Liquid crystal compound containing difluoromethoxy bridge bond and preparation method and application thereof
阅读说明：本技术 一种含二氟甲氧基桥键的液晶化合物及其制法与应用 (Liquid crystal compound containing difluoromethoxy bridge bond and preparation method and application thereof ) 是由 戴雄 姜坤 谢佩 张海威 孙建波 程友文 侯斌 唐怡杰 于 2020-03-18 设计创作，主要内容包括：本发明属于液晶化合物及其应用技术领域,具体涉及一种含二氟甲氧基桥键的液晶化合物及其制法与应用。所述含二氟甲氧基桥键的液晶化合物具有通式(I)所示结构。本发明所述液晶化合物具有较高的介电各向异性和低的旋转粘度,可以降低驱动电压,改善响应时间。(The invention belongs to the technical field of liquid crystal compounds and application thereof, and particularly relates to a liquid crystal compound containing a difluoromethoxy bridge bond, and a preparation method and application thereof. The liquid crystal compound containing the difluoromethoxy bridge bond has a structure shown in a general formula (I). The liquid crystal compound has higher dielectric anisotropy and low rotational viscosity, can reduce driving voltage and improve response time.)
1. A liquid crystal compound containing a difluoromethoxy bridge, characterized by having a structure represented by the general formula (I):
in the general formula (I), R and X are respectively and independently selected from-H, -Cl, -F, -CN, -OCN and-OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-OCF＝CF2，-OCF2CF3，-SCN、-NCS、-SF5、C1-C15Alkyl of (C)1-C15Alkoxy group of (C)2-C15Alkenyl or C2-C15And one or more hydrogens of said R or X may be optionally substituted with fluoro or chloro;
when said R or X contains one or at least two non-adjacent-CH2When it is a radical, said one or at least two non-adjacent-CH2-may be optionally substituted by-CH ═ CH-, -C ≡ C-, -COO-, -OOC-, -O-, or-S-;
A1、A2、A3、A4each independently selected from a single bond or one of the following groups:
Z1、Z2、Z3each independently selected from a single bond, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF-.
2. The liquid crystal compound of claim 1, wherein R is selected from H, C1-C5Alkyl or C1-C5And one or more hydrogens in said R may be optionally substituted with fluoro or chloro, preferably with fluoro;
x is selected from-CF3、-OCF3or-F;
A1、A2、A3and A4Each independently selected from a single bond or one of the following groups:
Z1、Z2and Z3Are all single bonds.
3. The liquid crystal compound according to claim 1 or 2, wherein the compound represented by the general formula (I) is selected from one or more of the following structures:
wherein R represents C1-C5X is selected from-CF3、-OCF3、-F。
4. A method for producing a liquid crystal compound according to any one of claims 1 to 3, characterized in that the synthetic route is as follows:
the method specifically comprises the following steps:
(a) reaction of Compound II-1 with butyllithium in tetrahydrofuran and then with CF2Br2Reacting to obtain a compound II-2;
(b) reacting the compound II-2 with the compound II-3 under the action of potassium carbonate to obtain a target compound;
wherein A is3Is composed ofR、X、A1、A2、A4、Z1、Z2And Z3Is as defined in any one of claims 1 to 3.
5. A method for producing a liquid crystal compound according to any one of claims 1 to 3, characterized in that the synthetic route is as follows:
the method specifically comprises the following steps:
(a) the compound II-4 is refluxed and dehydrated with 1, 3-propanedithiol by taking trifluoromethanesulfonic acid as a catalyst, and is filtered to obtain a compound II-5;
(b) reacting the compound II-3 with the compound II-5 by using triethylamine hydrogen fluoride as a dehydrating agent and bromine as a catalyst to obtain a target compound;
wherein A is3Is selected from R、X、A1、A2、A4、Z1、Z2And Z3Is as defined in any one of claims 1 to 3.
6. A liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 3.
7. The liquid crystal composition according to claim 6, wherein: the amount of the liquid crystal compound added is 1 to 80%, preferably 3 to 50%.
8. Use of the liquid crystal compound according to any one of claims 1 to 3 or the liquid crystal composition according to claim 6 or 7 in the field of liquid crystal displays.
