JPH07252273A - Silacyclohexane compound, its production and liquid crystal composition containing the compound - Google Patents

Abstract

PURPOSE:To obtain a new silacyclohexane compound having an expanded nematic liquid crystal phase and improved characteristics of liquid crystal substance and useful for liquid crystal display element, etc. CONSTITUTION:This silacyclohexane compound is expressed by formula I (R is a 1-10C straight-chain alkyl, a 1-10C mono or difluoroalkyl, etc.; at least one of the groups of formula II and formula III is a trans-1-sila-1,4-cyclohexylene or a trans-4-sila-1,4-cyclohexylene having H, F, Cl or CH3 substituent on 1- or 4-Si atom and the other is trans-1,4-cyclohexylene; X is CN, F, Cl, CF3, etc.; Z1 is H, F or Cl; Z2 is H or F), e.g. trans-4-(trans-4-(2-(3,4-difluorophenyl) ethyl)cyclohexyl)-1-n-propyl-lsilacyclohexane. The compound of formula I can be produced by the C-C bond forming reaction of a compound of formula R-M [M is MgP (P is a halogen), ZnP or Li] with a compound of formula IV (Q is a halogen, etc.), etc.

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 system, TN type (twisted nematic type), STN type (super twisted nematic type). , SBE type (super birefringence type),
DS type (dynamic scattering type), guest-host type, DAP type (aligned phase deformation type), PD type (polymer dispersion type) and O
There are various types such as MI type (optical mode interference type).
The most common display device is based on the Schut-Helfrich effect and has a twisted nematic structure.

The properties required of the liquid crystal composition used for these liquid crystal display devices are slightly different depending on the display system, but the liquid crystal temperature range is wide, moisture, air, light,
Stableness against heat, electric field, etc. is commonly required for all display methods. Furthermore, the liquid crystal composition has a low viscosity, and in the cell,
It is desirable to provide short address times, low threshold voltages and high contrast.

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

Among the liquid crystal compounds that can be these constituent components, one of the basic components that controls the electro-optical performance,
Conventionally, compounds having the following so-called cyclohexyl ring-cyclohexyl ring-ethylene-phenyl ring structure (ECCP structure) are known.

[Chemical 14] (See EP-125563)

[Chemical 15] (See EP-125563)

[Chemical 16] (See Tokuhei 4-501575)

[Chemical 17] (See Tokuhei 4-501575)

[Chemical 18] (See Tokuhei 4-501575)

[0006]

In recent years, as the applications of liquid crystal displays have expanded, the characteristics required of liquid crystal materials have become 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 characteristics of the liquid crystal material, and the above-mentioned conventional cyclohexyl ring-cyclohexyl ring-ethylene-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 a liquid crystal compound having an ECCP structure).

[0008]

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

[Chemical 19] However, 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 2 carbon atoms.
7 represents an alkoxyalkyl group having 7 or an alkenyl group having 2 to 8 carbon atoms.

[Chemical 20] as well as

[Chemical 21] 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.
Sila-1,4-cyclohexylene group or trans-4-
Sila-1,4-cyclohexylene group, the other is trans-1,4-cyclohexylene group, X is CN, F, Cl,
CF ₃ , OCF ₃ , OCHF ₂ , OCHFCl, CF ₂ C
1, represents an OCF ₂ Cl, R or OR group. Z ₁ represents H, F or Cl. Z ₂ represents H or F.

The present invention also relates to an organometallic reagent.

Embedded image RM (M represents MgP (P is a halogen atom), ZnP or Li)

[Chemical formula 23] (Q represents a halogen atom, an alkoxy group, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group or a p-toluenesulfonyl group.) With a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction. Which is a method for producing the silacyclohexane compound represented by the general formula (I).

The present invention also relates to an organometallic reagent.

[Chemical formula 24] When

[Chemical 25] (N and m are 0, 1 or 2 and represent an integer where n + m = 2) or by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction. It is a method for producing the silacyclohexane compound represented.

The present invention also relates to an organometallic reagent.

[Chemical formula 26] When

[Chemical 27] Is a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with the above.

The present invention also relates to an organometallic reagent.

[Chemical 28] When

[Chemical 29] Is a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with the above.

The present invention also relates to an organometallic reagent.

[Chemical 30] When

[Chemical 31] Is a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with the above.

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

The novel compound represented by the general formula (I) is
Specifically, it is a silacyclohexane compound having a ring structure represented by the following [Chemical Formula 32] to [Chemical Formula 39] and containing at least one trans-1- or trans-4-silacyclohexane ring. .

