CN107312549B - Liquid crystal compound containing dimethylbenzene and difluorometheneoxy linking group and application thereof - Google Patents

Liquid crystal compound containing dimethylbenzene and difluorometheneoxy linking group and application thereof Download PDF

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CN107312549B
CN107312549B CN201710432270.3A CN201710432270A CN107312549B CN 107312549 B CN107312549 B CN 107312549B CN 201710432270 A CN201710432270 A CN 201710432270A CN 107312549 B CN107312549 B CN 107312549B
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liquid crystal
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compound
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dimethylbenzene
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张伟
孟劲松
员国良
王瑾
张虎波
张莉
张芳苗
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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Abstract

The invention discloses a liquid crystal compound containing dimethylbenzene and difluorometheneoxy linking groups and application thereof. The compound is shown as a formula I. The compound of formula I provided by the invention contains dimethylbenzene and difluoromethyleneoxy (-CF) in the molecular structure2The liquid crystal compound of the O-) linking group not only has larger dielectric anisotropy, but also has extremely fast response speed and higher clearing point, and the performance has important significance for preparing liquid crystal mixture.

Description

Liquid crystal compound containing dimethylbenzene and difluorometheneoxy linking group and application thereof
The application is a divisional application of Chinese application with the name of 201510555389.0 invention, namely 'liquid crystal compound containing dimethylbenzene and difluoromethyleneoxy linking group and preparation method and application thereof', filed on 9/2/2015.
Technical Field
The invention relates to the field of preparation and application of liquid crystal compounds, in particular to a liquid crystal compound containing dimethylbenzene and difluoromethyleneoxy linking groups and application thereof.
Background
At present, the application range of liquid crystal compounds is expanding more and more, and the liquid crystal compounds can be applied to various displays, electro-optical devices, sensors and the like. The liquid crystal compounds used in the above display fields are various, and nematic liquid crystals are most widely used. Nematic liquid crystals have been applied in passive TN, STN matrix displays and systems with TFT active matrix.
Although the market for thin film transistor technology (TFT-LCD) applications is very large and the technology is mature in recent years, the demand for display technology is continuously increasing, especially in the aspects of achieving fast response, reducing driving voltage to reduce power consumption, etc. The liquid crystal material is one of important photoelectronic materials for liquid crystal displays, and plays an important role in improving the performance of the liquid crystal displays.
As liquid crystal materials, good chemical and thermal stability as well as stability to electric fields and electromagnetic radiation are required. As a liquid crystal material for thin film transistor (TFT-LCD) technology, it is required to have not only the above stability, but also a wide nematic phase temperature range, a suitable birefringence anisotropy, a very high resistivity, a good uv resistance, a high charge retention rate, and a low vapor pressure.
For a dynamic picture display application such as a liquid crystal television, in order to realize high quality display, eliminate display image sticking and tailing, the liquid crystal is required to have a fast response speed, and thus the liquid crystal is required to have a low rotational viscosity γ1(ii) a In addition, in order to reduce the power consumption of the apparatus, it is desirable that the driving voltage of the liquid crystal is as low as possible, so that it is important to increase the dielectric anisotropy Δ ∈ of the liquid crystal for the mixed liquid crystal.
A great deal of research shows that the liquid crystal molecule introduces a difluoromethyleneoxy (-CF)2After the O-) linking group, the rotational viscosity gamma of the liquid crystal is increased1And is reduced. In addition, due to difluoro ethyleneMethoxy (-CF)2The contribution of dipole moment of O-) bridge and the dipole moment of terminal fluorine atom are raised to some extent, so that the dielectric anisotropy Delta epsilon of liquid crystal molecule is increased. German Merck and Japanese Kohyo companies (CN1717468A, CN101143808A, CN101157862A, etc.) have disclosed that certain compounds having difluoromethyleneoxy linking groups (-CF) have different substituents2O-) liquid crystal compounds. But (-CF)2The introduction of the O-) group can greatly reduce the clearing point of the liquid crystal. When the liquid crystal mixture is prepared, a high-clearing-point compound with higher viscosity needs to be added for balancing (-CF)2The clearing point caused by the O-) group is reduced, thereby restricting the space for improving the response speed of the liquid crystal mixture.
