CN1153807A - Liquid crystalline compound replaced by fluorine containing group, liquid crystal composition, and liquid crystal display device - Google Patents

Abstract

Liquid crystalline compounds are disclosed which compounds are expressed by general formula (1) wherein substituents are as defined in the specification. The liquid crystalline compounds have a wide temperature range of nematic phase, low viscosity, large positive DELTA epsilon , high chemical stability, high miscibility with other liquid crystalline compounds at low temperatures, small temperature dependency of viscosity and DELTA epsilon , extremely high specific resistance (high voltage holding ratio), and good UV stability, and are preferably used for TFT. Also, disclosed are liquid crystal compositions containing the liquid crystalline compounds mentioned above, and liquid crystal display devices using the liquid crystal composition.

Description

Liquid crystalline cpd, liquid-crystal composition and liquid-crystal display that fluoro-containing group replaces

The present invention relates to a kind of liquid crystalline cpd and a kind of liquid-crystal composition.More particularly, the present invention relates to liquid crystalline cpd, a kind of liquid-crystal composition of described liquid crystalline cpd and the liquid-crystal display of making by described liquid-crystal composition of containing that a kind of novel fluoro-containing group replaces.

Liquid-crystal display is widely used in the display panel of clock and watch, box-like counter, various metering facility, automobile, word processor, electronic memo, printer, computer and TV.

These liquid-crystal displays utilize the optical anisotropy (Δ n) and the dielectric anisotropy (Δ ε) of liquid crystalline cpd.As display mode, dynamic scattering (DS) mode, host and guest (GH) mode, stable twisted nematic (TN) mode, STN Super TN type (STN) mode, thin film transistor (TFT) mode and ferroelectric liquid crystals (FLC) mode are known.As its energisation mode, static stimulation mode, timesharing addressing mode, active matrix energisation mode and double frequency excitation mode are known.Wherein, the TFT mode is subjected to everybody king-sized attention.

Though for the TFT mode, require liquid crystal material to have several specific characters, below three be considered to necessary denominators:

1) temperature range of liquid crystal material nematic phase should be wide to such degree, so that when various materials are added in the liquid-crystal composition, can not cause that the temperature range of liquid-crystal composition nematic phase descends.

2) be included in the low temperature range, the viscosity of liquid crystal material all is low.

3) liquid crystal material has big Δ ε.

In above-mentioned characteristic, 1) upper temperature limit that comprises requirement nematic phase is high and the fusing point of liquid crystal material is low, even so that also be difficult to being separated of the existing because liquid crystal material that crystallization deposition causes in low temperature range.

Characteristic 2) be an epochmaking factor for the liquid crystal molecule that in LCD panel, improves orientation to the speed of response of electric field) Phys.Lett.39A, 69 (1972)), in order to improve the display quality of liquid-crystal composition, the raising of the speed of response is the most urgent requirement at present.Now, the above-mentioned speed of response has less dependence to temperature, i.e. viewpoint from low temperatures display quality being degenerated, the temperature dependence that the viscosity of liquid crystal material is less and even at low temperatures liquid crystal material keep low viscosity all to be considered to important.

Requirement characteristic 3) reason is as follows:

In order to cut down the consumption of energy and to produce large-scale imaging screen, it is necessary reducing energizing voltage.Energizing voltage is threshold voltage (V particularly _Th) be the function of Δ ε, as The Representation Equation under using, $V_{\mathrm{th}}=k\sqrt{k/\mathrm{\Δ\ϵ}}$ In the formula, k is a rate constant, and K is an elastic constant.

As finding out,, need the compound of big positive Δ ε for cutting down the consumption of energy from aforesaid equation.

In addition, even at low temperatures, particularly in order to improve the liquid-crystal composition display quality and in wide temperature range, to keep high display quality, V _ThLittle temperature dependence needs.

In order to satisfy these requirements, the compound that big positive Δ ε is arranged has been carried out big quantity research.In the compound of having found, the Trifluoromethoxyphen-l derivative of the trifluoromethylbenzene radical derivative of formula (a) expression that proposes at Laid-open Japanese Patent Publication No.Sho 59-78129 and formula (b) expression that proposes at Laid-open WOJapanese Patent Publication No.Hei2-501311 is used as the example of the compound of king-sized Δ ε

Though these compounds have CF in molecular end ₃Or OCF ₃Tricyclic structure, but all are connected to trinucleated binding group with straight line and all are limited to covalent linkage.In fact, except Δ ε, these compounds can not satisfy desired characteristic fully.

Some have CF in molecular end ₃Or OCF ₃Compound remove in above-mentioned document China and foreign countries, also open in following document and patent: Liq.Cryst., 18 (4), 665 (1995), Laid-open WOJapanese Pnblication Nos.Sho 63-503226, Hei 3-503771, Hei 4-500214, Hei 4-500217, Hei 4-500682, Hei 4-501575, Hei, 4-501576, Hei 4-507104, Hei 5-502676 and Hei 6-504032, DE Nos.4004650A1,4013083,4106345,4108705A1 and 4113053A1 and EPNos.0439089A1 and 0449288.But, the physical parameter of these compounds is not fully described in these documents.

In addition, for TFT, the liquid crystalline cpd that is used for liquid-crystal composition environmental factors to external world is stable as steam, air, light and heat.

In order to obtain the required various characteristics of particular display, liquid crystalline cpd uses with the form of mixtures of several compounds.Therefore, need liquid crystalline cpd and other liquid crystalline cpds that good miscibility is arranged, even also good miscibility will be arranged at low temperatures, particularly because the environment for use of liquid crystalline cpd has enlarged now.

That is to say, for the liquid-crystal composition of TFT, may be used for wide temperature range in order to make composition, the liquid-crystal composition that the nematic phase is particularly arranged at low temperatures, do not have crystalline deposit and do not produce smectic phase needs.Therefore, for the liquid crystalline cpd that is used for TFT, with other liquid crystalline cpds the liquid crystalline cpd of fabulous miscibility being arranged at low temperatures is special needs.

TFT is useful on the integrated non-linearity device of the specific imaging part of conversion, and it is a class active matrix mode liquid-crystal display, and it is applicable to that high-level information shows, as is used for TV, computer, automobile and aircraft.The liquid-crystal composition that is used for these purposes also must have high ratio resistance (high-voltage keeps ratio) and good UV stability except that above-mentioned big positive Δ ε.When use did not have the liquid-crystal composition of these characteristics, in LCD panel, along with the decline of resistance, the contrast of imaging descended, and produces " imaging reservation " problem.In addition, liquid-crystal composition has the trend that shortens its work-ing life, when particularly encouraging under low voltage.

The liquid-crystal composition that an object of the present invention is to solve these problems in the above-mentioned background technology and provide a kind of like this TFT to use, it can satisfy required various characteristics, as wide nematic phase temperature range, lower viscosity, bigger positive Δ ε, high chemical stability, have high miscibility, viscosity and Δ ε that little temperature dependence, high ratio resistance (high voltage keep than) are arranged with other liquid crystalline cpds at low temperatures and good UV stability arranged simultaneously, and provide a kind of liquid-crystal composition that contains described liquid crystalline cpd.

Because the inventor's result of study, have found that, a kind of have the liquid crystalline cpd of above-mentioned characteristic to obtain by the liquid crystalline cpd modification, so that these compounds have trifluoromethyl or Trifluoromethoxyphen-l as the substituent example of known end, and simultaneously special main truss is arranged on feature, thereby finish the present invention.In order to achieve the above object, the present invention has following several respects: 1. the liquid crystalline cpd of a general formula (1) expression

Wherein, R ₁For the alkyl of 1-10 carbon atom is arranged, ring A is 1,4-phenylene or 1,4-cyclohexylidene, X ₁, X ₂, X ₃And X ₄Independent separately is hydrogen atom or fluorine atom, Y ₁Be CF ₃Or OCF ₃, m, n and p independently are 1 or 0 separately.

2. the liquid crystalline cpd of above-mentioned aspect 1, wherein n is 0, m is 1, X ₃Be fluorine atom, X ₄Be hydrogen atom.

3. the liquid crystalline cpd of above-mentioned aspect 1, wherein n is 1, and ring A is 1, and 4-cyclohexylidene, m and p all are 1, X ₃Be fluorine atom.

4. the liquid crystalline cpd of above-mentioned aspect 1, wherein n is 1, and ring A is 1, and 4-phenylene, m are 1, and p is 0, X ₁, X ₂And X ₄All be hydrogen atom, X ₃Be fluorine atom.

5. the liquid crystalline cpd of above-mentioned aspect 1, wherein n is 1, and ring A is 1, and 4-phenylene, m are 0, and p is 1, X ₁Be fluorine atom, X ₂Be hydrogen atom.

6. the liquid-crystal composition that contains the liquid crystalline cpd of each regulation among at least a above-mentioned aspect 1-5.

7. the liquid crystalline cpd that contains each regulation among at least a above-mentioned aspect 1-5 is as first compound and contain at least a liquid-crystal composition that is selected from arbitrary formula is represented in general formula (2), (3) and (4) compound as second component

In the formula, R ₂The alkyl that 1-10 carbon atom arranged, Y ₂Be fluorine atom, chlorine atom, OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂, L ₁, L ₂, L ₃And L ₄Independent separately is hydrogen atom or fluorine atom, Z ₁And Z ₂Independently be-(CH separately ₂) ₂-,-CH=CH-or a covalent linkage, a is 1 or 2.