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

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, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-
Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group or n-decyl group. (B) a mono- or difluoroalkyl group having 1 to 10 carbon atoms, that is, a fluoromethyl group, a 1-fluoroethyl group,
1-fluoropropyl group, 1-fluorobutyl group, 1-
Fluoropentyl group, 1-fluorohexyl group, 1-fluoroheptyl group, 1-fluorooctyl group, 1-fluorononyl group, 1-fluorodecyl group, 2-fluoroethyl group, 2-fluoropropyl group, 2-fluorobutyl group Group, 2-fluoropentyl group, 2-fluorohexyl group, 2-fluoroheptyl group, 2-fluorooctyl group, 2-fluorononyl group, 2-fluorodecyl group, 3
-Fluoropropyl group, 3-fluorobutyl group, 3-fluoropentyl group, 3-fluorohexyl group, 3-fluoroheptyl group, 3-fluorooctyl group, 3-fluorononyl group, 3-fluorodecyl group, 4-fluoro Butyl group, 4-fluoropentyl group, 4-fluorohexyl group, 4-fluoroheptyl group, 4-fluorooctyl group, 4-fluorononyl group, 4-fluorodecyl group, 5
-Fluoropentyl group, 5-fluorohexyl group, 5-
Fluoroheptyl group, 5-fluorooctyl group, 5-fluorononyl group, 5-fluorodecyl group, 6-fluorohexyl group, 6-fluoroheptyl group, 6-fluorooctyl group, 6-fluorononyl group, 6-fluorodecyl group Group, 7-fluoroheptyl group, 7-fluorooctyl group, 7-fluorononyl group, 7-fluorodecyl group, 8
-Fluorooctyl group, 8-fluorononyl group, 8-fluorodecyl group, 9-fluorononyl group, 9-fluorodecyl group, 10-fluorodecyl group, difluoromethyl group, 1,1-difluoroethyl group, 1,1 -Difluoropropyl group, 1,1-difluorobutyl group, 1,1-difluoropentyl group, 1,1-difluorohexyl group,
1,1-difluoroheptyl group, 1,1-difluorooctyl group, 1,1-difluorononyl group, 1,1-difluorodecyl group, 2,2-difluoroethyl group, 2,2
-Difluoropropyl group, 2,2-difluorobutyl group, 2,2-difluoropentyl group, 2,2-difluorohexyl group, 2,2-difluoroheptyl group, 2,2
-Difluorooctyl group, 2,2-difluorononyl group, 2,2-difluorodecyl group, 3,3-difluoropropyl group, 3,3-difluorobutyl group, 3,3-difluoropentyl group, 3,3-difluoro Hexyl group,
3,3-difluoroheptyl group, 3,3-difluorooctyl group, 3,3-difluorononyl group, 3,3-difluorodecyl group, 4,4-difluorobutyl group, 4,4
-Difluoropentyl group, 4,4-difluorohexyl group, 4,4-difluoroheptyl group, 4,4-difluorooctyl group, 4,4-difluorononyl group, 4,4-
Difluorodecyl group, 5,5-difluoropentyl group,
5,5-difluorohexyl group, 5,5-difluoroheptyl group, 5,5-difluorooctyl group, 5,5-difluorononyl group, 5,5-difluorodecyl group, 6,
6-difluorohexyl group, 6,6-difluoroheptyl group, 6,6-difluorooctyl group, 6,6-difluorononyl group, 6,6-difluorodecyl group, 7,7-
Difluoroheptyl group, 7,7-difluorooctyl group, 7,7-difluorononyl group, 7,7-difluorodecyl group, 8,8-difluorooctyl group, 8,8-difluorononyl group, 8,8-difluorodecyl group Base, 9,
9-difluorononyl group, 9,9-difluorodecyl group or 10,10-difluorodecyl group. (C) a branched chain alkyl group having 3 to 8 carbon atoms, that is, isopropyl group, sec-butyl group, isobutyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3
-Methylpentyl group, 1-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group Or a 3-methylheptyl group. (D) an alkoxyalkyl group having 2 to 7 carbon atoms, that is, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentoxymethyl group, a hexyloxymethyl group, a methoxyethyl group, an ethoxyethyl group,
A propoxyethyl group, a butoxyethyl group, a pentoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, a butoxypropyl group, a methoxybutyl group, an ethoxybutyl group, a propoxybutyl group, a methoxypentyl group or an ethoxypentyl group. (E) an alkenyl group having 2 to 8 carbon atoms, that is, a vinyl group,
1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1
-Hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group or 7-octenyl group.

