CN107345139B - Liquid crystal compound with negative dielectric anisotropy of isoamyl and application thereof - Google Patents

Liquid crystal compound with negative dielectric anisotropy of isoamyl and application thereof Download PDF

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CN107345139B
CN107345139B CN201610299396.3A CN201610299396A CN107345139B CN 107345139 B CN107345139 B CN 107345139B CN 201610299396 A CN201610299396 A CN 201610299396A CN 107345139 B CN107345139 B CN 107345139B
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liquid crystal
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CN107345139A (en
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田会强
储士红
高立龙
姜天孟
班全志
陈海光
苏学辉
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to the field of liquid crystal materials, in particular to an isoprene-based negative dielectric anisotropyA heterogeneous compound, a preparation method and an application thereof, wherein the compound has a structure shown in a formula (I): wherein R represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms; ring A represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; ring B represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; n is 0 or 1. The compound has the advantages of extremely high negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, and has important application value.

Description

Liquid crystal compound with negative dielectric anisotropy of isoamyl and application thereof
Technical Field
The invention belongs to the field of liquid crystal compounds and application thereof, and relates to a novel isoamyl negative dielectric anisotropy compound and a preparation method and application thereof.
Background
The liquid crystal material has great research value and good application prospect when being used as an environmental material in the fields of information display materials, organic optoelectronic materials and the like. Liquid crystal materials have many advantages as novel display materials, such as extremely low power consumption and low driving voltage. Compared with other materials, the material also has the advantages of small volume, light weight, long service life, large display information amount, no electromagnetic radiation and the like, can almost meet the requirements of various information displays, and is particularly suitable for TFT-LCD (thin film transistor technology) products.
In the TFT active matrix system, there are mainly a TN (Twisted Nematic) mode, an IPS (In-Plane Switching), an FFS (Fringe Field Switching) mode, a VA (Vertical Alignment) mode, and the like.
At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. However, the demand for display technology is continuously increasing, and liquid crystal displays are required to achieve faster response, reduce driving voltage to reduce power consumption, and the like.
The liquid crystal material plays an important role in improving the performance of the liquid crystal display, particularly reducing the rotational viscosity of the liquid crystal material and improving the dielectric anisotropy of the liquid crystal material. In order to improve the properties of materials and enable the materials to meet new requirements, the synthesis of novel structure liquid crystal compounds and the research of structure-property relationship become important work in the field of liquid crystal.
Disclosure of Invention
The first purpose of the invention is to provide a novel liquid crystal compound with negative dielectric anisotropy of isoprene class, which has the advantages of good negative dielectric anisotropy, good liquid crystal intersolubility, lower rotational viscosity and the like, and the compound is needed for improving liquid crystal materials and has important application value.
The liquid crystal compound has the following structure:
Figure BDA0000983796190000021
wherein R represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms; ring A represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; ring B represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; n is 0 or 1.
Preferably, in formula I, R represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms, ring A represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; ring B represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; n is 0 or 1.
As a more preferred embodiment, in the general formula I, R represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms, ring A represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-phenylene group in which 1 to 2 hydrogen atoms are substituted with fluorine atoms; and/or ring B represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-phenylene in which 1 to 2 hydrogen atoms are replaced by fluorine atoms; n is 0 or 1.
As a further preferable technical solution, the liquid crystal compound is selected from one of the following compounds:
Figure BDA0000983796190000022
Figure BDA0000983796190000031
in I-1 to I-16, R represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms;
as the best embodiment of the present invention, the liquid crystal compound is selected from one of the following compounds:
Figure BDA0000983796190000032
Figure BDA0000983796190000041
Figure BDA0000983796190000051
Figure BDA0000983796190000061
Figure BDA0000983796190000071
Figure BDA0000983796190000081
the second object of the present invention is to provide a method for preparing the liquid crystal compound.
The liquid crystal compound of the invention selects different synthetic routes according to different structures of ring B.
