JPH08283275A - Silacyclohexane compound, its production and liquid crystal composition containing the same compound - Google Patents

Abstract

PURPOSE: To obtain the subject new compound for liquid crystal display elements, etc., containing a silacyclohexane ring, having a nematic liquid crystal phase extended to low temperatures, excellent in viscosity and compatibility at a low temperature and capable of providing a liquid crystal composition having good response speed at a low temperature. CONSTITUTION: This new silacyclohexane compound is expressed by formula I [R is a 1-10C alkyl, a 1-10C mono or difluoroalkyl, a 2-7C alkoxylakyl or a 2-8C alkenyl; either one of A ring and B ring is a trans-1(4)-sila-1,4- cyclohexylene and another is trans-1,4-cyclohexylene or trans-1(4)-sila-1,4- cyclohexylene; Z in CN, F, Cl, CF3 , OCF3 , etc.; L1 is H or F; L2 is H, F or Cl]. The compound has a nematic liquid crystal extended to low temperatures and is useful for liquid crystal compositions. The compound is obtained by reacting an organometallic reagent of the formula RM [M is MgP (P is a halogen) with a compound of formula II (Z is a halogen).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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),
There are various types such as a DS type (dynamic scattering type), a guest-host type, a DAP type (deformation of aligned phase), and an OMI type (optically mode sensing type). The most common display devices are those that have a twisted nematic structure based on the Schatt-Helfrich effect.

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. Further, 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 also an important property that the constituent components of the liquid crystal composition can be easily mixed with each other.

Among the liquid crystal compounds which can be these constituents, a compound having a cyclohexyl ring-butylene-cyclohexyl ring-phenyl ring structure has been conventionally known.

[0006]

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

From this point of view, the present invention is a liquid crystal material newly developed for the purpose of improving the properties of the liquid crystal material, and has a conventional structure of cyclohexyl ring-butylene-cyclohexyl ring-phenyl ring structure. It is an object of the present invention to provide a liquid crystal compound having a silacyclohexane ring which is completely different from the liquid crystal compound.

[0008]

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

[Chemical formula 26] 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 alkyl group having 3 to 8 carbon atoms, and 2 to 7 carbon atoms.
Represents an alkoxyalkyl group or an alkenyl group having 2 to 8 carbon atoms.

[Chemical 27] as well as

[Chemical 28] Is at least one of trans-1- whose silicon at the 1- or 4-position has a substituent of H, F, Cl or CH ₃ or Ar (Ar represents a phenyl group or a tolyl group).
Sila-1,4-cyclohexylene or trans-4-sila
-1,4-cyclohexylene group, the other is trans-1,
4-cyclohexylene group, the above trans-1-sila-
1,4-cyclohexylene group or trans-4-sila
Represents a 1,4-cyclohexylene group. Z is CN, F,
Cl, CF ₃ , CClF ₂ , CHClF, OCF ₃ , OC
_{ClF 2, OCHF 2, OCHClF,} (O) q -CY =
CX ₁ X ₂ (q represents 0 or 1, Y and X ₁ each independently represent H, F or Cl, and X ₂ represents F or Cl), O (CH ₂ ) _r ( CF ₂ ) _s X (r and s represent 0, 1 or 2 and r + s represents a number of 2, 3 or 4, and X represents H, F or Cl), R or OR group. L ₁ represents H or F. L ₂ is H,
Represents F or Cl. The silacyclohexane compound having an aryl group on silicon is desilylated with an electrophile, and further reduced to give H, F, Cl on the silicon.
Alternatively, it is converted to a silacyclohexane compound having a CH ₃ substituent.

The present invention also provides a silacyclohexane compound represented by the above general formula (I), which is characterized by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction using a specific organometallic reagent. It is a manufacturing method. The manufacturing method is shown below.

Organometallic reagent

[Chemical 29] And silacyclohexane compound

Embedded image (However,

[Chemical 31] as well as

Embedded image Is at least one of trans-1-sila-1,4-wherein silicon at the 1-position or 4-position has a substituent of H, CH ₃ or Ar (Ar represents a phenyl group or a tolyl group).
Cyclohexylene group or trans-4-sila-1,4-
The other is a cyclohexylene group, and the other is a trans-1,4-cyclohexylene group, the above-mentioned trans-1-sila-1,4-cyclohexylene group or trans-4-sila-1,4-cyclohexylene group. L ₁ , L ₂ and Z are the same as in claim 1. M is MgP (P represents a halogen atom (preferably Cl, Br or I)), ZnP or Li, Q
Is a halogen atom or an alkoxy group (preferably having a carbon number of 1 to
4 alkoxy group), a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. )) And a silacyclohexane compound represented by the above general formula (I).

Organometallic reagent

[Chemical 33] When

Embedded image (N and m are 0, 1, 2, 3 or 4 and represent an integer where n + m = 4), and the production of the silacyclohexane compound represented by the above general formula (I) is characterized. Method.

Organometallic reagent

Embedded image When

Embedded image A method for producing a silacyclohexane compound represented by the above general formula (I), characterized by reacting with

Organometallic reagent

Embedded image When

[Chemical 38] A method for producing a silacyclohexane compound represented by the above general formula (I), characterized by reacting with

Organic gold reagent

[Chemical Formula 39] (M ′ is MgP, ZnP (P represents a halogen atom (preferably Cl, Br or I)) or B (OY ₁ ).
₂ (Y ₁ is H or an alkyl group (preferably having 1 to 6 carbon atoms)
Represents an alkyl group). ) Represents. )When

[Chemical 40] (Q 'represents a halogen, a methanesulfonyloxy group, a benzenesulfonyloxy group, a P-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group.) A method for producing a silacyclohexane compound.

In the silacyclohexane compound represented by the general formula (I),

Embedded image The precursor of

Embedded image And / or

[Chemical 43] (R, L ₁ , L ₂ , and Z are the same as above.)

[Chemical 44] Or / and

Embedded image The compound which is is desilylated with an electrophile.

Embedded image Or / and

[Chemical 47] (Wherein Q ″ represents Cl, Br, I or a trifluoromethanesulfonyloxy group), and then the compound is reduced or methylated.

Embedded image Or

[Chemical 49] The method for producing a silacyclohexane compound according to claim 1, wherein the silacyclohexane compound is converted into

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

The novel compound represented by the general formula (I) is
Specifically, a silacyclohexane compound having a ring structure represented by the following [Chemical Formula 50] to [Chemical Formula 57] and containing at least one trans-1- or trans-4-silacyclohexane ring is there.

Embedded image

[Chemical 51]

Embedded image

Embedded image

[Chemical 54]

[Chemical 55]

[Chemical 56]

[Chemical 57]

In the formula, R represents any of the following (a) to (e). (A) 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. (B) a mono- or difluoroalkyl group having 1 to 10 carbon atoms, 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-difluorobutyl, 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, 3,3-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-difluorononyl, 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 groups. (C) a branched 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- Methyl pentyl, 1-
Ethyl pentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl or 3-methylheptyl group. (D) an alkoxyalkyl group having 2 to 7 carbon atoms, that is, methoxymethyl, ethoxymethyl, propoxylmethyl,
Butoxymethyl, pentoxymethyl, methoxyethyl,
Ethoxyethyl, propoxyethyl, butoxyethyl,
Methoxypropyl, ethoxypropyl, propoxypropyl, methoxybutyl, ethoxybutyl, methoxypentyl or ethoxypentyl groups. (E) an alkenyl group 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.

W represents H, F, Cl or CH ₃ .

Z is CN, F, Cl, CF ₃ , CCl
F ₂ , CHClF, OCF ₃ , OCClF ₂ , OCHF ₂ ,
_{OCHClF, (O) q -CY =} CX 1 X 2 (q represents 0 or 1, Y and X ₁ are each, independently of one another H,
Represents F or Cl, and X ₂ represents F or Cl. ),
O (CH ₂ ) _r (CF ₂ ) _s X (r and s are 0, 1 or 2
And r + s is 2, 3 or 4, and X represents H, F or Cl. ), R or OR groups.

L ₁ represents H or F. L ₂ represents H, F or Cl.

[0022]

Embedded image Specific examples include the following.

Embedded image

Embedded image

[Chemical formula 61]

Embedded image

[Chemical formula 63]

[Chemical 64]

Embedded image

[Chemical formula 66]

Of these, the ring structure is
0], [Chemical Formula 52] and [Chemical Formula 54] are practically desirable.

Regarding R, the following (f) to (j) are practically desirable. (F) An ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl group among the linear alkyl groups having 2 to 7 carbon atoms. (G) Of mono- or difluoroalkyl groups, 2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2-fluoropentyl, 2-fluorohexyl, 2-
Fluoroheptyl, 4-fluorobutyl, 4-fluoropentyl, 4-fluorohexyl, 4-fluoroheptyl,
5-fluoropentyl, 5-fluorohexyl, 5-fluoroheptyl, 6-fluorohexyl, 6-fluoroheptyl, 7-fluoroheptyl, 2,2-difluoroethyl, 2,2-difluoropropyl, 2,2-difluoro Butyl, 2,2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-difluorohexyl, 4,4-difluoro Heptyl, 5,5-
Difluoropentyl, 5,5-difluorohexyl,
5,5-difluoroheptyl, 6,6-difluorohexyl, 6,6-difluoroheptyl or 7,7-difluoroheptyl group. (H) Isopropyl among the branched chain alkyl groups, 1-
A methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl or 2-ethylhexyl group. (I) A methoxymethyl, methoxyethyl, methoxypropyl, methoxypentyl, ethoxymethyl, ethoxyethyl, propoxymethyl or pentoxymethyl group among the alkoxyalkyl groups having 2 to 6 carbon atoms. (J) Of the alkenyl groups, vinyl, 1-propenyl,
3-butenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 6-heptenyl or 7-octenyl groups.