W, W ¹ and W ² are independently of each other H,
Represents F, Cl or CH ₃ .

X is CN, F, Cl, CF ₃ , OCF ₃ , O
CHF ₂ , OCHFCl, CF ₂ Cl, OCF ₂ Cl, R
Or represents OR.

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

[0019]

[Chemical 40] Specifically,

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44]

[Chemical formula 45]

[Chemical formula 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

[Chemical 53]

[Chemical 54]

[Chemical 55]

[Chemical 56]

[Chemical 57]

[Chemical 58]

[Chemical 59]

[Chemical 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

[Chemical 64] Etc.

Of these, the ring structure is described in [Chemical Formula 3]
The compounds of [2], [Chemical Formula 34] and [Chemical Formula 36] are practically desirable.

Regarding R, any of the following (f) to (j) is preferable. (F) A linear alkyl group having 3 to 7 carbon atoms, that is, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group or an n-heptyl group. (G) Among mono- or difluoroalkyl groups having 1 to 10 carbon atoms, 2-fluoroethyl group, 2-fluoropropyl group, 2-fluorobutyl group, 2-fluoropentyl group,
2-fluorohexyl group, 2-fluoroheptyl group, 4
-Fluorobutyl group, 4-fluoropentyl group, 4-fluorohexyl group, 4-fluoroheptyl group, 5-fluoropentyl group, 5-fluorohexyl group, 5-fluoroheptyl group, 6-fluorohexyl group, 6-fluoro Heptyl group, 7-fluoroheptyl group, 2,2-difluoroethyl group, 2,2-difluoropropyl group, 2,2
-Difluorobutyl group, 2,2-difluoropentyl group, 2,2-difluorohexyl group, 2,2-difluoroheptyl group, 4,4-difluorobutyl group, 4,4-
Difluoropentyl group, 4,4-difluorohexyl group, 4,4-difluoroheptyl group, 5,5-difluoropentyl group, 5,5-difluorohexyl group, 5,5
-Difluoroheptyl group, 6,6-difluorohexyl group, 6,6-difluoroheptyl group or 7,7-difluoroheptyl group. (H) of the branched chain alkyl groups, an isopropyl group, 1-
Methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group,
1-methylpentyl group, 2-methylpentyl group, 2-ethylhexyl group (i) C2-C6 alkoxyalkyl group, that is, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxypentyl group, ethoxymethyl group , Ethoxyethyl group, propoxymethyl group, pentoxymethyl group (j) Of the alkenyl groups, vinyl group, 1-propenyl group, 3-butenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1 -Hexenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group

For W, W ¹ and W ² , H, F or CH ₃
The group is practically desirable.

Regarding [Chemical 40], [Chemical 41],
[Chemical 42], [Chemical 44] to [Chemical 51], [Chemical 53]
[Chemical 55], [Chemical 59] to [Chemical 61], [Chemical 63],
[Chemical Formula 64] is preferable for practical use.

These compounds are organic metal reagents, halogen atoms, alkoxy groups, methanesulfonyl groups, trifluoromethanesulfonyl groups, benzenesulfonyl groups, p
-It is produced by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with a compound having a leaving group such as a toluenesulfonyl group. The details will be described below.

Organometallic reagent

[Image Omitted] RM

[Chemical formula 66] In reaction with

[Chemical formula 67] But

[Chemical 68] (W represents an H, F, Cl or CH ₃ group.), Examples of Q include a halogen atom and an alkoxy group,
In particular _Cl, Br, if OCH 3, _OCH 2 CH ₃ group, the carbon - silicon bond formation reaction proceeds easily and gives a high yield of the target product.

[Chemical formula 67] is

[Chemical 69] Or

[Chemical 70] , The carbon-carbon bond forming reaction is carried out in the presence of a catalytic amount of a copper salt. Examples of Q include a halogen atom, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, and a p-toluenesulfonyl group, and Br and I are particularly preferable because they give the target product in a high yield.

Organometallic reagent

[Chemical 71] When

[Chemical 72] In the reaction with (m, n) = (2,0) or (1,
In 1), these carbon-carbon bond forming reactions are carried out in the presence of catalytic amounts of copper salts. A compound that is MgP (P is a halogen atom), ZnP or Li as M, and a halogen atom, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group or a p-toluenesulfonyl group as Q can be used, but Br, in particular,
The I, p-toluenesulfonyl group is preferred because it gives the desired product in a high yield.