As a technical scheme, when n is 0 or 1, and ring B is 1, 4-phenylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine atoms, the synthetic route of the liquid crystal compound is as follows:
Figure BDA0000983796190000082
the method comprises the following specific steps:
Figure BDA0000983796190000083
and
Figure BDA0000983796190000084
synthesized by Suzuki reaction in the presence of palladium catalyst
Figure BDA0000983796190000085
Wherein, X1Represents Br, Cl or I, wherein R, n, ring A and ring B in the compound involved in each step correspond to groups represented by R, n, ring A and ring B in the obtained liquid crystal compound product (see the definition of the general formula I).
In the steps of the above method
Figure BDA0000983796190000086
And
Figure BDA0000983796190000091
the feeding molar ratio of (A) to (B) is 1: 0.8-1.6.
Preferably, the reaction temperature can be 50-150 ℃;
wherein the palladium catalyst is selected from one or more of tetrakis (triphenylphosphine) palladium, palladium carbon, bis (triphenylphosphine) palladium dichloride, palladium chloride, palladium acetate, bis (diphenylphosphino ferrocene) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
In the above process
Figure BDA0000983796190000092
The synthesis of (2) can be carried out by selecting different synthetic routes according to different values of n and different structures of the ring A.
When n is 0 or 1 and ring A is 1, 4-phenylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted with fluorine atoms, the synthetic route is as follows:
Figure BDA0000983796190000093
the method specifically comprises the following steps:
(1) under the catalysis of Lewis acid, with
Figure BDA0000983796190000094
And
Figure BDA0000983796190000095
is used as raw material and is obtained by Friedel-crafts acylation reaction
Figure BDA0000983796190000096
(2)
Figure BDA0000983796190000097
Through reduction reaction to obtain
Figure BDA0000983796190000101
Wherein, X in the compound involved in each step1Ring B and the resulting liquid-crystalline compound productX1And the group represented by the ring B corresponds to each other.
In the step 1) of the above-mentioned method,
Figure BDA0000983796190000102
the feeding molar ratio of the Lewis acid to the Lewis acid is 1: 1.0-3.0: 1.0 to 3.0;
preferably, the reaction temperature can be-10-80 ℃;
wherein the Lewis acid is selected from one or more of aluminum trichloride, zinc chloride, boron trifluoride diethyl etherate or ferric trichloride.
In the step 2), the reducing agent can be one or more selected from a hydrazine hydrate and potassium hydroxide system, a triethylsilane and trifluoroacetic acid system, and a triethylsilane and boron trifluoride diethyl etherate system.
When n is 1 and ring A is 1, 4-cyclohexylene, i.e.
Figure BDA0000983796190000103
The synthetic route is as follows:
Figure BDA0000983796190000104
the method specifically comprises the following steps:
(1)
Figure BDA0000983796190000105
reaction with triphenylphosphine to give
Figure BDA0000983796190000106
(2) To be provided with
Figure BDA0000983796190000111
And
Figure BDA0000983796190000112
as raw material, obtaining the product by wittig reaction
Figure BDA0000983796190000113
(3)
Figure BDA0000983796190000114
Through catalytic hydrogenation to obtain
Figure BDA0000983796190000115
Wherein each step involves ring B, X in the compound1With ring B, X in the resulting liquid crystal compound product1The radicals represented correspond.
In the step 1) of the above-mentioned method,
Figure BDA0000983796190000116
the feeding molar ratio of the catalyst to triphenylphosphine is 1.0: 0.9 to 1.5;
preferably, the reaction temperature can be 50-150 ℃;
in the step 2) of the said step,
Figure BDA0000983796190000117
the feeding molar ratio of the tert-butyl alcohol to potassium tert-butoxide is 1: 1.0-3.0: 1.0 to 3.0;
preferably, the reaction temperature can be-30 ℃;
in the step 3), the step of the method comprises the following steps,
Figure BDA0000983796190000118
the feeding mass ratio of the catalyst to the catalyst is 1: 0.03-0.15;
preferably, the reaction temperature can be 10-70 ℃;
wherein, the catalyst is selected from one or more of Pd/C, Raney nickel and Pt/C, and is preferably Pt/C.
As a second embodiment, when n is 0 or 1 and ring B is 1, 4-cyclohexenylene, i.e.
