CN106278812B - A kind of liquid-crystal compounds with negative dielectric anisotropic and combinations thereof and its application - Google Patents

A kind of liquid-crystal compounds with negative dielectric anisotropic and combinations thereof and its application Download PDF

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CN106278812B
CN106278812B CN201510354627.1A CN201510354627A CN106278812B CN 106278812 B CN106278812 B CN 106278812B CN 201510354627 A CN201510354627 A CN 201510354627A CN 106278812 B CN106278812 B CN 106278812B
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CN106278812A (en
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韩文明
徐爽
张文琦
严加浩
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Jiangsu He Cheng Display Technology Co Ltd
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Abstract

The invention discloses a kind of liquid-crystal compounds with negative dielectric anisotropic, the structure of the compound is shown in general formula I.Negative liquid crystal compound of the present invention, it is good with other liquid crystal components intermiscibilities with absolute value big negative dielectric anisotropic, higher reliability and relatively low viscosity, it is widely portable in liquid crystal display device.Liquid-crystal composition containing this compound can be applied in liquid crystal display.

Description

Liquid crystal compound with negative dielectric anisotropy, composition and application thereof
Technical Field
The invention relates to the field of liquid crystals, in particular to a liquid crystal compound with negative dielectric anisotropy, a composition comprising the liquid crystal compound and application of the liquid crystal compound.
Background
A display device containing a liquid crystalline compound can be widely used for displays such as clocks, calculators, document processors, and the like. These display devices utilize optical anisotropy, dielectric anisotropy, and the like of liquid crystal compounds.
The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase, but the most widely used is one using a nematic liquid crystal phase. Examples of the display mode include a Dynamic Scattering (DS), alignment mode Deformation (DAP), Guest Host (GH), Twisted Nematic (TN), Super Twisted Nematic (STN), Thin Film Transistor (TFT), Vertical Alignment (VA), lateral electric field switching (IPS), and Polymer Sustained Alignment (PSA) mode.
The liquid crystalline compound used in these display systems exhibits a liquid crystal phase in a wide temperature range centered around room temperature, is very stable under the conditions in which the display device is used, and has sufficient characteristics required for driving the display device.
Therefore, at present, a liquid crystal composition having desired characteristics is prepared by mixing several to several tens of liquid crystal compounds. These liquid crystal compositions are required to be stable to moisture, light, heat, and air which are generally present under the conditions of using a display element, stable to an electric field or electromagnetic radiation, and stable in chemical properties to a mixed compound. In addition, the liquid crystal composition is required to have appropriate values for characteristics such as optical anisotropy (Δ n) and dielectric anisotropy (Δ ∈), depending on the display mode and the shape of the display element. In addition, it is important that the liquid crystal composition has good solubility between the respective components.
In order to perform good liquid crystal display, it is preferable that the cell thickness of the liquid crystal display element constituting the liquid crystal display element is fixed to the value of optical anisotropy of the liquid crystal composition used (e. jackman (e.jakeman), et al, physical communication (pyhs.lett.), 39a.69 (1972)). Also, the response speed of the liquid crystal display element is inversely proportional to the square of the thickness of the cell used. Therefore, in order to manufacture a liquid crystal display device having a high-speed response which can be applied to display of a dynamic image (dynamic image) and the like, a liquid crystal composition having a large optical anisotropy value is required. As liquid crystal compounds having a large optical anisotropy value, various compounds have been developed, and in general, compounds having such a large optical anisotropy generally have a highly conjugated molecular structure, but the compounds tend to have poor compatibility with other liquid crystal compounds, and thus are difficult to be used as components of liquid crystal compositions having good electrical characteristics (electrical properties). In addition, a liquid crystalline compound used as a constituent component of a liquid crystal composition which requires high insulation (specific resistance) such as a thin film transistor liquid crystal display element is required to have high stability.