As for W, H, F and CH ₃ groups are practically desirable.

Regarding [Chemical Formula 58], the following are preferable.

Embedded image

[Chemical 68]

[Chemical 69]

Embedded image

Embedded image

These compounds are obtained by combining an organometallic reagent with a compound having a leaving group such as a halogen atom, an alkoxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. Produced by carbon-carbon bond formation or carbon-silicon bond formation. The details will be described below.

Organometallic reagent

Embedded image When

Embedded image (M is MgP, ZnP (P represents a halogen atom (preferably Cl, Br or I)) or Li, Q is a halogen atom, an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), methanesulfonyloxy. Group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group.)

[Chemical 74] But

[Chemical 75] (W ¹ represents H, CH ₃ or Ar group), Q
As the halogen atom or the alkoxy group, a Cl, Br, OCH ₃ , or OCH ₂ CH ₃ group is particularly preferable, and this carbon-silicon bond forming reaction easily proceeds to give the desired product in a high yield. This reaction is preferably 0-150 ° C.
It takes 1 to 5 hours. As a solvent, ether, T
An ether type such as HF and dioxane, a hydrocarbon type such as benzene, toluene, xylene and isooctane, and a mixture thereof can be used.

In addition,

[Chemical 76] But

Embedded image Or

Embedded image , The carbon-carbon bond forming reaction is carried out in the presence of a catalytic amount of a copper salt. As a copper salt, copper chloride (I), copper bromide (I), copper iodide (I), copper cyanide (I), etc. 1
Divalent copper salts, copper (II) chloride, copper (II) bromide, copper (II) iodide, copper (II) acetate, etc., copper complexes such as dilithium tetrachlorocuprate, etc. Can be mentioned. Q is preferably a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group, and is particularly preferable because Br and I give the desired product in a high yield. These reactions are 0-150 ° C
Under the circumstances, it is preferably carried out for 1 to 5 hours. The solvent is usually diethyl ether, tetrahydrofuran,
Examples thereof include dimethoxyethane and digram.

Organometallic reagent

Embedded image When

Embedded image Reaction with or organometallic reagents

[Chemical 81] When

[Chemical formula 82] In the reaction with, these carbon-carbon bond forming reactions are carried out in the presence of catalytic amounts of copper salts. As the copper salt, a monovalent copper salt such as copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) cyanide, copper (II) chloride, copper bromide (I)
I), copper (II) iodide, copper (II) acetate, and other divalent copper salts; and copper complexes such as dilithium tetrachlorocuprate and the like. As Q, it is preferable to use a compound which is a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group,
In particular, Br, I, and p-toluenesulfonyloxy groups are preferable because they give the desired product in high yield. These reactions are preferably carried out at 0 to 150 ° C. for 1 to 5 hours. Examples of the solvent usually include diethyl ether, tetrahydrofuran, dimethoxyethane, digram and the like.

Next, an organometallic reagent

[Chemical 83] When

[Chemical 84] In reaction with

Embedded image But

[Chemical 86] (W ¹ represents H, CH ₃ or Ar group.), Q is preferably a halogen atom or an alkoxy group, and particularly Cl, Br, OCH ₃ , OCH ₂ CH ₃ group, The carbon-silicon bond forming reaction easily proceeds to give the desired product in a high yield. This reaction is preferably 0-
It is carried out at 150 ° C for 1 to 5 hours. As the solvent, ethers such as ether, THF and dioxane, benzene,
Hydrocarbons such as toluene, xylene and isooctane, and mixtures thereof can be used.

In addition,

[Chemical 87] But

Embedded image Or

[Chemical 89] Where the carbon-carbon bond forming reaction is carried out in the presence of a catalytic amount of a copper salt. As the copper salt, a monovalent copper salt such as copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) cyanide, copper (II) chloride, copper bromide (I)
I), copper (II) iodide, copper (II) acetate, and other divalent copper salts; and copper complexes such as dilithium tetrachlorocuprate and the like. Q is a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, p-
A toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group can be preferably mentioned, but a Br, I, p-toluenesulfonyloxy group is particularly preferable because it gives the target product in a high yield. These reactions are preferably carried out at 0 to 150 ° C. for 1 to 5 hours. Examples of the solvent usually include diethyl ether, tetrahydrofuran, dimethoxyethane, digram and the like.

Organometallic reagents

[Chemical 90] (M 'is MgP (P is a halogen atom (preferably Cl,
Represents Br or I). ), ZnP or B (OY ₁ )
₂ (Y ₁ is H or an alkyl group (preferably having 1 to 6 carbon atoms)
Represents an alkyl group). ) Represents. )When

Embedded image The reaction with is carried out in the presence of a transition metal catalyst. Particularly, palladium compounds and nickel compounds are preferable as the catalyst.

For example, as a nickel catalyst, (1,3-
Examples thereof include bis (diphenylphosphino) propane) nickel chloride (II), (1,2-bis (diphenylphosphino) ethane) nickel chloride (II), and bis (triphenylphosphine) nickel chloride (II).

As the palladium catalyst, tetrakis (triphenylphosphine) palladium (0), di (1,2-bis (diphenylphosphino) ethane) palladium (0), bis (dibenzylideneacetone) palladium (0), etc. Is mentioned.

Q'is preferably a halogen atom, particularly C
l, Br, and I are preferable because they give the target compounds in high yield.

Among the silacyclohexane compounds represented by the general formula (I), the aryl silacyclohexane compounds in which W = Ar are chlorosilacyclohexane, fluorosilacyclohexane, as shown in the reaction formula of the partial structural formula below. Converted to hydrosilacyclohexane compound.

Embedded image

When an arylsilacyclohexane compound (a compound in which W is Ar in the general formula (I)) is reacted with an electrophile, a chlorosilacyclohexane compound (W in the general formula (I) is reacted by a halodecylation reaction.
A compound in which is Cl. The desilylation reaction is preferably 0 to 80 ° C., more preferably 10
It may be carried out at -40 ° C. The solvent is preferably a halogenated hydrocarbon, and specific examples thereof include chloromethylene, chloroform, carbon tetrachloride and the like.

Examples of the electrophile include halogen, hydrogen halide, metal halide, sulfonic acid derivative, acid halide, alkyl halide and the like. In particular, iodine, bromine, chlorine, iodine monochloride, hydrogen chloride, hydrogen bromide, hydrogen iodide, mercury (II) chloride, trimethylsilyl chlorosulfonate, acetyl chloride, acetyl bromide,
Benzoyl chloride and t-butyl chloride can be preferably exemplified. Further, in order to increase the reaction rate, Lewis acids such as aluminum chloride, zinc chloride, titanium tetrachloride and boron trifluoride may be added or light may be irradiated.

The obtained chlorosilacyclohexane compound is reacted with a fluoride salt such as cesium fluoride, copper (I) fluoride, antimony fluoride, zinc fluoride, calcium fluoride, and tetra-n-butylammonium fluoride. Then, a fluorosilacyclohexane compound (general formula (I)
In which W is F). The fluorination is preferably performed at 0 ° C to the reflux temperature of the solvent. Examples of the solvent include hexane, heptane, benzene, toluene and the like.

When the obtained chlorosilacyclohexane compound is reacted with CH ₃ M (M represents MgP (P represents a halogen atom), ZnP or Li),
A methylsilacyclohexane compound (when W is CH ₃ in the general formula (I)) is obtained.

Further, a chlorosilacyclohexane compound or a fluorosilacyclohexane compound is added to sodium hydride, calcium hydride, trialkylsilanes, boranes, metal hydrides such as dialkylaluminum, lithium aluminum hydride, sodium borohydride, Complex hydride compounds such as lithium borohydride, potassium borohydride, and tributylammonium borohydride (Co
When reacted with mild compounds and the like under mild conditions, a hydrosilacyclohexane compound (a compound in which W is H in the general formula (I)) is obtained. Such reduction reaction is preferably at -50 ° C to 100 ° C,
Further, it may be carried out at -20 ° C to 70 ° C. Examples of the solvent include ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, and the like.

When the compound produced here is a mixture of a trans form and a 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.

Embedded image

Embedded image

[Formula 93] [Formula 94]
(M) and (N) are (1) unsubstituted or substituted as 1
Or 1,2 or more F, Cl, Br, CN, trans-1,4-cyclohexylene group having an alkyl group, (2)
A ring in which one or two non-adjacent CH ₂ groups in the cyclohexane ring are replaced by O and S, (3) 1,
4-cyclohexenylene group, (4) unsubstituted or 1,4-phenylene group having 1 or 2 F, Cl, CH ₃ or CN group as a substituent, (5) 1,4-phenylene group Represents either a ring in which one or two CH groups in the ring have been replaced by N atoms.

A¹ , A² Is -CH₂CH₂-,-CH = CH
-, -C≡C, -CO₂-, -OCO-, -CH₂O-, -OCH₂
-Or represents a single bond.

I, j = 0, 1, 2 (where i + j = 1,
2,3, k = 0,1,2).

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 alkyl group having 3 to 8 carbon atoms, and 2 to 7 carbon atoms.
Or an alkenyl group having 2 to 8 carbon atoms.

L ₁ , L ₂ and Z have the same definitions as in formula (I).

In the above, when i and k are 2, a heterocyclic ring may be contained in (M), and when j is 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 or 2 or more.
˜50 mol%, preferably 5 to 30 mol%.
In addition, the liquid crystal composition may include, for example, a general formula for producing a colored guest-host system.

