This is purified by chromatography to give 6.3 g of the desired product.
(Yield 93%) was obtained. IR (liquid film) νmax: 2916, 2852, 209
6,1495,1238,982,883,835,8
10 cm ^-1 C-N transition temperature: 70.8 ° C NI transition temperature: 117.8 ° C

"Example 29" 4 '-(trans-4-
(3-Methylbutyl) -4-silacyclohexyl)-
Preparation of 3,4-difluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
3.0 g of 3-methylbutyl bromide in a mixture of ml
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 6.5 g of 4 '-(4-chloro-4-silacyclohexyl) -3,4-difluorobiphenyl.
(20 mmol) in 50 ml of THF,
4 '-(trans-4- (3-methylbutyl) -4-
Silacyclohexyl) -3,4-difluorobiphenyl was obtained. This is a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, which was separated by chromatography to give 6.5 g of trans isomer (yield 9
0%). IR (liquid film) νmax: 2956, 2914, 287
2,2846,2108,1603,1527,150
6,1497,1269,1184,987,893
889,816 cm ^-1 C-N transition temperature: 64.3 ° C NI transition temperature: 32.6 ° C (monotropic)

"Example 30" 4 '-(trans-4-
(3-methoxypropyl) -4-silacyclohexyl)
Preparation of -3,4-difluorobiphenyl 3 instead of 3-methylbutyl bromide of Example 29
Example 2 except that -methoxypropyl bromide was used
9'and 4 '-(trans-4- (3-
Methoxypropyl) -4-silacyclohexyl) -3,
4-difluorobiphenyl was obtained. This was purified by chromatography to obtain 6.3 g of the desired product (yield 93%). IR (liquid film) νmax: 2908, 2906, 285
0,2098,1605,1529,1506,126
5,1184,1109,984,885,877,8
10 cm ^-1 C-N transition temperature: 58.3 ° C NI transition temperature: 60.1 ° C

"Example 31" 4 '-(trans-4-
(4-Pentenyl) -4-silacyclohexyl) -3,
Preparation of 4-difluorobiphenyl 4 instead of 3-methylbutyl bromide of Example 29
By the same procedure as in Example 29 except that -pentenyl bromide was used, 4 '-(trans-4- (4-pentenyl) -4-silacyclohexyl) -3,4-difluorobiphenyl was obtained. This was purified by chromatography to obtain 6.3 g of the desired product (yield 93%). IR (liquid film) νmax: 2918, 2850, 210
8,1603,1527,1510,1508,150
6,1404,1269,985,877,812cm
^-1 C-N transition temperature: 34.6 ° C N-I transition temperature: 32.4 ° C (monotropic)

"Example 32" 4 '-(trans-4-
Preparation of ethyl-4-silacyclohexyl) -3,4-difluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
3.9 g (20 mmol) of 3,4-difluorobromobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. Subsequently, this solution was added with 5.7 g of 4- (trans-4-ethyl-4-silacyclohexyl) bromobenzene.
(20 mmol) and tetrakis (triphenylphosphine) palladium (0) in a catalytic amount of THF 50 m
4 '-(trans-4-ethyl-
4-Silacyclohexyl) -3,4-difluorobiphenyl was obtained. This was purified by chromatography to obtain 6.1 g of the desired product (yield 88%). IR (liquid film) νmax: 2927, 2924, 287
7, 2110, 1603, 1531, 1506, 140
2,1120,987,887,879,808 cm ^-1 C-N transition temperature: 39.0 ° C NI transition temperature: 37.8 ° C (monotropic)

"Example 33" 4 '-(trans-4-
n-propyl-4-methyl-4-silacyclohexyl)
Preparation of -3,4-difluorobiphenyl Instead of 4- (trans-4-ethyl-4-silacyclohexyl) bromobenzene of Example 32, 4- (tr
Example 32 except that ans-4-n-propyl-4-methyl-4-silacyclohexyl) bromobenzene was used.
Carried out in the same manner as in 4 ′-(trans-4-n-propyl-4-methyl-4-silacyclohexyl) -3,4
-Difluorobiphenyl was obtained. This was purified by chromatography to obtain 6.6 g of the desired product (yield 96%). IR (liquid film) νmax: 2956, 2918, 287
3,2100,1529,1504,1404,111
9,985,889,877,812, cm ^-1 C-I transition temperature: 62.0 ° C