In addition, among the above operation modes, IPS, VA, PSA, etc. are known as operation modes utilizing the vertical alignment of liquid crystal molecules, which can improve the drawback of the conventional display modes such as TN, STN, etc., i.e., the narrow viewing angle.
Further, liquid crystal compounds in which hydrogen on the benzene ring is substituted with fluorine have been studied in large quantities since the past as components of liquid crystal compositions having negative dielectric anisotropy that can be used in liquid crystal display elements of these operation modes.
For example, a (s-1) compound in which hydrogen on the benzene ring is substituted with fluorine and an alkyl group is provided on the side chain is studied in patent document JPH024725A, and a (s-2) compound in which hydrogen on the benzene ring is substituted with fluorine and an alkenyl group is provided on the side chain is studied in patent document JP 2002053602A.
Wherein R is1Represents an alkyl group, R2Represents an alkenyl group.
However, the dielectric anisotropy of the compound (s-1) is small, and the magnitude of the dielectric anisotropy is not sufficient either in the compound (s-2). Further, as compounds having an alkyl group in the side chain and a polar group such as a halogen as the side group, (s-3) compounds are disclosed in patent document JPH0753432A, and (s-4) compounds and (s-5) compounds are disclosed in patent documents JP2004035698A, JP2005537520A, JP2007031694A and JP 2007023071A.
In addition to this, JP2001316669A discloses a (s-6) compound having polar groups such as alkoxy groups on both side chains and halogen groups on the side chains, but does not disclose a 3-or 4-ring compound having 2, 3-dihalo-1, 4-phenylene groups as disclosed in the present invention, which is unsubstituted on both sides or has an unsubstituted side chain on one side and an alkyl, alkoxy or alkenyl group on the other side.
Wherein R is3Represents an alkyl group, R4Represents an alkoxy group.
In addition, there are the following aspects that need further improvement: since the (s-3) -based compounds have very low dielectric anisotropy and high viscosity, liquid crystal display devices cannot be driven by liquid crystal compositions containing these compounds. Further, the (s-4) -based compounds and the (s-5) -based compounds are not sufficiently large in dielectric anisotropy and high in viscosity, and are low in compatibility with other liquid crystalline compounds, and therefore cannot be contained in a liquid crystal composition in a small amount. Further, in the (s-6) compounds, since optical anisotropy is small and viscosity is high, driving voltage and the like cannot be reduced by a liquid crystal composition containing these compounds.
The above-described display element operating in the IPS mode, VA mode, or PSA mode is mainly composed of a liquid crystal composition having negative dielectric anisotropy, and in order to further improve the above-described characteristics and the like, the liquid crystal compound contained in the liquid crystal composition must have the characteristics shown in the following (1) to (8). Namely:
(1) has chemical stability and physical stability.
(2) Has a high transparency point. The clearing point is the liquid crystal phase-the isotropic phase is the transition temperature.
(3) With a lower temperature limit for the liquid crystal phase. The liquid crystal phase means a nematic phase and a smectic phase.
(4) Has a lower viscosity.
(5) Has proper optical anisotropy.
(6) Has appropriate negative dielectric anisotropy. The compound having a large dielectric anisotropy has a large viscosity in many cases.
(7) Proper elastic constant K33And K11(K33: flexural elastic constant, K11: splay spring constant); and
(8) excellent in compatibility with other liquid crystal compounds.
When a composition containing a chemically and physically stable liquid crystal compound as described in (1) is used for a display device, the voltage holding ratio can be increased.
Further, the composition containing the liquid crystalline compound having a high clearing point or a low lower limit temperature of the liquid crystal phase as described in (2) and (3) can expand the temperature range of the nematic phase and can be used as a display element in a wide temperature range.
Further, when a compound having a relatively low viscosity as described in (4) is used, the compound has a relatively large elastic constant K as described in (7)33The composition of the compound (3) can improve the response speed when used as a display element; when a display element using a composition containing a compound having an appropriate optical anisotropy as described in (5) is used, the contrast of the display element can be improved.