Embedded image (In the formula, R ′ and R ′ ″ are a substituted or unsubstituted alkyl group or a dialkylamino group, and in the case of a substituted alkyl group, those substituted with a plurality of fluorine atoms or not adjacent in the chain —CH ₂ — is O, S, NH, SO ₂ , O ₂
C, or

[Chemical 96] Or

[Chemical 97]Is replaced with. Z¹~ Z⁹Is hydrogen, methyl
Group, methoxy group (preferably methoxy having 1 to 4 carbon atoms)
Group) and a halogen group. Also, Z¹And Z², Z^FourAnd Z^Five,
Z⁷And Z⁸Is an aliphatic ring, an aromatic ring, or
Can form a nitrogen-containing aromatic ring. Y² Is
Represents a fluoroalkyl group. a = 0, 1, 2, b = 0,
1, 2, c = 0, 1 is shown, but when b = 0, it is always c
= 0. ) Azo dye represented by or a general formula

Embedded image (In the formula, X ^{1 to} X ⁵ are H, OH, halogen, CN, unsubstituted or substituent-containing amino group, unsubstituted or substituent-containing carboxylic acid ester, unsubstituted or substituent-containing phenyloxy group, unsubstituted Or a substituent-containing benzyl group, an unsubstituted or substituent-containing phenylthio group, an unsubstituted or substituent-containing phenyl group, an unsubstituted or substituent-containing cyclohexyloxycarbonyl group, or an unsubstituted or substituent-containing pyridyl or pyrimidyl group The anthraquinone-based dye represented by the formula (3) or an additive for changing the orientation of the dielectric anisotropy or the viscosity nematic phase can be contained.

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 device may have various undercoats, alignment control overcoats, polarizing plates, filters, reflective layers, etc., if necessary, and can be used as a multilayer cell, combined with other display devices, or using a semiconductor substrate. Alternatively, a variety of things such as using a light source can be used.

As a driving method of the liquid crystal display element, a dynamic scattering (DSM) method, a twisted nematic (TN) method, a guest-host (GH) method, a super twisted nematic (STN) method,
A method known in the liquid crystal display device industry such as a polymer dispersed liquid crystal (PDLC) method can be adopted.

Next, the method for producing the raw material used in the production method of the present invention will be described. A method for producing the following compound described in [Chemical Formula 7].

Embedded image

(1)

[Chemical 100] When there is silicon at the 1-position of, for example, Wittig reaction from silacyclohexanecarbaldehyde and hydrogenation for butylation, and further halogenation of the terminal, M
Obtained by coupling with an aromatic compound in the presence of g. Further, when Q is an alkoxy group, Mg
Obtained by alkoxylation in the presence.

[Chemical 101] (P represents halogen.)

(2)

Embedded image When there is silicon at the 1-position of, for example, silacyclohexanone is subjected to a coupling reaction with a Grignard reagent, dehydration,
A silacyclohexane compound is obtained by hydrogenation. Furthermore, halodecylation was performed, and t-in the presence of Mg.
It is obtained by coupling reaction with a butyl-dimethylsilicon compound, deprotection, and halogenation or sulfonylation. Further, when Q is an alkoxy group, it can be obtained by alkoxylation in the presence of Mg.

Embedded image (P represents halogen. TBDMS represents t-butyl-dimethylsilyl group.)

(3)

[Chemical 104] When there is a silicon at the 4-position, it can be obtained, for example, by protecting silacyclohexanone with TBDMS, coupling reaction with a Grignard reagent, deprotection, and halogenation or sulfonylation. Further, when Q is an alkoxy group, Mg
Obtained by alkoxylation in the presence.

Embedded image

(4)

[Chemical formula 106] When there is a silicon at the 4-position, it is obtained, for example, by coupling a halosilacyclohexane compound with a Grignard reagent, halodecylation, coupling with an aromatic compound, deprotection, halogenation or sulfonylation. Further, when Q is an alkoxy group, it can be obtained by alkoxylation in the presence of Mg.

[Chemical formula 107] (P represents halogen.)

A process for producing the following compounds described in [Chemical formula 11] and [Chemical formula 12].

[Chemical 108]

[Chemical 109]

(1)

[Chemical 110] When there is silicon at the 1-position of the above, for example, it is obtained by coupling silacyclohexanone with an aromatic compound, dehydrating, hydrogenating, desilylating, reducing or methylating. When the terminal is M, it is obtained in the presence of Mg and Zn.

[Chemical 111]

(2)

[Chemical 112] When there is silicon at the 4th position of, for example,

[Chemical 113] Is desilylated, coupled with an aromatic compound, and halogenated or sulfonylated to obtain the compound.

[Chemical 114] (P represents halogen.)

[Chemical 115] (P represents halogen.)

A process for producing the following compounds described in [Chemical Formula 15] and [Chemical Formula 16].

[Chemical formula 116]

[Chemical 117]

(1)

[Chemical 118] When there is silicon at the 1-position of, the compound can be obtained, for example, by subjecting a cyclohexane compound to a coupling reaction with a Grignard reagent, deprotection, halogenation or sulfonylation. When the terminal is M ′, it can be obtained by subjecting Q to the presence of Mg and Zn and further boric acid.

[Chemical formula 119]

(2)

[Chemical 120] When there is silicon at the 1-position of the above, it can be obtained, for example, by reducing silacyclohexanone, halogenating or sulfonylating it, and further performing desilylation, followed by coupling reaction with a Grignard reagent.

[Chemical 121]

(3)

[Chemical formula 122] When there is silicon at the 4-position, the compound can be obtained, for example, by subjecting silacyclohexanone to Wittig reaction, hydrogenation, desilylation, coupling with a Grignard reagent for deprotection, and halogenation or sulfonylation.

[Chemical 123]

(4)

[Chemical formula 124] When there is silicon at the 4th position of, for example,

Embedded image Is subjected to a Grignard reaction and decylated to obtain.

[Chemical formula 126] (P represents halogen.)

[0067]

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

Example 1 Preparation of trans-4- (4- (4-trans-4- (4-cyanophenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 1-chloro-4- (4- (trans-4- (4-cyanophenyl) cyclohexyl) butyl) -1-silacyclohexane 37.4 g (0.1 mol) and tetrahydrofuran (hereinafter abbreviated as "THF") 300 ml 2.5M in mixed solution
50 ml of THF solution of n-propyl magnesium chloride
(0.13 mol) was added dropwise. The resulting target product was a mixture of a trans form and a cis form with respect to the silacyclohexane ring. After the usual post-treatment, these were separated by chromatography to obtain 38.2 g of the target product in the trans form (yield: 8
8%).

Example 2 Preparation of trans-4- (4- (trans-4- (4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-n-butyl-1-silacyclohexane. 1-chloro-4- (4- (trans-4- (4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-silacyclohexane 41.5 g (0.1 mmol) and THF 30 ml
50 ml (0.13 mol) of a 2.5 M solution of n-butylmagnesium chloride in THF was added dropwise to the mixed solution of. The resulting target product was a mixture of a trans form and a cis form with respect to the silacyclohexane ring. After the usual post-treatment, these were separated by chromatography to obtain 43.7 g (yield 90%) of the target product in the trans form. Obtained.

"Example 3" trans-4- (4- (trans-4- (3-fluoro-4-difluoromethoxyphenyl) cyclohexyl) butyl)
Production of -1-ethyl-1-silacyclohexane. 1-chloro-4- (4- (trans-4- (3-fluoro-4-
Difluoromethoxyphenyl) cyclohexyl) butyl) -1-silacyclohexane 43.3 g (10 mmol)
To a mixed solution of 1 ml of THF and 30 ml of THF, 130 ml (0.13 mol) of a 1M solution of ethylmagnesium bromide in THF was added dropwise. The resulting target product was a mixture of a trans form and a cis form with respect to the silacyclohexane ring. After the usual post-treatment, these were separated by chromatography to obtain 42.7 g of the target product in the trans form (yield 87%). Obtained.

Example 4 trans-4- (4- (trans-4- (4-cyanophenyl) cyclohexyl) butyl) -1- (4-pentenyl)-
Production of 1-silacyclohexane. 1M 4-Pentenyl magnesium bromide in THF
130 ml (0.13 mol) of the solution was added dropwise to a solution of 14.0 g of zinc chloride in 200 ml of THF to obtain an organozinc reagent.
This was added to a solution of 41.0 g (0.1 mol) of 1-chloro-4- (4- (trans-4- (4-cyanophenyl) cyclohexyl) butyl) -1-silacyclohexane in 300 ml of THF. The resulting target product was a mixture of a trans form and a cis form with respect to the silacyclohexane ring. After the usual post-treatment, these were separated by chromatography to obtain 40.8 g (yield 95%) of the target product in the trans form. Obtained.

Example 5 Trans-4- (4- (trans-4- (3,5-difluoro
-4-Cyanophenyl) cyclohexyl) butyl) -1-n
-Preparation of pentyl-1-silacyclohexane. 1-chloro-4- (4- (trans-4- (3,5-difluoro-4-cyanophenyl) cyclohexyl) butyl) -1-
Silacyclohexane 41.0 g (0.1 mol) and THF
To 300 ml of the mixed solution, 50 ml (0.13 mol) of 2.5M n-pentylmagnesium chloride in THF was added dropwise. The resulting target product is a mixture of a trans form and a cis form with respect to the silacyclohexane ring,
These were separated by chromatography to obtain 44.6 g (yield 87%) of the target compound in trans form.

Example 6 Preparation of trans-4- (4- (trans-4- (4-trifluoromethylphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
22.1 g (0.1 mol) of 1-bromo-4-n-propyl-4-silacyclohexane was added dropwise to 0 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4-
(Trans-4- (4-bromobutyl) cyclohexyl)-
1-Trifluoromethylbenzene 36.3g (0.1mo
l) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (4-trifluoromethylphenyl) cyclohexyl) butyl) -1-n-
Propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 42.5 g of the trans form (yield 75%).