The liquid crystal is used as a core functional material of the liquid crystal display device, in order to meet the requirements of various performance parameters of the liquid crystal display device and to adapt to the process requirements of the liquid crystal display device, the liquid crystal material is required to have a wide variety of performance parameters, and any one monomer liquid crystal material cannot meet all the requirements, so that monomer liquid crystals with different performances are required to be synthesized, and the characteristics required by the LCD device are met by a method for blending mixed liquid crystals.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a liquid crystal compound containing dimethylbenzene and a difluoromethyleneoxy linking group and application thereof, so as to solve the problem that the clearing point of the existing liquid crystal compound with the difluoromethyleneoxy group is reduced and improve the response speed of the liquid crystal compound.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a liquid crystal compound containing dimethylbenzene and difluoromethyleneoxy linking groups, wherein the structural formula of the compound is shown as a general formula I,
Figure GDA0003150506850000021
wherein the content of the first and second substances,
Figure GDA0003150506850000022
is selected from
Figure GDA0003150506850000023
Any one of the groups;
X1、X2、X3selected from H, F, OCF3Any one of the above;
R1any one selected from straight-chain alkyl with 1-6 carbon atoms, straight-chain alkenyl with 2-6 carbon atoms and cycloalkyl with 3-6 carbon atoms;
m is selected from 0 or 1;
n is selected from 1 or 2.
The technical scheme of the invention is further improved as follows: the compound shown in the general formula I is a compound shown in formulas I-1 to I-4,
Figure GDA0003150506850000031
the technical scheme of the invention is further improved as follows: the compound shown in the general formula I is a compound shown in formulas I-1-1 to I-4-2,
Figure GDA0003150506850000032
Figure GDA0003150506850000041
Figure GDA0003150506850000051
Figure GDA0003150506850000061
the liquid crystal composition comprises a component A consisting of a compound shown in a general formula I, a component B consisting of one or two compounds shown in a general formula II, and a component C consisting of three to ten compounds shown in a general formula III, wherein the mass ratio of the component A to the component B to the component C is 1-40: 5-40: 5 to 80 parts of a first resin,
Figure GDA0003150506850000062
wherein the content of the first and second substances,
R1、R2any one selected from linear alkyl with 1-6 carbon atoms and linear alkenyl with 2-6 carbon atoms;
R3any one selected from H, F and straight-chain alkyl groups with 1-6 carbon atoms;
Figure GDA0003150506850000063
any one selected from the group consisting of 1, 4-cyclohexylene, 1, 4-phenylene and fluoro-1, 4-phenylene;
p is 2 or 3;
(F) represents H or F.
The technical scheme of the invention is further improved as follows: the compounds shown in the general formula II are specifically compounds shown in formulas II-1 to II-9,
Figure GDA0003150506850000064
Figure GDA0003150506850000071
the technical scheme of the invention is further improved as follows: the compound shown in the general formula III is specifically a compound shown in a formula III-3 to a formula III-10,
Figure GDA0003150506850000072
Figure GDA0003150506850000081
the technical scheme of the invention is further improved as follows: the mass ratio of the component A, the component B and the component C in the liquid crystal composition is 10-35: 15-35: 25 to 75.
The technical scheme of the invention is further improved as follows: the liquid crystal composition further comprises an additive which accounts for not more than 0.05 percent of the weight of the liquid crystal composition, and the additive is at least one of an antioxidant, an anti-ultraviolet agent and a chiral agent.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the liquid crystal compound containing the dimethylbenzene and the difluoromethyleneoxy linking group has a wide application range. Can be used as a base material for liquid crystal mixtures, or can be added as an additive to liquid crystal base materials composed of other types of compounds, for example, to improve the dielectric anisotropy Δ ∈, the rotational viscosity γ of liquid crystal mixtures1Threshold voltage VthContrast at low temperature, optical anisotropy Δ n, clearing point Cp, etc.
As can be seen from the monomer parameters of examples 1-8, the liquid crystal compounds containing a xylene and difluoromethyleneoxy linking group according to the invention have the outstanding advantage of having a high clearing point Cp, which facilitates the control of liquid crystal mixtures with a wide range of operating temperatures.
Response speed t of liquid crystal composition, thickness d of liquid crystal box and rotational viscosity gamma of liquid crystal1According to t-1d2Has a lower rotational viscosity γ1The response time of the liquid crystal of (3) is short. The molecular structure of the compound of the formula I provided by the invention contains dimethylbenzene and difluoromethyleneoxy (-CF)2The liquid crystal compound of the O-) linking group not only has larger dielectric anisotropy delta epsilon, but also has faster response speed t and lower rotational viscosity gamma1And good low-temperature properties, which are of great significance for the formulation of liquid-crystal mixtures.
