CN103361074B

CN103361074B - Comprise polyfluoro for the liquid crystalline cpd of unsaturated indenes ring and composition thereof and application

Info

Publication number: CN103361074B
Application number: CN201310274777.2A
Authority: CN
Inventors: 纪金山; 刘琦; 丁文全; 谭玉东
Original assignee: JIANGSU HECHENG NEW MATERIALS Co Ltd
Current assignee: JIANGSU HECHENG NEW MATERIALS Co Ltd
Priority date: 2013-07-01
Filing date: 2013-07-01
Publication date: 2015-08-26
Anticipated expiration: 2033-07-01
Also published as: CN103361074A

Abstract

The invention provides and comprise polyfluoro for the liquid crystalline cpd of unsaturated indenes ring and the liquid-crystal composition and the application that comprise described liquid crystalline cpd.Described liquid crystalline cpd is the compound with formula I, this compound has applicable optical anisotropy, large negative dielectric anisotropic, low viscosity, wide nematic temperature range, make the indicating meter of this compound of application have response speed, wider working range faster, and all can keep good display in various environment.Liquid-crystal composition of the present invention is that to have clearing point high, and optical anisotropy is large, and viscosity is little, the novel negative dielectric anisotropy liquid crystal composition that dielectric anisotropy is large.The present invention also provides the liquid crystal display device comprising described liquid-crystal composition.

Description

Liquid crystal compound containing polyfluorinated unsaturated indene ring and composition and application thereof

Technical Field

The invention relates to a liquid crystal compound, a composition containing the liquid crystal compound and application of the liquid crystal compound, in particular to a novel liquid crystal compound containing a polyfluorinated unsaturated indene ring, a liquid crystal composition containing the liquid crystal compound and application of the liquid crystal compound.

Background

Liquid crystal display devices are classified into types such as PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), and the like, according to a display mode of liquid crystal. The driving method of the element is classified into a PM (passive matrix) type and an AM (active matrix) type. PM is classified into static (static) and multiplex (multiplex) types. AM is classified into a TFT (thin film transistor), an MIM (metal insulator metal), and the like. The types of TFTs are amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to a manufacturing process. Liquid crystal display elements are classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both light sources of natural light and backlight, depending on the type of light source.

For displays with a substantially homeotropic (homeotropic) surface alignment, such as the above-mentioned ECB, VA or ASV mode displays, a specially tailored LC medium is required. For example, the LC medium should have a negative dielectric anisotropy and a low voltage Holding Ratio (HR) value after UV irradiation. Furthermore, for industrial applications in electro-optic displays, the LC media should generally have a high chemical resistance to moisture, air and physical effects, including heat, cold, radiation in the infrared, visible and ultraviolet regions, direct and alternating electric fields, and the viscosity of the LC phase in a suitable temperature range. For TV and monitor applications, LC media are required which have fast response times and low threshold voltages, in addition to good LTS (low temperature stability).

In the prior art, it is known from EP0637585a1 that the fluorinated indene ring type structure is mainly applied to ferroelectric liquid crystal displays. In US2007080324, US2011101270, US2006124896, the use of fluorinated indene ring structures for liquid crystal displays of VA, ECB, FFS, etc. modes is disclosed.

Disclosure of Invention

The invention fully utilizes the conjugated characteristic of the unsaturated indene ring, designs the rod-shaped liquid crystal structure at one side of the six-membered ring of the unsaturated indene ring, greatly enhances the conjugated stability of the structure through data comparison, and simultaneously optimizes the fluoro structures at different positions of the unsaturated indene ring, thereby obtaining the novel negative dielectric anisotropy liquid crystal compound with the properties of high clearing point, large optical anisotropy, small viscosity, large dielectric anisotropy and the like.

The invention aims to provide a novel liquid crystal compound containing a polyfluorinated unsaturated indene ring.

Another object of the present invention is to provide a synthesis method for synthesizing the liquid crystal compound.

It is still another object of the present invention to provide a liquid crystal composition comprising the liquid crystal compound.

The invention further aims to provide application of the liquid crystal composition in a liquid crystal element.

One aspect of the present invention provides a novel liquid crystal compound having a structure represented by general formula i:

wherein,

R¹¹and R¹²Each independently represents H, halogen, CN or CF having 1-15 carbon atoms₃Monosubstituted or halogenatedSubstituted or non-halogenated alkyl or alkoxy, having 2 to 15 carbon atoms, by CN or CF₃(ii) a mono-substituted or halogenated or non-halogenated alkanyl or alkoxyalkenyl group, wherein in said R¹¹And R¹²One or more-CH of₂The radicals-may each independently be replaced by-O-, -S-,-CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CO-O-, or-O-CO-substitution, with the proviso that oxygen atoms are not directly attached to each other;

A¹¹、A¹²and A¹³Each independently represents:

a) represents 1, 4-cyclohexenylene or 1, 4-cyclohexylene, in which one or more non-adjacent-CH groups₂-may be replaced by-O-or-S-; or

b) Represents 1, 4-phenylene in which one or more non-adjacent-CH-groups may be replaced by N;

wherein one or more H of the 1, 4-cyclohexenylene group, the 1, 4-cyclohexylene group and the 1, 4-phenylene group may be substituted with a halogen atom;

Z¹¹、Z¹²and Z¹³Each independently represents a single bond, -O-, -COO-, -OCO-, -CF₂O-、-OCF₂-、-CH₂O-、-CH₂CH₂-、-(CH₂)₄-、-C₂F₄-、-CH₂CF₂-、-CF₂CH₂-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, or-C ≡ C-;

X¹and X²Each independently represents H or halogen;

q, p and d each independently represent 0, 1 or 2, and 1. ltoreq. q + p + d. ltoreq.6.

In some preferred embodiments, the compound of formula i is preferably one or more of the following compounds:

wherein,

R¹¹represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkylalkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

R¹²represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkylalkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms, wherein in the R¹²One or more-CH of₂The radicals-may each independently be replaced by-O-, -S-,-CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CO-O-, or-O-CO-substitution, with the proviso that oxygen atoms are not directly attached to each other.