Example 7 trans-4- (4- (trans-4- (3-fluoro-4-cyanophenyl) cyclohexyl) butyl) -1-ethyl-
Production of 1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
20.7 g (0.1 mol) of 1-bromo-4-ethyl-4-silacyclohexane was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4-
(Trans-4- (4-bromobutyl) cyclohexyl)-
2-Fluorobenzonitrile (33.8 g, 0.1 mol) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (3-fluoro-4-cyanophenyl) cyclohexyl) butyl) -1-ethyl-1-
Silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography and the trans form was 27.9 g.
(Yield 72%) was obtained.

Example 8 trans-4- (4- (trans-4- (3,5-difluoro
Preparation of 4- (2-fluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
22.1 g (0.1 mol) of 1-bromo-4-n-propyl-4-silacyclohexane was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4
-(Trans-4- (4-bromobutyl) cyclohexyl)
A solution of 39.1 g (0.1 mol) of 2,2,6-difluoro-1- (2-fluoroethoxy) benzene in 500 ml of THF was added dropwise. After normal post-treatment, trans-4- (4-
(Trans-4- (3,5-difluoro-4- (2-fluoroethoxy) phenyl) cyclohexyl) butyl) -1-
n-Propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 36.6 g (yield 81%) of trans form.

Example 9 Preparation of trans-4- (4- (trans-4- (4-trifluoromethylphenyl) cyclohexyl) butyl) -1- (3-methylbutyl) -1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture, 1-bromo-4- (3-methylbutyl)-
2-4.9 g (0.1 mol) of 4-silacyclohexane was added dropwise to obtain a Grignard reagent. Subsequently, this solution was diluted with dilithium tetrachloro cue plate (Li ₂ CuCl ₄ ).
1 g and 4- (trans-4- (4-trifluoromethylphenyl) cyclohexyl) butyl tosylate 43.9
g (0.1 ml) was added dropwise to a solution of 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-4- (4-
Trifluoromethylphenyl) cyclohexyl) butyl) -1- (3-methylbutyl) -1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 37.3 g (yield 82%) of the trans form.

Example 10 trans-4- (4- (trans-4- (3,5-difluoro
-4-trifluoromethoxyphenyl) cyclohexyl)
Butyl) -1- (4-fluorobutyl) -1-silacyclohexane. Magnesium 2.5 g (0.1 lmol) and THF 300
To a mixture of ml, 1-bromo-4- (4-fluorobutyl)-
2-5.3 g (0.1 mol) of 4-silacyclohexane was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4- (4-bromobutyl) cyclohexyl) -2,6-difluoro-1-trifluoromethoxybenzene 41. It was added dropwise to a solution of 0.5 g (0.1 ml) in 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (3,5-difluoro-4-trifluoromethoxyphenyl) cyclohexyl) butyl) -1- (4-fluorobutyl) -1-sila Cyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 39.6 g (yield 80%) of trans form.

Example 11 Preparation of trans-4- (4- (trans-4- (4-fluorophenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
In 0 ml of the mixture 31.3 g of 4- (trans-4- (4-bromobutyl) cyclohexyl) -1-fluorobenzene
(0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 1-bromo-4-n-propyl-4.
-Silacyclohexane 22.1 g (0.1 mol) of THF
It was added dropwise to the 500 ml solution. After normal post-treatment, transformer
-4- (4- (trans-4- (4-fluorophenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give a trans form (19.6 g, yield 52%).
%) Was obtained.

Example 12 trans-4- (4- (trans-4- (3-fluoro-4-n
Preparation of -propylphenyl) -1-silacyclohexyl) butyl) -1-ethylcyclohexane. 2.5 g (0.11 mol) magnesium and THF3
4- (trans-4- (4-bromobutyl) -4-silacyclohexyl) -2-fluoro-1-propylbenzene (37.1 g, 0.1 mol) was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. . Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 20.7 g of 0.1-bromo-4-ethylcyclohexane (0.1 mol
l) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (3-fluoro-
4-n-Propylphenyl) -1-silacyclohexyl) butyl) -1-ethylcyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 20.3 g (yield 50%) of trans form.

Example 13 Preparation of trans-4- (4- (trans-4- (4-chlorophenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
In a mixture of 00 ml, 33.0 g of 4- (trans-4- (4-bromobutyl) cyclohexyl) -1-chlorobenzene
(0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 1-bromo-4-n-propyl-
4-Silacyclohexane 22.1 g (0.1 mol) TH
F500 ml solution was added dropwise. After usual work-up, trans-4- (4- (trans-4- (4-chlorophenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 20.0 g of the trans isomer (yield 51
%) Was obtained.

"Example 14" trans-4- (4- (trans-4- (3-fluoro-4--
n-Propylphenyl) cyclohexyl) butyl) -1-
Production of n-butyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 35.5 g (0.1 mol) of 4- (trans-4- (4-bromobutyl) cyclohexyl) -2-fluoro-1-propylbenzene was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 1-bromo-4.
-n-butyl-4-silacyclohexane 23.5 g (0.1
(mol) in 500 ml of THF. After usual post treatment, trans-4- (4- (trans-4- (3-fluoro
-4-n-propylphenyl) cyclohexyl) butyl)-
1-n-Butyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 19.8 g (yield 46%) of trans form.

Example 15 trans-4- (4- (trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl) -1-ethyl
-Production of 1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
34.9 g (0.1 mol) of 1- (trans-4- (4-bromobutyl) cyclohexyl) -3,4,5-trifluorobenzene was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 1-bromo-4.
-Ethyl-4-silacyclohexane 20.7g (0.1mo
l) was added dropwise to a solution of 500 ml of THF. After usual work-up, trans-4- (4- (trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl) -1-ethyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give trans-form 1.
9.7 g (yield 50%) was obtained.

Example 16 trans-4- (4- (trans-4- (4-chlorodifluoromethylphenyl) cyclohexyl) butyl) -1-n-
Production of pentyl-1-silacyclohexane. 2.5 g (0.11 ml) magnesium and 30 THF
2 ml of trans-4-bromomethyl-1-n-pentyl-1-silacyclohexane was added to 0 ml of the mixture.
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate and copper (I) iodide.
A solution of 0.1 g and 36.6 g (0.1 mol) of 4- (trans-4- (3-bromopropyl) cyclohexyl) -1-chlorodifluoromethylbenzene in 500 ml of THF was added dropwise. After usual work-up, trans-4- (4- (trans-4- (4-chlorodifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 38.3 g of the trans form (yield: 82
%) Was obtained.

Example 17 trans-4- (4- (trans-4- (3-fluoro-4-trifluoromethylphenyl) cyclohexyl) butyl)
Production of -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
2 ml of trans-4-bromomethyl-1-n-pentyl-1-silacyclohexane (0.1 mol) was added to 0 ml of the mixture.
l) was added dropwise to obtain a Grignard reagent. This solution is then treated with 0.5 g of dilithium tetrachlorocuprate and 44.3 g (0.1 ml) of 3- (trans-4- (3-fluoro-4-trifluoromethylphenyl) cyclohexyl) propyltosylate in 500 ml of THF. Dropped into the solution. After normal post-treatment, trans-4- (4- (trans-
4- (3-Fluoro-4-trifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 38.0 g of the trans form (yield 81
%) Was obtained.

Example 18 trans-4- (4- (trans-4- (3,5-difluoro
-Preparation of 4- (2,2-difluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
2 ml of trans-4-bromomethyl-1-n-pentyl-1-silacyclohexane was added to 0 ml of the mixture.
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate and copper (I) iodide.
0.1 g and 4- (trans-4- (3-iodopropyl) cyclohexyl) -2,6-difluoro-1- (2,2
-Difluoroethoxy) benzene 44.8 g (0.1 mo
l) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (3,5-difluoro-4- (2,2-difluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1 -Obtained silacyclohexane. After the usual post-treatment, the product was purified by chromatography to give 41.7 g of the trans form (yield 83
%) Was obtained.

Example 19 Preparation of trans-4- (4- (trans-4- (4-trifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4-bromomethyl-1-n-
Propyl-1-silacyclohexane 23.5 g (0.mo
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate and copper (I) iodide.
0.1 g and 36.5 g (0.1 mol) of 4- (trans-4- (3-bromopropyl) cyclohexyl) -1-trifluoromethoxybenzene were added dropwise to a solution of 500 ml of THF. After usual work-up, trans-4- (4- (trans-4- (4-trifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give a trans form (36.9 g, yield 84%).
I got

Example 20 trans-4- (4- (trans-4- (3,5-difluoro
Production of -4-trifluoromethylphenyl) -1-silacyclohexyl) butyl) -1-n-propylcyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
21.9 g (0.1 mol) of trans-4-bromomethyl-1-n-propylcyclohexane was added dropwise to 0 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4- (3-bromopropyl) -4-silacyclohexyl) -2,6-difluoro-1- Trifluoromethylbenzene 40.1 g (0.1 mol) THF 50
It was added dropwise to the 0 ml solution. After normal post-treatment, transformer-4-
(4- (trans-4- (3,5-difluoro-4-trifluoromethylphenyl) -1-silacyclohexyl) butyl) -1-n-propylcyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 37.2 g (yield 81%) of trans form.

Example 21 trans-4- (4- (trans-4- (4- (2-fluoroethoxy) phenyl) cyclohexyl) butyl) -1-n
-Preparation of pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
In a mixture of 00 ml, 4- (trans-4- (3-bromopropyl) cyclohexyl) -1- (2-fluoroethoxy)
34.3 g (0.1 mol) of benzene was added dropwise to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans.
It was added dropwise to a solution of 26.3 g (0.1 mol) of 4-bromomethyl-1-n-pentyl-1-silacyclohexane in 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (4- (2-fluoroethoxy) phenyl))
Cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 36.5 g of the trans form (yield 8
2%) was obtained.