Figure BDA0000983796190000121
The synthetic route is as follows:
Figure BDA0000983796190000122
the method specifically comprises the following steps:
(1)
Figure BDA0000983796190000123
metallation with organolithium reagent, and reaction with
Figure BDA0000983796190000124
Reacting to obtain
Figure BDA0000983796190000125
(2)
Figure BDA0000983796190000126
Dehydrating by acid catalysis to obtain
Figure BDA0000983796190000127
Wherein R, n, ring A and ring B in the compound involved in each step correspond to groups represented by R, n, ring A and ring B in the obtained liquid crystal compound product (see the definition of the general formula I).
In step 1) of the above process
Figure BDA0000983796190000131
Organic lithium reagent and
Figure BDA0000983796190000132
the feeding molar ratio of (A) to (B) is 1: 1.0-2.0: 0.8 to 1.5;
preferably, the reaction temperature can be between-50 and-100 ℃;
wherein the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium.
In the step 2) of the said step,
Figure BDA0000983796190000133
the feeding mol ratio of the acid to the raw materials is 1: 0.02-0.2;
preferably, the reaction temperature can be 80-140 ℃;
wherein, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and potassium bisulfate, and is preferably p-toluenesulfonic acid.
In the above process
Figure BDA0000983796190000134
The synthetic route of (a) is preferably as follows:
Figure BDA0000983796190000135
the method specifically comprises the following steps:
(1) to be provided with
Figure BDA0000983796190000141
As raw material, obtaining the product by wittig reaction
Figure BDA0000983796190000142
(2)
Figure BDA0000983796190000143
Through catalytic hydrogenation to obtain
Figure BDA0000983796190000144
(3)
Figure BDA0000983796190000145
Removing ethylene glycol under acid catalysis to obtain
Figure BDA0000983796190000146
Wherein R, n, ring A and ring B in the compound involved in each step correspond to groups represented by R, n, ring A and ring B in the obtained liquid crystal compound product.
In the step 1) of the above-mentioned method,
Figure BDA0000983796190000147
the feeding molar ratio of the tert-butyl alcohol to potassium tert-butoxide is 1: 1.0-3.0: 1.0 to 3.0;
preferably, the reaction temperature can be-30 ℃;
in the step 2) of the said step,
Figure BDA0000983796190000148
the feeding mass ratio of the catalyst to the catalyst is 1: 0.03-0.15;
preferably, the reaction temperature can be 10-70 ℃;
wherein, the catalyst is selected from one or more of Pd/C, Raney nickel and Pt/C, and is preferably Pd/C.
In the step 3), the step of the method comprises the following steps,
Figure BDA0000983796190000151
the feeding mass ratio of the acid to the raw materials is 1: 0.5-4.0;
preferably, the reaction temperature can be 30-100 ℃;
wherein, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid and p-toluenesulfonic acid, and is preferably formic acid.
As a third embodiment, when n is 0 or 1 and ring B is 1, 4-cyclohexylene, i.e.
Figure BDA0000983796190000152
The synthetic route is as follows:
Figure BDA0000983796190000153
the method specifically comprises the following steps:
Figure BDA0000983796190000154
through catalytic hydrogenation to obtain
Figure BDA0000983796190000155
Wherein R, n, ring A and ring B in the compound involved in each step correspond to groups represented by R, n, ring A and ring B in the obtained liquid crystal compound product (see the definition of the general formula I).
In the steps of the above-mentioned method,
Figure BDA0000983796190000161
the feeding mass ratio of the catalyst to the catalyst is 1: 0.03-0.15;
preferably, the reaction temperature can be 10-70 ℃;
wherein, the catalyst is selected from one or more of Pd/C, Raney nickel and Pt/C, and is preferably Pd/C.
As described above
Figure BDA0000983796190000162
Figure BDA0000983796190000163
And
Figure BDA0000983796190000164
can be synthesized by publicly available commercial methods or by methods known per se in the literature.
The method of the invention, if necessary, involves conventional post-treatment, such as: extracting with dichloromethane, ethyl acetate or toluene, separating liquid, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
The liquid crystal compound can be stably and efficiently obtained by the preparation method.