In some preferred embodiments, the compounds of formula i are particularly preferably one or more of the following compounds:

another object of the present invention is to provide a process for preparing the above compound, comprising the steps of:

1) adding I-a to tetrahydrofuran solvent

And CuCl, dropwise adding n-butyllithium at a temperature of between 72 ℃ below zero and 80 ℃ below zero, reacting at a temperature of between 20 ℃ below zero and 25 ℃ below zero to obtain a copper lithium solution, dissolving n-butyryl chloride in tetrahydrofuran, dropwise adding the n-butyryl chloride dissolved in the tetrahydrofuran into the copper lithium solution at a temperature of between 20 ℃ below zero and 25 ℃ below zero, reacting, and adding hydrochloric acid and water for hydrolysis after the reaction is finished to obtain a compound I-b;

2) adding the compound I-b, morpholine and glacial acetic acid into a formaldehyde aqueous solution, and heating and refluxing to obtain a compound I-c;

3) hybrid AlCl₃And NaCl, heating in an oil bath to form liquid, dropwise adding the compound I-c into the molten liquid for reaction, cooling the molten liquid, pouring the molten liquid into ice for hydrolysis, and adding hydrochloric acid to adjust the pH value to obtain a compound I-d;

4) adding the compound I-d and 1, 3-propanedithiol into a dichloromethane solution, dropwise adding boron trifluoride diethyl etherate at the temperature of below 10 ℃, and heating the obtained solution to room temperature and stirring to obtain a compound I-e;

5) adding the compound I-e into a dichloromethane solution, dissolving triethylamine complex hydrogen trifluoride and dibromohydantoin in the dichloromethane solution, dropwise adding at the temperature of below 70 ℃, standing at the temperature of between 72 ℃ below zero and 75 ℃, and stirring at room temperature to obtain a compound I-f;

7) adding the compound I-f into a tetrahydrofuran solvent, dropwise adding n-butyllithium at a temperature of between 72 ℃ below zero and 80 ℃ below zero, dropwise adding triisobutyl borate at a temperature of between 72 ℃ below zero and 80 ℃ below zero, naturally heating to 30 ℃ below zero after dropwise adding, adding water for hydrolysis, and regulating the pH value to 4-5 by using hydrochloric acid to obtain a compound I-g;

8) adding the compound I-h into tetrahydrofuran solvent

The compound I-g, sodium metaborate, water and PdCl₂.(PPh₃)₂And 80% hydrazine hydrate, heating and refluxing to obtain the liquid crystal compound shown in the general formula I

Another aspect of the present invention is to provide a liquid crystal composition comprising at least one liquid crystal compound of formula I, which may be one or more selected from the group consisting of compounds of formulae I-1 to I-30 or one or more selected from the group consisting of compounds of formulae I-1-1 to formula I-30-3.

It is a further object of the present invention to provide a liquid-crystalline medium based on a mixture of polar liquid-crystalline compounds of negative dielectric anisotropy, comprising:

1-20% by weight of the total composition of one or more compounds of formula I

One or more compounds of general formula (II) in an amount of 10-50% by weight based on the total weight of the composition

15-50% by weight of the total composition of one or more compounds of formula (III)

25-55% by weight of the total composition of one or more compounds of formula (IV)

Wherein,

R¹¹and R¹²Each independently represents H, halogen, CN or CF having 1-15 carbon atoms₃Alkyl or alkoxy which is monosubstituted or halogenated or not, CN or CF having 2 to 15C atoms₃(ii) a mono-substituted or halogenated or non-halogenated alkanyl or alkoxyalkenyl group, wherein in said R¹¹And R¹²One or more-CH of₂The radicals-may each independently be replaced by-O-, -S-,-CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CO-O-, or-O-CO-substitution, with the proviso that oxygen atoms are not directly attached to each other;

R²¹、R²²、R³¹and R³²Each independently represents H, halogen, CN or CF having 1-15 carbon atoms₃Alkyl or alkoxy which is monosubstituted or halogenated or not, CN or CF having 2 to 15C atoms₃(ii) a mono-substituted or halogenated or non-halogenated alkanyl or alkoxyalkenyl group, wherein in said R²¹、R²²、R³¹And R³²One or more-CH of₂The radicals may each independently beby-O-, -S-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CO-O-, or-O-CO-, with the proviso that oxygen atoms are not directly attached to each other;

R⁴¹and R⁴²Each independently represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms and a halogenated or non-halogenated alkanyl or alkoxyalkenyl group having 2 to 10 carbon atoms, wherein in the R⁴¹And R⁴²One or more-CH of₂-the groups may each be independently replaced by-O-, -S-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CO-O-or-O-CO-, with the proviso that oxygen atoms are not directly attached to each other;

L₁、L₂、L₃and L₄Each independently represents H or F, and L₁、L₂、L₃And L₄At least one of which is F;

z independently represents a single bond, -O-, -COO-, -OCO-, -CF₂-、-CF₂O-、-OCF₂-、-CH₂O-、-CH₂CH₂-、-（CH₂）₄-、-C₂F₄-、-CH₂CF₂-、-CF₂CH₂-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, or-C ≡ C-;

A¹¹、A¹²and A¹³Each independently represents:

ring (C)Ring (C)Andeach independently represent Andwherein saidOne or two non-adjacent-CH₂-may be replaced by-O-or-S-, saidEach of the above-mentioned H may be independently substituted by F, saidOne or two non-adjacent-CH-s may be replaced by N, saidOne or two non-adjacent-CH₂May be replaced by O, saidEach of the above-mentioned H may be independently substituted with F;

X¹and X²Each independently represents H or halogen;

m represents 1 or 2, n represents 0 or 1;

x represents 0 or 1;

q, p and d each independently represent 0, 1 or 2, and 1. ltoreq. q + p + d. ltoreq.6,

y and z independently represent 0, 1, 2, respectively, but y and z cannot simultaneously take 0.

In an embodiment of the present invention, it is preferable that the compound of formula i accounts for 3% to 15% of the total weight of the liquid crystal composition; the compound of the general formula II accounts for 15-40% of the total weight of the liquid crystal composition; the compound of the general formula III accounts for 18-40% of the total weight of the liquid crystal composition; the compound of the general formula IV accounts for 30-50% of the total weight of the liquid crystal composition;

in an embodiment of the present invention, the compound of the formula I is preferably one or more compounds selected from the group consisting of the compounds of the aforementioned formulae I-1 to I-30.