In addition, in the case where the liquid crystalline compound has a large negative dielectric anisotropy, the threshold voltage of the liquid crystal composition containing the compound can be lowered, and therefore, in the case of a display element using a composition containing a compound having an appropriate negative dielectric anisotropy as shown in (6), the driving voltage of the display element can be lowered and the power consumption can also be reduced. Further, by using a composition comprising a material having an appropriate elastic constant K as described in (7)33The composition of the compound (3) can be used as a display element, and can adjust the driving voltage and power consumption of the display element.
In order to exhibit characteristics that are difficult to be exhibited by a single compound, a liquid crystalline compound is generally used as a composition prepared by mixing with a plurality of other liquid crystalline compounds. Therefore, the liquid crystalline compound used in the display device preferably has good compatibility with other liquid crystalline compounds and the like as described in (8). Further, there are also the following cases: the display element can also be used in a wide temperature range including below freezing point, and therefore, a compound having good compatibility from a lower temperature range is preferable.
The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a liquid crystal compound having general physical properties required for liquid crystal compounds, stability against heat, light, and the like, optical anisotropy of an appropriate size, a wide nematic phase temperature range, and excellent compatibility with other liquid crystal compounds, and in particular, to provide a liquid crystal compound having negative dielectric anisotropy with a large absolute value, high reliability, and relatively low viscosity.
Disclosure of Invention
The purpose of the invention is as follows: an aspect of the present invention provides a negative liquid crystal compound having a negative dielectric anisotropy with a large absolute value, high reliability, and a relatively low viscosity.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a liquid crystal compound having negative dielectric anisotropy, which is a compound represented by the general formula i:
wherein,
r represents H, alkyl or alkoxy with 1-7 carbon atoms, or alkenyl with 2-7 carbon atoms;
is the same as orAnd each independently represents cyclohexyl, cyclopentyl or phenyl, wherein one or more-CH in the cyclohexyl or cyclopentyl group2-may be substituted by O, with the proviso that the heteroatoms are not directly attached to each other; one or more H of the phenyl groups may be substituted by F;
Z1and Z2The same or different, each independently represents a single bond, -CH2CH2-、-CH2O-、-CF2O-or-COO-;
n represents 0 or 1.
In some preferred embodiments, R represents H, an alkyl group having 1 to 7 carbon atoms, or an alkoxy group.
Preferably, R represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms.
More preferably, R represents an alkyl group having 2 to 5 carbon atoms.
In some preferred embodiments, Z is1And Z2The same or different, each independently represents a single bond, -CH2CH2-or-CH2O-。
In some preferred embodiments, theIdentical or different, each independently represents cyclohexyl, cyclopentyl or phenyl, wherein one or more H of the phenyl groups may be substituted by F.
Preferably, the compound of formula i is selected from the group consisting of:
and
wherein,
r independently represents H or alkyl or alkoxy with 1-7 carbon atoms or alkenyl with 2-7 carbon atoms;
Z3、Z4、Z5and Z6The same or different, each independently represents a single bond, -CH2CH2-or-CH2O-；
Represents cyclohexyl, cyclopentyl or phenyl;
L1、L2、L3and L4The same or different, each independently represents H or F.
Preferably, each R independently represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms; the above-mentionedRepresents cyclohexyl or phenyl.
More preferably, each of the R's independently represents an alkyl group having 2 to 5 carbon atoms.
Preferably, the compound of formula i is selected from the group consisting of:
and
wherein,
each R independently represents H, an alkyl group or an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms.
Preferably, each of the R independently represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms.
More preferably, each of the R's independently represents an alkyl group having 2 to 5 carbon atoms.