As can be seen from composition examples 9 to 11, the liquid crystal composition of the present invention has a large dielectric anisotropy Δ ∈, a high clearing point, and a high refractive index, and can simultaneously achieve a low driving voltage (large dielectric anisotropy Δ ∈), a wide temperature use environment (high clearing point), and a low liquid crystal cell thickness (high refractive index), and can be applied to a liquid crystal panel, and further save power and achieve a fast response.
The pure compound shown in the general formula I is colorless and shows higher stability to light, heat and chemical. In particular, the compound of formula I shows large dielectric anisotropy Deltaepsilon and good low-temperature properties such as response speed and contrast at low temperature, and also has the advantage of inhibiting the formation of smectic phases, which indicates that the liquid crystal mixture using the compound of formula I has better low-temperature storage stability.
The invention also provides an application of the liquid crystal compound containing the dimethylbenzene and the difluoromethyleneoxy linking group and the liquid crystal composition consisting of the liquid crystal compound containing the dimethylbenzene and the difluoromethyleneoxy linking group in the preparation of a liquid crystal display device material or an electro-optical display device material, and the liquid crystal display device material or the electro-optical display device material containing the liquid crystal compound containing the dimethylbenzene and the difluoromethyleneoxy linking group or the liquid crystal composition, and belongs to the protection scope of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
the invention discloses a liquid crystal compound containing dimethylbenzene and difluoromethyleneoxy linking group, the structural formula of the compound is shown as the general formula I,
Figure GDA0003150506850000091
wherein the content of the first and second substances,
Figure GDA0003150506850000092
is selected from
Figure GDA0003150506850000093
Any one of the groups;
X1、X2、X3selected from H, F, Cl, CF3、CHF2、OCF3And OCHF2Any one of the above;
R1any one selected from straight-chain alkyl with 1-6 carbon atoms, straight-chain alkenyl with 2-6 carbon atoms and cycloalkyl with 3-6 carbon atoms;
m is selected from 0 or 1;
n is selected from 1 or 2.
In particular, the compounds shown in the general formula I are compounds shown in formulas I-1 to I-4,
Figure GDA0003150506850000094
Figure GDA0003150506850000101
the invention also discloses a preparation method of the liquid crystal compound containing the dimethylbenzene and the difluoromethyleneoxy linking group,
the synthetic route of the compound shown as the general formula I is as follows,
Figure GDA0003150506850000102
the invention further discloses a liquid crystal composition consisting of a liquid crystal compound containing dimethylbenzene and a difluoromethyleneoxy linking group, wherein the liquid crystal composition comprises a component A consisting of a compound shown in a general formula I, a component B consisting of one or two compounds shown in a general formula II, and a component C consisting of three to ten compounds shown in a general formula III, and the mass ratio of the component A to the component B to the component C is 1-40: 5-40: 5 to 80 parts of a first resin,
Figure GDA0003150506850000111
wherein the content of the first and second substances,
R1、R2any one selected from linear alkyl with 1-6 carbon atoms and linear alkenyl with 2-6 carbon atoms;
R3any one selected from H, F and straight-chain alkyl groups with 1-6 carbon atoms;
Figure GDA0003150506850000112
any one or more selected from 1, 4-cyclohexylene, 1, 4-phenylene and fluoro-1, 4-phenylene;
p is 2 or 3;
(F) represents H or F.
Preferably, the mass ratio of the component A to the component B to the component C is 10-35: 15-35: 25 to 75. More preferably, the mass ratio of the component A to the component B to the component C is 5-10: 25:75, the mass ratio of the component A, the component B and the component C is specifically 5: 25:75 or 10: 25: 75.
the present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The specific meanings of the symbols in the examples and the test conditions were as follows:
cp: the unit ℃ represents the clearing point of the liquid crystal.
S-N: the unit C represents the melting point of the crystalline to nematic phase of the liquid crystal.
Δ n: optical anisotropy, Δ n ═ no-ne, where no is the refractive index of ordinary rays and ne is the refractive index of extraordinary rays, and the test conditions were 589nm, 25 ± 0.5 ℃.