8. the liquid crystalline cpd that contains each regulation among at least a above-mentioned aspect 1-5 is as first compound and contain at least a liquid-crystal composition that is selected from arbitrary formula is represented in general formula (5), (6), (7), (8) and (9) compound as second component

In the formula, R ₃For fluorine atom, the alkyl of 1-10 carbon atom is arranged or has the alkenyl of 2-10 carbon atom, any methylene radical in alkyl or alkenyl to be replaced by Sauerstoffatom, condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring B is 1,4-cyclohexylidene, 1, and 4-phenylene or 1,3-diox-1,5-two bases, ring C is 1,4-cyclohexylidene, 1,4-phenylene or pyrimidine-2,5-two bases, ring D is 1,4-cyclohexylidene or 1,4-phenylene, Z ₃For-(CH ₂) ₂-,-COO-or-covalent linkage, L ₅And L ₆Independence is hydrogen atom or fluorine atom separately, and b and c and oneself are 0 or 1 independently,

In the formula, R ₄For the alkyl of 1-10 carbon atom, L are arranged ₇Be hydrogen atom or fluorine atom, d is 0 or 1, In the formula, R ₅The alkyl that 1-10 carbon atom arranged, ring E and ring F independently are 1 separately, 4-cyclohexylidene or 1,4-phenylene, Z ₄And Z ₅Independently separately be-COO-or-covalent linkage, Z ₆Expression-COO-or-C ≡ C-, L ₈And L ₉Independent separately is hydrogen atom or fluorine atom, Y ₃Be fluorine atom, OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂, condition is to work as Y ₃Be OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂The time, L ₈And L ₉It all is hydrogen atom; E, f and g independently are 0 or 1 separately, In the formula, R ₆And R ₇Independent separately is the alkenyl that the alkyl of 1-10 carbon atom is arranged or 2-10 carbon atom arranged, and the arbitrary methylene radical in alkyl and alkenyl can be replaced by Sauerstoffatom, and condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring H is 1,4-cyclohexylidene, 1, and 4-phenylene or pyrimidine-2,5-two bases, ring I is 1,4-cyclohexylidene or 1,4-phenylene, Z ₆For-C ≡ C-,-COO-,-(CH ₂) ₂-,-CH=CH-C ≡ C-or-covalent linkage, Z ₇For-COO-or-covalent linkage,

In the formula, R ₈And R ₉Independent separately is the alkenyl that the alkyl of 1-10 carbon atom is arranged or 2-10 carbon atom arranged, and the arbitrary methylene radical in alkyl or alkenyl can be replaced by Sauerstoffatom, and condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring J is 1,4-cyclohexylidene, 1, and 4-phenylene or pyrimidine-2,5-two bases, ring K is 1,4-cyclohexylidene, 1, the 4-phenylene, the one or more hydrogen atoms on the ring can be replaced by fluorine atom or pyrimidine-2,5-two bases, ring L is 1,4-cyclohexylidene or 1,4-phenylene, Z ₈And Z ₁₀Independently be separately-COO-,-(CH ₂) ₂-or covalent linkage, Z ₉For-CH=CH-,-C ≡ C-,-COO-or-covalent linkage, h is 0 or 1.

9. the liquid crystalline cpd that contains each regulation among at least a above-mentioned aspect 1-5 is as first component, contain arbitrary formula is represented at least a general formula (2) that is selected from the above-mentioned aspect 7 regulation, (3) and (4) compound a part, and contain at least a liquid-crystal composition that is selected from arbitrary formula is represented in the general formula (5) stipulated in the above-mentioned aspect 8, (6), (7), (8) and (9) compound as the rest part of second component as second component.

10. liquid-crystal display that the liquid-crystal composition that uses each regulation among the above-mentioned aspect 6-9 is made.

Compound of the present invention with general formula (1) expression has been characterised in that by comprising 1,2-ethylidene or 1, the 4-butylidene has known trifluoromethyl or trifluoromethoxy on the phenylene simultaneously endways as 2 or 3 special frameworks that ring is formed of center key symbasis group.But the bicyclic compound (first kind) of these compound rough classification for representing with arbitrary formula in the formula (1-1)-(1-3); With the tricyclic compound that the arbitrary formula of formula (1-4)-(1-7) center ring is represented, wherein compound is 1,4-cyclohexylidene (second class); With the formula (1-8) or (1-9) tricyclic compound of expression, wherein the compound center ring is 1,4-phenylene, and connect 1, and the binding base of 4-phenylene and terminal phenyl are covalent linkage (the 3rd class); And the tricyclic compound of representing with arbitrary formula in the formula (1-10)-(1-15), wherein the compound center ring is 1, the 4-phenylene, and connect 1, the binding base of 4-phenylene and terminal phenylene are ethylene (the 4th classes).

In each formula, R ₁Above-mentioned identical implication is arranged.

The arbitrary compound of the present invention all have wide nematic phase temperature range, low viscosity, big positive Δ ε, high chemical stability, at low temperatures with the miscibility of other LCD compound object heights, high ratio resistance (high voltage keep than) and the stability high to UV, the Δ ε of these compounds and the dependence of viscosity temperature are extremely low.Therefore, these compounds are suitable for and make the component of TFT with liquid-crystal composition.

Optical anisotropy (Δ n) optically can be by suitably selecting R in the general formula (1) ₁, the ring A, X ₁, X ₂, X ₃, X ₄, m, n and p control, and represents compound of the present invention with these variablees.For example, when the bigger Δ n of hope, should select to contain more 1, the compound of the conduct ring A of 4-phenylene, and when wishing less Δ n should be selected to contain more 1, and the inferior hexamethylene of 4-is as the compound of ring A.

In compound of the present invention, the compound that comprises in the above-mentioned first kind demonstrates big positive Δ ε, low viscosity and high brocken spectrum especially, so these compounds extremely are fit to do the component of liquid-crystal composition.

Second compounds demonstrates fabulous nematic characteristic especially, therefore uses these compounds to demonstrate the preferred characteristics that does not occur smectic phase at low temperatures in liquid-crystal composition as the liquid-crystal composition of one of component.

Special brocken spectrum and the low viscosity that shows of the 3rd compounds, big positive Δ ε is arranged, viscosity increases little at low temperatures, particularly the dependence of the viscosity temperature of compound is little like this, even also be fabulous aspect the miscibility of other liquid crystalline cpds, so these compound utmost points are suitable as the component of liquid-crystal composition.

In addition, the 4th compounds demonstrates high brocken spectrum and low viscosity especially, big Δ ε and Δ n are arranged, viscosity increases little at low temperatures, particularly the dependence of the viscosity temperature of these compounds is little, with other liquid crystalline cpds good miscibility is arranged in addition in addition, so the also preferred component as liquid-crystal composition of these compounds.

Compound of the present invention is extremely preferably made the component of TFT with liquid-crystal composition.But, because these compounds have above-mentioned fabulous characteristic, therefore these compounds not only can be preferred for such use, and can be used for other purposes, as be used for TN mode, STN mode, host and guest's mode and polymer dispersion type liquid crystal display device, and as the liquid crystalline cpd of dynamic scattering mode.

Though the liquid-crystal composition that the present invention obtains can only be made up of first component of the liquid crystalline cpd that contains at least a general formula (1) expression, this liquid-crystal composition preferably also contains at least a compound that arbitrary formula is represented in above-mentioned general formula (2), (3) and (4) (hereinafter these compounds are called the 2nd A component) and/or at least a compound that arbitrary formula is represented in above-mentioned general formula (5), (6), (7), (8) and (9) (hereinafter these compounds are called the 2nd B component) that is selected from of being selected from as second component except that the compound of general formula (1).In addition, for temperature range, Δ n, Δ ε and the viscosity of regulating threshold voltage, mesomorphic phase, also can sneak into known compound in the liquid-crystal composition as the 3rd component.

In the 2nd A component, formula (2-1)-(2-15), (3-1)-(3-48) and (4-1)-(4-53) in the compound represented of arbitrary formula can be used as in the compound that is included in general formula (2), (3) or (4) expression, as the example of preferred compound.

In each formula, R ₂Above-mentioned identical implication is arranged.

The compound that arbitrary formula is represented in general formula (2)-(4) all has positive Δ ε and excellent heat resistance and chemical-resistant.Therefore, though these compounds are can not dispersive, but need high reliability particularly as high voltage when keeping TFT than (VHR) or big ratio resistance and using liquid-crystal composition when producing, can use these compounds, even when producing the liquid-crystal composition that STN display mode or general T N display mode use.

When production TFT used liquid-crystal composition, by the gross weight of liquid-crystal composition, the compound quantity of use was preferably 1-99% (weight), preferred 10-97% (weight), more preferably 40-95% (weight).

In the 2nd B component above-mentioned, in the compound of general formula (5), (6) or (7) expression, as the example of preferred compound can should be mentioned that formula (5-1)-(5-24), (6-1)-(6-3) and (7-1)-(7-17) in the compound represented of arbitrary formula.

In each formula, R ₃, R ₄And R ₅The identical meanings of as above pointing out is arranged.

The compound that arbitrary formula is represented in general formula (5)-(7) has big positive ε, therefore as reducing V _ThThe component of liquid-crystal composition.These compounds also are used to regulate viscosity and Δ n, improve brocken spectrum, widen the nematic scope and improve V _ThSlope.

In the 2nd B component, in the compound of general formula (8) or (9) expression as the example of preferred compound can mention formula (8-1)-(8-8) and (9-1)-(9-12) in the compound represented of arbitrary formula.

In the formula, R ₆, R ₇, R ₈And R ₉The identical meanings of as above mentioning is arranged.

Negative or the less positive Δ ε of the compound exhibits of general formula (8) or (9) expression.Wherein, the compound that general formula (8) is represented is mainly used in reduction viscosity and regulates Δ n, and the compound of general formula (9) expression is mainly used in the raising brocken spectrum and widen the nematic scope and/or adjusting Δ n.