Technical Field
The invention relates to the field of liquid crystal display materials, in particular to a liquid crystal compound containing a difluoromethoxy bridge bond and a preparation method and application thereof.
Background
Liquid crystals are currently widely used in the field of information display, and have been used in optical communications (s.t.wu, d.k.yang.reflective Liquid display. wiley, 2001). In recent years, the application fields of liquid crystal compounds have been remarkably widened to various display devices, electro-optical devices, electronic components, sensors, and the like. For this reason, many different structures have been proposed, particularly in the field of nematic liquid crystals, which have hitherto been most widely used in flat panel displays. Particularly in systems with TFT active matrices.
Liquid crystal display has experienced a long development route along with the discovery of liquid crystals. In 1888, the first liquid crystal material, cholesterol benzoate, was discovered by the austria phytologist Friedrich reintzer. In 1917, Manguin invented rubbing alignment method to make single domain liquid crystal and study optical anisotropy. The theory of scraping (Swarm) was established by e.bose in 1909 and supported by l.s.ormstein and f.zernike et al (1918), which were later discussed as statistical fluctuations by De Gennes. Oseen and h.zocher created continuum theory in 1933 and was perfected by f.c. frank (1958). M.born (1916) and k.lichtennecker (1926) discovered and studied the dielectric anisotropy of liquid crystals. In 1932, w.kast accordingly classified the nematic phase into two main classes, positive and negative. In 1927, v.freedericksz and v.zolonao found that nematic liquid crystals deformed under the action of an electric (or magnetic) field and had a voltage threshold (Freederichsz transition). This finding provides the basis for the fabrication of liquid crystal displays.
In 1968, R.Williams, RCA corporation in America, discovered that nematic liquid crystals form fringe domains under the action of an electric field and have a light scattering phenomenon. The g.h.heilmeir was subsequently developed into a dynamic scattering display mode and made the first Liquid Crystal Display (LCD) in the world. In the early seventies, Helfrich and Schadt invented the TN principle, and people made them into display devices (TN-LCD) by using the combination of TN photoelectric effect and integrated circuit, thus developing a broad prospect for the application of liquid crystal. Since the seventies, the application of liquid crystal in display has been developed in a breakthrough due to the development of large-scale integrated circuits and liquid crystal materials, and the Super Twisted Nematic (STN) mode proposed by t.scheffer et al in 1983-1985 and the Active Matrix (AM) mode proposed by p.brody in 1972 were adopted again. Conventional TN-LCD technology has been developed into STN-LCD and TFT-LCD technology, and although STN has scan lines up to 768 or more, problems of response speed, viewing angle and gray scale still exist when temperature rises, thus large area, high information content, high data rate, and the like,
The color display is mostly an active matrix display system. TFT-LCD has been widely used in direct view televisions, large screen projection televisions, computer terminal displays and some military instrument displays, and TFT-LCD technology is believed to have wider application prospects.
Where "active matrix" includes two types: 1. OMS (metal oxide semiconductor) or other diodes on a silicon wafer as a substrate. 2. A Thin Film Transistor (TFT) on a glass plate as a substrate.
The use of single crystal silicon as a substrate material limits the display size because of the many problems that arise with the assembly of parts of the display device and even the modules at their junctions. Thus, the second type of thin film transistor is a promising type of active matrix, and the photoelectric effect utilized is typically the TN effect. TFTs include compound semiconductors, such as CdSe, or TFTs based on polycrystalline or amorphous silicon.
At present, the technology of TFT-LCD products is mature, the technical problems of visual angle, resolution, color saturation, brightness and the like are successfully solved, and the display performance of the TFT-LCD products is close to or exceeds that of a CRT display. Large-sized and medium-sized TFT-LCD displays have gradually occupied the mainstream position of flat panel displays in their respective fields. However, the TFT-LCD still has many defects, such as not fast response, not low voltage, not high charge retention rate, etc., due to the limitation of the liquid crystal material itself. Therefore, it is important to find a single crystal compound having a low viscosity and a high dielectric anisotropy.
Liquid-crystalline monomers containing difluoromethoxy bridges were described in U.S. Pat. No. 5,5045229 by Merck, Germany, as early as 1989, but the corresponding compounds were not ideally obtained.