Δ ε: dielectric anisotropy, Δ ε ═ ε∥-ε⊥Wherein, epsilon∥Is a dielectric constant parallel to the molecular axis,. epsilon⊥Is vertical toThe dielectric constant of the molecular axis is 25 +/-0.5 ℃; 1 KHz; HP 4284A; 5.2 micron TN left-handed cassette.
γ 1: rotational viscosity in mPas units, test conditions 25. + -. 0.5 ℃.
VHR: voltage holding ratio (%) under the test conditions of 20 + -2 deg.C, voltage + -5V, pulse width 10ms, and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester.
The contrast ratio is the ratio of the bright state to the dark state of the liquid crystal display, and the determination method is as follows: filling liquid crystal into a liquid crystal box, attaching a polaroid and a normally white mode, determining a driving voltage according to the threshold voltage of the liquid crystal, leading out a lead of the attached liquid crystal box, testing the liquid crystal box under a constant backlight source, testing the light intensity of a bright state without applying voltage to the liquid crystal box, testing the light intensity of a dark state with applying voltage, and determining the ratio of the light intensity of the bright state to the light intensity of the dark state as the contrast.
The contrast change rate (%) at normal temperature and low temperature (contrast at normal temperature-contrast at low temperature)/contrast at normal temperature × 100 (%), the normal temperature being 25 ℃ and the low temperature being-20 ℃.
Cp represents the clearing point, which can be directly measured, and for compounds that cannot be directly measured, the fitting data can be calculated as follows:
in the process of preparing the mixed liquid crystal, a plurality of proper monomer liquid crystals are selected for mixing, so that a eutectic mixture can be formed, and the melting point of the liquid crystal is effectively reduced; meanwhile, the clearing point of the mixed liquid crystal can be improved by adding the monomer liquid crystal with the high clearing point, so that the mixed liquid crystal with the nematic phase temperature range meeting the requirement is prepared, and the clearing point and the concentration of the mixed liquid crystal and the monomer liquid crystal meet the following relational expression:
Tc＝∑XiTi
wherein Tc represents the clearing point of the mixed liquid crystal, XiDenotes the concentration of monomeric liquid crystal in the mixed liquid crystal, TiIndicating the clearing point of the monomeric liquid crystal.
Examples 1 to 8 are examples of producing liquid crystal compounds. The progress of the reaction is generally monitored by TLC, and the post-treatment after the completion of the reaction is generally water washing, extraction, combination of organic phases, drying, evaporation of the solvent under reduced pressure, recrystallization, and column chromatography, and those skilled in the art can implement the present invention as described below.
Example 1
Preparing a liquid crystal mixture shown in a formula I-2-14, wherein the structural formula is shown as follows,
Figure GDA0003150506850000131
the synthetic route is as follows,
Figure GDA0003150506850000132
specifically comprises six steps from a to f,
a) in an inert atmosphere, 242.4g (2.4mol) of the starting material
Figure GDA0003150506850000133
Dissolving in 1L tetrahydrofuran, cooling to-30 deg.C, adding 960ml n-butyl lithium dropwise, stirring for 30 min after dropwise addition. Under an inert atmosphere, 386g (2mol)
Figure GDA0003150506850000134
Dissolving in 1.5L tetrahydrofuran, cooling to-80 deg.C, maintaining constant temperature, dripping into prepared lithium diisopropylamide solution, stirring for 30 min while maintaining the temperature, introducing carbon dioxide into the reaction system, reacting for 1 hr, stopping introducing carbon dioxide, naturally heating, pouring the reaction solution into a mixture of 1L water and 0.5L concentrated hydrochloric acid, separating organic layer, extracting, washing with water, evaporating solvent, recrystallizing with toluene to obtain 308g white crystal
Figure GDA0003150506850000141
The yield thereof was found to be 64%.
b) 200g (0.83mol) of the product obtained in step a)
Figure GDA0003150506850000142
Dissolved in 1.5L toluene, 108g (1mol) of 1, 3-propanedithiol were added, the temperature was raised to 60 ℃ with stirring, and 150g (1mol) of trifluoromethanesulfonic acid (CF) was added dropwise3SO3H) Heating to reflux after adding, dividing water, reflux reacting for 12 hours, cooling, evaporating toluene, adding 1L methyl tert-butyl ether for washing, and suction filtering to obtain 220g product
Figure GDA0003150506850000143
The yield thereof was found to be 58%.