"Example 34" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -3,4-difluorobiphenyl Instead of 4- (trans-4-ethyl-4-silacyclohexyl) bromobenzene of Example 32, 4- (tr
ans-4-n-pentyl-4-silacyclohexyl)
The same procedure as in Example 32 was carried out except using bromobenzene to obtain 4 ′-(trans-4-n-pentyl-4-silacyclohexyl) -3,4-difluorobiphenyl. This was purified by chromatography to obtain 6.4 g of the desired product (yield 90%). IR (liquid film) νmax: 2958, 2916, 285
0,2108,1605,1527,1506,126
9,985,879,831,812 cm ^-1 C-N transition temperature: 48.1 ° C NI transition temperature: 63.8 ° C

"Example 35" 4 '-(trans-4-
n-pentyl-4-silacyclohexyl) -3,4
Preparation of 2 ′, 6′-tetrafluorobiphenyl 2,6-difluoro-4- (trans-4-n-pentyl) instead of 4- (trans-4-ethyl-4-silacyclohexyl) bromobenzene of Example 32. -4-
Example 4 was repeated except that silacyclohexyl) -1-bromobenzene was used, and 4 ′-(trans
-4-n-pentyl-4-silacyclohexyl) -3,
4,2 ', 6'-tetrafluorobiphenyl was obtained. This was purified by chromatography to give 6.7 g of the desired product.
(Yield 85%) was obtained. IR (liquid film) νmax: 2954, 2918, 284
5, 2110, 1639, 1491, 1410, 120
0,1119,1018,885,818 cm ^-1 C-I transition temperature: 63.1 ° C

"Example 36" 4 '-(trans-4-
n-pentyl-4-silacyclohexyl) -3,4
Preparation of 5,2′-tetrafluorobiphenyl In place of 4- (trans-4-ethyl-4-silacyclohexyl) bromobenzene of Example 32, 2-fluoro-4- (trans-4-n-pentyl-4-) was used. Silacyclohexyl) -1-bromobenzene, 3,4-
The procedure was the same as in Example 32 except that 3,4,5-trifluorobromobenzene was used instead of difluorobromobenzene, and 4 ′-(trans-4-n-pentyl-4-silacyclohexyl) -3 was used. , 4,5,2'-Tetrafluorobiphenyl was obtained. This was purified by chromatography to obtain 6.5 g of the desired product (yield 83%). IR (liquid film) νmax: 2956, 2920, 285
4,2102,1618,1537,1502,140
6,1120,1047,989,889,864,8
18 cm ^-1 C-N transition temperature: 23.7 ° C NI transition temperature: 3.8 ° C (monotropic)

"Example 37" 4 '-(trans-4-
Propyl-1 methyl-1-silacyclohexyl) -4-
Preparation of trifluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
To a mixture of ml, 4 '-(trans-4-propyl-
6.2 g (20 mmol) of 1-methyl-1-silacyclohexyl) bromobenzene was added dropwise to obtain a Grignard reagent. Then, this solution was dropped into a THF 50 ml solution in which 4.8 g (20 mmol) of p-trifluoromethoxybromobenzene and a catalytic amount of tetrakis (triphenylphosphine) palladium (0) were added, and 4 '-(tr
Ans-4-propyl-1 methyl-1-silacyclohexyl) -4-trifluoromethoxybiphenyl was obtained.
This is purified by chromatography to give 6.8 g of the desired product.
(Yield 87%) was obtained. IR (liquid film) νmax: 2956, 2910, 284
8,1518,1489,1259,1221,116
7,1115,804 cm ^-1 C-I transition temperature: -50 ° C or lower

"Example 38" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added to 4 ml of 4 '-(4-chloro-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl in 50 ml of THF.
Dropwise into solution, 4 '-(trans-4-n-pentyl-4-silacyclohexyl) -2'-fluoro-4-
Trifluoromethoxybiphenyl was obtained. This one is
Regarding the silacyclohexane ring, it was a mixture of trans isomer and cis isomer, and this was separated by chromatography to obtain 6.8 g of trans isomer (yield 80%). IR (liquid film) νmax: 2958, 2950, 285
4,2104,1624,1493,1259,121
3,1169, 989, 858, 818 cm ^-1 C-S transition temperature: 38.9 ° C SN transition temperature: -2.0 ° C (monotropic) NI transition temperature: 72.2 ° C