Disclosure of Invention
The first purpose of the invention is to provide a novel liquid crystal compound containing difluoromethoxy bridge bond, which has higher dielectric anisotropy and low rotational viscosity, can reduce driving voltage and improve response time.
The liquid crystal compound has a structure shown in a general formula (I):
in the general formula (I), R and X are respectively and independently selected from-H, -Cl, -F, -CN, -OCN and-OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-OCF＝CF2，-OCF2CF3，-SCN、-NCS、-SF5、C1-C15Alkyl of (C)1-C15Alkoxy group of (C)2-C15Alkenyl or C2-C15And one or more hydrogens of said R or X may be optionally substituted with fluoro or chloro;
when said R or X contains one or at least two non-adjacent-CH2When it is a radical, said one or at least two non-adjacent-CH2-may be optionally substituted by-CH ═ CH-, -C ≡ C-, -COO-, -OOC-, -O-, or-S-;
A1、A2、A3、A4each independently selected from a single bond or one of the following groups:
Z1、Z2、Z3each independently selected from a single bond, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF-.
Preferably, in the formula (I), R is selected from H, C1-C5Alkyl or C1-C5And one or more hydrogens in said R may be optionally substituted with fluoro or chloro, preferably with fluoro;
x is selected from-CF3、-OCF3or-F;
A1、A2、A3and A4Each independently selected from a single bond or one of the following groups:
Z1、Z2and Z3Are all single bonds.
Preferably, the compound represented by the general formula (I) is selected from one or more of the following structures:
wherein R represents C1-C5X is selected from-CF3、-OCF3、-F。
The second object of the present invention is to provide a method for preparing the above liquid crystal compound, wherein the synthetic route is as follows:
the method specifically comprises the following steps:
(a) reaction of Compound II-1 with butyllithium in tetrahydrofuran and then with CF2Br2Reacting to obtain a compound II-2;
(b) reacting the compound II-2 with the compound II-3 under the action of potassium carbonate to obtain a target compound;
wherein A is3Is composed ofR、X、A1、A2、A4、Z1、Z2And Z3The definition of (A) is as above.
The invention also provides another preparation method of the liquid crystal compound, and the synthetic route is as follows:
the method specifically comprises the following steps:
(a) the compound II-4 is refluxed and dehydrated with 1, 3-propanedithiol by taking trifluoromethanesulfonic acid as a catalyst, and is filtered to obtain a compound II-5;
(b) reacting the compound II-3 with the compound II-5 by using triethylamine hydrogen fluoride as a dehydrating agent and bromine as a catalyst to obtain a target compound;
wherein A is3Is selected from R、X、A1、A2、A4、Z1、Z2And Z3The definition of (A) is as above.
The third object of the present invention is to protect a liquid crystal composition containing the above liquid crystal compound. The amount of the liquid crystal compound added is preferably 1 to 80%, more preferably 3 to 50%. It is expected that the addition of the liquid crystal compound can further improve the dielectric anisotropy of the conventional liquid crystal composition, and has the technical effect of reducing the driving voltage of the device.
The fourth purpose of the invention is to protect the application of the liquid crystal compound and the composition containing the liquid crystal compound in the field of liquid crystal display. Preferably in a liquid crystal display device. The liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. The liquid crystal composition has the advantage of reducing the driving voltage after being applied to a liquid crystal display device.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise indicated, percentages in the present invention are weight percentages; temperatures are given in degrees celsius.
Example 1:
the synthetic route is as follows:
step 1: adding 32.6g (0.1mol) of compound BYLC-01-1 (reactant) and 240ml of tetrahydrofuran (solvent) into a reaction bottle, introducing nitrogen for protection, cooling to-60 ℃, dropwise adding 0.11mol of n-butyllithium (reactant), controlling the temperature in the dropwise adding process to be-55-60 ℃, and continuing to control the temperature and stir for reaction for 1 hour after dropwise adding. Cooling to-70 ℃, dropwise adding 31.5g (0.15mol) of difluorodibromomethane (reactant), controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuously controlling the temperature and stirring for reaction for 30 minutes after dropwise adding, heating to room temperature, adding 20ml of concentrated hydrochloric acid (used for regulating the pH value) and 50ml of water (solvent) for hydrolysis, separating liquid, extracting an aqueous phase by 100ml of dichloromethane (solvent), washing an organic phase to neutrality by water, evaporating the solvent to obtain a light yellow solid BYLC-01-2, wherein the yield is 90%, and the purity of a gas chromatography is 78%.