When (m, n) = (0,2), this reaction is carried out in the presence of a transition metal catalyst. Particularly, palladium compounds and nickel compounds are preferable as the catalyst. Examples of the palladium catalyst include zero-valent palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and di [1,2-bis (diphenylphosphino) ethane] palladium (0), or palladium acetate and palladium chloride. It is possible to use a divalent palladium compound such as the above, a complex compound consisting of these and a ligand, or a combination of these divalent palladium compounds and a reducing agent. Examples of the nickel catalyst include 1,2-bis (diphenylphosphino) ethane nickel (II) chloride, 1,3-bis (diphenylphosphino) propane nickel (II) chloride, and bis (triphenylphosphine) nickel (II). Examples thereof include divalent nickel compounds such as chloride and zero-valent nickel compounds such as tetrakis (triphenylphosphine) nickel (0). In particular, Cl, Br, and I are preferable as Q because they give the desired product in a high yield.

Organometallic reagent

[Chemical formula 73] When

[Chemical 74] In the reaction with, these carbon-carbon bond forming reactions are carried out in the presence of catalytic amounts of copper salts. As Q, a compound which is a halogen atom, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group or a p-toluenesulfonyl group can be used, but Br, I, and p-toluenesulfonyl group are particularly desirable in a high yield. It is preferable because it gives a product.

Next, an organometallic reagent

[Chemical 75] When

[Chemical 76] In reaction with

[Chemical 77] But

[Chemical 78] In the case of, Q includes a halogen atom and an alkoxy group, particularly Cl, Br, OCH ₃ , OCH ₂ C.
The H ₃ group is preferable because the carbon-silicon bond forming reaction easily proceeds to give the target product in a high yield.

[Chemical 77]

[Chemical 79] Or

[Chemical 80] (W represents an H, F, Cl or CH ₃ group), the carbon-carbon bond forming reaction is carried out in the presence of a catalytic amount of a copper salt. Examples of Q include a halogen atom, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, and a p-toluenesulfonyl group. Particularly, Br, I, and p-toluenesulfonyl group can be used as a target product at a high yield. It is preferable because it is given.

Next, an organometallic reagent

[Chemical 81] When

[Chemical formula 82] In reaction with

[Chemical 83] But

[Chemical 84] In the case of, Q includes a halogen atom and an alkoxy group, particularly Cl, Br, OCH ₃ , OCH ₂ C.
The H ₃ group is preferable because the carbon-silicon bond forming reaction easily proceeds to give the target product in a high yield.

[Chemical formula 83]

[Chemical 85] Or

[Chemical 86] Where the carbon-carbon bond forming reaction is carried out in the presence of a catalytic amount of a copper salt. Examples of Q include a halogen atom, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, and a p-toluenesulfonyl group. Particularly, Br, I, and p-toluenesulfonyl group can be used as a target product at a high yield. It is preferable because it is given.

Since 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 compounds specifically mixed to produce the liquid crystal composition are known compounds [Chemical Formula 87] and [Chemical Formula 88] shown below.
You can choose from.

[Chemical 87]

[Chemical 88]

In [Chemical Formula 87] and [Chemical Formula 88],
(M) and (N) represent any of the following. One or more F, C which are unsubstituted or substituted
1, Br, CN, trans-1,4 having an alkyl group
- trans -1 two CH ₂ groups not one or adjacent in cyclohexylene cyclohexane ring is replaced O, to S,
4-cyclohexylene group, 1,4-cyclohexenylene group, unsubstituted or substituted with 1 or 2 F, Cl, C
1,4-phenylene group having H ₃ or CN group 1,4-phenylene group in which 1 or 2 CH groups in the ring are replaced by N atoms

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

L (el) and m are 0, 1, 2 (where l
+ M = 1, 2, 3), and n is 0, 1, 2.

R is hydrogen, 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.
Is an alkoxyalkyl group or an alkenyl group having 2 to 8 carbon atoms.

X is CN, F, Cl, CF ₃ , OCF ₃ , O
CHF ₂ , OCHFCl, CF ₂ Cl, OCF ₂ Cl, R
OR, Z ₁ represents H, F or Cl, and Z ₂ represents H or F.

In the above, l (el) and n are 2
In case of, during (M), when m is 2, during (N),
Each may contain a heterocyclic ring.