Though the compound that arbitrary formula is represented in general formula (5)-(9) all is can not dispersive, particularly, can use these compounds when producing STN display mode or general T N display mode when use liquid-crystal composition, even when production TFT uses liquid-crystal composition.

When the liquid-crystal composition of STN display mode in the production general T N display mode, by the gross weight of liquid-crystal composition, the compound quantity of use is preferably 1-99% (weight), preferred 10-97% (weight), more preferably 40-95% (weight).

TFT that can be by using aforesaid method production improves V with the liquid-crystal composition of the present invention of liquid-crystal composition display instrument _ThSlope and visual angle.Equally, can improve the speed of response of liquid crystal display apparatus by the compound of the present invention that uses general formula (1) expression, because these compounds have low viscosity.

Liquid-crystal composition of the present invention preferably contains the liquid crystalline cpd of at least a general formula (1) expression, and its amount is for 0.1-99% (weight), to produce fabulous characteristic.

Liquid-crystal composition of the present invention is for example used a kind of like this method usually with traditional method production, wherein each component is at high temperature mixed making it mutual dissolving, perhaps each component is dissolved in making it in the organic solvent to mix, and under reduced pressure boils off solvent then.

In addition, liquid-crystal composition of the present invention can improve and optimize by adding suitable additive according to purposes.Such additive is that everybody is familiar with in this specialty and describes in detail in many documents.Usually, add the chiral dopant etc. that the spirane structure make liquid crystal is regulated required torsional angle and avoided the effect of detorsion.

In addition, when dichroic dye such as merocyanine type, styrene type, azo-type, azomethine type, azoxy type, quino type, anthraquinone type and tetrazine type add fashionablely, liquid-crystal composition of the present invention can be used as host and guest (GH) mode liquid-crystal composition.

Liquid-crystal composition of the present invention even can be used as polymer-dispersed liquid crystal display instrument (PDLCD) and use liquid-crystal composition, be representative or be representative with the NCAP that forms the microcapsule preparation by nematic liquid crystal, be used for automatically controlled double refraction (ECB) mode and dynamic scattering (DS) mode with the polymer network liquid crystal display instrument (PNLCD) by in liquid crystal, forming the polymer manufacture of three-dimensional net structure.

Though liquid-crystal composition of the present invention generates with method above-mentioned, also can mention following composition 1-21 as the example of composition:

In the example of following composition, name these compounds according to the listed regulation of table 1.Promptly the left side end group represents that with r-, rO-, rOs-, Vr-, rVs-or rVsVk-(wherein r, s and k are the integer more than 1 or 1; Bonding radical is represented with Z, E, T, V or CF20; Ring structure represents with B, B (F), B (F, F), H, Py, D or Ch, and right side end group usefulness-F ,-CL ,-C ,-CF ₃,-OCF ₃,-OCF ₂H ,-w ,-Ow or-EMe represents (wherein w is the integer more than 1 or 1).Be connected to the number of The compounds of this invention identical with shown in the following example.

Table 1

Left distal end group symbol group	Binding group symbol
		C rH 2r+1-???????????????????????????r- C rH 2r+1O-??????????????????????????rO- C rH 2r+1OC sH 2s-???????????????????rOs- CH 2＝CHCrH 2r-??????????????????????Vr- C rH 2r+1CH＝CHC sH 2s-??????????????rVs- C rH 2r+1CH＝CHC sH 2sCH＝CHC kH 2k-?rVsVk-	????-CH 2CH 2-?????????2 ????-COO-???????????????E ????-C≡C-??????????????T ????-CH＝CH-????????????V ????-CF 2O-????????????CF 2O

Composition example 13-H2B (F)-CF3 (No.1) 5.0%5-H2B (F)-CF3 (No.3) 5.0%7-HB (F)-F 4.0%2-HHB (F)-F 13.4%3-HHB (F)-F 13.3%5-HHB (F)-F 13.3%2-H2HB (F)-F 6.4%3-H2HB (F)-F 3.2%5-H2HB (F)-F 6.4%2-HBB (F)-F 7.5%3-HBB (F)-F 7.5%5-HBB (F)-F 15.0% composition example 23-H2H2B (F)-OCF3 (No.24) 10.0%3-H2H2B (F, F)-CF3 (No.29) 10.0%3-H2H2B (F, F)-OCF3 (No.34) 10.0%5-H2HB (F, F)-F 3.0%3-HHB (F, F)-F 10.0%4-HHB (F, F)-F 6.0%3-HH2B (F, F)-F 3.0%5-HH2B (F, F)-F 3.0%3-HBB (F, F)-F 12.0%5-HBB (F, F)-F 12.0%3-H2BB (F, F)-F 4.0%3-HBEB (F, F)-F 3.0%3-HHEB (F, F)-F 6.0%4-HHEB (F, F)-F 2.0%5-HHEB (F, F)-F 2.0%3-HHHB (F, F)-and F 2.0%3-HH2BB (F, F)-F 2.0%

Composition example 33-HB (F) 2B (F)-OCF3 (No.60) 5.0%3-HB (F) 2B (F, F)-OCF3 (No.70) 5.0%7-HB (F, F)-F 4.0%

377-HB(F)-F??????????????????????7.0％2-HHB(F)-F????????????????????13.4％3-HHB(F)-F????????????????????13.3％5-HHB(F)-F????????????????????13.3％2-H2HB(F)-F????????????????????4.0％3-H2HB(F)-F????????????????????2.0％5-H2HB(F)-F????????????????????4.0％3-H2HB(F，F)-F?????????????????3.0％5-H2HB(F，F)-F?????????????????3.0％3-HHB(F，F)-F??????????????????8.0％3-HH2B(F，F)-F?????????????????8.0％5-HH2B(F，F)-F?????????????????7.0％

Composition example 4 43-H2BB (F)-CF3 (No.39) 6.0%3-H2BB (F)-OCF3 (No.44) 5.0%3-HB (F) 2B (F, F)-OCF3 (No.70) 11.0%3-HB-CL 7.0%7-HB (F, F)-and F 10.0%2-HBB (F)-F 5.0%3-HBB (F)-F 5.0%5-HBB (F)-F 10.0%2-HHB-CL 5.0%4-HHB-CL 10.0%5-HHB-CL 5.0%5-HBB (F, F)-F 11.0%3-HB (F) VB-2 5.0%3-HB (F) VB-3 5.0%

Composition example 5 55-H2B (F)-CF3 (No.3) 5.0%3-H4B (F)-CF3 (No.13) 5.0%3-HB (F) 2B (F)-OCF3 (No.60) 11.0%3-H2H2B (F)-OCF3 (No.24) 5.0%7-HB (F)-F 5.0%7-HB (F, F)-F 3.0%5-H2B (F)-F 3.0%2-HHB (F)-F 3.0%3-HHB (F)-F 3.0%5-HHB (F)-F 3.0%2-HBB (F)-F 7.0%3-HBB (F)-F 7.0%5-HBB (F)-F 14.0%3-HHB-F 2.0%2-HBB-F 3.0%3-HBB-F 3.0%3-HB (F) TB-2 6.0%3-HB (F) TB-3 6.0%3-HB (F) TB-4 6.0%

Composition example 63-H2BB (F)-CF3 (No.39) 8.0%3-H2H2B (F, F)-CF3 (No.29) 7.0%5-HEB-F 2.5%7-HEB-F 2.5%2-HHB (F)-F 8.0%3-HHB (F)-F 8.0%5-HHB (F)-F 8.0%2-HBB (F)-F 2.5%3-HBB (F)-F 5.0%5-HBB (F)-F 2.5%4-H2BB (F)-F 5.0%5-H2BB (F)-F 6.0%3-H2HB (F, F)-F 10.0%3-HHB (F, F)-F 10.0%3-HH2B (F, F)-and F 5.0%5-HH2B (F, F)-F 8.0%5-HHEBB-F 2.0%

Composition example 73-H2B (F)-CF3 (No.1) 10.0%3-H2BB (F)-CF3 (No.39) 4.0%V2-HB-C 9.0%1V2-HB-C 9.0%3-HB-C 4.0%1O1-HB-C 8.0%2O1-HB-C 4.0%2-HHB-C 3.0%3-HHB-C 3.0%3-HH-4 10.0%1O1-HH-5 8.0%2-BTB-O1 11.0%3-HHB-1 8.0%3-HHB-3 9.0%

The physical parameter of said composition is as follows:

N-I point: 62.8 ℃

Viscosity (20 ℃): 18.3mPas

Δn(25℃)：?????0.112

Δε(25℃)：????7.4

V _th(20℃)：????1.68V

Composition example 83-HB (F) 2B (F)-OCF3 (No.60) 3.0%3-H2H2B (F; F)-OCF3 (No.34) 3.0%V2-HB-C 12.0%1V2-HB-C 11.0%1V2-BEB (F, F)-C 5.0%2-BTB-1 8.0%4-BTB-O2 8.0%5-BTB-O1 6.0%3-HH-4 3.0%3-HH-EMe 3.0%3-H2BTB-2 4.0%3-H2BTB-3 4.0%3-H2BTB-4 4.0%2-H2BTB-3 4.0%2-H2BTB-2 4.0%3-HB (F) TB-2 6.0%3-HB (F) TB-3 6.0%3-HB (F) TB-4 6.0%