"Example 39" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -3-fluoro-4-difluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a solution of 4 '-(4-chloro-4-silacyclohexyl) -3-fluoro-4-difluoromethoxybiphenyl (7.4 g, 20 mmol) in 50 ml of THF to obtain 4'-(trans-4. -N-pentyl-
4-Silacyclohexyl) -3-fluoro-4-difluoromethoxybiphenyl was obtained. This was a mixture of a trans isomer and a cis isomer regarding the silacyclohexane ring, and this was separated by chromatography to obtain 6.6 g of the trans isomer (yield 81%). IR (liquid film) νmax: 2956, 2920, 285
2,2100,1593,1500,1402,114
2,1113,1061,987,887,879,8
12 cm ^-1 C-S transition temperature: 21.3 ° C S-N transition temperature: 30.8 ° C NI transition temperature: 83.5 ° C

"Example 40" 4 '-(trans-4-
Preparation of n-propyl-4-silacyclohexyl) -3-fluoro-4-difluoromethoxybiphenyl Performed in the same manner as in Example 39 except that n-propyl bromide in Example 39 was used in place of n-pentyl bromide. 4 '-(trans-4-n-propyl-4-
Silacyclohexyl) -3-fluoro-4-difluoromethoxybiphenyl was obtained. This was a mixture of a trans isomer and a cis isomer regarding the silacyclohexane ring, and this was separated by chromatography to obtain 6.1 g of the trans isomer (yield 80%). IR (liquid film) νmax: 2956, 2918, 210
2,1593,1500,1402,1140,111
1,1063,889,814 cm ^-1 C-S transition temperature: 33.9 ° C S-N transition temperature: 33.0 ° C (monotropic) NI transition temperature: 86.6 ° C

"Example 41" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 3.0 g of n-pentyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 4 '-(4-chloro-4-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl (7.8 g, 20 mmol) in THF 50 m.
It was added dropwise to the 1 solution to obtain 4 ′-(trans-4-n-pentyl-4-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl. This was a mixture of a trans isomer and a cis isomer regarding the silacyclohexane ring, and this was separated by chromatography to obtain 6.6 g of the trans isomer (yield 82%). IR (liquid film) νmax: 2920, 2852, 210
2,1601,1502,1381,1362,123
0,1146,1101,1038,877,822c
m ^-1 C-S transition temperature: 23.5 ° C NI transition temperature: 47.7 ° C

"Example 42" 4 '-(trans-4-
Production of n-propyl-4-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl Performed in the same manner as in Example 41 except that n-propyl bromide in Example 41 was used in place of n-pentyl bromide. Then, 4 '-(trans-4-n-propyl-4-
Silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl was obtained. This product was a mixture of a trans form and a cis form with respect to the silacyclohexane ring, and this was separated by chromatography to obtain 6.3 g of the trans form (yield 80%). IR (liquid film) νmax: 2904, 2840, 210
4,1599,1502,1404,1362,123
0,1115,1063,876,814 cm ^-1 C-S transition temperature: 43.1 ° C NI transition temperature: 45.5 ° C

"Example 43" 4 '-(trans-4-
Production of n-propyl-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl Performed in the same manner as in Example 38 except that n-propyl bromide in Example 38 was used instead of n-pentyl bromide. Then, 4 '-(trans-4-n-propyl-4-
Silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl was obtained. This was a mixture of trans and cis isomers with respect to the silacyclohexane ring, and this was separated by chromatography to obtain 6.4 g of the trans isomer (yield 81%). IR (KBr disc) νmax: 2958, 29
24, 2848, 2114, 1624, 1589, 14
93, 1273, 1209, 1163, 989, 88
9,825 cm ^-1 C-N transition temperature: 57.7 ° C NI transition temperature: 81.9 ° C

