CN105131972A - Liquid crystal compound containing dimethylbenzene and difluoro methyleneoxy linking group and preparing method and application thereof - Google Patents

Liquid crystal compound containing dimethylbenzene and difluoro methyleneoxy linking group and preparing method and application thereof Download PDF

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CN105131972A
CN105131972A CN201510555389.0A CN201510555389A CN105131972A CN 105131972 A CN105131972 A CN 105131972A CN 201510555389 A CN201510555389 A CN 201510555389A CN 105131972 A CN105131972 A CN 105131972A
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liquid
obtains
difluoro
linking group
liquid crystal
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CN105131972B (en
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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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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
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    • C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
    • C09K2019/0429—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being a carbocyclic or heterocyclic discotic unit
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    • C09K2019/0444—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
    • 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 a difluoro methyleneoxy linking group and a preparing method and application thereof. The compound is shown as the formula I. According to the molecular structure of the compound in the formula I, the liquid crystal compound containing the dimethylbenzene and the difluoro methyleneoxy (-CF2O-) linking group is high in dielectric anisotropy and has high response speed and a high clearing point more importantly, and the performance is of great significance in liquid crystal compound blending.

Description

Liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro and preparation method thereof and application
Technical field
The present invention relates to the preparations and applicatio field of liquid crystalline cpd, be specifically related to a kind of liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro and preparation method thereof and application.
Background technology
At present, it is more and more wider that the range of application of liquid crystalline cpd is expanded, and it can be applicable in polytype indicating meter, electro-optical device, sensor.For liquid crystalline cpd of a great variety in above-mentioned display field, wherein nematic liquid crystal is most widely used.Nematic liquid crystal has been applied in passive TN, STN matrix display and has had in the system of tft active matrix.
For thin-film transistor technologies (TFT-LCD) Application Areas, although market is very huge in recent years, technology is also ripe gradually, people to the requirement of technique of display also in continuous raising, especially in realization response fast, driving voltage is reduced to reduce the aspects such as power consumption.Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.
As liquid crystal material, need to have good chemistry and thermostability and the stability to electric field and electromagnetic radiation.And as thin-film transistor technologies (TFT-LCD) liquid crystal material, not only need to have as outside upward stability, also should have the performances such as wider nematic temperature range, suitable degree of birefringence anisotropy, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate and low-steam pressure.
For dynamic menu display application, as LCD TV, in order to realize high-quality display, eliminating display frame ghost and hangover, requiring that liquid crystal has very fast response speed, therefore require that liquid crystal has lower rotary viscosity γ 1; In addition, in order to reduce equipment energy consumption, wish that the driving voltage of liquid crystal is low as far as possible, so the dielectric anisotropy Δ ε improving liquid crystal is significant to mixed liquid crystal.
Large quantity research shows, liquid crystal molecule introduces sub-the methoxyl group (-CF of a difluoro 2o-), after linking group, the rotary viscosity γ of liquid crystal can be made 1decrease.In addition due to sub-the methoxyl group (-CF of difluoro 2o-) contribution of the moment of dipole of bridge, the moment of dipole of end group fluorine atom is also improved to some extent, thus the dielectric anisotropy Δ ε of liquid crystal molecule is increased to some extent.What Merck KGaA and Japanese Chisso Corporation (CN1717468A, CN101143808A, CN101157862A etc.) had disclosed that some have a different substituents has the sub-methoxyl group linking group of difluoro (-CF 2o-) liquid crystalline cpd.But (-CF 2o-) introducing of group can make the clearing point of liquid crystal significantly reduce.The high clearing point compound adding viscosity larger is needed to balance (-CF when allocating liquid crystal compound 2o-) clearing point that group causes declines, thus constrains the space of liquid crystal compound response speed lifting.
Liquid crystal is as the Core Feature material of liquid crystal display device, in order to meet the requirement of the various performance perameters of liquid crystal display device, in order to adapt to the processing requirement of liquid crystal display device, liquid crystal material is needed to have multiple performance perameter widely, and any one monomeric liquid crystal material all can not meet all these requirements, therefore need the monomer liquid crystal that synthesis performance is different, met the characteristic of LCD device requirement by the method for allocating mixed liquid crystal.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro and preparation method thereof and application, the problem that the clearing point existed to improve the existing liquid crystalline cpd with the sub-methoxyl group of difluoro declines, promotes the response speed of liquid crystal compound.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
Liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro, the structural formula of described compound as shown in general formula I,
Wherein,
be selected from any one in group;
X 1, X 2, X 3be selected from H, F, Cl, CF 3, CHF 2, OCF 3and OCHF 2in any one;
R 1be selected from carbon atom be 1 ~ 6 straight chained alkyl, carbonatoms be 2 ~ 6 straight-chain alkenyl, carbonatoms be any one in the cycloalkyl of 3 ~ 6;
M is selected from 0 or 1;
N is selected from 1 or 2.