Composition example 93-H2B (F)-CF3 (No.1) 3.0%5-H2B (F)-CF3 (No.3) 3.0%3-H4B (F)-CF3 (No.13) 3.0%2O1-BEB (F)-C 4.0%3O1-BEB (F)-C 3.0%5O1-BEB (F)-C 4.0%1V2-BEB (F, F)-C 15.0%3-HHEB-F 5.0%5-HHEB-F 5.0%3-HBEB-F 6.0%3-HHB-F 3.0%3-HB-O2 10.0%3-HH-4 5.0%3-HHB-1 8.0%3-HHB-3 6.0%3-HHB-O1 4.0%3-H2BTB-2 4.0%3-H2BTB-3 4.0%3-HB (F) TB-2 5.0%

Composition example 103-H2H2B, (F)-OCF3, (No.24) 6.0%3-H2BB, (F)-OCF3, (No.44) 3.0%2-HB, (F)-C 14.0%3-HB, (F)-C 13.0%5-HB, (F)-C 9.0%2-BB-C 13.0%2-BEB-C 12.0%3-BEB-C 4.0%2-HHB, (F)-C 6.0%3-HHB, (F)-C 6.0%2-HHB-C 3.0%3-HHB-C 3.0%3-PyBB-F 8.0% composition example 115-H2B, (F)-CF3, (No.3) 3.0%3-HB, (F) 2B, (F; F )-OCF3 ( No.60 ) 3.0％2-BB-C 8.0％4-BB-C 6.0％2-HB-C 10.0％3-HB-C 10.0％3-HHB-F 4.0％2-HHB-C 3.0％3-HHB-C 3.0％3-HBEBB-C 2.0％5-PyB-F 6.0％3-PyBB-F 6.0％2-BTB-O1 2.0％2-HHB-1 6.0％3-HHB-1 8.0％3-HHB-3 15.0％3-HHB-O1 5.0％123-H2B ( F )-CF3 ( No.1 ) 5.0％3-DB-C 5.0％4-DB-C 12.0％5-DB-C 8.0％2-BEB-C 10.0％5-PyB ( F )-F 7.0％2-PyB-2 1.4％3-PyB-2 1.3％4-PyB-2 1.3％6-PyB-O5 1.5％6-PyB-O6 1.5％3-HEB-O4 5.0％4-HEB-O2 3.7％3-HEB-O2 3.1％1O-BEB-2 2.5％5-HEB-1 3.7％4-HEB-4 5.0％3-HHB-3 13.0％3-HHB-O1 4.0％2-PyBH-3 4.0％3-PyBB-2 2.0％133-H2BB ( F )-CF3 ( No.39 ) 6.0％3-H2H2B ( F )-OCF3 ( No.24 ) 7.0％5-HB-F 9.0％6-HB-F 7.0％7-HB-F 7.0％5-HB-3 5.0％3-HB-O1 5.0％2-HHB-OCF3 5.0％3-HHB-OCF3 5.0％4-HHB-OCF3 5.0％5-HHB-OCF3 7.0％3-HH2B-OCF3 2.0％5-HH2B-OCF3 3.0％3-HH2B-F 3.0％5-HH2B-F 3.0％5-HBB ( F )-F 5.0％5-HH2B ( F )-F 9.0％3-HB ( F ) BH-3 3.0％5-HB ( F ) BH-3 2.0％5-HB ( F ) BH-5 2.0％143-H2H2B ( F； F)-CF3 (No.29) 6.0%3-HB (F) 2B (F; F)-OCF3 (No.70) 8.0%5-HB-F 4.0%7-HB-F 7.0%3-HHB-OCF3 12.0%5-HHB-OCF3 8.0%3-H2HB-OCF3 5.0%5-H2HB-OCF3 5.0%2-HHB (F)-F 6.6%3-HHB (F)-F 6.7%5-HHB (F)-F 6.7%4-H2HB (F; F)-F 5.0%5-H2HB (F; F)-F 5.0%3-HH2B (F; F)-F 8.0%4-HH2B (F; F )-F 7.0％153-H2B ( F )-CF3 ( No.1 ) 6.0％5-H2B ( F )-CF3 ( No.3 ) 4.0％2O1-BEB ( F )-C 6.0％3O1-BEB ( F )-C 5.0％5O1-BEB ( F )-C 3.0％V-HB-C 10.0％1V-HB-C 10.0％3-HB-C 11.0％2-HHB-C 4.0％3-HHB-C 5.0％4-HHB-C 4.0％5-HHB-C 4.0％3-HB-O2 7.0％V-HHB-1 7.0％V-HBB-2 4.0％3-H2BTB-2 4.0％3-H2BTB-3 3.0％3-H2BTB-4 3.0％163-HB ( F ) 2B ( F )-OCF3 ( No.60 ) 10.0％3-H2H2B ( F )-OCF3 ( No.24 ) 5.0％2-HB ( F )-C 10.0％3-HB ( F )-C 10.0％3-HB-O2 10.0％V-HH-5 5.0％V2-HH-3 5.0％2-BTB-O1 10.0％V-HHB-1 10.0％V-HBB-2 5.0％1V2-HBB-2 5.0％3-HHB-O1 5.0％3-H2BTB-2 5.0％3-H2BTB-3 5.0％173-HB ( F ) 2B ( F )-OCF3 ( No.60 ) 3.0％3-H2H2B ( F； F)-physical parameter of CF3 (No.29) 3.0%V2-HB-C 12.0%1V2-HB-C 11.0%1V2-BEB (F, F)-C 5.0%2-BTB-1 8.0%4-BTB-O2 8.0%5-BTB-O1 6.0%3-HH-4 3.0%3-HH-EMe 3.0%3-H2BTB-2 4.0%3-H2BTB-3 4.0%3-H2BTB-4 4.0%2-H2BTB-2 4.0%2-H2BTB-3 4.0%3-HB (F) TB-2 6.0%3-HB (F) TB-3 6.0%3-HB (F) VB-4 6.0% said composition is as follows:

N-I point: 91.4 ℃

Viscosity (20 ℃): 25.0mPas

Δn(25℃)：?????0.198

Δε(25℃)：????7.4

V _th(20℃)：????1.68V

Composition example 183-H2B (F)-CF3 (No.1) 4.0%5-H2B (F)-CF3 (No.3) 4.0%2O1-BEB (F)-C 4.0%3O1-BEB (F)-C 4.0%501-BEB (F)-C 4.0%1V2-BEB (F, F)-C 14.0%3-HBEB-F 6.0%3-HHEB-F 5.0%5-HHEB-F 5.0%3-HHB-F 3.0%3-HB-O2 10.0%3-HH-4 6.0%3-HHB-1 8.0%3-HHB-3 6.0%3-HHB-O1 4.0%3-H2BTB-2 4.0%3-H2BTB-3 4.0%3-HB (F) TB-2 5.0%

The physical parameter of said composition is as follows:

N-I point: 88.0 ℃

Viscosity (20 ℃): 27.0mPas

Δn(25℃)：?????0.122

Δε(25℃)：????18.1

V _Th(20 ℃): 1.24V composition example 193-H2B (F)-CF3 (No.1) 4.0%3-HB (F) 2B (F, F)-OCF3 (No.70) 2.0%2-BB-C 8.0%4-BB-C 6.0%2-HB-C 10.0%3-HB-C 10.0%3-HHB-F 4.0%2-HHB-C 3.0%3-HHB-C 3.0%3-HBEBB-C 2.0%5-PyB-F 6.0%3-PyBB-F 6.0%2-BTB-O1 2.0%2-HHB-1 6.0%3-HHB-1 8.0%3-HHB-3 15.0%3-HHB-O1 5.0%

The physical parameter of said composition is as follows:

N-I point: 90.9 ℃

Viscosity (20 ℃): 21.9mPas

Δn(25℃)：?0.140

Δε(25℃)：9.2

V _th(20℃)：1.79V

Composition example 203-H2H2B, (F)-OCF3, (No.24) 2.0%3-H2BB, (F)-OCF3, (No.44) 4.0%2-HB, (F)-C 14.0%3-HB, (F)-C 12.0%5-HB, (F)-C 10.0%2-BB-C 12.0%4-BEB-C 12.0%3-BEB-C 4.0%2-HHB, (F)-C 6.0%3-HHB, (F)-C 6.0%2-HHB-C 2.0%3-HHB-C 4.0%3-PyBB-F 8.0%3-HB, (F) EB, (F)-C 4.0%

The physical parameter of said composition is as follows:

N-I point: 56.8 ℃

Viscosity (20 ℃): 51.6mPas

Δn(25℃)：?????0.143

Δε(25℃)：????18.0

V _Th(20 ℃): 0.91V composition example 213-H2B, (F)-CF3, (No.1) 5.0%3-DB-C 5.0%4-DB-C 12.0%5-DB-C 8.0%2-BEB-C 10.0%5-PyB, (F)-F 7.0%2-PyB-2 1.4%3-PyB-2 1.3%4-PyB-2 1.3%6-PyB-O4 2.0%6-PyB-O5 1.0%3-HEB-O4 5.0%4-HEB-O2 3.8%3-HEB-O2 3.0%1O-BEB-2 2.4%5-HEB-1 3.8%4-HEB-4 5.0%3-HHB-3 13.0%3-HHB-O1 4.0%2-PyBH-3 4.0%2-PyBB-2 2.0%

The physical parameter of said composition is as follows:

N-Ip point: 53.6 ℃

Viscosity (20 ℃): 29.6mPas

Δn(25℃)：??????0.109

Δε(25℃)：?????9.3

V _th(20℃)：?????1.23V

The compound of the present invention of general formula (1) expression can be easy to produce with the general technology of Synthetic Organic Chemistry, for example " Organic Synthesis ", " OrganicReactions " and " Jikken Kagaku Kouza (Course of ChemicalExperiments) " in the appropriate combination of technology of description.The synthesis example of these compounds is expressed as follows, wherein R ₁, Y ₁, X ₃And X ₄The identical meanings of as above mentioning is arranged, and q is 1 or 0.The compound that the right side is represented is represented in the abbreviation of left side expression respectively below.