In some embodiments, it is particularly preferred that the compound is selected from the group consisting of:
and
the invention provides a preparation method of a liquid crystal compound with negative dielectric anisotropy, which comprises the following steps:
1) synthesis of intermediate B
To a three-necked flask was added 23.8g of compound A shown in the following table,250mL of anhydrous tetrahydrofuran, reducing the temperature to-78 ℃ under the protection of nitrogen, dropwise adding 42mL of 2.4mol/L n-hexane solution of n-BuLi, keeping the temperature at-78 ℃ after dropwise adding, stirring for 1h, and then dropwise adding 23g B (i-BuO)3And 80mL of anhydrous tetrahydrofuran, keeping the temperature at-78 ℃ after the dropwise addition, stirring for 1h, naturally heating to room temperature, pouring the reaction solution into a mixture of 100mL of 5% diluted hydrochloric acid and 200g of ice, stirring, separating liquid, extracting a water layer with ethyl acetate, combining oil layers, evaporating to remove a solvent, adding petroleum ether, pulping, and filtering to obtain a white solid intermediate B;
2) synthesis of Compound C
A three-necked flask was charged with 17.7g of intermediate B, 12.1g of 2, 3-difluorobromobenzene, 100mL of toluene, 50mL of ethanol, 50mL of water, 26.6g of sodium carbonate, and 0.35g of Pd (PPh) under nitrogen protection3)4Heating and refluxing for 6h, cooling to room temperature, adding 100mL of water, separating, extracting water layer with 100mL of toluene, combining oil layers, evaporating to remove solvent, and purifying by column chromatography to obtain a white solid compound C, as shown in the following table;
the preparation method of the liquid crystal compound with negative dielectric anisotropy comprises the following steps:
1) synthesis of Compound E
15.8g of Compound D, 19.3g of 2, 3-difluorobromobenzene, 120mL of toluene, 60mL of ethanol, 60mL of water, 42.4g of sodium carbonate, nitrogen were added to a three-necked flaskUnder gas protection, 0.5g Pd (PPh) was added3)4Heating and refluxing for 6h, cooling to room temperature, adding 100mL of water, separating, extracting a water layer with 100mL of toluene, combining oil layers, evaporating to remove a solvent, and purifying by column chromatography to obtain a white solid compound E;
2) synthesis of Compound F
Adding 15.4g of compound E and 200mL of anhydrous tetrahydrofuran into a three-necked flask, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 30mL of 2.4mol/L n-hexane solution of n-BuLi, keeping the temperature at-78 ℃ after dropwise adding, stirring for 1h, and then dropwise adding 17gB (i-BuO)3And 60mL of anhydrous tetrahydrofuran, keeping the temperature at-78 ℃ after dropwise addition, stirring for 1h, naturally heating to room temperature, pouring the reaction solution into a mixture of 100mL of 5% diluted hydrochloric acid and 200g of ice, stirring, separating, extracting a water layer with ethyl acetate, combining oil layers, removing a solvent by evaporation, adding 150mL of petroleum ether at 90-120 ℃, pulping, and filtering to obtain a white solid compound F;
3) synthesis of Compound G
Adding 11.5G of compound F, 100mL of dichloromethane and 30mL of dioxane into a three-necked bottle, cooling to 0 ℃, dropwise adding 15G of 30% hydrogen peroxide, stirring at room temperature for 3 hours after dropwise adding, then adding 100mL of water, separating liquid, extracting a water layer by using dichloromethane, combining oil layers, washing with water and detecting by using starch-KI test paper until the starch-KI test paper does not change color, and evaporating to remove a solvent to obtain a white-like solid compound G;
4) synthesis of Compound H
Adding 9.9G of compound G, 200mL of DMF, 13G of compound i, 6.6G of anhydrous potassium carbonate and 0.7G of KI into a three-necked bottle, stirring for 4H at 90 ℃, cooling to room temperature after the reaction is finished, pouring the reaction solution into a mixed solution of 200mL of toluene and 500mL of water, separating the solution, extracting a water layer from the toluene, combining oil layers, washing to be neutral by water, evaporating the solvent, and purifying by column chromatography to obtain a white solid compound H;
the compound i is propyl cyclohexyl methanol p-toluenesulfonate, ethyl cyclohexyl methanol p-toluenesulfonate, butyl cyclohexyl methanol p-toluenesulfonate or amyl cyclohexyl methanol p-toluenesulfonate;
the compound H is 2C1OWWW, 3C1OWWW, 4C1OWWW and 5C1 OWWW.