In an embodiment of the invention, the compound of formula ii is preferably one or more compounds from the group consisting of:

wherein,

R²¹represents halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

R²²represents H, halogen, halogenated or non-halogenated alkyl or alkoxy having 1 to 10 carbon atomsA radical, a halogenated or unhalogenated alkalkenyl or alkoxyalkenyl radical having 2 to 10 carbon atoms;

in an embodiment of the present invention, the compound of the general formula (iii) is preferably one or more compounds selected from the group consisting of:

wherein,

R³¹represents halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

R³²represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

in an embodiment of the present invention, the compound of the general formula (iv) is preferably one or more compounds selected from the group consisting of:

wherein,

R⁴¹represents halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 8 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

R⁴²represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 8 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 8 carbon atoms.

In an embodiment of the invention, it is preferred that the compound of formula I comprises from 5 to 15% by weight of the total composition; the compound of the general formula II accounts for 15-35% of the total weight of the composition; the compound of the general formula III accounts for 15-35% of the total weight of the composition; the compound of formula IV is present in an amount of 30 to 50% by weight of the total composition.

Another aspect of the present invention is to provide a method for synthesizing the liquid crystal compound of the present invention, which is represented by the following reaction scheme:

1) synthesis of I-b

Adding I-a, CuCl and THF into a three-neck flask, cooling to-78 ℃ by using liquid nitrogen under the protection of nitrogen, controlling the temperature to be-72 to-80 ℃, dropwise adding n-butyl lithium (2.5 mol/l), keeping the temperature for 0.5h at the temperature, and heating to-20 to-25 ℃ for reaction for 1 h. Dissolving n-butyryl chloride in THF, dropping into prepared copper-lithium reagent at-20 deg.C to-25 deg.C, reacting at the temperature for 2 hr, sampling, TLC detecting, adding dilute hydrochloric acid and water for hydrolysis, extracting with ethyl acetate, mixing organic phases, washing with water for 2 times, washing with saturated salt solution for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporating the solvent, and performing 200-300-mesh silica gel column chromatography to evaporate the solvent to obtain a light yellow liquid which is a compound I-b;

2) synthesis of I-c

Adding I-b, morpholine, 37% formaldehyde aqueous solution and glacial acetic acid into a single-mouth bottle, heating and refluxing for 4h, sampling and sending to GC, and completing the reaction. Cooling to room temperature, extracting with dichloromethane, mixing organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporating the solvent, and performing 200-mesh and 300-mesh silica gel column chromatography to evaporate the solvent to obtain a yellow liquid which is a compound I-c;

3) synthesis of I-d

Adding AlCl into a single-mouth bottle₃NaCl, oil bath heating to 140 deg.C, stirring to melt completely to form liquid, and dripping I-3 into the molten liquidDripping in the body, heating to 180 deg.C, reacting for 2 hr, sampling, TLC detecting to remove raw material, cooling the molten liquid, pouring into prepared ice cake, hydrolyzing, adding hydrochloric acid to adjust pH to 2, extracting with dichloromethane, mixing organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, and collecting anhydrous Na₂SO₄Drying, evaporating to remove the solvent, performing 200-mesh and 300-mesh silica gel column chromatography to obtain a light yellow solid, and recrystallizing once to obtain an off-white solid which is a compound I-d;

4) synthesis of I-e

Adding I-d, 6.5g of 1, 3-propanedithio, DCM and nitrogen into a three-necked flask, cooling to 0 ℃ in an ice water bath, dropwise adding boron trifluoride diethyl etherate at the temperature of below 10 ℃, stirring for 4 hours at room temperature after dropwise adding, detecting by TLC (thin layer chromatography), quenching and hydrolyzing ice with sodium bisulfite aqueous solution, extracting with dichloromethane, combining organic phases, washing for 2 times, washing with saturated salt water for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporating the solvent, carrying out 200-mesh and 300-mesh silica gel column chromatography, evaporating the solvent, and recrystallizing to obtain a white solid which is a compound I-e;

6) synthesis of I-f

Adding I-e, DCM, evacuating nitrogen, cooling liquid nitrogen to-75 ℃, dissolving triethylamine complex hydrogen trifluoride and dibromohydantoin in DCM, dropwise adding, controlling the temperature to be below-70 ℃, keeping the temperature for 2h after completing dropwise adding from-72 ℃ to-75 ℃, stirring for 2h at room temperature, and sampling TLC without raw material treatment. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating the solvent, and carrying out 200-mesh and 300-mesh silica gel column chromatography to evaporate the solvent to obtain a light yellow solid which is a compound I-f;

7) synthesis of I-g

Adding THF (140 ml) of I-f into a three-necked bottle, evacuating nitrogen, cooling liquid nitrogen to-78 ℃ under protection, controlling the temperature to be-72 to-80 ℃, dropwise adding n-butyllithium (2.5 mol/l), keeping the temperature for 30min after dropwise adding, controlling the temperature to be-72 to-80 ℃, dropwise adding triisobutyl borate, keeping the temperature for 0.5h after dropwise adding, naturally heating to-30 ℃, adding water for hydrolysis, adjusting the pH value to be 4-5 by using dilute hydrochloric acid, extracting by using ethyl acetate, combining organic phases, washing for 2 times, washing for 1 time by using saturated salt, directly evaporating a solvent, adding isobutanol, adding 60-90 P.E. for pulping, and performing suction filtration to obtain a white solid which is a compound I-g;

8) synthesis of I

Adding I-g into a single-mouth bottle,sodium metaborate, THF, water, PdCl₂.(PPh₃)₂80% hydrazine hydrate. After heating to initiate reflux, reflux was maintained for 2.5h and sample TLC was monitored for completion. Extracting with dichloromethane, mixing organic phases, washing with water for 2 times, washing with saturated salt for 1 time, drying with anhydrous Na2SO4, evaporating to remove solvent, adding P.E. to remove polar solvent, dissolving with P.E. to obtain solution, performing column chromatography with 60-100 mesh silica gel column, and washing with equal volume of P.E. once. And (4) spin-drying the solvent, and recrystallizing to obtain a white solid, namely the compound I.

In another aspect of the invention, an electro-optical liquid crystal display is provided, comprising the liquid crystal composition of the invention.

The liquid crystal medium comprising the liquid crystal composition is determined by performing a combination experiment on the compounds and comparing the compounds with a control, and has the characteristics of high clearing point, large optical anisotropy, small viscosity and large dielectric anisotropy

The liquid crystal composition of the invention can be used in active matrix addressed electro-optical liquid crystal displays based on the ECB, PALC or IPS effect

As mentioned above, the liquid crystal composition of the present invention can be used in VA-TFT applications such as MVA, PVA and ASV. They are further suitable for IPS and PALC applications in the case of negative dielectric anisotropy. The image display effect is good, and the phenomenon of smear is avoided. And the low temperature of the nematic phase can reach-30 ℃, and the requirement of low-temperature operation can be met. At low temperature (-30 ℃), storage for more than 1000 hours had substantially no effect on its performance. The voltage has small change along with the temperature, and the response is fast at low temperature.