DIBAL: diisobutyl aluminium hydride

PTS: tosic acid monohydrate

Pd-C: palladium-carbon

R-Ni: Raney nickel

LAH: lithium aluminium hydride

FSDF: fluorine sulphonyl difluoroacetic acid methyl esters

DPAE: diethyl phosphino-ethyl acetate

Chloranil: tetrachloro-right-benzoquinones

The preparation of first kind compound among the present invention (compound of general formula (1) expression, n is 0):

The method preparation that these compounds are mentioned below preferably using:

That is to say that the carboxylic acid that makes according to the EP0315050 disclosed method carries out esterification with general method, obtain ester (12).Use the DIBAL ester reduction then, make aldehyde (13).Aldehyde reacts with the phenyl-magnesium-bromide (14) that 3-fluoro-4-replaces again, in the presence of acid catalyst such as PTS and sulfuric acid, carry out dehydration reaction then, carry out hydrogenation reaction with catalyzer such as Pd-C and R-Ni again and make compound (1), it is the example of first kind compound of the present invention.

When the substituting group Y1 in the compound (1) is trifluoromethyl, this compound even can be by following reaction path production:

That is to say that according to the carboxylic acid Can.J.Chem.46 of above-mentioned EP0315050 disclosed method preparation, 466 (1968) methods of describing are handled, and obtain acyl chlorides (15).Acyl chlorides and 3-fluoro-phenyl-magnesium-bromide (16) are according to Tetrahedron Lett., and 25,4805 (1984) the method reactions of describing make ketone (17).

Ketone and LAH carry out reduction reaction, carry out dehydration reaction under acidic conditions, carry out hydrogenation reaction then, obtain compound (18), then according to Org.Synth., and I, 323 (1941) methods of describing are carried out iodination reaction, obtain iodide (19).Iodide and FSDS (20) are according to Tetrahedron, and 48,6555 (1992) methods of describing are carried out the trifluoromethylation reaction, obtain above-mentioned first kind compound (1) among the present invention, and wherein Y1 is a trifluoromethyl.

The present invention's second compounds (compound of general formula (1) expression, wherein n is 1, and ring A is 1, and 4-cyclohexylidene, m and p are 1, X ₃Be fluorine atom) preparation:

These compounds can preferably prepare with following method:

That is to say, according to Chem.Ber., 121, the cyclohexanone derivative (21) of 219 (1988) the methods preparations of describing and DPAE be according to Org.Synth., V, 542 (1973) the methods reactions of describing, carry out hydrogenation reaction then, carry out reduction reaction with DIBAL again, make aldehyde (22).

The phenyl-magnesium-bromide or 3 that aldehyde and 3-fluoro-4-replace, dehydration reaction is carried out in phenyl-magnesium-bromide (23) reaction that 4-two fluoro-4-replace then under acidic conditions, carry out hydrogenation reaction with above-mentioned identical mode, makes second compounds (1).

The present invention's the 3rd compounds (compound of general formula (1) expression, wherein n is 1, and ring A is 1, and 4-phenylene, m are 1, and p is 0, X ₁, X ₂And X ₄Be hydrogen atom, X ₃Be fluorine atom) preparation:

These compounds can preferably prepare with following method:

That is to say, Grignard reagent (14) is added in the iodide (24) of the method preparation of describing according to WO9014405, according to as J.Org.Chem., 42,1821 (1977) methods of describing are carried out crosslinking reaction, thereby make the present invention's the 3rd compounds (1).

In the 3rd compounds (1), its Y1 is the compound even the available following method preparation of trifluoromethyl:

That is to say, 3-fluorophenyl magnesium bromide is added in the above-mentioned cyclohexanone derivative (21), under acidic conditions, carry out dehydration reaction then, carry out dehydrogenation reaction, carry out iodination reaction again, make iodide (25) with Chloranil.Iodide react by the identical mode of preparation first kind compound with FSDS (20) then, make the present invention's the 3rd compounds (1).

The present invention's the 4th compounds (compound of general formula (1) expression, wherein n is 1, and ring A is 1, and 4-phenylene, m are 0, and p is 1, X ₁Be fluorine atom, X ₂Be hydrogen atom) preparation:

These compounds can preferably prepare with following method:

That is to say that according to Mol.Cryst.Liq.Cryst., the cyano compound that 82,331 (1982) methods of describing make is hydrolyzed, esterification then obtains compound (26).These compounds carry out above-mentioned LAH reduction reaction, press Org.Synth., I, 5 (1941) methods of describing are handled with Hydrogen bromide and are generated bromide, use J.Am.Chem.Soc., 93,195 (1971) methods of describing are carried out cyanogenation, with Grignard reagent (27) reaction, obtain ketone (28) then.Ketone and LAH carry out reduction reaction, carry out dehydration reaction under acidic conditions, carry out hydrogenation reaction again, make the present invention's the 4th compounds (1).

According to the present invention, can be met the liquid crystalline cpd of desired characteristic, as wide nematic phase temperature range, low viscosity, big positive Δ ε, high chemical stability, little, high with temperature dependency with miscibility, viscosity and the Δ ε of other LCD compound object heights at low temperatures ratio resistance value (high-voltage keeps ratio) and good UV stability, these liquid crystalline cpd particularly suitables are as the TFT liquid crystalline cpd.

Therefore, when liquid crystalline cpd of the present invention is used as the component of liquid-crystal composition, except that liquid crystalline cpd has in other liquid crystal materials the fabulous solubleness, also have the novel liquid crystalline compositions of other desired physical properties to obtain by six-ring, substituting group and/or the binding base in the unit of suitable selection formation molecule.

With reference now to embodiment, for a more detailed description to the present invention.But, should be appreciated that the present invention never is subjected to the restriction of these specific embodiments.In each embodiment, C is a crystalline phase, and N is that nematic phase, S are that smectic phase and I are each homogeny liquid crystal, and in each embodiment, the unit of transformation temperature is ℃.

Embodiment 1

The preparation of 1-trifluoromethyl-2-fluoro-4-(2-(4-propyl group cyclohexyl) ethyl) benzene is (with the compound of general formula (1) expression, wherein R ₁Be propyl group, m is 1, and n and p are 0, X ₁, X ₂And X ₄Be hydrogen atom, X is a fluorine atom, Y ₁Be trifluoromethyl; Compound N is o.1):

Behind the mixture heating up backflow 3h with 4-propyl group cyclohexyl acetic acid (100mmol) and thionyl chloride (150mmol), under reduced pressure remove excessive thionyl chloride, obtain the crude product (100mmol) of acyl chlorides with vent fan.

Below-50 ℃, to be added drop-wise to by ferric acetyl acetonade (5mmol) and 300ml dry toluene are added in the mixture that makes in this acyl chlorides (100mmol) by the Grignard reagent of 3-bromofluorobenzene (110mmol), magnesium (110mmol) and 100ml tetrahydrofuran (THF) (hereinafter claiming THF) preparation, under identical temperature, stir 1h.The reaction product that so obtains is added in the 200ml 6M hydrochloric acid, then with toluene extraction (100ml * 2).Use the anhydrous magnesium sulfate drying extract, boil off solvent, the residue that so obtains crystallization from 50ml ethanol obtains 2-fluoro-4-(1-oxo-2-(4-propyl group cyclohexyl) ethyl) benzene (75mmol).

Sodium borohydride (75mmol) is added in product (75mmol) and the 200ml alcoholic acid mixture, temperature is remained on below 10 ℃, and at room temperature stir 3h.50ml 6M hydrochloric acid and 200ml water are added in the reaction product that so obtains, use ethyl acetate extraction (100ml * 4) then.Under reduced pressure from extract, boil off solvent, obtain 2-fluoro-4-(1-hydroxyl-2-(4-propyl group cyclohexyl) ethyl) benzene residue (75mmol).

100ml toluene and 1.5g tosic acid monohydrate are added in the residue (70mmol), and reflux 4h, remove the water of generation simultaneously.After the cooling, reaction product is transferred to separatory funnel, wash (100 * 3) with water, use anhydrous magnesium sulfate drying, under reduced pressure distill then steaming solvent, thereby obtain 2-fluoro-4-(2-(4-propyl group cyclohexyl) vinyl) benzene crude product (66mmol).

70ml ethanol, 60ml ethyl acetate and 3g 5%Pd/C catalyzer be added in the crude product (66mmol) obtain mixture.This mixture is stirred 4h under nitrogen atmosphere, leach catalyzer then, boil off solvent again.The residue that so obtains carries out silica gel column chromatography and separates (irrigation: heptane) also with recrystallization method purifying (ethanol 25ml * 2), obtain 2-fluoro-4-(2-(4-third cyclohexyl) ethyl) benzene (34mmol).

Iodine (34mmol), acid iodide (18mmol), 100ml acetate, 20ml water and 20ml tetracol phenixin are added in the product (34mmol) of purifying and obtain mixture, 12h then refluxes mixture heating up.After the cooling, 500ml water is added in the reaction product, uses toluene (200ml) extraction then.Extract with anhydrous magnesium sulfate drying after, under reduced pressure steam solvent, obtain yellow oil product.

Heating is by being added to the mixture that makes in the yellow oil product with thiocarbamide (264mmol) and ethanol (600ml), and the homogeneous phase solution that will so obtain is at room temperature placed and spent the night then.