The proportion of the silacyclohexane compound of the present invention in the liquid crystal phase is 1 to 50% by weight, preferably 5 to 30% by weight, of one kind or two or more kinds thereof. Further, the liquid crystal composition may contain a polychromatic dye for forming a colored guest-host system, or an additive for changing the dielectric anisotropy, the viscosity, and the orientation of the nematic phase.

The liquid crystal phase thus formed is used as a liquid crystal display device by enclosing it between transparent substrates having electrodes of a desired shape. This element may have various undercoats, alignment control overcoats, polarizing plates, filters, reflective layers, and the like, if necessary. Further, various types such as a multi-layer cell, a combination with another display element, a semiconductor substrate, or a light source can be used.

As a driving method of the liquid crystal display device, a dynamic scattering (DSM) method, a twisted nematic (TN) method, a super twisted nematic (STN) method, a polymer dispersion (PD) method, a guest host (GH) method, etc., A method known in the liquid crystal display device industry can be adopted.

[0045]

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

[Example 1] Trans-4- (trans-
Preparation of 4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane 0.5 g (21 mmol) of magnesium and tetrahydrofuran (hereinafter referred to as "THF") 50
In a mixture of ml, 2.5 g of n-propyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, the solution was added to 1-chloro-4- (trans-4- (2
-(3,4-Difluorophenyl) ethyl) cyclohexyl) -1-silacyclohexane 7.4 g THF50
It was added dropwise to the ml solution. Since the obtained reaction mixture was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, it was separated by chromatography after usual post-treatment, and trans-4- (trans-4- (2- (3 ，
4-difluorophenyl) cyclohexyl) -1-n-
Propyl-1-silacyclohexane 5.8 g (yield 80
%) Was obtained. IR νmax: 2920, 2852, 2100, 15
20,1286,887,818 cm ^-1 C-S transition point: 7.6 ° C, S-N transition point: 18.5 ° C NI transition point: 74.8 ° C

Example 2 Trans-4- (trans-4- (2- (3,4,5-trifluorophenyl) ethyl) cyclohexyl) -1-n was prepared in the same manner as in Example 1.
-Pentyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2922, 28
52, 2100, 1620, 1531, 1446, 13
52,1234,1041,835 cm ^-1 C-N transition point: 21.9 ° C NI transition point: 57.8 ° C

Example 3 Trans-4- (trans-4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n was prepared in the same manner as in Example 1.
-Propyl-1-fluoro-1-silacyclohexane was obtained.

Example 4 Trans-4- (trans-4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n was prepared in the same manner as in Example 1.
-Pentyl-1-silacyclohexane was obtained.

Example 5 In the same manner as in Example 1, trans-4- (trans-4- (2- (4-chloro-3-)
Fluorophenyl) ethyl) cyclohexyl) -1-n
-Propyl-1-methyl-1-silacyclohexane was obtained.

Example 6 In the same manner as in Example 1, trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-n-pentyl-
1-Silacyclohexane was obtained.

Example 7 Trans-4- (trans-4- (2- (4-chlorophenyl) ethyl) cyclohexyl) -1-n-pentyl-1 was prepared in the same manner as in Example 1.
-Silacyclohexane was obtained.

Example 8 Trans-4- (trans-4- (2- (4-cyanophenyl) ethyl) cyclohexyl) -1-n-pentyl-1 was prepared in the same manner as in Example 1.
-Silacyclohexane was obtained.

Example 9 Trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-allyl-in the same manner as in Example 1.
1-Silacyclohexane was obtained.

Example 10 Trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1- (3-methoxypropyl) -1-in the same manner as in Example 1. Silacyclohexane was obtained.

Example 11 trans-1- (trans-4-n-propylcyclohexyl) -4- (2- (4
Preparation of -fluorophenyl) ethyl) -1-silacyclohexane 0.5 g (21 mmol) magnesium and THF 50
To a mixture of ml, trans-1- (trans-4-n-
Propylcyclohexyl) -4-bromomethyl-1-silacyclohexane (6.3 g, 20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 50 mg of triethyl phosphate, 10 mg of copper (I) iodide and 3.9 g of p-fluorobenzyl bromide (20 mmo).
l) was added dropwise to a solution of 50 ml of THF. After the usual post-treatment, 6.1 g of trans-1- (trans-4-n-propylcyclohexyl) -4- (2- (4-fluorophenyl) ethyl) -1-silacyclohexane (yield 85
%) Was obtained. IR νmax: 2916, 2841, 2089, 15
10,1223,891,820 cm ^-1 C-N transition point: 39.9 ° C, NI transition point: 56.7 ° C

Example 12 In the same manner as in Example 11, trans-4- (trans-4-ethylcyclohexyl) -1- (2- (4-fluorophenyl) ethyl)-
1-Silacyclohexane was obtained.