The liquid crystal composition is obtained by optimally combining and proportioning a large amount of known liquid crystal compounds, and the clearing point Cp is between 75 and 100 ℃, preferably between 80 and 96 ℃; the viscosity eta is 13-35mm²·s^-1(20 ℃) preferably between 16 and 30mm²·s^-1(20 ℃) is between; an optical anisotropy Deltan of between 0.05 and 0.20 (20 ℃), preferably between 0.08 and 0.15 (20 ℃); the negative dielectric anisotropy Delta is between-2.6.0 and-4.5 (20 ℃), preferably between-2.8 and-4.0 (20 ℃).

The liquid crystal composition of the present invention may also further contain additives known to those skilled in the art and described in the literature, such as pleochroic dyes, chiral agents, antistatic agents, and the like.

In the present invention, unless otherwise specified, the proportions are weight ratios, all temperatures are in degrees centigrade, and the thickness of the box selected for the response time data test is 7 μm.

Drawings

FIG. 1 shows a mass spectrum of 2I (3F) PC 3-2;

FIG. 2 shows a mass spectrum of 2I (3F) PC 3-3;

FIG. 3 shows a mass spectrum of 2I (3F) PC 3-4;

FIG. 4 shows a mass spectrum of 2I (3F) PC 3-5;

FIG. 5 shows a mass spectrum of 2I (3F) PC 3-6;

FIG. 6 shows a mass spectrum of 2I (3F) PC 3;

FIG. 7 shows a mass spectrum of 2I (3F) P3.

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.

The liquid crystal displays used in the following embodiments are all VA-TFT liquid crystal display devices, have a cell thickness d =7 μm, and are composed of a polarizer (polarizer), an electrode substrate, and the like. The display device is in a normally white mode, i.e. when no voltage difference is applied between the row and column electrodes, a viewer perceives a pixel color that is white. The upper and lower polarizer axes on the substrate are at a 90 degree angle to each other. The space between the two substrates is filled with an optical liquid crystal material.

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

Take the following structure as an example:

the structure is represented by the code in table 1: it can be represented as 2I (3F) PC3, again as:

it can be represented as nCP2POm, and n in the code represents the C atom number of the left-end alkyl group, for example, n is "3", i.e., the alkyl group is-C3H 7; c in the code represents cyclohexane; o in the code represents an oxygen atom; p in the code represents phenylene; in the code, m represents the number of C atoms in the alkyl group at the right end, and for example, m is "1", that is, it represents that the alkyl group at the right end is-CH 3.

The shorthand codes of the test items in the embodiments are respectively expressed as:

the ingredients used in the examples below, except for the compound of formula (I), were synthesized by known methods or obtained commercially. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds.

Liquid crystal compositions were prepared according to the compounding ratios of the liquid crystal compositions specified in the following examples. The liquid crystal composition is prepared according to the conventional method in the field, such as heating, ultrasonic wave, suspension and the like, and is mixed according to the specified proportion.

Liquid crystal compositions given in the following examples were prepared and studied. The composition of each liquid crystal composition and the results of the performance parameter test thereof are shown below.

Example 1

The synthetic route for the compound 2I (3F) PC3 prepared is shown below,

the specific process steps are as follows:

1) synthesis of 2I (3F) PC3-2

19.3g of 2I (3F) PC3-1, 5.5g of CuCl and 200ml of tetrahydrofuran are added into a 500ml three-necked bottle, nitrogen is evacuated, liquid nitrogen is cooled to-78 ℃ under protection, 42ml of n-butyl lithium (2.5 mol/l) is dropwise added at the temperature of-72 ℃ to-80 ℃, and after the temperature is kept for 0.5h, the temperature is raised to-20 ℃ to-25 ℃ for reaction for one hour. Dissolving 10.7g of n-butyryl chloride in 50ml of tetrahydrofuran, dropwise adding the solution into the prepared copper-lithium reagent at a temperature of between 20 ℃ below zero and 25 ℃ below zero, reacting at the temperature for 2 hours, sampling, detecting no raw material by thin-layer chromatography, adding dilute hydrochloric acid and water for hydrolysis, extracting with ethyl acetate (200 ml. times.3), combining organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporating the solvent, passing through a 200-mesh 300-mesh silica gel column, and evaporating the solvent to obtain 11.3g of a light yellow liquid which is a compound 2I (3F) PC3-2, MS m/z: 184 (M)⁺)。

2) Synthesis of 2I (3F) PC3-3

To a 500ml single neck flask was added 9.3g of 2I (3F) PC3-2, 2.2g of morpholine, 9.3g of 37% aqueous formaldehyde, 200ml of glacial acetic acid, heated to reflux for 4h, sampled for GC and the reaction was complete. After cooling to room temperature, dichloromethane extraction (200 ml x 3) was carried out, the organic phases were combined, washed 2 times with water, 1 time with saturated brine and anhydrous Na₂SO₄Drying, distilling off the solvent, passing through a small amount of 200-300 silica gel column, and distilling off the solvent to obtain 9.3g of a yellow liquid which is the compound 2I (3F) PC3-3, MS m/z: 196 (M)⁺)。

3) Synthesis of 2I (3F) PC3-4

To a 500ml single neck bottle was added 53.2g of AlCl₃14.1g of NaCl, heating to 140 ℃ in an oil bath, stirring until the NaCl is completely melted to form liquid, dropwise adding 7.9g of 2I (3F) PC3-3 into the molten liquid, heating to 180 ℃ after the dropwise addition, sampling after reacting for 2 hours, detecting no raw material through thin layer chromatography, cooling the molten liquid once, pouring into prepared ice cubes, hydrolyzing, adding hydrochloric acid to adjust the pH to 2, extracting with dichloromethane (200 ml. x.3), combining organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, and washing with anhydrous Na₂SO₄Drying, solvent evaporation, passage through a small amount of 200-300 silica gel column to give a pale yellow solid, which after recrystallization once gives 6.3g of an off-white solid as compound 2I (3F) PC3-4, MS m/z: 196 (M)⁺)。