Filter out sedimentary needle crystal, water decomposes down at 90 ℃, with the extraction of 100ml heptane, uses anhydrous magnesium sulfate drying then.Under reduced pressure boil off solvent, the residue that so obtains is recrystallization from 20ml ethanol, obtains 1-iodo-2-fluoro-4-(2-(4-propyl group cyclohexyl) ethyl) benzene (10mmol).

Fluorosulfonyl difluoroacetic acid methyl esters (100mmol), cupric iodide (10mmol) and 20ml dimethyl formamide be added in this product (10mmol) obtain mixture, under 90 ℃, mixture is stirred 2h then.In the reaction product that 100ml water is so obtained, with the extraction of 100ml toluene, water (50ml * 3) washing then.Behind anhydrous magnesium sulfate drying, under reduced pressure boil off solvent, the residue that so obtains carries out silica gel column chromatography and separates (eluent: heptane), carry out purifying by recrystallization (ethanol 10ml * 2) then, obtain 5.5mmol purpose compound (productive rate: 55%).

Various spectroscopic datas are supported its structure well.The transformation temperature of compound is the C-I point: 11.7 ℃.

1,3 ( No.2-18 ) ：No.2 1--2--4- ( 2- ( 4- ) ) 3 1--2--4- ( 2- ( 4- ) ) C-I：21.4℃4 1--2--4- ( 2- ( 4- ) ) 5 1--2--4- ( 2- ( 4- ) ) 6 1--2--4- ( 2- ( 4- ) ) 7 1--2--4- ( 4- ( 4- ) ) 8 1--2--4- ( 4- ( 4- ) ) 9 1--2--4- ( 4- ( 4- ) ) 10 1--2--4- ( 4- ( 4- ) ) 11 1--2--4- ( 4- ( 4- ) ) 12 1--2--4- ( 4- ( 4- ) ) 13 1--2--4- ( 2- ( 4- ) ) 14 1--2--4- ( 2- ( 4- ) ) 15 1--2--4- ( 2- ( 4- ) ) 16 1--2--4- ( 2- ( 4- ) ) 17 1--2--4- ( 2- ( 4- ) ) 18 1--2--4- ( 2- ( 4- ) )

Embodiment 2

1-trifluoromethoxy-2-fluoro-4-(2-(preparation of 4-(2-(4-propyl group cyclohexyl) ethyl) benzene (compound of general formula (1) expression, wherein R ₁For propyl group, m, n and p are 1, ring A is 1,4-cyclohexylidene, X ₁, X ₂And X ₄Be hydrogen atom, X ₃Be fluorine atom, Y ₁Be trifluoromethoxy; Compound N is o.19):

Be lower than under 0 ℃ in temperature, will be added drop-wise to by the Grignard reagent that 3-fluoro-4-trifluoro-methoxyl bromobenzene (55mmol), magnesium (55mmol) and 80ml THF make in the mixture according to 4-(2-(the 4-propyl group cyclohexyl) ethyl) cyclohexyl-acetaldehyde (50mmol) (as the raw material of The compounds of this invention (second class)) of the above-mentioned method preparation for preparing aldehyde (22) and 50ml THF.After reactant at room temperature stirred 3h, add 200ml 6M hydrochloric acid, use ethyl acetate (100ml * 2) extraction then.The extract anhydrous magnesium sulfate drying boils off solvent then.

100ml toluene and 1g tosic acid monohydrate are added in the residue that so obtains, and reflux 4h removes the water of generation simultaneously then.After the cooling, reaction product is poured in the separating funnel, water (100ml * 3) washing, use anhydrous magnesium sulfate drying, distillation under reduced pressure then, steam solvent, therefore obtain thick 1-trifluoromethyl-2-fluoro-4-(2-(4-(2-(4-propyl group cyclohexyl) ethyl) cyclohexyl) vinyl) benzene (43mmol).

50ml ethanol, 50ml ethyl acetate and 2g 5%Pd-C catalyzer be added in this product (43mmol) obtain mixture, under nitrogen atmosphere, mixture is stirred 3h.Filter out catalyzer, steam solvent then, the residue that so obtains carries out silica gel column chromatography and separates (eluent: heptane), use recrystallization method purifying (ethanol 10ml * 2) then, obtain 16.5mmol purpose compound (productive rate: 33%).

All fine this structure of support of various spectroscopic datas.The transformation temperature C-N point of compound is 50.3 ℃, and the N-I point is 101.7 ℃.

2, ( No.20-80 ) ：No20 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) ) 21 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) ) 22 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) ) 23 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) ) 24 20 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) ) 25 1--2--4- ( 2- ( 4- ( 2- ( 4- ) ) ) )

C-N point:50.3 ℃; N-I point: 101.7 ℃ of 25 ' 1-trifluoromethoxy-2-fluoro-4-(2 (4-(2-(4-butyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 26 1-trifluoromethoxies-2-fluoro-4-(2-(4-(2-(4-amyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 27 1-trifluoromethoxies-2-fluoro-4-(2-(4-(2-(4-hexyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 28 1-trifluoromethoxies-2-fluoro-4-(2-(4-(2-(4-heptyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 29 1-trifluoromethyls-2,6-two fluoro-4-(2-(4-(2-(4-propyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene

C-N point: 88.9 ℃, N-I point: 81.9 ℃ of 30 1-trifluoromethyl-2,6-two fluoro-4-(2-(4-(2-(4-butyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 31 1-trifluoromethyls-2,6-two fluoro-4-(2-(4-(2-(4-amyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 32 1-trifluoromethyls-2,6-two fluoro-4-(2-(4-(2-(4-hexyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 33 1-trifluoromethyls-2,6-two fluoro-4-(2-(4-(2-(4-heptyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 34 1-trifluoromethoxies-2,6-two fluoro-4-(2-(4-(2-(4-propyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 35 1-trifluoromethoxies-2,6-two fluoro-4-(2-(4-(2-(4-butyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 36 1-trifluoromethoxies-2,6-two fluoro-4-(2-(4-(2-(4-amyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 37 1-trifluoromethoxies-2,6-two fluoro-4-(2-(4-(2-(4-hexyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene 38 1-trifluoromethoxies-2,6-two fluoro-4-(2-(4-(2-(4-heptyl cyclohexyl) ethyl) cyclohexyl) ethyl) benzene

Embodiment 3

4 '-preparation of (2-(4-propyl group cyclohexyl) ethyl)-3-fluoro-4-trifluoromethoxy biphenyl (compound of general formula (1) expression, wherein R ₁Be propyl group, m and n are 1, and p is 0, and ring A is 1,4-phenylene, X ₁, X ₂And X ₄Be hydrogen atom, X ₃Be fluorine atom, Y ₁Be trifluoromethoxy; Compound N is o.39):

The mixture heating up that the conduct that will prepare according to the method that above-mentioned WO9014405 describes prepares 1-iodo-4-(2-(4-propyl group cyclohexyl) ethyl) benzene (50mmol), 100ml THF and the Palladous chloride (1mmol) of the raw material of the 3rd compounds refluxes, the Grignard reagent that in 1h 3-fluoro-4-trifluoro-methoxyl bromobenzene (55mmol), magnesium (55mmol) and 80ml THF is prepared is added dropwise to then, and then backflow 1h.After the cooling, 200ml 6M hydrochloric acid is added in the reaction product, uses toluene (100ml * 2) extraction then.Use the anhydrous magnesium sulfate drying extract, boil off solvent then.The residue that so obtains carries out silica gel column chromatography and separates (eluent: heptane), use recrystallization method purifying (ethanol 10ml * 2) then, obtain 39mmol purpose compound (productive rate: 78%).

Various spectroscopic datas are supported this structure fully.The transformation temperature C-N point of compound: 64.9 ℃, N-I point: 87.9 ℃.

According to the method for embodiment 3, following the 3rd compounds (compound N is o.40-48): the No.40 4 ' of preparation-(2-(4-propyl group cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl

The C-I point: 88.5 ℃ 41 4 '-(2-(4-butyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl 42 4 '-(2-(4-amyl group cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl 43 4 '-(2-(4-hexyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl 44 4 '-(2-(4-heptyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl 45 4 '-(2-(4-butyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethoxy biphenyl 46 4 '-(2-(4-amyl group cyclohexyl) ethyl)-3-fluoro-4-trifluoromethoxy biphenyl 47 4 '-(2-(4-hexyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethoxy biphenyl 48 4 '-(2-(4-heptyl cyclohexyl) ethyl)-3-fluoro-4-trifluoromethoxy biphenyl.

Embodiment 4

The preparation of 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-propyl group cyclohexyl) benzene) ethyl) benzene (compound of general formula (1) expression, wherein R ₁For propyl group, m are 0, n and p are 1, ring 1,4-phenylene, X ₁And X ₃Be fluorine atom, X ₂And X ₄Be hydrogen atom, Y ₁Be trifluoromethoxy; Compound N is o.49):

Behind the mixture heating up backflow 3h with 2-fluoro-4-(4-propyl group cyclohexyl) phenylacetic acid (100mmol) and thionyl chloride (150mmol), under reduced pressure remove excessive thionyl chloride, obtain acyl chlorides crude product (100mmol) with vent fan.

Be lower than-50 ℃ in temperature and will be added drop-wise in the mixture of this acyl chlorides product (100mmol), ferric acetyl acetonade (5mmol) and the dried toluene of 300ml restir 1h under identical temperature by the Grignard reagent of 3-fluoro-4-trifluoro-methoxyl bromobenzene (110mmol), magnesium (110mmol) and 100ml THF preparation down.The reaction product that so obtains is added in the 200ml 6M hydrochloric acid, uses toluene (100ml * 2) extraction then.Use the anhydrous magnesium sulfate drying extract, steam solvent then.The residue that so obtains is recrystallization from 50ml ethanol, obtains 1-trifluoromethoxy-2-fluoro-4-(1-oxo-2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) ethyl) benzene (70mmol).