Step 2: 4.55g (0.01mol) of compound BYLC-01-2 (reactant), 50ml of DMSO (solvent), 0.02mol of anhydrous potassium carbonate (reactant) and 2g (0.012mol) of BYLC-01-3 (reactant) were added to a reaction flask, and the mixture was stirred and heated to 65 to 70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 30ml of dichloromethane (solvent), adding 100ml of water into the filtrate, stirring, separating liquid, extracting the water layer with 20ml of dichloromethane (solvent), washing the organic phase with water to neutrality, evaporating the solvent to dryness, dissolving the concentrate in 50ml of toluene (solvent), passing through a silica gel column for decolorization, eluting with toluene (solvent), collecting the eluent and evaporating the solvent to dryness, and recrystallizing the obtained product with anhydrous ethanol (solvent) for 3 times to obtain 2g of white needle-like crystal BYLC-01 with the yield of 40%.
Gas phase purity (GC): 99.9 percent;
melting point: 80.9 ℃;
mass spectrometry fragmentation: 524.1 (molecular ion peak).
Example 2
The synthetic route is as follows:
step 1: adding 23.2g (0.1mol) of compound BYLC-02-1 (reactant) and 200ml of tetrahydrofuran (solvent) into a reaction bottle, introducing nitrogen for protection, cooling to-60 ℃, dropwise adding 0.11mol of n-butyllithium (reactant), controlling the temperature in the dropwise adding process to be-55-60 ℃, and continuing to control the temperature and stir for reaction for 1 hour after dropwise adding. Cooling to-70 ℃, dropwise adding 31.5g (0.15mol) of difluorodibromomethane (reactant), controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuously controlling the temperature and stirring for reaction for 30 minutes after dropwise adding, heating to room temperature, adding 20ml of concentrated hydrochloric acid (used for regulating the pH value) and 50ml of water (solvent) for hydrolysis, separating liquid, extracting an aqueous phase by 100ml of dichloromethane (solvent), washing an organic phase to neutrality by water, evaporating the solvent to obtain a light yellow liquid BYLC-01-2, wherein the yield is 90%, and the purity of a gas chromatography is 77%.
Step 2: 3.6g (0.01mol) of compound BYLC-02-2 (reactant), 50ml of DMSO (solvent), 0.02mol of anhydrous potassium carbonate (reactant) and 2g (0.012mol) of BYLC-01-3 (reactant) were added to a reaction flask, and the mixture was stirred and heated to 65 to 70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 30ml of dichloromethane (solvent), adding 100ml of water into the filtrate, stirring, separating liquid, extracting the water layer with 20ml of dichloromethane (solvent), washing the organic phase with water to neutrality, evaporating the solvent to dryness, dissolving the concentrate in 50ml of toluene (solvent), passing through a silica gel column for decolorization, eluting with toluene (solvent), collecting the eluent and evaporating the solvent to dryness, and recrystallizing the obtained product with anhydrous ethanol (solvent) for 3 times to obtain 1.7g of white needle crystal BYLC-02 with the yield of 40%.
Gas phase purity (GC): 99.9 percent;
mass spectrometry fragmentation: 430.1 (molecular ion peak).
Example 3
The synthetic route is as follows:
step 1: 31.6g (0.1mol) of compound BYLC-03-1 (reactant) and 240ml of tetrahydrofuran (solvent) are added into a reaction bottle, nitrogen is introduced for protection, the temperature is reduced to-60 ℃, 0.11mol of n-butyllithium (reactant) is dripped, the temperature is controlled between-55 ℃ and-60 ℃ in the dripping process, and the temperature is controlled and stirred continuously for reaction for 1 hour after dripping. Cooling to-70 ℃, dropwise adding 31.5g (0.15mol) of difluorodibromomethane (reactant), controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuously controlling the temperature and stirring for reaction for 30 minutes after dropwise adding, heating to room temperature, adding 20ml of concentrated hydrochloric acid (used for regulating the pH value) and 50ml of water (solvent) for hydrolysis, separating liquid, extracting an aqueous phase by 100ml of dichloromethane (solvent), washing an organic phase to neutrality by water, evaporating the solvent to obtain a light yellow solid BYLC-03-2, wherein the yield is 90%, and the purity of a gas chromatography is 80%.