4) Synthesis of 2I (3F) PC3-5

Adding 5.9g of 2I (3F) PC3-4, 6.5g of 1, 3-propanedithiol and 150ml of dichloromethane into a 250ml three-necked bottle, evacuating nitrogen, cooling to 0 ℃ in an ice water bath, dropwise adding 20ml of boron trifluoride diethyl etherate at the temperature of below 10 ℃, stirring for 4 hours at room temperature after dropwise adding, detecting no raw material by thin-layer chromatography, adding an aqueous solution of sodium bisulfite into ice to quench and hydrolyze, extracting with dichloromethane (200 ml x 3), combining organic phases, washing for 2 times, washing with saturated salt water for 1 time, and washing with anhydrous Na₂SO₄Drying, solvent evaporation, passage through a small amount of 200-300 silica gel column, solvent evaporation, recrystallization to give 7.7g of a white solid as compound 2I (3F) PC3-5, MS m/z: 286 (M)⁺)。

5) Synthesis of 2I (3F) PC3-6

Adding 5.72g of 2I (3F) PC3-5 and 100ml of dichloromethane into a 250ml three-necked flask, evacuating nitrogen, cooling liquid nitrogen to-75 ℃, dissolving 21ml of triethylamine complex hydrogen trifluoride and 5.75g of dibromohydantoin into 50ml of dichloromethane, dropwise adding at the temperature of-70 ℃ or below, keeping the temperature from-72 ℃ to-75 ℃ for 2h, stirring at room temperature for 2h, sampling, and detecting by thin layer chromatography without raw material treatment. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating the solvent, passing through a small amount of 200-300 silica gel column, evaporating the solvent to obtain 5g of light yellow solid which is compound 2I (3F) PC3-6, MS m/z: 198 (M)⁺)。

6) Synthesis of 2I (3F) PC3-7

Adding 3g of 2I (3F) PC3-6 into a 250ml three-necked bottle, 140ml of tetrahydrofuran, evacuating nitrogen, cooling liquid nitrogen to-78 ℃ under protection, controlling the temperature to be-72 to-80 ℃, dropwise adding 7.2ml of n-butyl lithium (2.5 mol/l), controlling the temperature to be-72 to-80 ℃ after finishing dropping and keeping the temperature for 30min, then controlling the temperature to be-72 to-80 ℃, dropwise adding 4.5g of triisobutyl borate, naturally heating to-30 ℃ after keeping the temperature for 0.5h after dropping, adding water for hydrolysis, adjusting the pH to 4-5 by using dilute hydrochloric acid, extracting ethyl acetate (200 ml 3), combining organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, directly evaporating the solvent, adding 50ml of water with isobutanol, adding 100ml of 60-90 petroleum ether for pulping, and performing suction filtration to obtain 2.9g of white solid which is a compound 2I (3F) PC 3-7.

7) Synthesis of 2I (3F) PC3

To a 100ml single neck flask was added 2.4g of 2I (3F) PC3-7, 3.372g of propylcyclohexylbromobenzene, 2.07g of sodium metaborate, 45ml of tetrahydrofuran, 15ml of water, 0.22g of PdCl2.(PPh3)2,0.17g of 80% hydrazine hydrate. After heating to initiate reflux, samples were taken after maintaining reflux for 2.5h and the reaction was monitored by thin layer chromatography for completion. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating to remove solvent, adding petroleum ether to remove polar solvent, dissolving with 100ml petroleum ether, passing through 15g60-100 mesh silica gel column, and washing with equal volume of petroleum ether once. The solvent was dried by spinning and recrystallized to give 2.4g of a white solid. Compound 2I (3F) PC 3. MS m/z: 398 (M +).

Liquid crystal properties of compound 2I (3F) PC 3:

Δn：0.1250 Δ：-4.2 Cp：70

example 2

The synthetic route for the preparation of compound 2I (3F) P3 is shown below,

the specific process steps are as follows:

synthesis of 2I (3F) P3-2 through 2I (3F) P3-7 is as in example 1.

1) Synthesis of 2I (3F) P3

To a 100ml single neck flask was added 2.4g of 8, 2.4g of propylbromobenzene, 2.07g of sodium metaborate, 45ml of tetrahydrofuran, 15ml of water, 0.22g of PdCl₂.(PPh₃)₂0.17g of 80% hydrazine hydrate. After heating to initiate reflux, samples were taken after maintaining reflux for 2.5h and the reaction was monitored by thin layer chromatography for completion. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating to remove solvent, adding petroleum ether to remove polar solvent, dissolving with 100ml petroleum ether, passing through a 15g60-100 mesh silica gel column, and washing with equal volume of petroleum ether once. The solvent was dried by spinning and recrystallized to give 2.2g of a white solid. Is compound 9. MS m/z: 316 (M +).

Liquid crystal properties of compound 2I (3F) P3:

Δn：0.1271 Cp：-71 Δ：-5.0

example 3

The synthetic route for the preparation of compound I (4F) P3 is shown below,

the specific process steps are as follows:

1) synthesis of I (3F) PC3-11

19.3g of I (3F) PC3-1 and 200ml of tetrahydrofuran are added into a 500ml three-necked bottle, nitrogen is evacuated, liquid nitrogen is cooled to-78 ℃ under protection, temperature is controlled to be-72 ℃ to-80 ℃, 42ml of n-butyl lithium (2.5 mol/l) is dripped, heat preservation is carried out for 0.5h after dripping, 5.45g of CuCl solid powder is added in batches (temperature is controlled to be below-65 ℃) and is heated to-20 ℃ to-25 ℃ after heat preservation is carried out for 0.5h after-65 ℃ to-75 ℃ for reaction for one hour. Dissolving 6.35g of 3-chloropropionyl chloride in 100ml of tetrahydrofuran, controlling the temperature to be between 20 ℃ below zero and 25 ℃ below zero, dropwise adding the prepared copper-lithium reagent, reacting for 2 hours at the temperature after dropwise adding, and taking outDetecting no material by thin layer chromatography, adding diluted hydrochloric acid and water for hydrolysis, extracting with ethyl acetate (200 ml. about.3), mixing organic phases, washing with water for 2 times, washing with saturated salt solution for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporating the solvent, passing through a 200-mesh 300-mesh silica gel column, and evaporating the solvent to obtain 12.3g of a light yellow liquid which is a compound I (3F) PC3-11, MS m/z: 204(M +).