Sodium borohydride (70mmol) is added in recrystallized product (70mmol) and the 200ml alcoholic acid mixture, temperature is remained on below 10 ℃, at room temperature stir 3h then.50ml 6M hydrochloric acid and 200ml water are added in the reaction product that so obtains, use ethyl acetate (100ml * 4) extraction then.Under reduced pressure steam solvent, obtain 1-trifluoromethoxy-2-fluoro-4-(1-hydroxyl-2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) ethyl) benzene (65mmol) residue.

100ml toluene and 1.5g tosic acid monohydrate are added in the residue (65mmol), and reflux 4h removes generation water simultaneously then.Pour reaction product into separating funnel after the cooling, anhydrous magnesium sulfate drying is used in water (100ml * 3) washing then.Under reduced pressure boil off solvent, obtain thick 1-trifluoromethoxy-2-fluoro-4-(1-hydroxyl-2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) vinyl) benzene (59mmol).

Under hydrogen atmosphere, crude compound (59mmol), 70ml ethanol, 60ml ethyl acetate and 3g 5%Pd/C mixture of catalysts are stirred 4h.

After filtering out catalyzer, steam solvent, the residue that so is able to is carried out silica gel column chromatography separate (eluent: heptane), use recrystallization method purifying (ethanol 25ml * 2) then, obtain 28mmol purpose compound (productive rate: 48%).

Various spectroscopic datas are supported this structure fully.The transformation temperature of compound is the C-I point: 43.8 ℃.

4, ( No.50-78 ) ：No.50 1--4- ( 2- ( 2--4- ( 4- ) ) ) 51 1--4- ( 2- ( 2--4- ( 4- ) ) ) 52 1--4- ( 2- ( 2--4- ( 4- ) ) ) 53 1--4- ( 2- ( 2--4- ( 4- ) ) ) 54 1--4- ( 2- ( 2--4- ( 4- ) ) ) 55 1--4- ( 2- ( 2--4- ( 4- ) ) ) 56 1--4- ( 2- ( 2--4- ( 4- ) ) ) 57 1--4- ( 2- ( 2--4- ( 4- ) ) ) 58 1--4- ( 2- ( 2--4- ( 4- ) ) ) 59 1--4- ( 2- ( 2--4- ( 4- ) ) ) 60 1--2--4- ( 2- ( 2--4- ( 4- ) ) ) 61 1--2--4- ( 2- ( 2--4- ( 4- ) ) ) 62 1--2--4- ( 2- ( 2--4- ( 4- ) ) ) 63 1--2--4- ( 2- ( 2--4- ( 4- ) ) ) 64 1--2--4- ( 2- ( 2--4- ( 4- ) ) )

C-I point: 43.8 ℃ of 65 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-butyl cyclohexyl) phenyl) ethyl) benzene 66 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-amyl group cyclohexyl) phenyl) ethyl) benzene 67 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-hexyl cyclohexyl) phenyl) ethyl) benzene 68 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-heptyl cyclohexyl) phenyl) ethyl) benzene 69 1-trifluoromethyls-2,6-two fluoro-4-(2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) ethyl) benzene 70 1-trifluoromethyls-2,6-two fluoro-4-(2-(2-fluoro-4-(4-butyl cyclohexyl) phenyl) ethyl) benzene 71 1-trifluoromethyls-2,6-two fluoro-4-(2-(2-fluoro-4-(4-amyl group cyclohexyl) phenyl) ethyl) benzene 72 1-trifluoromethyls-2,6-two fluoro-4-(2-(2-fluoro-4-(4-hexyl cyclohexyl) phenyl) ethyl) benzene 73 1-trifluoromethyls-2,6-two fluoro-4-(2-(2-fluoro-4-(4-heptyl cyclohexyl) phenyl) ethyl) benzene 74 1-trifluoromethoxies-2,6-two fluoro-4-(2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) ethyl) benzene 75 1-trifluoromethoxies-2,6-two fluoro-4-(2-(2-fluoro-4-(4-butyl cyclohexyl) phenyl) ethyl) benzene 76 1-trifluoromethoxies-2,6-two fluoro-4-(2-(2-fluoro-4-(4-amyl group cyclohexyl) phenyl) ethyl) benzene 77 1-trifluoromethoxies-2,6-two fluoro-4-(2-(2-fluoro-4-(4-hexyl cyclohexyl) phenyl) ethyl) benzene 78 1-trifluoromethoxies-2,6-two fluoro-4-(2-(2-fluoro-4-(4-heptyl cyclohexyl) phenyl) ethyl) benzene

Embodiment 5 (Application Example 1)

Preparation contains liquid-crystal composition A:4-(4-propyl group cyclohexyl) benzyl cyanogen 24% (weight) 4-(4-amyl group cyclohexyl) benzyl cyanogen 36% (weight) 4-(4-heptyl cyclohexyl) benzyl cyanogen 25% (weight) 4-(4-propyl group phenyl) the benzyl cyanogen 15% (weight) of following compound

Liquid-crystal composition A has following physical parameter: 72.4 ℃ of Δ ε of brocken spectrum: the V of 11.0 Δ n:0.137 viscosity (20 ℃) the thick 9 μ m in 27.0mPas pond _Th: 1.78V

85% (weight) liquid-crystal composition A mixes with The compounds of this invention 1-trifluoromethoxy-2-fluoro-4-(2-(4-propyl group cyclohexyl) ethyl) benzene (compound N o.1) that 15% (weight) embodiment 1 obtains, and makes liquid-crystal composition A1-1.Composition A1-1 has following physical parameter: brocken spectrum: 49.3 ℃ of Δ ε: 10.5 (extrapolated values: 7.7) Δ n:0.117 (extrapolated value: 0.004) viscosity (20 ℃) 24.8mPas (extrapolated value: 12.3m

Pas) V of the thick 8.7 μ m in pond _Th: 1.35VVHR (100 ℃): 99.8%

When composition A 1-1 placed 60 days down at-20 ℃, do not observe crystalline deposit yet in refrigerator.

Embodiment 6 (Application Example 2)

Make liquid-crystal composition A1-2 with embodiment 5 identical modes, different is to replace compound N o.1 with 1-trifluoromethyl-2-fluoro-4-(2-(4-amyl group cyclohexyl) ethyl) benzene (compound N o.3).Composition A1-2 has following physical parameter: Δ ε: 10.6 Δ n:0.120 viscosity (20 ℃) 25.2mPas (extrapolated values: 19.6m

Pa·s)

Embodiment 7 (Application Example 3)

Make liquid-crystal composition A2-1 with embodiment 5 identical modes, different is to replace compound N o.1 with 1-trifluoromethoxy-2-fluoro-4-(2-(4-(2-(4-propyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene (compound N o.19).Composition A2-1 has following physical parameter: Δ ε: 10.4 Δ n:0.128 viscosity (20 ℃) 25.9mPasV _Th: 1.74V

Embodiment 8 (Application Example 4)

Make liquid-crystal composition A2-2 with embodiment 5 identical modes, different is that o.1 6-two fluoro-4-(2-(4-(2-(4-propyl group cyclohexyl) ethyl) cyclohexyl) ethyl) benzene (compound N o.29) replace compound N with 1-trifluoromethoxy-2.Composition A2-2 has following physical parameter: Δ ε: 11.6 Δ n:0.127 viscosity (20 ℃) 35.0mPasV _Th: 1.70V

Embodiment 9 (Application Example 5)

Make liquid-crystal composition A3-1 with embodiment 5 identical modes, different is with 4 '-o.1 (2-(4-propyl group cyclohexyl) ethyl)-3-fluoro-4-trifluoromethyl-biphenyl (compound N is o.40) replace compound N.Composition A3-1 has following physical parameter: Δ ε: 11.3 Δ n:0.137 viscosity (20 ℃) 29.6mPas (extrapolated value:

48.6mPa·s)V _th：??????????????????????1.74V

Embodiment 10 (Application Example 6)

Make liquid-crystal composition A4-1 with embodiment 5 identical modes, different is to replace compound N o.1 with 1-trifluoromethoxy-2-fluoro-4-(2-(2-fluoro-4-(4-propyl group cyclohexyl) phenyl) ethyl) benzene (compound N o.49).Composition A4-1 has following physical parameter: Δ ε: 11.1 Δ n:0.139 viscosity (extrapolated value) 37.4mPas.

Comparative Examples 1

As the example that has near the control compounds of first kind compound of the present invention (compound N o.3) structure, can be chosen in disclosed compound (control compounds 1) among the Laid-open WO Japanese PatentPublication No.sho 63-503226 with formula (C) expression, in Laid-open Japanese Patent Publication NoHei 2-111734 disclosed with the compound (control compounds 2) of formula (d) expression and in Laid-open Japanese Patent Publication No Sho 61-207347 disclosed compound (control compounds 3) with formula (e) expression, and measure their physical parameter (brocken spectrum (C-I) point), the Δ ε of viscosity that the liquid-crystal composition extrapolation for preparing with following method obtains and the liquid-crystal composition that contains these compounds.

Prepare liquid-crystal composition by method identical among the embodiment 6, o.3 different is in the above-mentioned control compounds a kind ofly is used for replacing compound N, makes comparative liquid crystal composition B1-1, B1-2 and B1-3 respectively.