The preparation method of the liquid crystal compound with negative dielectric anisotropy comprises the following steps:
1) synthesis of Compound J
Adding 23.8g of compound A and 250mL of anhydrous tetrahydrofuran into a three-necked flask, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 42mL of 2.4mol/L n-hexane solution of n-BuLi, stirring at-78 ℃ for 1h after dropwise adding, then dropwise adding a mixture consisting of 25.4g I2 and 150mL of anhydrous tetrahydrofuran, stirring at-78 ℃ for 1h after dropwise adding, naturally heating to room temperature, pouring the reaction solution into a mixture of 100mL of 5% dilute hydrochloric acid and 200g of ice, stirring, separating liquid, extracting a water layer with ethyl acetate, combining an oil layer, washing the oil layer with sodium thiosulfate aqueous solution, washing the oil layer with water to neutrality, evaporating to remove the solvent, and purifying by column chromatography to obtain a light yellow solid compound J;
2) synthesis of Compound K
A three-necked flask is charged with 25.6g of compound J prepared in step 1), 18.9g of compound F, 100mL of toluene, 50mL of ethanol, 50mL of water, 29.7g of sodium carbonate, and 0.4g of Pd (PPh) under nitrogen3)4Heating and refluxing for 6h, cooling toAdding 100mL of water at room temperature, separating liquid, extracting an aqueous layer with 100mL of toluene, combining oil layers, evaporating to remove a solvent, and purifying by column chromatography to obtain a white solid compound K;
in another aspect of the present invention, there is also provided a liquid crystal composition comprising at least one compound represented by formula i.
Another aspect of the present invention provides a liquid crystal display comprising the liquid crystal composition of the present invention.
Has the advantages that: the liquid crystal compound of the present invention has general physical properties required for liquid crystal compounds, stability to heat, light, and the like, optical anisotropy of an appropriate size, a wide nematic phase temperature range, and excellent compatibility with other liquid crystal compounds. Compared with the known compound with the same structure, the liquid crystal compound has excellent compatibility with other liquid crystal compounds and low viscosity, and has lower viscosity, higher negative dielectric anisotropy, higher voltage holding ratio and higher reliability compared with similar compounds.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
For convenience of expression, in the following examples, the group structures of the liquid crystal compounds are represented by the codes listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
Compounds of the following formula are exemplified:
the structural formula is represented by the code listed in Table 1, and can be expressed as: nCWW, wherein n in the code represents the number of C atoms of the left alkyl group, e.g., n is "2", i.e., the alkyl group is-C2H5(ii) a C in the code represents cyclohexane; w in the code represents 2, 3-difluoro-1, 4-phenylene.
The abbreviated codes of the test items in the following examples are as follows:
cp (. degree. C.): clearing points (nematic-isotropic phase transition temperature)
Δ n: refractive index anisotropy (589nm, 25 ℃ C.)
Δ ε: dielectric anisotropy (1KHz, 25 ℃ C.)
γ 1: torsional viscosity (mPas at 25 ℃ C.)
VHR: voltage holding ratio (%)
Wherein, the refractive index anisotropy is obtained by testing an Abbe refractometer under a sodium lamp (589nm) light source at 25 ℃; the dielectric test cell was of the type TN90, the cell thickness being 7 μm.
And delta epsilon | -epsilon ⊥, where epsilon | is the dielectric constant parallel to the molecular axis and epsilon ⊥ is the dielectric constant perpendicular to the molecular axis, under the test conditions of 25 ℃, 1KHz, test cell type TN90, and cell thickness of 7 μm.