"Example 44" 4 '-(trans-4-
n-propyl-4-silacyclohexyl) -2 ', 4-
Preparation of difluorobiphenyl Magnesium 0.5 g (21 mmol) and THF 50
In a mixture of ml, 2.5 g of n-propyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 4 '-(4-chloro-4-silacyclohexyl) -3,5-difluoro-4-difluoromethoxybiphenyl (7.8 g, 20 mmol) in THF 50 m.
It was added dropwise to the 1 solution to obtain 4 '-(trans-4-n-propyl-4-silacyclohexyl) -2', 4-difluorobiphenyl. This is a mixture of trans-form and cis-form with respect to the silacyclohexane ring, which is separated by chromatography to give the trans-form 5.
4 g (yield 82%) was obtained. IR (KBr disc) νmax: 2958, 29
18,2845,2108,1603,1489,14
00, 1225, 1122, 985, 887, 841,
825 cm ^-1 C-N transition temperature: 69.2 ° C NI transition temperature: 71.1 ° C

"Example 45" 4 '-(trans-4-
n-pentyl-4-silacyclohexyl) -2 ', 4-
Preparation of difluorobiphenyl The procedure of Example 44 was repeated except that n-pentyl bromide in Example 44 was used in place of n-propyl bromide, and 4 '-(trans-4-n-pentyl-4-) was used.
Silacyclohexyl) -2 ', 4-difluorobiphenyl was obtained. This is related to the silacyclohexane ring,
It was a mixture of the trans form and the cis form, which was separated by chromatography to obtain 5.7 g of the trans form (yield 80%). IR (KBr disc) νmax: 2956, 29
18, 2846, 2104, 1603, 1489, 14
06, 1225, 1122, 987, 887, 845
823 cm ^-1 C-N transition temperature: 72.2 ° C NI transition temperature: 72.6 ° C

"Example 46" 4 '-(trans-4-
(4-Fluorobutyl) -4-silacyclohexyl)-
Preparation of 4-trifluoromethoxybiphenyl 0.5 g (21 mmol) magnesium and THF 50
4-fluorobutyl bromide 3.1 was added to the ml mixture.
g (20 mmol) was added dropwise to obtain a Grignard reagent.
Subsequently, this solution was added dropwise to a solution of 7.4 g (20 mmol) of 4 '-(4-chloro-4-silacyclohexyl) -4-trifluoromethoxybiphenyl in 50 ml of THF, and 4'-(trans-4- (4 -Fluorobutyl) -4-silacyclohexyl) -4-trifluoromethoxybiphenyl was obtained. This is a mixture of trans-form and cis-form with respect to the silacyclohexane ring,
This was separated by chromatography to obtain 5.8 g of trans isomer (yield 71%).

"Example 47" 4 '-(trans-4-
(4-fluoropentyl) -4-silacyclohexyl)
Production of -3,4-difluorobiphenyl 0.5 g (21 mmol) magnesium and THF 50
4-fluoropentyl bromide 3.
4 g (20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 4 '-(4-chloro-4-silacyclohexyl) -3,4-difluorobiphenyl 6.
It was added dropwise to a solution of 5 g (20 mmol) in 50 ml of THF to obtain 4 ′-(trans-4- (4-fluoropentyl) -4-silacyclohexyl) -3,4-difluorobiphenyl. This is a mixture of trans-form and cis-form with respect to the silacyclohexane ring, which was separated by chromatography to give the trans-form 6.3.
g (yield 74%) was obtained.

"Example 48" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -2,3-difluoro-4-ethoxybiphenyl 4 '-(4-chloro-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxy of Example 38. The same procedure as in Example 38 was carried out except that 4 ′-(4-chloro-4-silacyclohexyl) -2,3-difluoro-4-ethoxybiphenyl was used instead of biphenyl,
4 '-(trans-4-n-pentyl-4-silacyclohexyl) -2,3-difluoro-4-ethoxybiphenyl was obtained. This is a mixture of a trans isomer and a cis isomer with respect to the silacyclohexane ring, which was separated by chromatography to give 6.8 g of the trans isomer.
(Yield 85%) was obtained. IR (KBr disc) νmax: 2920, 28
99, 2846, 2112, 1502, 1473, 13
15, 1296, 1145, 1076, 879, 818
cm ^-1 C-N transition temperature: 74.7 ° C N-I transition temperature: 139.1 ° C