c) 220g (0.48mol) of the product obtained in step b)
Figure GDA0003150506850000144
Dissolving with 1L dichloromethane, cooling to-75 deg.C under the protection of inert gas, and adding 97g (0.96mol) triethylamine and 88g (0.5mol) dropwise
Figure GDA0003150506850000145
After the 1L of dichloromethane solution is added, the reaction is carried out for 1 hour under the condition of heat preservation, 161g (1.44mol) of triethylamine trifluoride is dripped, the reaction is carried out for 30 minutes under the condition of heat preservation, 160g (1.44mol) of Br2 is further dripped, the temperature is naturally raised to-20 ℃ after the reaction is carried out for 30 minutes under the condition of heat preservation, the reaction liquid is poured into 1L of saturated solution of sodium bisulfite, the solution is separated, extracted, washed, filtered by a silica gel column and concentrated, and 42g of product is obtained
Figure GDA0003150506850000146
The yield thereof was found to be 13%.
d) 164g (1mol) of the starting material
Figure GDA0003150506850000147
174g (1mol) of m-bromofluorobenzene, 2L of methylbenzene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction liquid is poured into 2L of water, liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product with ethanol are carried out, thus obtaining the product
Figure GDA0003150506850000151
193g, yield 90%.
e) 214g (1mol) of the product obtained in step d)
Figure GDA0003150506850000152
Dissolving in 2L tetrahydrofuran, charging nitrogen to replace air, cooling to-80 deg.C, dropping 443ml (1.1mol) n-butyl lithium to obtain lithium reagent, dropping 125g (1.2mol) trimethyl borate solution in 500ml tetrahydrofuran to replace lithium, naturally heating to 0 deg.C, pouring into 2L water, adding 200ml concentrated hydrochloric acid, separating liquid, extracting, washing with water, evaporating to obtain 168g product
Figure GDA0003150506850000153
The yield thereof was found to be 65%.
f) 258g (1mol) of the product obtained in step e)
Figure GDA0003150506850000154
And 458g (1.1mol) of the product obtained in step c)
Figure GDA0003150506850000155
3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyst 3g palladium tetratriphenylphosphine are mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, the product is recrystallized by toluene, 467g is obtained
Figure GDA0003150506850000156
The yield thereof was found to be 85%.
Example 2
Preparing a liquid crystal mixture shown in a formula I-2-16, wherein the structural formula is shown as follows,
Figure GDA0003150506850000157
the synthetic route is as follows,
Figure GDA0003150506850000161
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000162
b) Reference example 1 step b) obtained
Figure GDA0003150506850000163
c) Reference example 1 step c) obtained
Figure GDA0003150506850000164
d) 176g (1mol) of the starting material
Figure GDA0003150506850000165
174g (1mol) of m-bromofluorobenzene, 2L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction liquid is poured into 2L of water, liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product by ethanol are carried out, and 203g of the product is obtained
Figure GDA0003150506850000171
The yield thereof was found to be 90%.
e) 226g (1mol) of the product obtained in step d)
Figure GDA0003150506850000172
Dissolving in 2L tetrahydrofuran, charging nitrogen to replace air, cooling to-80 deg.C, dropping 443ml (1.1mol) n-butyl lithium to obtain lithium reagent, dropping 125g (1.2mol) trimethyl borate solution in 500ml tetrahydrofuran to replace lithium, naturally heating to 0 deg.C, pouring into 2L water, adding 200ml concentrated hydrochloric acid, separating liquid, extracting, washing with water, evaporating to dryness to obtain 175g product
Figure GDA0003150506850000173
The yield thereof was found to be 65%.
f) 270g (1mol) of the product obtained in step e)
Figure GDA0003150506850000174
And 458g (1.1mol) from step c)
Figure GDA0003150506850000175
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, and the product is recrystallized by toluene to obtain 477g of product
Figure GDA0003150506850000176
The yield thereof was found to be 85%.