VHR is obtained by testing by using a TOYO6254 type liquid crystal physical property evaluation system; the test temperature was 60 ℃, the test voltage was 5V, and the test time was 166.7 ms.
In the following examples, monomers of the compounds used and related reagents, except for the compounds of formula I and related subformulas thereof, are commercially available.
Example 1
The synthetic route of compound 3CWW is shown below:
the compound A and the 2, 3-difluorobromobenzene are all from Jiangsu and New materials forming company Limited.
The preparation process comprises the following steps:
1) synthesis of Compound B
Adding 23.8g of compound A and 250mL of anhydrous THF (tetrahydrofuran) into a 1L three-necked flask, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 42mL of n-BuLi n-hexane solution (2.4mol/L), keeping the temperature at-78 ℃ after dropwise adding, stirring for 1h, and then dropwise adding 23g B (i-BuO)3And 80mL of anhydrous TFT, stirring at-78 deg.C for 1h, naturally heating to room temperature, adding the reaction solution into a mixture of 100mL of 5% diluted hydrochloric acid and 200g of ice, stirring, separating, and extracting water with ethyl acetateCombining oil layers, evaporating to remove the solvent, adding 150mL of petroleum ether with the temperature of 90-120 ℃, pulping, and filtering to obtain 17.7g of a white solid compound B, wherein the yield is as follows: 62.8%, HPLC>95％。
2) Synthesis of Compound C
A500 mL three-necked flask was charged with 17.7g of Compound B, 12.1g of 2, 3-difluorobromobenzene, 100mL of toluene, 50mL of ethanol, 50mL of water, 26.6g of sodium carbonate, and 0.35g of Pd (PPh) under nitrogen protection3)4Heating and refluxing for 6h, cooling to room temperature, adding 100mL of water, separating, extracting a water layer with 100mL of toluene, combining oil layers, evaporating to remove a solvent, and purifying by column chromatography to obtain a white solid compound C11.8 g, wherein the yield is as follows: 53.7%, GC>99％，DSC：C 70.1I，MS：M+350(80％)266(14％)252(100％)239(66％)。
Referring to the synthesis of compound C, starting material a was replaced in step (1) with the compounds listed in the following table (alternative compounds to compound a were all from Jiangsu and New materials Co., Ltd.) and the resulting compounds were prepared as follows:
example 2
The synthetic route for compound 3C1OWW is shown below:
propylcyclohexylmethanol p-toluenesulfonate was from Jiangsu and New materials Co.
The preparation process comprises the following steps:
1) synthesis of Compound E
A500 mL three-necked flask was charged with 15.8g of Compound D, 19.3g of 2, 3-difluorobromobenzene, 120mL of toluene, 60mL of ethanol, 60mL of water, 42.4g of sodium carbonate, and 0.5g of Pd (PPh) under nitrogen protection3)4Heating and refluxing for 6h, cooling to room temperature, adding 100mL of water, separating, extracting a water layer with 100mL of toluene, combining oil layers, evaporating to remove a solvent, and purifying by column chromatography to obtain a white solid compound E15.4 g, wherein the yield is as follows: 68.1%, GC>98％。
2) Synthesis of Compound F
Adding 15.4g of compound E and 200mL of anhydrous THF into a 500mL three-necked flask, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 30mL of n-BuLi n-hexane solution (2.4mol/L), keeping the temperature at-78 ℃ after dropwise adding, stirring for 1h, and dropwise adding 17g of B (i-BuO)3And 60mL of anhydrous TFT, keeping the temperature at-78 ℃ after dropwise addition, stirring for 1h, naturally heating to room temperature, pouring the reaction solution into a mixture of 100mL of 5% diluted hydrochloric acid and 200g of ice, stirring, separating, extracting a water layer with ethyl acetate, combining oil layers, evaporating to remove a solvent, adding 150mL of petroleum ether at 90-120 ℃, pulping, and filtering to obtain a white solid compound F11.5 g, wherein the yield is as follows: 62.6% by HPLC>95％。
3) Synthesis of Compound G
Adding 11.5G of compound F, 100mL of dichloromethane and 30mL of dioxane into a 500mL three-necked bottle, cooling to 0 ℃, dropwise adding 15G of 30% hydrogen peroxide, stirring at room temperature for 3 hours after dropwise adding is finished, then adding 100mL of water, separating liquid, extracting a water layer by dichloromethane, combining oil layers, washing with water and detecting by using starch-KI test paper until the starch-KI test paper does not change color, and evaporating to remove the solvent to obtain 9.9G of a white-like solid compound G, wherein the yield is as follows: 96%, GC > 97%.