"Example 49" 4 '-(trans-4-
Preparation of n-pentyl-4-silacyclohexyl) -4-chloro-3,5-difluorobiphenyl 4 '-(4-chloro-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxy of Example 38. 4 ′ was carried out in the same manner as in Example 38 except that 4 ′-(4-chloro-4-silacyclohexyl) -4-chloro-3,5-difluorobiphenyl was used instead of biphenyl.
-(Trans-4-n-pentyl-4-silacyclohexyl) -4-chloro-3,5-difluorobiphenyl was obtained. This is a mixture of a trans isomer and a cis isomer with respect to the silacyclohexane ring, which was separated by chromatography to give 6.3 g of the trans isomer (yield 8
0%). IR (KBr disc) νmax: 2916, 28
46, 2102, 1639, 1578, 1437, 13
96, 1198, 1093, 1018, 887, 83
1,816 cm ^-1 C-N transition temperature: 75.0 ° C NI transition temperature: 69.0 ° C (monotropic)

"Example 50" 4 '-(trans-4-
n-pentyl-4-silacyclohexyl) -2 ', 6'
-Preparation of difluoro-4-trifluoromethoxybiphenyl In place of 4 '-(4-chloro-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl of Example 38, 4'-(4-chloro -4-Silacyclohexyl) -2 ', 6'-difluoro-4-trifluoromethoxybiphenyl was used and carried out in the same manner as in Example 38 to give 4'-(trans-4-n-pentyl-4-. Silacyclohexyl) -2 ', 6'-difluoro-4-trifluoromethoxybiphenyl was obtained. This was a mixture of a trans isomer and a cis isomer regarding the silacyclohexane ring, and this was separated by chromatography to obtain 7.3 g of the trans isomer (yield 81%). IR (KBr disc) νmax: 2958, 29
20,2852,2127,1637,1566,14
31, 1269, 1227, 1157, 1018, 88
9,850,816 cm ^-1 C-I transition temperature: 62.7 ° C

Example 51 Trans-4- (2- (trans-4- (3,4-difluorophenyl) cyclohexyl) ethyl) -1-ethyl-1-cyclohexane 4
3 mol%, trans-4- (2- (trans-4-
17 mol% of (3,4-difluorophenyl) cyclohexyl) ethyl) -1-n-propyl-1-cyclohexane and trans-4- (2- (trans-4- (3,4)
-Difluorophenyl) cyclohexyl) ethyl) -1
The liquid crystal mixture A composed of 40 mol% of -n-pentyl-1-cyclohexane has the following properties. C-N transition temperature: -10.7 ° C N-I transition temperature: 93.8 ° C Threshold voltage (5 μm cell, 32 Hz): 2.50 V Refractive index anisotropy Δn (589 nm): 0.0720

It consists of 85 mol% of this mixture A and 15 mol% of 4 '-(trans-4-n-pentyl-4-silacyclohexyl) -2'-fluoro-4-trifluoromethoxybiphenyl obtained in Example 38. The liquid crystal mixture exhibited the following properties. C-N transition temperature: -16.1 ° C N-I transition temperature: 90.6 ° C Threshold voltage (5 μm cell, 32 Hz): 2.20 V Refractive index anisotropy Δn (589 nm): 0.0809

As described above, by adding the compound of the present invention, the nematic phase is expanded to a low temperature, that is, the fluidity (low viscosity) is given at a low temperature, the refractive index anisotropy is increased, and the driving threshold voltage is increased. Was reduced.

[0095]

INDUSTRIAL APPLICABILITY The liquid crystal compound of the present invention in which Si is introduced as a ring-constituting element has the effect of increasing the refractive index anisotropy and, in comparison with the conventional liquid crystal compound having a BCH structure of a similar hydrocarbon ring, Have the advantage of. (1) The following low-temperature performance is improved by having the nematic liquid crystal expanded to a low temperature. (2) The viscosity can be reduced at low temperature, and the response speed at low temperature can be improved. (3) Compatibility at low temperature is improved.

Further, the liquid crystal compound in which the substituent X in the general formula (I) is not R or OR has the effect of lowering the threshold voltage because of its large dielectric anisotropy, in addition to the above advantages.