2) Synthesis of I (3F) PC3-12

Into a 500ml single-neck bottle was added 79.8g of AlCl₃21g of NaCl, heating to 140 ℃ in an oil bath, stirring until the NaCl is completely melted to form liquid, dripping 12.3g of I (3F) PC3-11 into the molten liquid, heating to 180 ℃ after dripping, sampling after reacting for 2h, detecting no raw material by thin layer chromatography, cooling the molten liquid once, pouring into prepared ice blocks, hydrolyzing, adding hydrochloric acid to adjust the pH to 2, extracting with dichloromethane (200 ml. x.3), combining organic phases, washing with water for 2 times, washing with saturated salt for 1 time, and washing with anhydrous Na₂SO₄Drying, solvent evaporation, passage through a small amount of 200-300 silica gel column to give a pale yellow solid which, after one recrystallization, gives 9.8g of an off-white solid as compound I (3F) PC3-12, MS m/z: 168 (M)⁺)。

3) Synthesis of I (3F) PC3-13

Adding 9.8g of I (3F) PC3-12, 12.6g of 1, 3-propanedithiol and 150ml of dichloromethane into a 250ml three-necked bottle, evacuating nitrogen, cooling to 0 ℃ in an ice-water bath, dropwise adding 40ml of boron trifluoride diethyl etherate at the temperature of below 10 ℃, stirring for 4 hours at room temperature after dropwise adding, detecting no raw material by thin-layer chromatography, adding an aqueous solution of sodium bisulfite into ice to quench and hydrolyze, extracting with dichloromethane (200 ml. times.3), combining organic phases, washing for 2 times, washing with saturated salt for 1 time, and washing with anhydrous Na₂SO₄Drying, evaporation of the solvent, passage through a small amount of 200-300 silica gel column, evaporation of the solvent and recrystallization to give 13.5g of a white solid as compound I (3F) PC3-13, MS m/z: 258 (M)⁺)。

4) Synthesis of I (3F) PC3-14

To a 500ml three-necked flask was added 12.9g of I (3F) PC3-13, 200ml of methylene chloride, evacuated with nitrogen, and liquid nitrogenAnd (3) cooling to-75 ℃, dissolving 52ml of triethylamine complex hydrogen trifluoride and 14.3g of dibromohydantoin in 80ml of dichloromethane, dropwise adding at the temperature of-70 ℃, keeping the temperature for 2h after dropwise adding from-72 ℃ to-75 ℃, stirring for 2h at room temperature, sampling, and detecting by thin layer chromatography without raw material treatment. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating the solvent, passing through a small amount of 200-300 silica gel column, evaporating the solvent to obtain 9g of light yellow solid, namely compound I (3F) PC3-14, MS m/z: 170 (M)⁺)。

5) Synthesis of I (3F) PC3-15

Adding 4.67g of I (3F) PC3-14 into a 250ml three-neck flask, 140ml of tetrahydrofuran, evacuating nitrogen, cooling liquid nitrogen to-78 ℃ under protection, controlling the temperature to be-72-80 ℃, dropwise adding 13.2ml of n-butyl lithium (2.5 mol/l), keeping the temperature for 30min after dropwise adding, controlling the temperature to be-72-80 ℃, dropwise adding 8.3g of triisobutyl borate, keeping the temperature for 0.5h after dropwise adding, naturally heating to be-30 ℃, adding water for hydrolysis, adjusting the pH value to 4-5 by using dilute hydrochloric acid, extracting ethyl acetate (200 ml x 3), combining organic phases, washing with water for 2 times, washing with saturated salt water for 1 time, directly evaporating the solvent, adding 50ml of isobutanol 3 to take out water, adding 100ml of 60-90 petroleum ether for pulping, sucking and filtering to obtain 4.7g of white solid which is the compound I (3F) PC 3-3615.

6) Synthesis of I (3F) PC3

Into a 250ml single neck flask was added 4.3g of I (3F) PC3-15, 6.744g of propylcyclohexylbromobenzene, 4.14g of sodium metaborate, 90ml of tetrahydrofuran, 30ml of water, 0.44g of PdCl₂.(PPh₃)₂0.34g of 80% hydrazine hydrate. After heating to initiate reflux, samples were taken after maintaining reflux for 2.5h and the reaction was monitored by thin layer chromatography for completion. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating to remove solvent, adding petroleum ether to remove polar solvent, adding 100ml petroleum ether to dissolve, passing through 15g60-100 mesh silica gel column, and washing with equal volume of petroleum ether once. The solvent was dried by spinning and recrystallized to give 5.9g of a white solid. Is compound I (3F))PC3，MS m/z：370（M⁺)。

Liquid crystal properties of compound I (3F) PC 3:

Δn：0.1246 Δ：-43 Cp：66

example 4

The synthetic route for the preparation of compound I (4F) P3 is shown below,

the specific process steps are as follows:

i (3F) P3-1 to I (3F) P3-15 are the same as in example 3.

1) Synthesis of I (3F) P3

To a 250ml single neck flask was added 4.3g of 14, 4.8g of propylbromobenzene, 4.14g of sodium metaborate, 90ml of tetrahydrofuran, 30ml of water, 0.44g of PdCl₂.(PPh₃)₂0.34g of 80% hydrazine hydrate. After heating to initiate reflux, samples were taken after maintaining reflux for 2.5h and the reaction was monitored by thin layer chromatography for completion. Dichloromethane extraction (200 ml x 3), combined organic phases, water washing 2 times, saturated brine washing 1 time, anhydrous Na₂SO₄Drying, evaporating to remove solvent, adding petroleum ether to remove polar solvent, dissolving with 100ml petroleum ether, passing through a 15g60-100 mesh silica gel column, and washing with equal volume of petroleum ether once. The solvent was dried by spinning and recrystallized to give 4.6g of a white solid. Is compound 16, MS m/z: 288 (M)⁺)。

Liquid crystalline properties of compound I (3F) P3:

Δn：0.1266 Cp：-78 Δ：-5.12

examples 5 to 8 below are the results of the performance test of the liquid crystal composition of the present invention.