"Example 22" trans-4- (4- (trans-4- (3-fluoro-4--
Production of (2,2-difluorovinyloxy) phenyl) cyclohexyl) butyl) -1-n-butyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 4- (trans-4- (3-bromopropyl) cyclohexyl) -2-fluoro-1- (2,2-
Difluorovinyloxy) benzene 37.7 g (0.1 mo
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of dilithium tetrachlorocuprate and 32.5 g (0.1 mol) of THF 5 of trans-4-n-butyl-4-silacyclohexaylmethyl tosylate.
It was added dropwise to the 00 ml solution. After normal post-treatment, trans-
4- (4- (trans-4- (3-fluoro-4- (2,2-
Difluorovinyloxy) phenyl) cyclohexyl) butyl) -1-n-butyl-1-silacyclohexane was obtained.
After the usual post-treatment, the product was purified by chromatography to obtain 37.1 g (yield 79%) of trans form.

Example 23 trans-4- (4- (trans-4- (4- (2,2-difluorovinyl) phenyl) cyclohexyl) butyl)-
Production of 1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To a mixture of 0 ml, 34.3 g (0.1 mol) of 4- (trans-4- (3-bromopropyl) cyclohexyl) -1- (2,2-difluorovinyl) benzene was added dropwise to obtain a Grignard reagent. Then, this solution was added to a solution of 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 26.3 g (0.1 mol) of trans-4-bromomethyl-1-n-pentyl-1-silacyclohexane in 500 ml of THF. Dropped. After normal post-treatment, trans-4- (4-
(Trans-4- (4- (2,2-difluorovinyl) phenyl) cyclohexyl) butyl) -1-n-pentyl-1
-Silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 31.6 g of trans form.
(Yield 71%) was obtained.

Example 24 Preparation of trans-4- (4- (trans-4- (3-fluoro-4-ethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture 4- (trans-4- (3-bromopropyl) cyclohexyl) -2-fluorophenetole 34.
3 g (0.1 mol) was added dropwise to obtain a Grignard reagent.
This solution is subsequently treated with 0.5 g of triethyl phosphate,
Copper (I) iodide 0.1 g and trans-4-bromomethyl-1-n-pentyl-1-silacyclohexane 26.3 g
(0.1 mol) was added dropwise to a solution of 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-4- (3-
Fluoro-4-ethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained.
After the usual post-treatment, the product was purified by chromatography to obtain 36.0 g of trans isomer (yield 81%).

Example 25 Preparation of trans-4- (4- (trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl) -1-n-pentyl-4-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 33.5 g (0.1 mol) of 1- (trans-4- (3-bromopropyl) cyclohexyl) -3,4,5-trifluorobenzene was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4-.
21.9 g (0.1 mol) of n-pentyl-1-chloromethyl-1-silacyclohexane was added dropwise to a solution of 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-
4- (3,4,5-Trifluorophenyl) cyclohexyl) butyl) -1-n-pentyl-4-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 34.7 g (yield 79%) of trans form.

Example 26 Preparation of trans-4- (4- (trans-4- (4-chlorofluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.1 mol) and THF 30
To 0 ml of the mixture, trans-4- (2-bromoethyl) -1
27.7 g of n-pentyl-1-silacyclohexane (0.
1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 33.4 g (0.1 mol of 4- (trans-4- (2-bromoethyl) cyclohexyl) -1-fluorochloromethylbenzene. ) Was added dropwise to a solution of 500 ml of THF. After usual work-up, trans-4- (4- (trans-4- (4-chlorofluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post treatment, the product was purified by chromatography to give 39.3 g of the trans form (yield 87
%) Was obtained.

Example 27 Preparation of trans-4- (4- (trans-4- (3-fluoro-4-chlorodifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (2-bromoethyl)-
1-n-pentyl-1-silacyclohexane 27.7g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 37.0 g of 4- (trans-4- (2-bromoethyl) cyclohexyl) -2-fluoro-1-difluorochloromethylbenzene. (0.1 mol) T
It was added dropwise to a 500 ml HF solution. After the usual post-treatment, trans-4- (4- (trans-4- (3-fluoro-4-chlorodifluoromethylphenyl) cyclohexyl) butyl)
-1-n-Pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 43.2 g of trans isomer (yield 89%).

Example 28 trans-4- (4- (trans-4- (3,5-difluoro
-Preparation of 4-trifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.1 mol) and THF 30
To 0 ml of the mixture, trans-4- (2-bromoethyl) -1
27.7 g of n-pentyl-1-silacyclohexane (0.
1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, the solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1-trifluoromethylbenzene 37. 0.1 g (0.1 mol) TH
F500 ml solution was added dropwise. After the usual post-treatment, trans-4- (4- (trans-4- (3,5-difluoro-4-trifluoromethylphenyl) cyclohexyl) butyl)
-1-n-Pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 39.0 g of trans isomer (yield 80%).

Example 29 trans-4- (4- (trans-4- (4- (2,2-difluoroethoxy) phenyl) cyclohexyl) butyl)
Production of -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture, trans-4- (2-bromoethyl) -1
27.7 g of n-pentyl-1-silacyclohexane (0.
1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4- (2-bromoethyl) cyclohexyl) -1- (2,2-difluoroethoxy) benzene 34. 7 g (0.1 mol) of THF50
It was added dropwise to the 0 ml solution. After normal post-treatment, transformer-4-
(4- (trans-4- (4- (2,2-difluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give the trans form 3
3.9 g (yield 73%) was obtained.

Example 30 trans-4- (4- (trans-4- (3,5-difluoro
Production of -4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (2-bromoethyl)-
1-n-pentyl-1-silacyclohexane 27.7g
(0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1-difluoromethoxybenzene 36. It was added dropwise to a solution of 9 g (0.1 mol) in 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (3,5-difluoro-
4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 44.2 g of trans isomer (yield 91%).

Example 31 Preparation of trans-4- (4- (trans-4- (4-ethylphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 29.5 g of 4- (trans-4- (2-bromoethyl) cyclohexyl) -ethylbenzene
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (2-bromoethyl) -1-n-propyl-1-silacyclohexane 24.
It was added dropwise to a solution of 9 g (0.1 mol) in 500 ml of THF.
After the usual post-treatment, trans-4- (4- (trans-4-
(4-Ethylphenyl) cyclohexyl) butyl) -l-
n-Propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 31.4 g (yield: 82%) of the trans form.

Example 32 trans-4- (4- (trans-4- (4-chloro-3,
5-difluorophenyl) cyclohexyl) butyl) -1
-Preparation of n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
4- (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1-chlorobenzene (33.8 g, 0.1 mol) was added dropwise to 0 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of dilithium tetrachlorokyuplate and 32.5 of trans-4-n-propyl-4-silacyclohexylethyl tosylate.
g (0.1 mol) was added dropwise to a solution of 50 ml of THF. After normal post-treatment, trans-4- (4- (trans-4- (4-
Chloro-3,5-difluorophenyl) cyclohexyl)
Butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 34.4 g (yield 81%) of trans form.

Example 33 Trans-4- (4-trans-4- (4- (2,2-difluorovinyloxy) phenyl) cyclohexyl) butyl)
Preparation of -l-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
34.5 g (0.1 mol) of 4- (trans-4- (2-bromoethyl) cyclohexyl) -1- (2,2-difluorovinyloxy) benzene was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (2-bromoethyl) -1-n-pentyl-1.
-Silacyclohexane 27.7 g (0.1 mol) of THF
It was added dropwise to the 500 ml solution. After normal post-treatment, transformer
-4- (4- (trans-4- (4- (2,2-difluorovinyloxy) phenyl) cyclohexyl) butyl) -1-n
-Pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 36.8 g (yield 80%) of the trans form.

Example 34 trans-4- (4- (trans-4- (4- (2,2-difluorovinyloxy) -3,5-difluorophenyl))
Preparation of cyclohexyl) butyl) -1-n-butyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 4- (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1- (2,2
3-difluorovinyloxy) benzene 38.1 g (0.
1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 26.3 g of trans-4- (2-bromoethyl) -1-n-butyl-1-silacyclohexane.
(0.1 mol) was added dropwise to a solution of 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-4- (4-
(2,2-Difluorovinyloxy) -3,5-difluorophenyl) cyclohexyl) butyl) -1-n-butyl-
1-Silacyclohexane was obtained. After the usual work-up, the product was purified by chromatography to give the trans form 41.2.
g (yield 85%) was obtained.

Example 35 trans-4- (4- (trans-4- (4- (1,2-difluorovinyl) -2,6-difluorophenyl) cyclohexyl) butyl) -1-n-butyl- Production of 1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture 4- (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1-
(1,2-difluorovinyl) benzene 36.5 g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (2-bromoethyl) -1-n-butyl-1-silacyclohexane 26.3.
g (0.1 mol) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4-
(4- (1,2-difluorovinyl) -2,6-difluorophenyl) cyclohexyl) butyl) -1-n-butyl-
1-Silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give the trans form 35.4.
g (yield 76%) was obtained.

Example 36 Trans-4- (4- (trans-4- (4- (2,2,2-
Preparation of trifluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (3-bromopropyl) -1-n-pentyl-1-silacyclohexane 29. lg
(0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4-bromomethylcyclohexyl) -1- (2,2,2-trifluoroethoxy) benzene 35. 1 g (0.1 mol) of THF
It was added dropwise to the 500 ml solution. After normal post-treatment, transformer
-4- (4- (trans-4- (4- (2,2,2-trifluoroethoxy) phenyl) cyclohexyl) butyl)
-1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 38.0 g of trans isomer (yield 79%).

"Example 37" trans-4- (4- (trans-4- (3-fluoro-4--
Preparation of chlorofluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (3-bromopropyl) -1-n-pentyl-1-silacyclohexane 29.1
g (0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 33.8 g of 4- (trans-4-bromomethylcyclohexyl) -2-fluoro-1-chlorofluoromethylbenzene (0. 1 mol) of THF5
It was added dropwise to the 00 ml solution. After normal post-treatment, trans-
4- (4- (trans-4- (3-fluoro-4-chlorofluoromethylphenyl) cyclohexyl) butyl) -1-n
-Pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 40.7 g (yield 87%) of trans form.