The liquid crystal compound of the present invention is widely used as a base material constituting a main part of a liquid crystal phase, as in the conventional BCH structure liquid crystal compound having a similar hydrogen monoxide ring, depending on the selection of the substituents of the composition. it can.

Since the liquid crystal compound in which the substituent X in the general formula (I) is R or OR has a dielectric anisotropy close to zero, it may cause dynamic scattering (DS) or deformation of the aligned phase (DAP effect). It is preferable to use it for the liquid crystal phase of the display solution. Further, compounds in which X is other than that are preferably used for producing a liquid crystal phase having a large positive dielectric anisotropy for use in a display element based on a twisted nematic cell or a corosteric-nematic phase transition.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Kinsei Niigata Prefecture Nakakubiki-gun Kubiki-mura Large number 28 Nishifukushima 1 Shinsei Chemical Industry Co., Ltd. Synthetic Technology Research Institute (72) Inventor Tatsushi Kaneko Nikgata Pref. 1 of 28, Nishi-Fukushima, Kunagi-gun, Shinetsu Chemical Industry Co., Ltd. (72) Inventor, Ryuichi Saito 1 of 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata 1 Shin-Etsu Chemical Co., Ltd. (72) Inventor Hideshi Kurihara 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Shin-Etsu Chemical Co., Ltd. Corporate Research Center

Claims (7)

[Claims] 1. A silacyclohexane compound represented by the following general formula (I): [Chemical 1] In the formula, R is a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, and 2 to 7 carbon atoms. It represents an alkoxyalkyl group or an alkenyl group having 2 to 8 carbon atoms. [Chemical 2] Represents a trans-1-sila-1,4-cyclohexylene or trans-4-sila-1,4-cyclohexylene group in which silicon at the 1- or 4-position has a substituent of H, F, Cl or CH _3. . X is CN, F, Cl, CF ₃ , CF ₂ C
1, CHFCl, OCF ₃ , OCHF ₂ , OCF ₂ Cl,
It represents an OCHFCl, R or OR group (R is the same as defined in formula (I)). Y ₂ and Z each independently represent H or F. Y ₁ represents H, F or Cl. 2. An organometallic reagent RM (R is the same as defined in the general formula (I) of claim 1, M is MgP or ZnP (P
Represents a halogen atom) or Li. ) And a silacyclohexane compound (W represents an H, F, Cl or CH ₃ group, Q represents a halogen atom or an alkoxy group, and X, Y ₁ , Y ₂ and Z are the same as defined in the general formula (I) of claim 1. The manufacturing method of the silacyclohexane compound of Claim 1 by reaction with a. 3. An organometallic reagent (R and Z are the same as defined in the general formula (I) of claim 1,
M'is M or B (OR ') ₂ (R' represents a Me group or an H atom), and Represents a trans-1-sila-1,4-silacyclohexylene or trans-4-sila-1,4-cyclohexylene group in which the silicon at the 1- or 4-position has a H or CH ₃ substituent. ) And an aromatic compound The silacyclohexane compound according to claim 1, which is obtained by reaction with P ¹ represents Cl, Br or I, and X, Y ₁ and Y ₂ are the same as defined in the general formula (I) of claim 1. Manufacturing method. 4. An organometallic reagent embedded image (X, Y ₁ and Y ₂ are the same as defined in the general formula (I), M ′
Is the same as the definition in [Chemical Formula 4] of Claim 3. ) And a silacyclone hexane compound (R and Z are the same as defined in the general formula (I) of claim 1,
P ¹ is the same as the definition in [Chemical formula 6] of claim 3, Is the same as the definition in [Chemical Formula 5] of claim 3. The method for producing a silacyclohexane compound according to claim 1, which comprises reacting with 5. A silacyclohexane compound embedded image (R is the same as the definition in the general formula (I) of claim 1, and W and Q are the same as the definition in [formula 3] of claim 2).
Organometallic reagent (X, Y ₁ and Y ₂ are the same as defined in the general formula (I) of claim 1, M is MgP or ZnP (P is a halogen atom) or Li). Process for producing silacyclohexane compound. 6. A liquid crystal composition comprising the silacyclohexane compound according to claim 1. 7. A liquid crystal display device comprising the liquid crystal composition according to claim 6.