A third object of the present invention is to protect a composition containing the liquid crystal compound. The liquid crystal compound is 1-60% by mass of the composition, preferably 3-50% by mass, and more preferably 5-25% by mass.
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 compound or the composition containing the liquid crystal compound has good negative dielectric anisotropy and low rotational viscosity, so that the driving voltage is effectively reduced, the response speed of a liquid crystal display device is improved, and the liquid crystal compound or the composition containing the liquid crystal compound has the characteristics of moderate optical anisotropy value, high charge retention rate, good liquid crystal intersolubility, excellent low-temperature working effect performance and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents the rotational viscosity (mPa.s, 25 ℃).
Example 1 the liquid crystal compound has the formula:
Figure BDA0000983796190000171
the synthetic route for the preparation of compound BYLC-01 is shown below:
Figure BDA0000983796190000172
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-01-1:
adding 31.4g of bromobenzene and 32.0g of aluminum trichloride into a reaction bottle, controlling the temperature to be minus 5-5 ℃, dropwise adding 30.1g of isovaleryl chloride, preserving the temperature for reaction for 30min after dropwise adding, naturally returning the temperature to the room temperature, stirring for reaction for 6h, quenching the reaction by using 200ml of 2M hydrochloric acid aqueous solution, carrying out conventional post-treatment, and recrystallizing ethanol to obtain light yellow solid (compound BYLC-01-1)44.2g, GC: 99.7 percent and the yield is 92 percent;
(2) synthesis of Compound BYLC-01-2:
44.2g of compound BYLC-01-1, 55ml of triethylsilane and 40ml of trifluoroacetic acid were charged in a reaction flask, and stirred at room temperature for 8 hours for conventional post-treatment, followed by purification by chromatography and spin-drying of the solvent to obtain 34.5g of a colorless liquid (compound BYLC-01-2), GC: 98.4 percent and yield 83 percent;
(3) synthesis of Compound BYLC-01:
under the protection of nitrogen, 25.9g of 2, 3-difluoro-4-propoxybenzeneboronic acid, 22.6g of BYLC-01-2, 150ml of N, N-dimethylformamide, 50ml of deionized water, 15.6g of anhydrous potassium carbonate and 0.4g of palladium tetratriphenylphosphine were added into a reaction flask, and the mixture was heated under reflux for 6 hours. Conventional work-up was carried out, purification by chromatography, elution with n-hexane and recrystallization with ethanol gave 26.1g of a white solid (compound BYLC-01), GC: 99.7%, yield: 82 percent.
The obtained white solid BYLC-01 was analyzed by GC-MS and the M/z of the product was 318.1(M +).
1H-NMR(300MHz,CDCl3):0.88-2.69(m,16H)，3.63-3.95(m,2H),6.83-7.75(m,6H)。
Example 2
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0000983796190000181
Figure BDA0000983796190000191
Figure BDA0000983796190000201
Figure BDA0000983796190000211
Example 3
The structural formula of the liquid crystal compound is as follows:
Figure BDA0000983796190000212
the synthetic route for the preparation of compound BYLC-03 is shown below:
Figure BDA0000983796190000213
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-03-1:
adding 30.2g of bromoisopentane, 57.6g of triphenylphosphine and 40ml of N, N-dimethylformamide into a reaction bottle, controlling the temperature to be 110-120 ℃ for reacting for 8 hours, cooling to be below 80 ℃, adding 250ml of toluene, freezing to be about-20 ℃, and performing suction filtration to obtain 69.2g of white solid (compound BYLC-03-1) with the yield of 84%;
(2) synthesis of Compound BYLC-03-3:
under the protection of nitrogen, 98.5g of compound BYLC-03-1 and 400ml of tetrahydrofuran are added into a reaction bottle, 26.8g of potassium tert-butoxide is added at the temperature of-10-5 ℃, the reaction is carried out for 30min, 37.8g of compound BYLC-03-2 is dropwise added at the temperature of-10-5 ℃, then the temperature is naturally returned to the room temperature, the reaction is carried out for 3h, 300ml of water is added for quenching reaction, the conventional aftertreatment is carried out, and the light yellow liquid (compound BYLC-03-3) is obtained by chromatographic purification, wherein 42.7g of the light yellow liquid (compound BYLC-03-3: 98.6%, yield: 93 percent;