Example 38 trans-4- (4- (trans-4- (3,5-difluoro
-Preparation of 4-chlorodifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (3-bromopropyl) -1-n-pentyl-1-silacyclohexane 29.1
g (0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 37.4 g of 4- (trans-4-bromomethylcyclohexyl) -2,6-difluoro-1-chlorodifluoromethylbenzene ( 0.1 mol) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, Trans-4- (4- (trans-4- (3,5-difluoro-
4-chlorodifluoromethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 38.7 g (yield 77%) of trans form.

Example 39 trans-4- (4- (trans 4- (3-fluoro-4-
Production of (2,2-difluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture, trans-4- (3-bromopropyl)
1-n-propyl-1-silacyclohexane 29.1g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4-bromomethylcyclohexyl) -2-fluoro-1- (2,2-difluoroethoxy) benzene 35. 0.1 g (0.1 mol)
Was added dropwise to a solution of THF in 500 ml. After normal post-treatment,
Trans-4- (4- (trans-4- (3-fluoro-4-
(2,2-Difluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 37.1 g (yield: 82%) of the trans form.

Example 40 trans-4- (4- (trans-4- (3,5-difluoro-4- (2,2,3,3-
Preparation of tetrafluoropropoxy) phenyl) cyclohexyl) butyl) -1-ethyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and TH
To a mixture of 300 ml of F, 29.1 g of trans-4- (3-bromopropyl) -1-ethyl-1-silacyclohexane.
(0.1 mol) was added dropwise to obtain a Grignard reagent. The solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (trans-4-bromomethylcyclohexyl) -2,6-difluoro-1- (2.
2,3,3-Tetrafluoropropoxy) benzene 4
It was added dropwise to a solution of 1.9 g (0.1 mol) in 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-
4- (3,5-Difluoro-4- (2,2,3,3-tetrafluoropropoxy) phenyl) cyclohexyl) butyl) -1-ethyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 42.6 g (yield 84%) of the trans form.

Example 41 Trans-4- (4- (trans-4- (4-ethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-
Production of silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
In a mixture of 00 ml, 29.7 g (0.1 mol) of 4- (trans-4-bromomethylcyclohexyl) phenetol
Was added dropwise to obtain a Grignard reagent. Then add this solution
0.5 g of triethyl phosphate, copper (I) iodide 0.
1 g and trans-4- (3-bromopropyl) -1-n
-Pentyl-1-silacyclohexane 29.1 g (0.1 m
ol) was added dropwise to a solution of 500 ml of THF. After the usual post-treatment, trans-4- (4- (trans-4- (4-ethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1
-Silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give 33.2 g of trans form.
(Yield 78%) was obtained.

Example 42 trans-4- (4- (trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl) -1- (3-
Production of methoxypropyl) -1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture 1- (trans-4-bromomethylcyclohexyl) -3,4,5-trifluorobenzene 30.
7 g (0.1 mol) was added dropwise to obtain a Grignard reagent.
This solution is subsequently treated with 0.5 g of triethyl phosphate,
500 g of THF containing 0.1 g of copper (I) iodide and 29.3 g (0.1 mol) of trans-4- (3-bromopropyl) -1- (3-methoxypropyl) -1-silacyclohexane.
l was added dropwise to the solution. After normal post-treatment, transformer-4-
(4- (trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl) -1- (3-methoxypropyl) -1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give the trans form 3
1.4 g (71% yield) was obtained.

Example 43 Trans-4- (4- (trans-4- (4- (1,2-difluorovinyl) phenyl) cyclohexyl) butyl)-
Production of 1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
4- (trans-4-bromomethylcyclohexyl) -1- (1,2-difluorovinyl) was added to 00 ml of the mixture.
31.5 g (0.1 mol) of benzene was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 26.3 g (0.1 mol of trans-4- (3-bromopropyl) -1-n-propyl-1-silacyclohexane. ) THF50
It was added dropwise to the 0 ml solution. After normal post-treatment, transformer-4
-(4- (trans-4- (4- (1,2-difluorovinyl) phenyl) cyclohexyl) butyl) -1-n-
Propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 36.5 g (yield 87%) of the trans form.

Example 44 trans-4- (4- (trans-4- (2,3-difluoro
-4-ethoxyphenyl) cyclohexyl) butyl) -1-
Production of n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture 4- (trans-4-bromomethylcyclohexyl) -2,3-difluorophenetole 33.3
g (0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (3-bromopropyl) -1-n-propyl-1-silacyclohexane 2
It was added dropwise to a solution of 6.3 g (0.1 mol) in 500 ml of THF. After normal post-treatment, trans-4- (4- (trans-
4- (2,3-Difluoro-4-ethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to give a trans form (37.6 g, yield 86%).
I got

Example 45 Preparation of trans-4- (4- (trans-4- (3,4-difluorophenyl) cyclohexyl) butyl) -1- (3-fluoropropyl) -1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To 00 ml of the mixture 1- (trans-4-bromomethylcyclohexyl) -3,4-difluorobenzene 28.9
g (0.1 mol) was added dropwise to obtain a Grignard reagent. Then, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper iodide and 28.1 g (0.1 mol of trans-4- (3-bromopropyl) -1- (3-fluoropropyl) -1-silacyclohexane. ) Was added dropwise to a solution of 500 ml of THF. After usual work-up, trans-4- (4- (trans-4- (3,4-difluorophenyl) cyclohexyl) butyl) -1- (3-fluoropropyl) -1-silacyclohexane was obtained. After the usual post-treatment, the product was purified by chromatography to obtain 33.7 g (yield: 82%) of trans form.

Example 46 Trans-4- (4- (trans-4- (4-chlorodifluoromethoxyphenyl) cyclohexyl) butyl) -1-n
Production of -propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
Trans-4- (4-bromobutyl) -1 was added to 0 ml of the mixture.
27.7 g of n-propyl-1-silacyclohexane (0.
1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (4-bromocyclohexyl).
-1-difluorochloromethoxybenzene 34.0g
(0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans isomer and cis isomer with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4-
17.9 g (yield 39%) of (4-chlorodifluoromethoxyphenyl) cyclohexyl) butyl) 1-n-propyl-1-silacyclohexane was obtained.

"Example 47" trans-4- (4- (trans-4- (3-fluoro-4-
Preparation of trifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (4-bromobutyl)
-1-n-propyl-1-silacyclohexane 27.7g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 34.1 g (0.1 mol) of 4- (4-bromocyclohexyl) -2-fluoro-1-trifluoromethoxybenzene. It was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans isomer and cis isomer with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (3-fluoro-4 -Trifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1
-20.4 g (yield 45%) of silacyclohexane was obtained.

"Example 48" trans-4- (4- (trans-4- (3,5-difluoro-
Preparation of 4- (2,2,3,3,3-pentafluoropropoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (4-bromobutyl)
-1-n-propyl-1-silacyclohexane 27.7
(0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (4-bromocyclohexyl) -2,6-difluoro-1- (2,2,3,3,3-).
Pentafluoropropoxy) benzene 42.3 g (0.
1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (3,
5-difluoro-4- (2,2,3,3,3-pentafluoropropoxy) phenyl) cyclohexyl) butyl)
19.0 g of -1-n-propyl-1-silacyclohexane
(Yield 35%) was obtained.

Example 49 trans-4- (4- (trans-4- (3-fluoro-4-
Production of (2,2,2-trifluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (4-bromobutyl)
-1-n-pentyl-1-silacyclohexane 30.5g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4- (4-bromocyclohexyl) -2-fluoro-1- (2,2,2-trifluoroethoxy) benzene 35. 0.5 g (0.1 mol) of THF5
It was added dropwise to the 00 ml solution. The resulting target product was a mixture of trans isomer and cis isomer with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (3-fluoro-4 -(2
2,2-Trifluoroethoxy) phenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane (19.4 g, yield 40%) was obtained.

“Example 50” trans-4- (4- (trans-4- (3-fluoro-4-difluoromethoxyphenyl) -1-silacyclohexyl))
Butyl) -1-n-pentylcyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, trans-4- (4-bromobutyl)
-1 -n-pentylcyclohexane 28.9g (0.1mo
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was treated with 4- (trans-4-chloro-4-silacyclohexyl) -2-fluoro-1-difluoromethoxybenzene 2
A solution of 9.5 g (0.1 mol) in 500 ml of THF was added dropwise. The resulting target product is a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, and is purified by chromatography after usual post-treatment to give trans-4- (4-
(Trans-4- (3-fluoro-4-difluoromethoxyphenyl) -1-silicahexyl) butyl) -1-n-
41.8 g (yield 89%) of pentylcyclohexane was obtained.

Example 51 Preparation of trans-4- (4- (trans-4- (3,4-difluorophenyl) cyclohexyl) butyl) -1-n-pentyl-4-methyl-4-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
In a mixture of 00 ml, 4- (4-bromocyclohexyl)-
34.1 g (0.1 mol) of 1,2-difluorobenzene was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate and 0.1 g of copper (I) iodide.
g and trans-4- (4-bromobutyl) -1-n-pentyl-4-methyl-4-silacyclohexane 31.9 g
(0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans isomer and cis isomer with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4-
(3,4-Difluorophenyl) cyclohexyl) butyl) -1-n-pentyl-4-methyl-4-silacyclohexane (16.7 g, yield 38%) was obtained.