Result's following (o.3 compound N also is shown in down together with the result of liquid-crystal composition A1-2 (embodiment 6)):

	Brocken spectrum (℃)	Extrapolated viscosity (mPas)		???Δε
					Compound 21.4 19.6 A1-2 10.6 of the present invention (compound N o.3)
Control compounds 1	????10	????20.8	????B1-1	???????8.3
					Control compounds 2	????-30	????-8.2	????B1-2	???????10.9
Control compounds 3	????0	????-12.2	????B1-3	???????10.9

From The above results as can be seen: o.3 with regard to compound N of the present invention, do not obtain brocken spectrum decline and viscosity increase with extrapotation, this compound has very big Δ ε, comparing this with control compounds 1 is owing to introduce 1 in the center of molecule, the 2-ethylidene is although this compound has fluorine atom as substituting group in the side position.

The effect of introducing ethylene contradicts with old ordinary skill general knowledge.For example, the following knowledge of it and prior art is conflicting: ethylene is introduced control compounds 2 can make brocken spectrum descend, simultaneously extrapotation viscosity increase bigger than the control compounds 3 of not introducing ethylene.This is certain astonishing fact.

Comparative Examples 2

As the control compounds that the structure (compound N o.19) near the present invention's second compounds is arranged, can be chosen among the above-mentioned Laid-open Japanese Patent PublicationNo Hei 2-501311 disclosed, with (wherein n is 3) of formula (b) expression, particularly use the compound of formula (f) expression.

Its transformation temperature is as follows:

C39SB68N?148.6I

This control compounds 4 is clear to demonstrate strong smectic character.Therefore, when this compound was used as a component, the liquid-crystal composition that makes produced smectic phase at low temperatures.On the contrary, introducing two ethylene does not have smectic phase as the The compounds of this invention (compound N o.19) of center keyed jointing base, and only shows nematic phase (reference example 2), therefore the compound of the present invention shortcoming resemble the control compounds not.

Comparative Examples 3

As the control compounds that the structure (compound N o.4) near the present invention's the 3rd compounds is arranged (different is that hydrogen atom is changed to central phenylene position by the position that fluorine atom replaces from terminal phenylene position), can be chosen in Liq, Cryst., 18 (4), describe in 665 (1995), particularly the compound (control compounds 5) of formula (g) expression.

The Δ ε of the physical parameter of compound and the liquid-crystal composition that contains control compounds measures with method identical in the Comparative Examples 1 with Δ n.The result is as follows: brocken spectrum: 80.4 ℃ of viscosity (20 ℃) (extrapolated value): 52.0mPas Δ ε: 11.0 Δ n:0.138

From this Comparative Examples as can be seen, the brocken spectrum of compound of the present invention (compound N o.40) is compared than about 8 ℃ of compound 5 height, and low viscosity is arranged.Discover that from another compound N Δ ε, Δ n and viscosity o.40 has less temperature dependence, particularly the viscosity increase is very little at low temperatures, and with other liquid crystalline cpds fabulous miscibility is arranged.

Comparative Examples 4

As the control compounds (different be hydrogen atom changed to position on the phenylene of center from the position on the terminal phenylene by the position of fluorine atom) of being afraid of structure near the present invention's the 4th compounds (compound N o.49) is arranged, can be chosen in Liq.Cryst., 18 (4), describe in 665 (1995), particularly use the compound of formula (k) expression.

The physical parameter of compound, the Δ ε that contains the liquid-crystal composition (B4-1) of control compounds measures with method identical in the Comparative Examples 1 with Δ n.The result is as follows: brocken spectrum: 43 viscosity (20 ℃) (extrapolated value): 52.0mPas Δ ε: 11.0 Δ n:0.138

From Comparative Examples as can be seen, compound of the present invention (compound N o.49) is compared with control compounds 6, and roughly the same or higher brocken spectrum, Δ ε and Δ n are arranged, and lower viscosity is particularly arranged.

Equally, discover that compound N Δ ε, Δ n and viscosity o.49 has less temperature dependence, and with other liquid crystalline cpds fabulous miscibility is arranged from another.

Claims (10)

1. the liquid crystalline cpd of a general formula (1) expression Wherein, R ₁For the alkyl of 1-10 carbon atom is arranged, ring A is 1,4-phenylene or 1,4-cyclohexylidene, X ₁, X ₂, X ₃And X ₄Independent separately is hydrogen atom or fluorine atom, Y ₁Be CF ₃Or OCF ₃, m, n and p independently are 1 or 0 separately.

2. according to the liquid crystalline cpd of claim 1, wherein n is 0, and m is 1, X ₃Be fluorine atom, X ₄Be hydrogen atom.

3. according to the liquid crystalline cpd of claim 1, wherein n is 1, and ring A is 1, and 4-cyclohexylidene, m and p all are 1, X ₃Be fluorine atom.

4. according to the liquid crystalline cpd of claim 1, wherein n is 1, and ring A is 1, and 4-phenylene, m are 1, and p is 0, X ₁, X ₂And X ₄All be hydrogen atom, X ₃Be fluorine atom.

5. according to the liquid crystalline cpd of claim 1, wherein n is 1, and ring A is 1, and 4-phenylene, m are 0, and p is 1, X ₁Be fluorine atom, X ₂Be hydrogen atom.

6. liquid-crystal composition that contains the liquid crystalline cpd of each regulation among at least a claim 1-5.

7. liquid-crystal composition, the liquid crystalline cpd that it contains each regulation among at least a claim 1-5 is as first compound and contain at least a liquid-crystal composition that is selected from arbitrary formula is represented in general formula (2), (3) and (4) compound as second component

In the formula, R ₂The alkyl that 1-10 carbon atom arranged, Y ₂Be fluorine atom, chlorine atom, OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂, L ₁, L ₂, L ₃And L ₄Independent separately is hydrogen atom or fluorine atom, Z ₁And Z ₂Independently be-(CH separately ₂) ₂-,-CH=CH-or a covalent linkage, a is 1 or 2.

8. liquid-crystal composition, the liquid crystalline cpd that it contains each regulation among at least a claim 1-5 is as first compound and contain at least a liquid crystal compound that is selected from arbitrary formula is represented in general formula (5), (6), (7), (8) and (9) compound as second component In the formula, R ₃For fluorine atom, the alkyl of 1-10 carbon atom is arranged or has the alkenyl of 2-10 carbon atom, any methylene radical in alkyl or alkenyl to be replaced by Sauerstoffatom, condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring B is 1,4-cyclohexylidene, 1, and 4-phenylene or 1,3-diox-1,5-two bases, ring C is 1,4-cyclohexylidene, 1,4-phenylene or pyrimidine-2,5-two bases, ring D is 1,4-cyclohexylidene or 1,4-phenylene, Z ₃For-(CH ₂) ₂-,-COO-or-covalent linkage, L ₅And L ₆Independence is hydrogen atom or fluorine atom separately, and b and c and oneself are 0 or 1 independently, In the formula, R ₄For the alkyl of 1-10 carbon atom, L are arranged ₇Be hydrogen atom or fluorine atom, d is 0 or 1, In the formula, R ₅The alkyl that 1-10 carbon atom arranged, ring E and ring F independently are 1 separately, 4-cyclohexylidene or 1,4-phenylene, Z ₄And Z ₅Independently separately be-COO-or-covalent linkage, Z ₆Expression-COO-or-C=C-, L ₈And L ₉Independent separately is hydrogen atom or fluorine atom, Y ₃Be fluorine atom, OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂, condition is to work as Y ₃Be OCF ₃, OCF ₂H, CF ₃, CF ₂H or CFH ₂The time, L ₈And L ₉It all is hydrogen atom; E, f and g independently are 0 or 1 separately,

In the formula, R ₆And R ₇Independent separately is the alkenyl that the alkyl of 1-10 carbon atom is arranged or 2-10 carbon atom arranged, and the arbitrary methylene radical in alkyl and alkenyl can be replaced by Sauerstoffatom, and condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring H is 1,4-cyclohexylidene, 1, and 4-phenylene or pyrimidine-2,5-two bases, ring I is 1,4-cyclohexylidene or 1,4-phenylene, Z6 be-C=C-,-COO-,-(CH ₂) ₂-,-CH=CH-C=C-or-covalent linkage, Z ₇For-COO-or-covalent linkage,

In the formula, R ₈And R ₉Independent separately is the alkenyl that the alkyl of 1-10 carbon atom is arranged or 2-10 carbon atom arranged, and the arbitrary methylene radical in alkyl or alkenyl can be replaced by Sauerstoffatom, and condition is certainly not have two or more methylene radical to be replaced by Sauerstoffatom continuously; Ring J is 1,4-cyclohexylidene, 1, and 4-phenylene or pyrimidine-2,5-two bases, ring K is 1,4-cyclohexylidene, 1, the 4-phenylene, the one or more hydrogen atoms on the ring can be replaced by fluorine atom or pyrimidine-2,5-two bases, ring L is 1,4-cyclohexylidene or 1,4-phenylene, Z ₈And Z ₁₀Independently be separately-COO-,-(CH ₂) ₂-or covalent linkage, Z ₉For-CH=CH-,-C=C-,-COO-or-covalent linkage, h is 0 or 1.

9. liquid-crystal composition, it contains the liquid crystalline cpd of each regulation among at least a claim 1-5 as first component, contain arbitrary formula is represented at least a general formula (2) that is selected from the claim 7 regulation, (3) and (4) compound a part, and contain at least a liquid-crystal composition that is selected from arbitrary formula is represented in the general formula (5) stipulated in the claim 8, (6), (7), (8) and (9) compound as the rest part of second component as second component.

10. liquid crystal display apparatus made from the liquid-crystal composition of each regulation among the claim 6-9.