(3) synthesis of Compound BYLC-03-4:
42.7g of compound BYLC-03-3, 1.5g of platinum carbon, 60ml of toluene and 200ml of ethanol are added into a reaction bottle, hydrogen is replaced twice, the pressure is 0.1MPa, the temperature is controlled to be 10-20 ℃, hydrogenation reaction is carried out for 6 hours, and conventional post-treatment is carried out to obtain light yellow liquid (compound BYLC-03-4), 41.4g of compound, GC: 93.3%, yield: 97 percent;
(4) synthesis of Compound BYLC-03:
under the protection of nitrogen, 13.1g of 2, 3-difluoro-4-ethoxyphenylboronic acid, 15.4g of BYLC-03-4, 120ml of N, N-dimethylformamide, 40ml of deionized water, 11.6g of anhydrous potassium carbonate and 0.3g of palladium tetratriphenylphosphine were added to a reaction flask, and the mixture was heated under reflux for 6 hours. Conventional work-up was carried out, purification was carried out by chromatography, elution was carried out with n-hexane, and recrystallization was carried out with ethanol + n-hexane to obtain 10.8g of a white solid (compound BYLC-03), GC: 99.8%, yield: 56 percent.
The obtained white solid BYLC-03 was analyzed by GC-MS and the M/z of the product was 386.2(M +).
1H-NMR(300MHz,CDCl3):0.87-2.72(m,24H)，3.63-3.95(m,2H),6.83-7.76(m,6H)。
Example 4
According to the technical scheme of the embodiment 3, the following liquid crystal compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0000983796190000221
Figure BDA0000983796190000231
Example 5
The structural formula of the liquid crystal compound is as follows:
Figure BDA0000983796190000241
the synthetic route for the preparation of compound BYLC-05 is shown below:
Figure BDA0000983796190000242
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-05-2:
adding 80.2g of compound BYLC-03-1 and 400ml of tetrahydrofuran into a reaction bottle under the protection of nitrogen, controlling the temperature to be-5 ℃, adding 21.8g of potassium tert-butoxide, reacting for 30min, controlling the temperature to be-5 ℃, dropwise adding 35.7g of compound BYLC-05-1, naturally returning to room temperature, reacting for 3h, adding 200ml of water, quenching, reacting, performing conventional aftertreatment, and performing chromatographic purification to obtain colorless liquid (compound BYLC-05-2):41.2g, GC: 97.1%, yield: 94 percent;
(2) synthesis of Compound BYLC-05-3:
adding 41.2g of compound BYLC-05-2, 1.6g of 5% palladium carbon, 40ml of toluene and 100ml of ethanol into a reaction bottle, replacing twice with hydrogen, carrying out hydrogenation reaction for 6 hours at the pressure of 0.2MPa and the temperature of 10-30 ℃, and carrying out conventional aftertreatment to obtain colorless liquid (compound BYLC-05-3), 39.6g of compound, GC: 95.8%, yield: 96 percent;
(3) synthesis of Compound BYLC-05-4:
adding 39.6g of compound BYLC-05-3, 60ml of formic acid and 150ml of toluene into a reaction bottle, controlling the temperature to be 50-60 ℃ for reaction for 4 hours, and carrying out conventional aftertreatment to obtain light yellow liquid (compound BYLC-05-4), 32.3g of light yellow liquid, GC: 92.5%, yield: 96 percent;
(4) synthesis of Compound BYLC-05-5:
15.8g of 2, 3-difluorophenetole and 130ml of tetrahydrofuran are added into a reaction bottle, 0.12mol of n-hexane solution of n-butyllithium is dripped into the reaction bottle at the temperature of between 70 ℃ below zero and 80 ℃ below zero, the reaction is carried out for 1 hour after dripping, a solution consisting of 25.0g of BYLC-05-4 and 30ml of tetrahydrofuran is dripped into the reaction bottle at the temperature of between 70 ℃ below zero and 80 ℃ below zero, and then the reaction bottle is naturally cooled to 30 ℃ below zero. Acidification was performed by adding 100ml of 2M aqueous hydrochloric acid solution, and conventional post-treatment was performed, and the solvent was spin-dried to obtain 40.8g of a pale yellow liquid (compound BYLC-05-5), GC (cis + trans): 91.2% and yield 100%;
(5) synthesis of Compound BYLC-05:
40.8g of BYLC-05-5, 0.5g of p-toluenesulfonic acid and 200ml of toluene are added into a reaction flask, reflux dehydration is carried out for 6 hours, conventional post-treatment is carried out, and the mixture is purified by chromatography, eluted by normal hexane and recrystallized by ethanol and normal hexane to obtain white solid (compound BYLC-05):23.2g, GC: 99.7%, yield: 57 percent;
the resulting white solid BYLC-05 was analyzed by GC-MS and the M/z of the product was 390.2(M +).