Example 3
Preparing a liquid crystal mixture shown in a formula I-2-18, wherein the structural formula is shown as follows,
Figure GDA0003150506850000177
the synthetic route is as follows,
Figure GDA0003150506850000181
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000182
b) Reference example 1 step b) obtained
Figure GDA0003150506850000183
c) Reference example 1 step c) obtained
Figure GDA0003150506850000184
d) 190g (1mol) of the starting material
Figure GDA0003150506850000185
174g (1mol) of m-bromofluorobenzene, 2L of methylbenzene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction liquid is poured into 2L of water, liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product with ethanol are carried out, and 216g of the product is obtained
Figure GDA0003150506850000191
The yield thereof was found to be 90%.
e) 240g (1mol) of the product obtained in step d)
Figure GDA0003150506850000192
Dissolving in 2L tetrahydrofuran, charging nitrogen to replace air, cooling to-80 deg.C, dropping 443ml (1.1mol) n-butyl lithium to obtain lithium reagent, dropping 125g (1.2mol) trimethyl borate solution in 500ml tetrahydrofuran to replace lithium, naturally heating to 0 deg.C, pouring into 2L water, adding 200ml concentrated hydrochloric acid, separating liquid, extracting, washing with water, evaporating to obtain 184g product
Figure GDA0003150506850000193
The yield thereof was found to be 65%.
f) 184g (1mol) of the product from step e)
Figure GDA0003150506850000194
And 458g (1.1mol) from step c)
Figure GDA0003150506850000195
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, and the product is recrystallized by toluene to obtain 489g of product
Figure GDA0003150506850000196
The yield thereof was found to be 85%.
Example 4
Preparing a liquid crystal mixture shown in a formula I-2-15, wherein the structural formula is shown as follows,
Figure GDA0003150506850000197
the synthetic route is as follows,
Figure GDA0003150506850000201
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000202
b) Reference example 1 step b) obtained
Figure GDA0003150506850000203
c) Reference example 1 step c) obtained
Figure GDA0003150506850000204
d) 176g (1mol) of the starting material
Figure GDA0003150506850000205
174g (1mol) of m-bromofluorobenzene, 2L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction liquid is poured into 2L of water, liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product by ethanol are carried out, and 203g of the product is obtained
Figure GDA0003150506850000211
The yield thereof was found to be 90%.
e) 226g (1mol) of the product obtained in step d)
Figure GDA0003150506850000212
Dissolved in 2L tetrahydrofuranFilling nitrogen to replace air, cooling to-80 ℃, dropwise adding 443ml (1.1mol) of n-butyllithium to obtain a lithium reagent, dropwise adding 125g (1.2mol) of trimethyl borate 500ml tetrahydrofuran solution to replace lithium, naturally heating to 0 ℃, pouring into 2L of water, adding 200ml of concentrated hydrochloric acid, separating, extracting, washing with water, and evaporating to obtain the product
Figure GDA0003150506850000213
175g, yield 65%.
f) 270g (1mol) of the product obtained in step e)
Figure GDA0003150506850000214
And 458g (1.1mol) from step c)
Figure GDA0003150506850000215
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, and the product is recrystallized by toluene to obtain 477g of product
Figure GDA0003150506850000216
The yield thereof was found to be 85%.
Example 5
Preparing a liquid crystal mixture shown as a formula I-2-1-1, wherein the structural formula is shown as follows,
Figure GDA0003150506850000217
the synthetic route is as follows,
Figure GDA0003150506850000221
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000222
b) Reference example 1 step b) obtained
Figure GDA0003150506850000223
c) Reference example 1 step c) obtained
Figure GDA0003150506850000224
d) 170g (1mol) of the starting material
Figure GDA0003150506850000225
174g (1mol) of m-bromofluorobenzene, 2L of methylbenzene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction liquid is poured into 2L of water, liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product by ethanol are carried out, 198g of the product is obtained
Figure GDA0003150506850000231
The yield thereof was found to be 90%.
e) 220g (1mol) of the product obtained in step d)
Figure GDA0003150506850000232
Dissolving in 2L tetrahydrofuran, charging nitrogen to replace air, cooling to-80 deg.C, dropping 443ml (1.1mol) n-butyl lithium to obtain lithium reagent, dropping 125g (1.2mol) trimethyl borate solution in 500ml tetrahydrofuran to replace lithium, naturally heating to 0 deg.C, pouring into 2L water, adding 200ml concentrated hydrochloric acid, separating liquid, extracting, washing with water, evaporating to dryness to obtain 171g product
Figure GDA0003150506850000233
The yield thereof was found to be 65%.
f) 264g (1mol) of the product obtained in step e)
Figure GDA0003150506850000234
And 458g (1.1mol) of the product obtained in step c)
Figure GDA0003150506850000235
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration, and the product is recrystallized by toluene to obtain 472g of product
Figure GDA0003150506850000236
The yield thereof was found to be 85%.