4) Synthesis of Compound H
Adding 9.9G of compound G, 200mL of DMF, 13G of propylcyclohexyl methanol p-toluenesulfonate, 6.6G of anhydrous potassium carbonate and 0.7G of KI into a 500mL three-necked bottle, stirring at 90 ℃ for 4 hours, cooling to room temperature after the reaction is finished, pouring the reaction liquid into a mixed liquid of 200mL of toluene and 500mL of water, separating the liquid, extracting a water layer from the toluene, combining oil layers, washing to be neutral by water, evaporating the solvent, and purifying by column chromatography to obtain a white solid compound H11.1G, wherein the yield is as follows: 73%, GC>99％，DSC：C 91.4I，MS：M+380(15％)242(100％)138(30％)。
Referring to the synthesis method of compound H, compound 2C1OWW can be prepared by replacing propylcyclohexylmethanol p-toluenesulfonate with ethylcyclohexylmethanol p-toluenesulfonate in step (4). The compound 4C1OWW can be prepared by replacing propylcyclohexylmethanol p-toluenesulfonate with butylcyclohexylmethanol p-toluenesulfonate in the step (4). The compound 5C1OWW can be prepared by exchanging propylcyclohexylmethanol p-toluenesulfonate for pentylcyclohexylmethanol p-toluenesulfonate in step (4):
example 3
The synthetic route of compound 3CWWW is shown below:
the preparation process comprises the following steps:
1) synthesis of Compound J
A1L three-necked flask was charged with 23.8g of Compound A, 250mLTHF water is cooled to-78 ℃ under the protection of nitrogen, 42mL n-BuLi normal hexane solution (2.4mol/L) is added dropwise, after the dropwise addition is finished, the temperature is kept at-78 ℃ and the stirring is carried out for 1h, and then 25.4gI is added dropwise2And 150mL of anhydrous TFT, keeping the temperature at-78 ℃ after dropwise addition, stirring for 1h, naturally heating to room temperature, pouring the reaction solution into a mixture of 100mL of 5% diluted hydrochloric acid and 200g of ice, stirring, separating, extracting a water layer with ethyl acetate, combining oil layers, washing an oil layer with sodium thiosulfate aqueous solution, washing the oil layer with water to be neutral, evaporating to remove a solvent, and purifying by column chromatography to obtain a light yellow solid compound J25.6 g, wherein the yield is as follows: 70%, GC>98％。
2) Synthesis of Compound K
A500 mL three-necked flask was charged with 25.6g of Compound J, 18.9g of Compound F, 100mL of toluene, 50mL of ethanol, 50mL of water, 29.7g of sodium carbonate, and 0.4g of Pd (PPh) under nitrogen3)4Heating and refluxing for 6h, cooling to room temperature, adding 100mL of water, separating, extracting a water layer with 100mL of toluene, combining oil layers, evaporating to remove a solvent, and purifying by column chromatography to obtain a white solid compound K17g, wherein the yield is as follows: 52.6%, GC>99％，DSC：C 145.8I，MS:M+462(100％)378(10％)364(95％)351(57％)。
Referring to the synthesis of compound K, starting material a was replaced in step (1) with the compounds listed in the following table, and the compounds of the following structure were prepared:
example 4
The compound 3CWW and the compound 3CCWW obtained by the synthesis method in the above example were mixed with a host liquid crystal (host) in a weight ratio of 10%: 90% mixing, good miscibility and no crystallization, and the physical parameters of the compounds are extrapolated as follows:
compound (I) Cp Δn Δε γ1 VHR(％)
3CWW 14.4 0.115 -5.2 151 98.1
3CCWW 193.8 0.114 -5.0 404 98.2