1H-NMR(300MHz,CDCl3):0.88-1.90(m,31H)，3.63-3.95(m,2H),5.65-5.95(m,1H),6.35-7.37(m,2H)。
Example 6
According to the technical scheme of the example 5, the following liquid crystal compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0000983796190000251
Figure BDA0000983796190000261
Example 7
The structural formula of the liquid crystal compound is as follows:
Figure BDA0000983796190000262
the synthetic route for the preparation of compound BYLC-07 is shown below:
Figure BDA0000983796190000263
the method comprises the following specific steps:
synthesis of Compound BYLC-07:
adding 20.0g of compound BYLC-05, 1.0g of 5% palladium carbon, 40ml of toluene and 70ml of ethanol into a reaction bottle, performing hydrogen replacement twice, performing hydrogenation reaction for 6 hours at the pressure of 0.2MPa and the temperature of 10-30 ℃, performing conventional post-treatment, performing chromatographic purification, eluting with n-hexane, and recrystallizing with ethanol and n-hexane to obtain a white solid (compound BYLC-07), wherein the weight ratio of the compound BYLC-05 to the n-hexane is 9.2g, and the GC: 99.9%, yield: 46 percent.
The resulting white solid BYLC-07 was analyzed by GC-MS and the M/z of the product was 392.2(M +).
1H-NMR(300MHz,CDCl3):0.88-2.75(m,34H)，3.53-4.15(m,2H),6.36-6.95(m,2H)。
Example 8
According to the technical scheme of the example 7, the following liquid crystal compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0000983796190000271
Figure BDA0000983796190000281
Experimental example 1
The data of the performance parameters of the liquid crystal compound BYLC-01 prepared in example 1 and the data of the performance parameters of the liquid crystal compound of comparative example 1 (another known and common similar liquid crystal compound) are compared and collated, and the detection results are shown in Table 1:
table 1: results of Property measurement of liquid Crystal Compound
Figure BDA0000983796190000282
The detection results in table 1 clearly show that the negative dielectric anisotropy, clearing point and optical anisotropy of the liquid crystal compound provided by the invention are equivalent to those of the traditional compound with a similar chemical structure, but the liquid crystal compound provided by the invention has lower rotational viscosity, good liquid crystal intersolubility and excellent low-temperature working effect, the rotational viscosity of the liquid crystal composition is effectively reduced, and the response time is improved.
Experimental example 2
The data of the liquid crystal compound performance parameters of the compound BYLC-03 prepared in example 3 and the comparative example 2 (another similar liquid crystal compound is known to be common) are compared and the detection results are shown in Table 2:
table 2: results of Property measurement of liquid Crystal Compound
Figure BDA0000983796190000291
The detection results in table 2 clearly show that the negative dielectric anisotropy, clearing point and optical anisotropy of the liquid crystal compound provided by the invention are equivalent to those of the traditional compound with similar chemical structure, but the liquid crystal compound provided by the invention has lower rotational viscosity, good liquid crystal intersolubility and excellent low-temperature working effect, the rotational viscosity of the liquid crystal composition is effectively reduced, and the response time is improved.