Example 6
Preparing a liquid crystal mixture shown as a formula I-2-5-1, wherein the structural formula is shown as follows,
Figure GDA0003150506850000237
the synthetic route is as follows,
Figure GDA0003150506850000241
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000242
b) Reference example 1 step b) obtained
Figure GDA0003150506850000243
c) 220g (0.48mol) of the product obtained in step 2)
Figure GDA0003150506850000244
Dissolving with 1L dichloromethane, cooling to-75 deg.C under the protection of inert gas, and adding 97g (0.96mol) triethylamine and 121g (0.5mol) dropwise
Figure GDA0003150506850000245
1L of dichloromethane solution, and after the addition, the reaction is carried out by heat preservation1 hour, 161g (1.44mol) of triethylamine trihydrofluoride is added dropwise, the reaction is carried out for 30 minutes after the dropwise addition, and 160g (1.44mol) of Br is added dropwise2After dropping and reacting for 30 minutes under the condition of heat preservation, naturally heating to-20 ℃, pouring the reaction solution into 1L of saturated solution of sodium bisulfite, separating, extracting, washing with water, passing through a silica gel column, and concentrating to obtain 44g of the product (6-a) with the yield of 19%.
d) Reference example 1 step d) obtained
Figure GDA0003150506850000251
e) Reference example 1 step e) obtained
Figure GDA0003150506850000252
f) 258g (1mol) of the product obtained in step e)
Figure GDA0003150506850000253
And 530g (1.1mol) of the product (6-a) obtained in the step c), 3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed to carry out SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing, concentration and recrystallization of the product with toluene to obtain 524g of the product
Figure GDA0003150506850000254
The yield thereof was found to be 85%.
Example 7
Preparing a liquid crystal mixture shown as a formula I-2-7-1, wherein the structural formula is shown as follows,
Figure GDA0003150506850000255
the synthetic route is as follows,
Figure GDA0003150506850000261
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000262
b) Reference example 1 step b) obtained
Figure GDA0003150506850000263
c) 220g (0.48mol) of the product obtained in step b)
Figure GDA0003150506850000264
Dissolving with 1L dichloromethane, cooling to-75 deg.C under the protection of inert gas, and adding 97g (0.96mol) triethylamine and 113g (0.5mol) dropwise
Figure GDA0003150506850000265
After the completion of the addition, the reaction was carried out for 1 hour with keeping warm, 161g (1.44mol) of triethylamine trihydrofluoride was added dropwise thereto, the reaction was carried out for 30 minutes with keeping warm, and 160g (1.44mol) of Br was added dropwise thereto2After dropping and keeping the temperature for reaction for 30 minutes, naturally heating to-20 ℃, pouring the reaction solution into 1L of saturated solution of sodium bisulfite, separating, extracting, washing with water, passing through a silica gel column, and concentrating to obtain 38g of product
Figure GDA0003150506850000271
The yield thereof was found to be 17%.
d) Reference example 1 step d) obtained
Figure GDA0003150506850000272
e) Reference example 1 step e) obtained
Figure GDA0003150506850000273
f) 258g (1mol) of the product of step e)
Figure GDA0003150506850000274
And 512g (1.1mol) of product from step c)
Figure GDA0003150506850000275
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, and the product is recrystallized by toluene to obtain 510g of the product
Figure GDA0003150506850000276
The yield thereof was found to be 85%.
Example 8
Preparing a liquid crystal mixture shown as a formula I-1-2-1, wherein the structural formula is shown as follows,
Figure GDA0003150506850000277
the synthetic route is as follows,
Figure GDA0003150506850000281
specifically comprises six steps from a to f,
a) reference example 1 step a) obtained
Figure GDA0003150506850000282
b) Reference example 1 step b) obtained
Figure GDA0003150506850000283
c) Reference example 1 step c) obtained
Figure GDA0003150506850000284
f) 458g (1.0mol) of the product from step c)
Figure GDA0003150506850000285
180g(1.1mol)
Figure GDA0003150506850000286
3L of toluene, 500ml of ethanol, 1.5L of water, 159g (1.5mol) of sodium carbonate and 3g of palladium tetratriphenylphosphine as a catalyst are uniformly mixed, heated and refluxed for SUZUKI reaction for 4 hours, then the reaction solution is poured into 2L of water for liquid separation, extraction, water washing, silica gel column passing and concentration are carried out, the product is recrystallized by toluene, and 387g of product is obtained
Figure GDA0003150506850000291
The yield thereof was found to be 85%.