Example 13 In the same manner as in Example 11, trans-1- (trans-4-n-propylcyclohexyl) -4- (2- (3,4-difluorophenyl)).
Ethyl) -1-silacyclohexane was obtained.

Example 14 Trans-4- (trans-4- (2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n-pentyl was prepared in the same manner as in Example 11. -1-Silacyclohexane was obtained.

Example 15 Trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was prepared in the same manner as in Example 11. Obtained. IR νmax: 2918, 2850, 2100, 15
12,1232,887,823 cm ^-1 C-N transition point: 18.3 ° C, S-N transition point 63.5 ° C NI transition point, 98.4 ° C

[Example 16] Trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) -1-silacyclohexyl) -1- was prepared in the same manner as in Example 11.
n-Pentyl-1-silacyclohexane was obtained.

Example 17 In the same manner as in Example 11, trans-4- (trans-4-n-pentylcyclohexyl) -1- (2- (3,4-difluorophenyl))
Ethyl) -1-methyl-1-silacyclohexane was obtained.

Example 18 Trans-4- (trans-4- (2- (4-methoxyphenyl) ethyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane was prepared in the same manner as in Example 11. Obtained.

Example 19 Trans-1- (trans-4-n-propylcyclohexyl) -4- (2- (3,5-difluoro-4-difluoromethoxyphenyl) was prepared in the same manner as in Example 11. Ethyl) -1-silacyclohexane was obtained.

Example 20 Trans-4- (trans-4- (2- (4-propylphenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was prepared in the same manner as in Example 11. Obtained.

Example 21 Production of trans-4- (trans-4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane 0.5 g magnesium ( 21 mmol) and THF50
4.8 g (20 mmol) of p-trifluoromethoxybromobenzene was added dropwise to the mixture of ml to obtain a Grignard reagent. Subsequently, this solution was treated with 10 mg of copper (I) chloride, 10 mg of copper (II) chloride and trans-4- (2-bromoethyl) cyclohexyl) -1-n-propyl-1.
-7.3 g (20 mmol) of silacyclohexane TH
F50 ml solution was added dropwise. After the usual post-treatment, trans-4- (trans-4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n-
Propyl-1-silacyclohexane 6.6 g (yield 80
%) Was obtained.

Example 22 Trans-1- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -4-n-pentyl-1-silacyclohexane was prepared in the same manner as in Example 21. Obtained.

Example 23 Trans-1- (trans-4-n-pentylcyclohexyl) -4- (2- (4-fluorophenyl) ethyl) -1-silacyclohexane was prepared in the same manner as in Example 21. Obtained. IR νmax: 2916, 2845, 2094, 15
10, 1223, 887, 823 cm ^-1 C-N transition point: 21.3 ° C, NI transition point 67.1 ° C

Example 24 Trans-4- (trans-4-n-propylcyclohexyl) -1- (2- (4-fluorophenyl) ethyl) -1-silacyclohexane was prepared in the same manner as in Example 21. Obtained.

Example 25 Preparation of trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-iso-butyl-1-silacyclohexane Magnesium 0.5 g (21 mmol) And THF50
5.7 g (20 mmol) of 4- (p-fluorophenyl) cyclohexybromide was added dropwise to the mixture of ml to obtain a Grignard reagent. Subsequently, this solution was added dropwise to a solution of 10 mg of copper (I) iodide, 50 mg of triethyl phosphate and 4.7 g (20 mmol) of 4-bromo-1-iso-butyl-1-silacyclohexane in 50 ml of THF. The obtained reaction mixture was a mixture of trans-form and cis-form with respect to the silacyclohexane ring, so after the usual post-treatment, it was separated by chromatography,
4.7 g of trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-iso-butyl-1-silacyclohexane (yield 65%)
Got

Example 26 Trans-1- (trans-4 (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -4-n-pentyl-1-silacyclohexane was prepared in the same manner as in Example 25. Got

Example 27 trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl)
Preparation of cyclohexyl) -1-n-pentyl-1-silacyclohexane Magnesium 0.5 g (21 mmol)
1-n-pentyl-4 in a mixture of 50 ml and THF.
-Bromo-1-silacyclohexane 5.0 g (20 mm
ol) was added dropwise to obtain a Grignard reagent. Subsequently, the solution was treated with 4- (3,4-difluorophenethyl) -1-bromocyclohexane (6.1 g, 20 mmol) in THF.
It was added dropwise to the 50 ml solution. The resulting target product was separated by chromatography to give trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane. 6.5 g (yield 80%) was obtained.