The parent liquid crystal (host) is 20% of the following compound: 40%: mixing the following components in a ratio of 40%:
and
the performance parameter test results are as follows:
Cp：112 Δn：0.08 Δε：5.0 γ1：169 VHR(％)：98.2。
comparative example 1
Compounds ref.1 and ref.2 of the following structures are each present in 10% by weight with the parent liquid crystal (host): 90% mixing, good miscibility and no crystallization, and the physical parameters of the compounds are extrapolated as follows:
the compound 3CWW and the compound 3CCWW in example 4 have a larger negative dielectric anisotropy, a higher voltage holding ratio, and a higher reliability than ref.1 and ref.2 in comparative example 1.
Example 5
Compound 3C1OWW, compound 3CWWW, compound 3PWW and the host liquid crystal (host) were mixed in a weight ratio of 10%: 90% of the mixture, good miscibility of the two and no crystallization phenomenon, and the liquid crystal parameters of the compound 3C1OWW, the compound 3CWW and the compound 3PWW are tested by an extrapolation method as follows:
compound (I) Cp Δn Δε γ1
3C1OWW 14.4 0.112 -5.9 215
3CWWW 97.3 0.157 -6.3 413
3PWW 47 0.208 -5.0 144
Comparative example 2
Compounds of the following structures ref.3, ref.4 and ref.5 are each present in a 10% by weight ratio to the parent liquid crystal (host): 90% mixing, good miscibility and no crystallization, and the physical parameters of the compounds are extrapolated as follows:
compared with the compounds Ref.3, Ref.4 and Ref.5 in the comparative example 2, the compounds 3C1OWW, 3CWW and 3PWW in the example 5 have larger negative dielectric anisotropy and obviously lower viscosity, can be used for preparing a liquid crystal display and achieves very good technical effect.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A liquid crystal compound with negative dielectric anisotropy is shown as a general formula I:
wherein,
r represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms;
identical or different, each independently represents cyclohexyl, cyclopentyl or phenyl, wherein one or more-CH's in said cyclohexyl or cyclopentyl group2May be substituted by O, with the proviso that the O atoms are not directly linked to each other; one or more H of the phenyl groups may be substituted by F;
Z1and Z2The same or different, each independently represents a single bond, -CH2CH2-or-CH2O-；
n represents 0 or 1.
2. The liquid crystal compound having negative dielectric anisotropy according to claim 1, wherein the compound represented by the general formula i is selected from the group consisting of:
and
wherein,
Z3、Z4、Z5and Z6The same or different, each independently represents a single bond, -CH2CH2-or-CH2O-；
Represents cyclohexyl, cyclopentyl or phenyl;
L1、L2、L3and L4The same or different, each independently represents H or F.
3. The liquid crystal compound having negative dielectric anisotropy according to claim 2, wherein the compound isRepresents cyclohexyl or phenyl.
4. The liquid crystal compound having negative dielectric anisotropy according to claim 1, wherein the compound represented by the general formula i is selected from the group consisting of:
and
5. the liquid crystal compound having negative dielectric anisotropy according to claim 1, wherein the compound represented by the general formula i is selected from the group consisting of:
and
6. a liquid crystal composition comprising a compound according to any one of claims 1 to 5.
7. A liquid crystal display comprising the liquid crystal composition of claim 6.
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