Step 2: 4.45g (0.01mol) of compound BYLC-03-2 (reactant), 50ml of DMSO (solvent), 0.02mol of anhydrous potassium carbonate (reactant) and 2g (0.012mol) of BYLC-01-3 (reactant) were added to a reaction flask, and the mixture was stirred and heated to 65 to 70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 30ml of dichloromethane (solvent), adding 100ml of water into the filtrate, stirring, separating liquid, extracting the water layer with 20ml of dichloromethane (solvent), washing the organic phase with water to neutrality, evaporating the solvent to dryness, dissolving the concentrate in 50ml of toluene (solvent), passing through a silica gel column for decolorization, eluting with toluene (solvent), collecting the eluent and evaporating the solvent to dryness, and recrystallizing the obtained product with absolute ethyl alcohol (solvent) for 3 times to obtain 2g of white needle-like crystal BYLC-03 with the yield of 40%.
Gas phase purity (GC): 99.9 percent;
melting point: 86 ℃;
mass spectrometry fragmentation: 514.1 (molecular ion peak).
Example 4
The synthetic route is as follows:
step 1: 50.4g (0.2mol) of trans-propylcyclohexyl-cyclohexanecarboxylic acid (BYLC-04-1), 28mL of 1, 3-propanedithiol, 25mL of trifluoromethanesulfonic acid, 90mL of toluene and 90mL of isooctane were added into a 1L three-necked flask, a water separator was installed at one side port, the mixture was heated to reflux, reacted for 6 hours, slowly cooled to 0 ℃ and filtered to obtain a solid. And (5) carrying out next feeding after drying.
Step 2: A1L three-necked flask was charged with 100mL of methylene chloride, 20mL of triethylamine and 33.6g of 5-trifluoromethyl-2-hydroxy-thiophene (BYLC-01-3), cooled to 20 ℃ and added with a solution composed of an onium trifluoromethanesulfonate (BYLC-04-2) and 100mL of methylene chloride, and stirred for 1 hour. The temperature is controlled below-75 ℃, 38g of triethylamine hydrofluoride is added dropwise, and stirring is continued for 1 hour. Controlling the temperature below-75 ℃, and carrying out post-treatment after the solution consisting of 8mL of bromine and 15mL of dichloromethane is cooled to-10 ℃. Adding 0.5L of water into a 5L bucket, starting stirring, pouring the reaction liquid, stirring for minutes, slowly adding sodium bicarbonate solid (generating a large amount of gas) until the pH of the solution is nearly neutral, standing for liquid separation, extracting the water phase once by using 250ml of dichloromethane, combining organic phases, spin-drying the solvent at 70 ℃ to obtain a viscous substance, recrystallizing for three times by using 2 times of ethanol and 0.5 time of petroleum ether, and carrying out suction filtration and air drying on a white solid BYLC-04. Theoretical yield: 84.8g, actual yield: 53.4g, yield 63%.
Gas phase purity (GC): 99.9 percent;
mass spectrometry fragmentation: 424.1 (molecular ion peak).
Example 5
The synthetic route is as follows:
step 1: 64.4g (0.2mol) of trans-propylcyclohexyl dibenzoic acid (BYLC-05-1), 28mL of 1, 3-propanedithiol, 25mL of trifluoromethanesulfonic acid, 90mL of toluene and 90mL of isooctane are added into a 1L three-necked flask, a water separator is arranged at one side port, the temperature is raised to reflux, the reaction is carried out for 6 hours, the mixture is slowly cooled to 0 ℃, and the solid is obtained by suction filtration. And (5) carrying out next feeding after drying.