Example 28 Trans-1- (trans-4-n-butylcyclohexyl) -4- (2- (4-fluorophenyl) ethyl) was prepared in the same manner as in Example 27.
-1-Silacyclohexane was obtained.

Example 29 Preparation of trans-4- (trans-4- (2- (3,4,5-trifluorophenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane Magnesium 0 0.5 g (21 mmol) and THF50
In a mixture of ml, 2.5 g of n-propyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added to 1-chloro-4- (trans-4- (2-
(3,4,5-Trifluorophenyl) ethyl) cyclohexyl) -1-silacyclohexane 7.8 g (20 m
(mol) in 50 ml of THF. The obtained reaction mixture was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring. Therefore, after the usual post-treatment, the reaction mixture was separated by chromatography to give trans-4- (trans-4- (2- (3 , 4,5-trifluorophenyl)
Ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane 6.1 g (yield 80%) was obtained. IR (KBr disc) νmax: 2922, 28
52, 2100, 1620, 1531, 1446, 13
52,1234,1041,845 cm ^-1 C-S transition point: 11.9 ° C, S-N transition point: 19.6 ° C NI transition point: 58.6 ° C

Example 30 Preparation of trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane Magnesium 0.5 g (21 mmol) And THF50
In a mixture of ml, 3.1 g of n-propyl bromide (2
0 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added to 1-chloro-4- (trans-4- (2-
(4-Fluorophenyl) ethyl) cyclohexyl)-
1-Silacyclohexane 6.8 g (20 mmol) of T
It was added dropwise to a 50 ml HF solution. The reaction mixture obtained is
Since the silacyclohexane ring is a mixture of a trans form and a cis form, it is separated by chromatography after usual post-treatment to give trans-4- (trans-4- (2
-(4-fluorophenyl) ethyl) cyclohexyl)
6.4 g of -1-n-pentyl-1-silacyclohexane
(Yield 85%) was obtained. C-N transition point: 21.3 ° C, NI transition point: 67.1 ° C N-I transition point: 58.6 ° C

Example 31 Trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl)
Preparation of cyclohexyl) -1- (4-pentenyl) -1-silacyclohexane 0.5 g (21 mmol) magnesium and THF 50
In a mixture of ml, 4-bromopentene 3.0 g (20 m
(mol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was added to 1-chloro-4- (trans-4- (2-
(3,4-Difluorophenyl) ethyl) cyclohexyl) -1-silacyclohexane 7.1 g THF 50 m
1 solution. The obtained reaction mixture was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring. Therefore, after the usual post-treatment, the reaction mixture was separated by chromatography to give trans-4- (trans-4- (2- (3 , 4
-Difluorophenyl) ethyl) cyclohexyl) -1
-(4-Pentenyl) -1-silacyclohexane 6.5
g (yield 83%) was obtained.

Example 32 Trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl)
Cyclohexyl) -1- (3-methoxypropyl) -1
-Production of silacyclohexane 0.5 g (21 mmol) magnesium and THF 50
To a mixture of 3 ml, 3-methoxypropyl bromide 3.
1 g (20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 1-chloro-4- (trans-
4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-silacyclohexane 7.1 g (2
0 mmol) in 50 ml of THF was added dropwise. The obtained reaction mixture was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring. Therefore, after the usual post-treatment, the reaction mixture was separated by chromatography to give trans-4- (trans-4- (2- (3 , 4-Difluorophenyl) ethyl) cyclohexyl) -1- (3-methoxypropyl) -1-silacyclohexane 6.5 g (81% yield)
Got

Example 33 Trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl)
Preparation of cyclohexyl) -1- (3-methylbutyl) -1-silacyclohexane 0.5 g (21 mmol) magnesium and THF 50
3.0 g of 3-methylbutyl bromide in a mixture of ml
(20 mmol) was added dropwise to obtain a Grignard reagent. Subsequently, this solution was mixed with 1-chloro-4- (trans-4-
(2- (3,4-Difluorophenyl) ethyl) cyclohexyl) -1-silacyclohexane 7.1 g THF
It was added dropwise to the 50 ml solution. Since the obtained reaction mixture was a mixture of trans isomer and cis isomer with respect to the silacyclohexane ring, it was separated by chromatography after usual post-treatment to give trans-4- (trans-4- (2-
6.9 g (yield 88%) of (3,4-difluorophenyl) ethyl) cyclohexyl) -1- (3-methylbutyl) -1-silacyclohexane was obtained.