Example 5

The liquid crystal composition of the present invention is prepared according to the compounds and weight percentages listed in table 2, and is filled between two substrates of a liquid crystal display for performance test, and the test data is shown in the following table:

TABLE 2 liquid crystal composition formulations and their test properties

Name of monomer	Weight percent (wt.%) of	Results of performance parameter testing
			3CWO1	8	△n=0.100
3CWO2	8	γ1=123
			3C1OWO1	4	Cp=90.0℃
3C1OWO2	4	η=18.6mpa.s
			3CPWO1	4	△ε=-3.0
3CPWO2	5
			3CC1OWO1	5
3CC1OWO2	6
			4CC1OWO2	6
5CCV	25
			3CCV	10
3CC1OC5	5
			3I(3F)PC3	5
3I(3F)PP3	5

The composition has proper optical anisotropy and large negative dielectric anisotropy, has low viscosity, high response speed and high clearing point, and is suitable for negative liquid crystal panels of mobile phones.

Example 6

The liquid crystal composition of the present invention is prepared according to the compounds and weight percentages listed in table 3, and is filled between two substrates of a liquid crystal display for performance test, and the test data is shown in the following table:

TABLE 3 liquid crystal composition formula and its test performance

Name of monomer	Weight percent (wt.%) of	Results of performance parameter testing
			3CWO1	9	△n=0.087
3CWO2	9	γ1=115
			3C1OWO1	3	Cp=80.5℃
3C1OWO2	3	η=16.5mpa.s
			3CPWO1	4	△ε=-2.9
3CC1OWO1	6
			3CC1OWO2	6
4CC1OWO2	6
			3CC1OC5	6
5CCV	23
			3CCV1	10
3CC1OC4	5
			3I(3F)PC3	5
3I(3F)P2	5

The composition has proper clearing point and large negative dielectric anisotropy, has high response speed and is suitable for television panels with fast response.

Example 7

The liquid crystal composition of the present invention is prepared according to the compounds and weight percentages listed in table 4, and is filled between two substrates of a liquid crystal display for performance test, and the test data is shown in the following table:

TABLE 4 liquid crystal composition formula and its test performance

Name of monomer	Weight percent (wt.%) of	Results of performance parameter testing
			3PWP1	6	△n=0.116
3PWP2	6	γ1=150
			3C1OWO1	4	Cp=95.5℃
3C1OWO2	4	η=27.5mpa.s
			3CC1OWO1	4	△ε=-3.62
3CC1OWO2	6
			4CC1OWO2	6
3CPWO1	5
			3CPWO2	5
5CCV	20
			3CCV1	10
VCCP1	14
			2I(3F)PC3	5
2I(3F)P3	5

The composition has great negative dielectric anisotropy and great optical anisotropy, and is suitable for wide-temperature VA display.

Example 8

The liquid crystal composition of the present invention is prepared according to the compounds and weight percentages listed in table 5, and is filled between two substrates of a liquid crystal display for performance test, and the test data is shown in the following table:

TABLE 5 liquid crystal composition formulations and their test properties

Name of monomer	Weight percent (wt.%) of	Results of performance parameter testing
			3PWP1	8	△n=0.132
3PWP2	8	γ1=148
			3C1OWO1	4	Cp=90.5℃
3C1OWO2	4	η=26.5mpa.s
			3CC1OWO1	4	△ε=-3.9
3CC1OWO2	5
			4CC1OW2	5
3CPWO1	9
			3CPWO2	8
5CC2	20
			3CC2	10
3CCP1	5
			2I(3F)P3	3
2I(3F)PC3	3
			I(3F)PP3	4

The composition has high clearing point, large optical anisotropy and large negative dielectric anisotropy, and is suitable for use in a high-gradient VA display.

The above examples illustrate the compounds and embodiments of the present invention, and the above examples are given only to aid and understand the present invention and its core ideas; meanwhile, a person skilled in the art can change the specific mode and the application scope thereof according to the idea of the present invention, and in summary, the information in the description should not be construed as limiting the present invention.

Claims

1. A liquid crystal compound of the general formula I:

wherein,

R¹¹and R¹²Each independently represents H, an alkyl group having 1 to 15 carbon atoms;

A¹¹、A¹²and A¹³Each independently represents:

a) represents a1, 4-cyclohexylene group; or

b) Represents a1, 4-phenylene group;

wherein one or more H of the 1, 4-phenylene groups may be substituted with a halogen atom;

Z¹¹、Z¹²and Z¹³Each independently represents a single bond, -O-, -COO-, -OCO-, -CF₂O-or-CH₂O-；

X¹And X²Each independently represents H or halogen;

q, p and d each independently represent 0 or 1, and 1. ltoreq. q + p + d. ltoreq.6.

2. The liquid crystal compound according to claim 1, characterized in that: the compounds of formula i are selected from the group consisting of:

wherein R is¹¹Represents H, an alkyl group having 1 to 10 carbon atoms;

R¹²represents an alkyl group having 1 to 10 carbon atoms.

3. Liquid crystal composition according to claim 1 or 2, characterized in that the compound of general formula i is selected from one or more of the following compounds:

4. a method for producing the liquid crystal compound according to any one of claims 1 to 3, comprising the steps of:

1) adding I-a to tetrahydrofuran solvent

8) adding the compound I-h into tetrahydrofuran solvent

5. A liquid crystal composition comprising at least one liquid crystal compound of general formula (i) according to any one of claims 1 to 3.

6. A liquid crystal composition of claim 5 comprising:

1-20% by weight of the total composition of at least one compound of general formula (i) according to any one of claims 1 to 3;

And

Wherein,

R²¹、R²²、R³¹and R³²Each independently represents H, halogen, CN or CF having 1-15 carbon atoms₃Alkyl or alkoxy which is monosubstituted or halogenated or not, CN or CF having 2 to 15C atoms₃(ii) a mono-substituted or halogenated or non-halogenated alkanyl or alkoxyalkenyl group, wherein in said R²¹、R²²、R³¹And R³²One or more-CH of₂-the groups may each be independently replaced by-O-, -S-, -CH ═ CH-, -CH ═ CF-, -CF ═ CH-, -CF ═ CF-, -CO-O-, or-O-CO-, with the proviso that the oxygen atoms are not directly attached to each other;