Example 52 trans-4- (4- (trans-4- (2,3-difluoro
Production of -4-ethoxyphenyl) -1-silacyclohexyl) butyl) -1-n-pentylcyclohexane. 2.5 g (0.11 mol) magnesium and THF3
In a mixture of 00 ml, 4- (4-bromocyclohexyl)-
31.9 g of 2,3-difluorophenetole (0.1 mo
l) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate and copper (I) iodide.
0.1 g and trans-4- (4-bromobutyl) -1-
30.5 g of n-pentyl-1-silacyclohexane (0.
1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after usual post-treatment to obtain trans-4- (4- (trans-4- (2,
18.0 g (yield 39%) of 3-difluoro-4-ethoxyphenyl) -1-silacyclohexyl) butyl) -1-n-pentylcyclohexane was obtained.

"Example 53" trans-4- (4- (trans-4- (3-fluoro-4
Preparation of-(1,2-difluorovinyl) phenyl) cyclohexyl) butyl) -1-n-propylcyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To 0 ml of the mixture 4- (4-bromocyclohexyl) -2-
31.9 g (0.1 mol) of fluoro-1- (1,2-difluorovinyl) benzene was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with triethyl phosphate 0.
5 g, copper (I) iodide 0.1 g and trans-4- (4
-Bromobutyl) -1-n-propyl-1-silacyclohexane (27.7 g, 0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product is a mixture of trans-form and cis-form with respect to the cyclohexane ring, and after the usual post-treatment, it is purified by chromatography to give trans-4- (4-
(Trans-4- (3-fluoro-4- (1,2-difluorovinyl) phenyl) cyclohexyl) butyl) -1-
16.6 g of n-propylcyclohexane (yield 38
%)Obtained.

Example 54 Trans-4- (4- (trans-4- (2,3-difluoro
-4-ethylphenyl) cyclohexyl) butyl) -1-n
-Preparation of pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
In 0 ml of the mixture 4- (4-bromocyclohexyl)-
2,3-difluoro-1-ethylbenzene 30.3g
(0.1 mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (4-bromobutyl) -1-n-pentyl-1-silacyclohexane 30.
It was added dropwise to a solution of 5 g (0.1 mol) of THF in 500 ml.
The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, which was purified by chromatography after the usual post-treatment to obtain trans-4- (4- (trans-
16.9 g (yield 38%) of 4- (2,3-difluoro-4-ethylphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained.

Example 55 Trans-4- (4- (trans-4- (4- (1,2,2-
Trifluorovinyloxy) phenyl) cyclohexyl)
Butyl) -1-n-butyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
4- (4-bromocyclohexyl) -1 in 0 ml of the mixture
-(1,2,2-trifluorovinyloxy) benzene 3
3.5 g (0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is then treated with triethyl phosphate 0.5
g, copper (I) iodide 0.1 g and trans-4- (4-
Bromobutyl) -1-n-butyl-1-silacyclohexane (29.1 g, 0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and after purification by usual post-treatment, it was purified by chromatography to give trans-4- (4- (trans-4- (4- ( 1,7.1 g of 1,2,2-trifluorovinyloxy) phenyl) hexyl) butyl) -1-n-butyl-1-silacyclohexane (yield 37%)
Obtained.

Example 56 trans-4- (4- (trans-4- (4-chlorofluoromethoxyphenyl) cyclohexyl) butyl) -1-n-
Production of propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To the mixture (00 ml), trans-4- (4- (4-bromocyclohexyl) butyl) -1-n-propyl-1-silacyclohexane (36.0 g, 0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of tetrakistriphenylphosphine palladium and 1-bromo-4.
-Chlorofluoromethoxybenzene 24.0g (0.1m
ol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (4-chlorofluoromethoxy Phenyl) cyclohexyl) butyl)
15.2-g of -1-n-propyl-1-silacyclohexane
(Yield 35%) was obtained.

Example 57 Preparation of trans-4- (4- (trans-4- (3-fluoro-4-chlorodifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To the mixture (00 ml), trans-4- (4- (4-bromocyclohexyl) butyl) -1-n-propyl-1-silacyclohexane (36.0 g, 0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of tetrakistriphenylphosphine palladium and 1-bromo-4.
-Chlorodifluoromethoxy-3-fluorobenzene 2
It was added dropwise to a solution of 7.6 g (0.1 mol) in 500 ml of THF. The resulting target product was a mixture of trans isomer and cis isomer with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (3-fluoro-4 -Chlorodifluoromethoxyphenyl) cyclohexyl) butyl) -1-n-propyl-
11.9 g (yield 25%) of 1-silacyclohexane was obtained.

Example 58 trans-4- (4- (trans-4- (3-fluoro-4-
Production of (3,3,3-trifluoropropoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To the mixture (00 ml), trans-4- (4- (4-bromocyclohexyl) butyl) -1-n-propyl-1-silacyclohexane (36.0 g, 0.1 mol) was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of tetrakistriphenylphosphine palladium and 1-bromo-4.
-(3,3,3-Trifluoropropoxy) -3-fluorobenzene 28.7 g (0.1 mol) in THF 500 ml
Dropped into the solution. The resulting target product is a mixture of trans-form and cis-form with respect to the cyclohexane ring.
(4- (trans-4- (3-fluoro-4- (3,3,3
15.3 g (yield 32%) of -trifluoropropoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained.

"Example 59" trans-4- (4- (trans-4- (3-fluoro-4-
(3-chloropropoxy) phenyl) cyclohexyl)
Butyl) -1-n-propyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To a mixture of 0 ml, 34.0 g (0.1 mol) of trans-4- (4- (4-bromocyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was added dropwise to obtain a Grignard reagent. This solution is then treated with 0.5 g of tetrakistriphenylphosphine palladium and 1-bromo-4-
(3-chloropropoxy) -3-fluorobenzene 26.
It was added dropwise to a solution of 8 g (0.1 mol) in 500 ml of THF.
The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, which was purified by chromatography after the usual post-treatment to obtain trans-4- (4- (trans-
14.7 g (yield 32%) of 4- (3-fluoro-4- (3-chloropropoxy) phenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane was obtained.

Example 60 Trans-4- (4- (trans-4- (4-trifluoromethoxyphenyl) cyclohexyl) butyl) -1-ethyl
-1-Production of silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
To a mixture of 0 ml, 34.5 g (0.1 mol) of trans-4- (4- (4-bromocyclohexyl) butyl) -1-ethyl-1-silacyclohexane was added dropwise to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of tetrakistriphenylphosphine palladium and 24. l-bromo-4-trifluoromethoxybenzene. lg (0.1 mol) of T
It was added dropwise to a 500 ml HF solution. The resulting target product is a mixture of trans-form and cis-form with respect to the cyclohexane ring, which is purified by chromatography after usual post-treatment.
13.4 g of trans-4- (4- (trans-4- (4-trifluoromethoxyphenyl) cyclohexyl) butyl) -1-ethyl-1-silacyclohexane (yield 31%)
Obtained.

"Example 61" trans-4- (4- (trans-4- (4-chloro-3-
Fluorophenyl) cyclohexyl) butyl) -1-n-
Production of propyl-l-silacyclohexane. 2.5 g (0.11 mol) of magnesium and THF3
20.9 g (0.1 mol) of 1-bromo-3-fluoro-4-chlorobenzene was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (4- (4-bromocyclohexyl) butyl) -1-
36.0 g of n-propyl-1-silacyclohexane (0.
1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after usual post-treatment to obtain trans-4- (4- (trans-4- (4-
Chloro-3-fluorophenyl) cyclohexyl) butyl) -l-n-propyl-l-silacyclohexane 13.2
g (yield 32%) was obtained.

Example 62 of trans-4- (4- (trans-4- (2,3-difluoro-4-n-propylphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane Manufacturing. 2.5 g (0.11 mol) magnesium and THF3
To a mixture of 00 ml, 1-bromo-2,3-difluoro-4
-23.5 g (0.1 mol) of propylbenzene was added dropwise to obtain a Grignard reagent. The solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4- (4- (4- (4-bromocyclohexyl) butyl) -1-n-propyl-1-silacyclohexane 36. 0
g (0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-
4- (2,3-difluoro-4-n-propylphenyl) cyclohexyl) butyl) -1-n-propyl-1-silacyclohexane (14.9 g, yield 34%) was obtained.

Example 63 Transformer-4- (4- (trans-4- (4- (1,2,2
-Preparation of trifluorovinyl) -3,5-difluorophenyl) cyclohexyl) butyl) -1-n-pentyl-l-silacyclohexane. 2.5 g (0.11 mol) magnesium and THF3
To 00 ml of the mixture, 1-bromo-3,5-difluoro-4
-(1,2,2-trifluorovinyl) benzene 27.
3 g (0.1 mol) was added dropwise to obtain a Grignard reagent.
This solution is subsequently treated with 0.5 g of triethyl phosphate,
0.1 g of copper (I) iodide and trans-4- (4- (4-
Bromocyclohexyl) butyl) -1-n-pentyl-1-
Silacyclohexane 38.8 g (0.1 mol) THF
It was added dropwise to the 500 ml solution. The resulting target product was a mixture of a trans form and a cis form with respect to the cyclohexane ring, and after the usual post-treatment, the product was purified by chromatography to give trans-4- (4- (trans-4- (4- (1, There was obtained 19.1 g (yield 38%) of 2,2-trifluorovinyl) -3,5-difluorophenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane.