Experimental example 3
The data of the performance parameters of the liquid crystal compound BYLC-05 prepared in example 5 and the data of the performance parameters of the liquid crystal compound of comparative example 3 (another known and common similar liquid crystal compound) are compared and the detection results are shown in Table 3:
table 3: results of Property measurement of liquid Crystal Compound
Figure BDA0000983796190000292
The detection results in table 3 clearly show that the negative dielectric anisotropy, clearing point and optical anisotropy of the liquid crystal compound provided by the invention are equivalent to those of the conventional compound with a similar chemical structure, but the liquid crystal compound provided by the invention has lower rotational viscosity, good liquid crystal intersolubility and excellent low-temperature working effect, the rotational viscosity of the liquid crystal composition is effectively reduced, and the response time is improved.
Experimental example 4
The performance parameter data of the compound BYLC-07 prepared in example 7 and the liquid crystal compound of comparative example 4 (another similar liquid crystal compound known to be common) are compared and the detection results are shown in table 4:
table 4: results of Property measurement of liquid Crystal Compound
Figure BDA0000983796190000301
The detection results in table 4 clearly show that the negative dielectric anisotropy, clearing point and optical anisotropy of the liquid crystal compound provided by the invention are equivalent to those of the conventional compound with a similar chemical structure, but the liquid crystal compound provided by the invention has lower rotational viscosity, good liquid crystal intersolubility and excellent low-temperature working effect, the rotational viscosity of the liquid crystal composition is effectively reduced, and the response time is improved.
Compared with an n-amyl compound, the isoamyl liquid crystal compound provided by the invention shortens the molecular chain length of alkyl, has small change of space volume, can obviously improve the thermal stability, chemical stability and optical stability of the liquid crystal compound, improves the mechanical property, dielectric property and other properties of the liquid crystal compound, reduces the rotational viscosity of the liquid crystal compound, and can effectively improve the rotational viscosity of a liquid crystal composition, thereby improving the response time of a liquid crystal display.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (9)

1. An isopentyl negative dielectric anisotropy liquid crystal compound, characterized in that: has the following structure:
Figure DEST_PATH_IMAGE001
wherein R represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms.
2. The liquid crystal compound according to claim 1, characterized in that: the liquid crystal compound is selected from one of the following compounds:
Figure 321057DEST_PATH_IMAGE002
。
3. a method for producing a liquid crystal compound according to claim 1, characterized in that: when n is 0 and ring B is 1, 4-phenylene, the liquid crystal compound is synthesized as follows:
Figure DEST_PATH_IMAGE003
the method comprises the following specific steps:
Figure 300514DEST_PATH_IMAGE004
and
Figure DEST_PATH_IMAGE005
synthesized by Suzuki reaction in the presence of palladium catalyst
Figure 644033DEST_PATH_IMAGE006
；
Wherein R is as defined in claim 1; ring A represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-phenylene group in which 1 to 4 hydrogen atoms are substituted with fluorine atoms; x1Represents Br, Cl or I.
4. The production method according to claim 3, characterized in that: the above-mentioned
Figure DEST_PATH_IMAGE007
The synthetic route of (2) is as follows:
Figure 39242DEST_PATH_IMAGE008
the method specifically comprises the following steps:
(1) under the catalysis of Lewis acid, with
Figure DEST_PATH_IMAGE009
And
Figure 915931DEST_PATH_IMAGE010
is used as raw material and is obtained by Friedel-crafts acylation reaction
Figure DEST_PATH_IMAGE011
；
（2）
Figure 800711DEST_PATH_IMAGE011
Through reduction reaction to obtain
Figure 67744DEST_PATH_IMAGE012
。
5. A liquid crystal composition comprising 1 to 60% by mass of the compound according to claim 1 or 2.
6. The liquid crystal composition according to claim 5, comprising 3 to 50% by mass of the compound according to claim 1 or 2.
7. The liquid crystal composition according to claim 6, comprising 5 to 25% by mass of the compound according to claim 1 or 2.
8. Use of a compound according to claim 1 or 2 or a composition according to any one of claims 5 to 7 in a liquid crystal display device.
9. The use according to claim 8, wherein the liquid crystal display device is a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.
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