The performance parameters of the liquid crystal compounds prepared in examples 1 to 8 are shown in the following table.
Figure GDA0003150506850000292
Figure GDA0003150506850000301
Example 9
A liquid crystal composition M1 was prepared in accordance with the following mass ratios of the respective components.
According to the mass ratio of 25:75 between the component B and the component C, 25 parts of the liquid crystal compound shown in the general formula II is used for forming the component B, and the compound shown in the general formula III is used for forming the component C, so that the liquid crystal composition M1 is prepared.
Figure GDA0003150506850000302
Figure GDA0003150506850000311
Example 10
A liquid crystal composition a was prepared in the following mass ratios of the respective components.
Figure GDA0003150506850000312
Figure GDA0003150506850000321
Example 11
Preparing a liquid crystal composition b according to the following mass ratio of the components
Figure GDA0003150506850000322
The results of the performance tests of the liquid crystal compositions of examples 9 to 11 are shown in the following table.
Figure GDA0003150506850000323
Figure GDA0003150506850000331
As can be seen from examples 9 to 11, the compounds represented by the general formula I are added into the liquid crystal composition, so that the dielectric anisotropy delta epsilon of the liquid crystal composition is increased, and the rotational viscosity gamma of the mixture is reduced1And the contrast change is small at low temperature.

Claims (7)

1. A liquid crystal compound comprising a dimethylbenzene and a difluoromethyleneoxy linkage, characterized in that: the structural formula of the compound is shown as follows,
Figure FDA0003152793520000011
2. a liquid crystal composition comprising a liquid crystal compound having a dimethylbenzene and a difluoromethyleneoxy linking group, wherein: the liquid crystal composition comprises a compound as shown in claim 1 as a component A, a component B consisting of one or two compounds shown in a general formula II, and a component C consisting of a compound III-1 and three to ten compounds shown in a general formula III, wherein the mass ratio of the component A to the component B to the component C is 1-40: 5-40: 5 to 80 parts of a first resin,
Figure FDA0003152793520000012
wherein the content of the first and second substances,
R1、R2any one selected from linear alkyl with 1-6 carbon atoms and linear alkenyl with 2-6 carbon atoms;
R3any one selected from H, F and straight-chain alkyl groups with 1-6 carbon atoms;
Figure FDA0003152793520000013
any one selected from the group consisting of 1, 4-cyclohexylene, 1, 4-phenylene and fluoro-1, 4-phenylene;
p is 2 or 3;
(F) represents H or F.
3. The liquid crystal composition of claim 2, wherein the liquid crystal compound comprises a dimethylbenzene and a difluoromethyleneoxy linkage: the compounds shown in the general formula II are specifically compounds shown in formulas II-1 to II-9,
Figure FDA0003152793520000021
4. the liquid crystal composition of claim 2, wherein the liquid crystal compound comprises a dimethylbenzene and a difluoromethyleneoxy linkage:
the compound shown in the general formula III is specifically a compound shown in a formula III-3 to a formula III-10,
Figure FDA0003152793520000022
Figure FDA0003152793520000031
5. the liquid crystal composition of claim 2, wherein the liquid crystal compound comprises a dimethylbenzene and a difluoromethyleneoxy linkage: the mass ratio of the component A, the component B and the component C in the liquid crystal composition is 10-35: 15-35: 25 to 75.
6. The liquid crystal composition of claim 2, wherein the liquid crystal compound comprises a dimethylbenzene and a difluoromethyleneoxy linkage: the liquid crystal composition comprises the following components:
Figure FDA0003152793520000032
Figure FDA0003152793520000041
。
7. the liquid crystal composition comprising a liquid crystal compound having a xylene and difluoromethyleneoxy linkage as claimed in claim 5, wherein: the liquid crystal composition further comprises an additive which accounts for not more than 0.05 percent of the weight of the liquid crystal composition, and the additive is at least one of an antioxidant, an anti-ultraviolet agent and a chiral agent.
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含氟三环类液晶单体的介晶性研究;李娟利等;《液晶与显示》;20090215;第24卷(第1期);第9-14页 *

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