Example 64 Preparation of trans-4- (4- (trans-4- (3,4-difluorophenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
1-Bromo-3,4-difluorobenzene (19.3 g, 0.1 mol) was added dropwise to 0 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4-.
(4- (4-bromocyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane 38.8 g (0.1 mo
l) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and was purified by chromatography after the usual post-treatment to give trans-4- (4- (trans-4- (3,4 −
Difluorophenyl) cyclohexyl) butyl) -1-
13.8 g (yield 33%) of n-pentyl-1-silacyclohexane was obtained. C-N transition temperature: 28 ° C, NI transition temperature: 52 ° C IR (liquid film) νmax: 2922, 2850, 209
8, 1608, 1518, 1290, 1209, 111
5,976,887,816 cm ^-1

Example 65 Trans-4- (4- (trans-4- (3,4,5-
Preparation of trifluorophenyl) -1-silacyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane. Magnesium 2.5 g (0.11 mol) and THF 30
21.1 g (0.1 mol) of 1-bromo-3,4,5-trifluorobenzene was added dropwise to 0 ml of the mixture to obtain a Grignard reagent. This solution is subsequently treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans.
-4- (4- (4-Bromo-1-silacyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane 40.4
g (0.1 mol) was added dropwise to a solution of 500 ml of THF. The resulting target product was a mixture of trans-form and cis-form with respect to the cyclohexane ring, and after the usual post-treatment, it was purified by chromatography to give trans-4- (4- (trans-
13.1 g (yield 29%) of 4- (3,4,5-trifluorophenyl) -1-silacyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane was obtained.

Example 66 Preparation of trans-4- (4- (trans-4- (3,5-difluoro-4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-silacyclohexane . Magnesium 2.5g (0.11mo1) and THF3
35.1 g (0.1 mol) of trans-4- (2-bromoethyl) -1-n-pentyl-1-phenyl-1-silacyclohexane was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was treated with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and 4-
500 ml of THF containing 36.9 g (0.1 mol) of (trans-4- (2-bromoethyl) cyclohexyl) -2,6-difluoro-1-difluoromethoxybenzene.
Dropped into the solution. After the usual post-treatment, 4- (4- (trans-4- (3,5-difluoro-4-difluoromethoxyphenyl) cyclohexyl) butyl) -1-n-pentyl-1-phenyl-1-silacyclohexane was added. Obtained. To the compound obtained at room temperature, 300 ml of a 1.0 M solution of iodine monochloride in carbon tetrachloride was added and stirred for 30 minutes, and the reaction mixture was concentrated under reduced pressure to give 4- (4- (trans-4-
(3,5-Difluoro-4-difluoromethoxyphenyl) cyclohexyl) butyl-1-chloro-1-n-pentyl-1-silacyclohexane was obtained. The obtained condensate was dissolved in 200 ml of THF, a mixture of 4.0 g of lithium aluminum hydride and 50 ml of THF was added dropwise at 0 ° C, and the mixture was stirred for 1 hour. After that, 200 ml of 5% dilute hydrochloric acid
And extracted with ethyl acetate. The obtained extract was washed with brine, dried, concentrated, and separated by silica gel chromatography to give the target compound in the trans form as 43.
8 g (shrinkage 90%) were obtained.

Example 67 Trans-4- (4- (trans-4- (3,4,5-
Trifluorophenyl) cyclohexyl) butyl-1-
Production of propyl-1-silacyclohexane. Magnesium 2.5g (0.11mo1) and THF3
30.7 g (0.1 mol) of 1- (trans-4-bromomethylcyclohexyl) -3,4,5-trifluorobenzene was added dropwise to 00 ml of the mixture to obtain a Grignard reagent. Subsequently, this solution was added with 0.5 g of triethyl phosphate, 0.1 g of copper (I) iodide and trans-4.
38.1 g (0.1 mol) of-(3-bromopropyl) -1-propyl-1-tolyl-1-silacyclohexane
Was added dropwise to a solution of THF in 500 ml. After the usual post-treatment, 4- (4-trans-4- (3,4,5-trifluorophenyl) cyclohexyl) butyl-1-propyl-1-tolyl-1-silacyclohexane was obtained. To the compound obtained at room temperature, 300 ml of a 1.0 M solution of iodine monochloride in carbon tetrachloride was added and stirred for 30 minutes, the reaction mixture was concentrated under reduced pressure, and 4- (4- (trans-4- (3,4,5. −
Trifluorophenyl) cyclohexyl) butyl-1-
Chloro-1-propyl-1-silacyclohexane was obtained. The obtained condensate was dissolved in 200 ml of THF, a mixture of 4.0 g of lithium aluminum hydride and 50 ml of THF was added dropwise at 0 ° C, and the mixture was stirred for 1 hour. Then 5%
It was poured into 200 ml of diluted hydrochloric acid and extracted with ethyl acetate. The obtained extract was washed with brine, dried and concentrated, and separated by silica gel chromatography to obtain 30.6 g of the target compound in the trans form (shrinkage 69.2%).

[0135]

INDUSTRIAL APPLICABILITY The liquid crystal compound of the present invention in which Si is introduced as a ring-constituting element has a nematic liquid crystal phase expanded to a low temperature as compared with a conventional liquid crystal compound having a CQCP structure of a similar hydrocarbon ring. A performance improvement such as is observed. (1) Viscosity can be reduced at low temperatures, and the response speed is improved especially in the low temperature range. (2) Compatibility at low temperature is improved.

Further, the liquid crystal compound in which Z in the general formula (I) is neither R nor OR has the effect of lowering the threshold voltage because of its large dielectric anisotropy, in addition to the above advantages. . Further, the liquid crystal compound of the present invention has a CEC of a conventional similar hydrocarbon ring depending on the selection of the substituent.
Like the P-structured liquid crystal compound, it can be widely used as a base material that constitutes the main part of the liquid crystal phase.

Further, the substituent Z in the general formula (I) is R,
Since the liquid crystal compound of OR has a dielectric anisotropy close to zero, it is particularly useful as a liquid crystal phase for display based on dynamic scattering (DS) or deformation of the aligned phase (DAP effect). Also,
The compounds in which Z is other than that are particularly useful for the preparation of a liquid crystal phase having a large positive dielectric anisotropy for use in a display device 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, Kikugi-gun, Shinetsu Chemical Industry Co., Ltd. (72) Inventor, Kazuyuki Asakura 1 of 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata 1 Shin-Etsu Chemical Co., Ltd. In-house (72) Mutsuo Nakajima Mutsoo Nakajima 28-1, Nishi-Fukushima, Kubiki Village, Nakakubiki-gun, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd.

Claims (10)

[Claims] 1. A silacyclohexane compound represented by the following general formula (I): Embedded image 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 alkyl group having 3 to 8 carbon atoms, and 2 to 7 carbon atoms.
Represents an alkoxyalkyl group or an alkenyl group having 2 to 8 carbon atoms. Embedded image And Is at least one of trans-1-sila in which the silicon at the 1- or 4-position has a substituent of H, F, Cl, CH ₃ or Ar (Ar represents a phenyl group or a tolyl group).
-1,4-cyclohexylene or trans-4-sila-
1,4-cyclohexylene group, the other is trans-1,4
-Cyclohexylene group, the above trans-1-sila-1,
4-cyclohexylene group or trans-4-sila-1,
Represents a 4-cyclohexylene group. Z is CN, F, C
1, CF ₃ , CClF ₂ , CHClF, OCF ₃ , OCC
_{lF 2, OCHF 2, OCHClF,} (O) q -CY = C
X ₁ X ₂ (q represents 0 or 1, Y and X ₁ each independently represent H, F or Cl, and X ₂ represents F or Cl), O (CH ₂ ) _r ( CF ₂ ) _s X (r and s represent 0, 1 or 2 and r + s represents a number of 2, 3 or 4, and X represents H, F or Cl), R or OR group. L ₁ represents H or F. L ₂ is H, F
Or represents Cl. 2. At least one of the following in claim 1. And Is a trans-1-sila-1,4-cyclohexylene group or a trans-4-sila-1,4-cyclohexylene group in which the silicon at the 1-position or 4-position has a substituent of H, F, Cl or CH _3. A silacyclohexane compound. 3. An organometallic reagent And [Chemical 7] (However, And Is at least one of trans-1-sila-1,4-wherein silicon at the 1-position or 4-position has a substituent of H, CH ₃ or Ar (Ar represents a phenyl group or a tolyl group).
Cyclohexylene group or trans-4-sila-1,4-
The other is a cyclohexylene group, and the other is a trans-1,4-cyclohexylene group, the above-mentioned trans-1-sila-1,4-cyclohexylene group or trans-4-sila-1,4-cyclohexylene group. L ₁ , L ₂ and Z are the same as in claim 1. M is MgP (P represents a halogen atom),
ZnP or Li, Q is a halogen atom, an alkoxy group,
It represents a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. 2.) The method for producing a silacyclohexane compound according to claim 1, wherein 4. An organometallic reagent And [Chemical 11] The method for producing a silacyclohexane compound according to claim 1, wherein (n, m are 0, 1, 2, 3 or 4 and represents an integer of n + m = 4). 5. An organometallic reagent And [Chemical 13] The method for producing a silacyclohexane compound according to claim 1, which is characterized by reacting with. 6. An organometallic reagent embedded image And [Chemical 15] The method for producing a silacyclohexane compound according to claim 1, which is characterized by reacting with. 7. An organometallic wiping agent embedded image (M 'is MgP, ZnP (P represents a halogen atom.)
Alternatively, it represents B (OY ₁ ) ₂ (Y ₁ represents H or an alkyl group). ) And [Chemical 17] (Q 'represents a halogen, a methanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group.) The silacyclohexane compound according to claim 1, wherein Production method. 8. A partial structural formula among the silacyclohexane compounds represented by the general formula (I): And / or Is [Chemical 20] Or By desilylation of the compound of Or (Wherein Q ″ represents Cl, Br, I or a trifluoromethanesulfonyloxy group), and then the compound is reduced or methylated to give Or The method for producing a silacyclohexane compound according to claim 1, wherein the silacyclohexane compound is converted into 9. A liquid crystal composition comprising the compound according to claim 1. 10. A liquid crystal display device comprising the liquid crystal composition according to claim 9.