Step 2: A1L three-necked flask was charged with 100mL of methylene chloride, 20mL of triethylamine and 33.6g of 5-trifluoromethyl-2-hydroxy-thiophene (BYLC-01-3), cooled to 20 ℃ and added with a solution composed of an onium trifluoromethanesulfonate (BYLC-05-2) and 100mL of methylene chloride, and stirred for 1 hour. The temperature is controlled below-75 ℃, 38g of triethylamine hydrofluoride is added dropwise, and stirring is continued for 1 hour. Controlling the temperature below-75 ℃, and carrying out post-treatment after the solution consisting of 8mL of bromine and 15mL of dichloromethane is cooled to-10 ℃. Adding 0.5L of water into a 5L bucket, stirring, pouring the reaction liquid, stirring for minutes, slowly adding sodium bicarbonate solid (generating a large amount of gas) until the pH of the solution is nearly neutral, standing for liquid separation, extracting the water phase once by using 250ml of dichloromethane, combining organic phases, spin-drying the solvent at 70 ℃ to obtain a viscous substance, recrystallizing for three times by using 2 times of ethanol and 0.5 time of petroleum ether, and carrying out suction filtration and air-drying on the white solid. Theoretical yield: 95.3g, actual yield: 53.3g, yield 56%.
Gas phase purity (GC): 99.9 percent;
mass spectrometry fragmentation: 476.5 (molecular ion peaks).
Example 6
According to the technical scheme of the embodiment 2, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Among them, R, X was selected as shown in Table 1.
TABLE 1
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 7
According to the technical scheme of the embodiment 2, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
The R, X selection is shown in Table 2.
TABLE 2
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 8
According to the technical scheme of the embodiment 2, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
The R, X selection is shown in Table 3.
TABLE 3
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 9
According to the technical scheme of the embodiment 1, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
The R, X selection is shown in Table 4.
TABLE 4
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 10
According to the technical scheme of the embodiment 3, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
The R, X selection is shown in Table 5.
TABLE 5
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 11
According to the technical scheme of the embodiment 4, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
Among them, R, X was selected as shown in Table 6.
TABLE 6
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 12
According to the technical scheme of the embodiment 3, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
Among them, R, X was selected as shown in Table 7.
TABLE 7
R
X
H
CF3
CH3
CF3
C2H5
CF3
C3H7
CF3
C4H9
CF3
C5H11
CF3
H
OCF3
CH3
OCF3
C2H5
OCF3
C3H7
OCF3
C4H9
OCF3
C5H11
OCF3
H
F
CH3
F
C2H5
F
C3H7
F
C4H9
F
C5H11
F
Example 13
According to the technical scheme of the embodiment 3, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
The selection of R, X is shown in Table 8.
TABLE 8
Example 14
According to the technical scheme of the embodiment 3, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
The selection of R, X is shown in Table 9.
TABLE 9
Example 15
According to the technical scheme of the embodiment 3, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
The R, X selection is shown in Table 10.
Watch 10
Example 16
According to the technical scheme of the embodiment 1, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Among them, R, X was selected as shown in Table 12.
TABLE 12
Example 17
According to the technical scheme of the embodiment 1, the liquid crystal compound with the following structural general formula can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
The selection of R, X is shown in Table 13.
Watch 13
Examples of the experiments
The experimental examples relate to the determination of the relevant properties of the compounds described in examples 1 to 5.
According to the conventional detection method in the field, the detection of gamma 1 is measured by a viscometer, the detection of delta n is measured by an Abbe refractometer, and the detection of delta epsilon is measured by a capacitance reactance tester of HP-4284A, which is available from Hewlett-packard company.
And obtaining various performance parameters of the liquid crystal compound through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); γ 1 represents rotational viscosity (mpa.s, 25 ℃); DELTA ε represents the dielectric anisotropy (25 ℃, 1000 Hz).
The data of the performance parameters of the liquid crystal compounds prepared in examples 1 to 5 and the data of the performance parameters of the liquid crystal compounds in comparative examples 1 to 5 were compared and the detection results are shown in Table 14:
table 14: results of Property measurement of liquid Crystal Compound
As is apparent from the detection results in table 14, the liquid crystal compound provided by the present invention has higher dielectric anisotropy Δ ∈ and lower rotational viscosity γ 1, and can reduce driving voltage and improve response time, compared with the conventional compound having a similar chemical structure.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
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