The further improvement of technical solution of the present invention is: shown in described general formula I, compound is specially the compound shown in formula I-1 to I-4,
The further improvement of technical solution of the present invention is:
Shown in described general formula I, compound is specially the compound shown in formula I-1-1 to I-4-2,
Technical scheme of the present invention also discloses the preparation method of the liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro,
The synthetic route of compound shown in described general formula I is,
Specifically comprise the following steps a ~ step f totally six steps,
A) in an inert atmosphere, will be dissolved in after being cooled to-30 DEG C in tetrahydrofuran (THF) and add n-Butyl Lithium, drip rear insulated and stirred 30 minutes, obtain lithium diisopropylamine, for subsequent use.In an inert atmosphere, will be dissolved in tetrahydrofuran (THF) the lithium diisopropylamine being cooled to and keeping constant temperature to be added dropwise to after-80 DEG C preparing, drip rear insulated and stirred 30 minutes, maintain the temperature in reaction system and pass into carbonic acid gas, react 1 hour, stop logical carbonic acid gas, naturally heat up, reaction solution is poured in the mixed solution of water and hydrochloric acid, separate organic layer, extraction, washing, steams neat solvent, the product re crystallization from toluene obtained, obtains white crystal
B) by step a) gained be dissolved in toluene, add 1,3-dimercaptopropane, be warming up to 60 DEG C under stirring, drip trifluoromethanesulfonic acid, be warming up to backflow after adding, point water, back flow reaction 12 hours, cooling, evaporate to dryness toluene, adds methyl tertiary butyl ether and washes, suction strainer, obtain product
C) by step b) gained dissolve with methylene dichloride, protection of inert gas borehole cooling to-75 DEG C, drip triethylamine and dichloromethane solution, add rear insulation reaction 1 hour, drip trihydrofluoride triethylamine, drip off insulation reaction 30 minutes, then be added dropwise to Br 2, drip off insulation reaction and be naturally warming up to-20 DEG C after 30 minutes, reaction solution is poured in the saturated solution of sodium bisulfite, separatory, extraction, and silicagel column is crossed in washing, concentrated, obtains
D) will m-bromofluorobenzene, toluene, ethanol, water, sodium carbonate and catalyzer tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, and reaction solution is poured into water, separatory, extraction, and silicagel column is crossed in washing, and concentrated, product ethyl alcohol recrystallization, obtains
E) by steps d) gained be dissolved in tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drips n-Butyl Lithium lithium generation, obtains lithium reagent, the tetrahydrofuran solution dripping trimethyl borate after adding again replaces lithium, after being naturally warming up to 0 DEG C, is poured into water, adds hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains
F) by step e) gained with step c) gained toluene, ethanol, water, sodium carbonate and catalyzer tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, and reaction solution is poured into water, separatory, extraction, and silicagel column is crossed in washing, and concentrated, product re crystallization from toluene, obtains
Technical scheme of the present invention further discloses the liquid-crystal composition of the liquid crystalline cpd composition containing the sub-methoxyl group linking group of dimethyl benzene and difluoro, it is characterized in that: described liquid-crystal composition comprises the component A be made up of compound shown in general formula I, the B component be made up of one or both compounds shown in general formula I I, the component C be made up of three to ten kinds of compounds shown in general formula III, the mass ratio of described component A, B component, component C is 1 ~ 40: 5 ~ 40: 5 ~ 80
Wherein,
R 1, R 2be selected from carbonatoms be 1 ~ 6 straight chained alkyl, carbonatoms be any one in the straight-chain alkenyl of 2 ~ 6;
R 3be selected from H, F, carbonatoms is any one in the straight chained alkyl of 1 ~ 6;
be selected from Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene any one or a few;
P is 2 or 3;
(F) H or F is represented.
The further improvement of technical solution of the present invention is: the compound shown in described general formula I I is specially the compound shown in formula II-1 to formula II-9,
The further improvement of technical solution of the present invention is: the compound shown in described general formula III is specially the compound shown in formula III-1 to formula III-10,
The further improvement of technical solution of the present invention is: in described liquid-crystal composition, the mass ratio of component A, B component, component C is 10 ~ 35: 15 ~ 35: 25 ~ 75.
The further improvement of technical solution of the present invention is: also comprise the additive that the weight percentage accounting for liquid-crystal composition is not more than 0.05% in described liquid-crystal composition, and described additive is at least one in antioxidant, anti ultraviolet agent, chiral agent.
Owing to have employed technique scheme, the technical progress that the present invention obtains is:
The liquid crystalline cpd containing dimethyl benzene and the sub-methoxyl group linking group of difluoro of the present invention, has wider range of application.The base mateiral of liquid crystal compound can be used as, in the middle of the liquid crystal base mateiral that the compound that also likely can add other types to as adding material forms, such as, improve the parameter such as the contrast gradient under dielectric anisotropy Δ ε, the rotary viscosity γ 1 of liquid crystal compound, threshold voltage vt h, low temperature, optical anisotropy Δ n, clearing point Cp.