Next, the liquid crystal composition of the present invention was produced by adding the compound of the present invention obtained in the above Examples to the existing liquid crystal composition.

[Embodiment 34] 2- (trans-4-n-
Pentylcyclohexyl) -1- (3,4-difluorophenyl) ethane 34% 1,2-difluoro-4-
[Trans-4- (trans-4-n-propylcyclohexyl) cyclohexyl] benzene 15% and 2-
A liquid crystal mixture consisting of 51% of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1- (3,4-difluorophenyl) ethane was -17 to
It exhibits a nematic liquid crystal phase in the temperature range of 63 ° C. 60% of this mixture and the trans-4- (2-
(3,4-difluorophenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was added to 4
The mixture added with 0 wt% had a C—N transition point: −27 ° C.
The NI transition point was 70 ° C.

[0081]

The liquid crystal compound of the present invention having Si introduced as a ring-constituting element has an expanded nematic liquid crystal phase. In addition to the above advantages, the liquid crystal compound in which X in the general formula (I) is not R or OR has the effect of lowering the threshold voltage because of its large dielectric anisotropy.

The liquid crystal compound of the present invention can be widely used as a base material constituting a main part of a liquid crystal phase, similarly to the conventional ECCP structure liquid crystal compound of similar hydrocarbon, depending on the selection of the substituent. The substituent X in the general formula (I) is R,
Since the liquid crystal compound of OR has a dielectric anisotropy close to zero, dynamic scattering (DS) or deformation of the aligned phase (DAP effect)
Are particularly useful for liquid crystal phases for display based on. In addition, compounds in which X is other than that are particularly useful for producing 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.

Front page continuation (72) Inventor Go Kinsei Nakagibiki-gun, Niigata Prefecture Kubiki-mura, Daiji 28-1 Nishi-Fukushima, Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (72) Inventor, Tatsushi Kaneko, Nigita-ken, Nakakubiki-gun 1 in 28, Nishi-Fukushima, Shinjuku Chemical Industry Co., Ltd. (72) Inventor Ryuichi Saito 1 in 28, Nishiki Fukushima, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. (72) ) Inventor Hideshi Kurihara 3-2-1 Sakado, Takatsu-ku, Kawasaki City, Kanagawa Prefecture Shin-Etsu Chemical Co., Ltd.

Claims (8)

[Claims] 1. A silacyclohexane compound represented by the following general formula (I): [Chemical 1] However, 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 2 carbon atoms.
7 represents an alkoxyalkyl group having 7 or an alkenyl group having 2 to 8 carbon atoms. [Chemical 2] And 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.
Sila-1,4-cyclohexylene group or trans-4-
Sila-1,4-cyclohexylene group, the other is trans-1,4-cyclohexylene group, X is CN, F, Cl,
CF ₃ , OCF ₃ , OCHF ₂ , OCHFCl, CF ₂ C
1, represents an OCF ₂ Cl, R or OR group. Z ₁ represents H, F or Cl. Z ₂ represents H or F. 2. An organometallic reagent RM (M is MgP (P represents a halogen atom), ZnP or Li) and ## STR5 ## (Q represents a halogen atom, an alkoxy group, a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group or a p-toluenesulfonyl group.) With a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction. The method for producing a silacyclohexane compound according to claim 1. 3. An organometallic reagent And [Chemical 7] (N and m are 0, 1 or 2 and represent the integer which is n + m = 2) by the carbon-carbon bond forming reaction or the carbon-silicon bond forming reaction. Method for producing compound. 4. An organometallic reagent And [Chemical 9] The method for producing a silacyclohexane compound according to claim 1, which is carried out by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with. 5. An organometallic reagent embedded image And [Chemical 11] The method for producing a silacyclohexane compound according to claim 1, which is carried out by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with. 6. An organometallic reagent And [Chemical 13] The method for producing a silacyclohexane compound according to claim 1, which is carried out by a carbon-carbon bond forming reaction or a carbon-silicon bond forming reaction with. 7. A liquid crystal composition comprising the silacyclohexane compound according to claim 1. Description: 8. A liquid crystal display device comprising the liquid crystal composition according to claim 7.