R⁴¹and R⁴²Each independently represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms and a halogenated or non-halogenated alkanyl or alkoxyalkenyl group having 2 to 10 carbon atoms, wherein in the R⁴¹And R⁴²One or more-CH of₂-the groups may each be independently replaced by-O-, -S-, -CH ═ CH-, -CH ═ CF-, -CF ═ CH-, -CF ═ CF-, -CO-O-, or-O-CO-, with the proviso that the oxygen atoms are not directly attached to each other;

z independently represents a single bond, -O-, -COO-, -OCO-, -CF₂-、-CF₂O-、-OCF₂-、-CH₂O-、-CH₂CH₂-、-(CH₂)₄-、-C₂F₄-、-CH₂CF₂-、-CF₂CH₂-, -CH ═ CH-, -CH ═ CF-, -CF ═ CH-, -CF ═ CF-or-C ≡ C-;

ring (C)Ring (C)Each independently represent Wherein saidOne or two non-adjacent-CH₂-may be replaced by-O-or-S-, saidEach of the above-mentioned H may be independently substituted by F, saidOne or two non-adjacent-CH-s may be replaced by N, saidOne or two non-adjacent-CH₂May be replaced by O, saidEach of the above-mentioned H may be independently substituted with F;

m represents 1 or 2, n represents 0 or 1;

x represents 0 or 1;

7. Liquid crystal composition according to claim 6, characterized in that the compound of general formula (II) is selected from one or more compounds from the group consisting of:

wherein,

R²²represents H, halogen, a halogenated or non-halogenated alkyl or alkoxy group having 1 to 10 carbon atoms, a halogenated or non-halogenated alkenyl or alkoxyalkenyl group having 2 to 10 carbon atoms;

the compound of formula (iii) is selected from one or more compounds of the group consisting of:

wherein,

R³²represents H, halogen, halogenated or unhalogenated alkyl or alkoxy having 1 to 10 carbon atoms, having 2 to 10 carbon atomsAn alkyl or alkoxy alkenyl radical which may or may not be halogenated;

the compound of formula (iv) is selected from one or more compounds of the group consisting of:

wherein,

8. The liquid crystal composition of claim 6, wherein the compound of formula i comprises 5% to 15% by weight of the total composition; the compound of the general formula II accounts for 15-35% of the total weight of the composition; the compound of the general formula III accounts for 15-35% of the total weight of the composition; the compound of formula IV is present in an amount of 30 to 50% by weight of the total composition.

9. The liquid crystal composition of claim 6, wherein the liquid crystal composition comprises:

compound 3CWO1 accounting for 8 percent of the total weight of the liquid crystal composition

Compound 3CWO2 accounting for 8 percent of the total weight of the liquid crystal composition

4% by weight of compound 3C1OWO1 based on the total weight of the liquid crystal composition

4% by weight of compound 3C1OWO2 based on the total weight of the liquid crystal composition

Compound 3CPWO1 at 4% by weight of the total liquid crystal composition

Compound 3CPWO2 at 5% by weight of the total liquid crystal composition

Compound 3CC1OWO1 accounting for 5 percent of the total weight of the liquid crystal composition

Compound 3CC1OWO2 accounting for 6 percent of the total weight of the liquid crystal composition

Compound 4CC1OWO2 accounting for 6 percent of the total weight of the liquid crystal composition

Compound 5CCV accounting for 25 percent of the total weight of the liquid crystal composition

Compound 3CCV accounting for 10 percent of the total weight of the liquid crystal composition

Compound 3CC1OC5 at 5% of the total weight of the liquid crystal composition

Compound 3I (3F) PC3 at 5% by weight of the total liquid crystal composition

Compound 3I (3F) PP3 at 5% by weight of the total liquid crystal composition

Alternatively, the liquid crystal composition comprises:

compound 3CWO1 accounting for 9 percent of the total weight of the liquid crystal composition

Compound 3CWO2 accounting for 9 percent of the total weight of the liquid crystal composition

3% of compound 3C1OWO1 based on the total weight of the liquid crystal composition

3% of compound 3C1OWO2 based on the total weight of the liquid crystal composition

Compound 3CPWO1 at 4% by weight of the total liquid crystal composition

Compound 3CC1OWO1 accounting for 6 percent of the total weight of the liquid crystal composition

Compound 3CC1OC5 at 6% of the total weight of the liquid crystal composition

Compound 5CCV accounting for 23 percent of the total weight of the liquid crystal composition

Compound 3CCV1 accounting for 10 percent of the total weight of the liquid crystal composition

Compound 3CC1OC4 at 5% of the total weight of the liquid crystal composition

Compound 3I (3F) PC3 at 5% by weight of the total liquid crystal composition

Compound 3I (3F) P2 at 5% by weight of the total liquid crystal composition

Alternatively, the liquid crystal composition comprises:

compound 3PWP1 at 6% of the total weight of the liquid crystal composition

Compound 3PWP2 at 6% of the total weight of the liquid crystal composition

Compound 3CC1OWO1 accounting for 4 percent of the total weight of the liquid crystal composition

Compound 3CPWO1 at 5% by weight of the total liquid crystal composition

Compound 3CPWO2 at 5% by weight of the total liquid crystal composition

Compound 5CCV accounting for 20 percent of the total weight of the liquid crystal composition

Compound VCCP1 accounting for 14 percent of the total weight of the liquid crystal composition

Compound 2I (3F) PC3 at 5% by weight of the total liquid crystal composition

Compound 2I (3F) P3 at 5% by weight of the total liquid crystal composition

Alternatively, the liquid crystal composition comprises:

compound 3PWP1 in an amount of 8% by weight based on the total weight of the liquid crystal composition

Compound 3PWP2 in an amount of 8% by weight based on the total weight of the liquid crystal composition

Compound 3CC1OWO2 accounting for 5 percent of the total weight of the liquid crystal composition

Compound 4CC1OW2 accounting for 5 percent of the total weight of the liquid crystal composition

Compound 3CPWO1 in an amount of 9% by weight based on the total weight of the liquid crystal composition

Compound 3CPWO2 in an amount of 8% by weight based on the total weight of the liquid crystal composition

Compound 5CC2 accounting for 20 percent of the total weight of the liquid crystal composition

Compound 3CC2 accounting for 10 percent of the total weight of the liquid crystal composition

Compound 3CCP1 in an amount of 5% by weight based on the total weight of the liquid crystal composition

3% by weight of the total liquid crystal composition of compound 2I (3F) P3

3% by weight of the total liquid crystal composition of Compound 2I (3F) PC3

4% by weight of compound I (3F) PP3 based on the total weight of the liquid crystal composition

10. Use of a liquid crystal composition according to any of claims 5-9 in the manufacture of an electro-optical device.

11. An active-matrix-addressed electro-optical liquid-crystal display based on the ECB, PALC or IPS effect, comprising a liquid-crystal composition according to any one of claims 5 to 9.