The rotary viscosity γ of the response speed t of liquid-crystal composition and the thickness d of liquid crystal cell, liquid crystal 1meet t ∝ γ 1d 2relation, therefore there is lower rotary viscosity γ 1its time of response of liquid crystal shorter.And in formula I molecular structure provided by the invention, containing dimethyl benzene and sub-the methoxyl group (-CF of difluoro 2o-) liquid crystalline cpd of linking group, not only has larger dielectric anisotropy Δ ε, the more important thing is to have response speed t, lower rotary viscosity γ faster simultaneously 1with good low-temperature performance, for allotment liquid crystal compound, this performance has great importance.
Shown in pure general formula I, compound is colourless, and shows higher to light, heat, chemical stability.Especially compounds exhibit shown in formula I has gone out large dielectric anisotropy Δ ε and good low-temperature performance as the response speed under low temperature and contrast gradient, and also there is the advantage suppressing to form smectic phase, this liquid crystal compound showing to employ compound shown in formula I has good low-temperature storage stability.
The dimethyl benzene and the sub-liquid crystalline cpd of methoxyl group linking group of difluoro and the liquid-crystal composition of composition thereof of containing provided by the invention is preparing the application in liquid crystal display device material or electro-optical display part material; and comprise containing the sub-liquid crystalline cpd of methoxyl group linking group of dimethyl benzene and difluoro or the liquid crystal display device material of liquid-crystal composition or electro-optical display part material, also belong to protection scope of the present invention.
Embodiment
The invention discloses the liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro, the structural formula of described compound as shown in general formula I,
Wherein,
be selected from any one in group;
X 1, X 2, X 3be selected from H, F, Cl, CF 3, CHF 2, OCF 3and OCHF 2in any one;
R 1be selected from carbon atom be 1 ~ 6 straight chained alkyl, carbonatoms be 2 ~ 6 straight-chain alkenyl, carbonatoms be any one in the cycloalkyl of 3 ~ 6;
M is selected from 0 or 1;
N is selected from 1 or 2.
Particularly, compound shown in general formula I is specially the compound shown in formula I-1 to I-4,
The preparation method also disclosing liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro of the present invention,
The synthetic route of compound shown in general formula I is,
The present invention further discloses the liquid-crystal composition of the liquid crystalline cpd composition containing the sub-methoxyl group linking group of dimethyl benzene and difluoro, liquid-crystal composition comprises the component A be made up of compound shown in general formula I, the B component be made up of one or both compounds shown in general formula I I, the component C be made up of three to ten kinds of compounds shown in general formula III, the mass ratio of described component A, B component, component C is 1 ~ 40: 5 ~ 40: 5 ~ 80
Wherein,
R 1, R 2be selected from carbonatoms be 1 ~ 6 straight chained alkyl, carbonatoms be any one in the straight-chain alkenyl of 2 ~ 6;
R 3be selected from H, F, carbonatoms is any one in the straight chained alkyl of 1 ~ 6;
be selected from Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene any one or a few;
P is 2 or 3;
(F) H or F is represented.
Preferably, the mass ratio of described component A, B component, component C is 10 ~ 35: 15 ~ 35: 25 ~ 75.More preferably the mass ratio of described component A, B component, component C is 5 ~ 10: 25: 75, and the mass ratio of described component A, B component, component C is for being specially 5: 25: 75 or 10: 25: 75.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
The concrete meaning of the symbol in embodiment and test condition as follows:
Cp: unit DEG C, represents the clearing point of liquid crystal.
S-N: unit DEG C, represents that the crystalline state of liquid crystal is to nematic fusing point.
Δ n: optical anisotropy, Δ n=no-ne, wherein, no is the specific refractory power of ordinary light, and ne is the specific refractory power of extraordinary ray, and test condition is, 589nm, 25 ± 0.5 DEG C.
Δ ε: dielectric anisotropy, Δ ε=ε ∥-ε ⊥, wherein, ε ∥for being parallel to the specific inductivity of molecular axis, ε ⊥for the specific inductivity perpendicular to molecular axis, test condition is 25 ± 0.5 DEG C; 1KHz; HP4284A; 5.2 the left-handed box of micron TN.
γ 1: rotary viscosity, unit mpas, test condition is 25 ± 0.5 DEG C.
VHR: voltage retention (%), test condition is 20 ± 2 DEG C, voltage is ± 5V, pulse width is 10ms, voltage hold-time 16.7ms.Testing apparatus is TOYOModel6254 liquid crystal property comprehensive tester.
Contrast gradient is liquid-crystal display on state of and the ratio of dark-state, its measuring method is as follows: liquid crystal is poured into liquid crystal cell, paste polaroid, normal white mode, according to the threshold voltage determination driving voltage of liquid crystal, then draws wire by the liquid crystal cell posted, test under constant backlight, to liquid crystal cell not making alive test on state of light intensity, making alive test dark-state light intensity, on state of is contrast gradient with the ratio of dark-state light intensity.
Contrast gradient × 100 (%) under normal temperature low temperature contrast gradient velocity of variation (%)=(under normal temperature under contrast gradient-low temperature contrast gradient)/normal temperature, normal temperature is 25 DEG C, and low temperature is-20 DEG C.
Cp represents clearing point, and this clearing point can directly measure and obtain, and for the compound that cannot directly measure, can calculate its fitting data as follows:
Due in the modulation process of mixed liquid crystal, by selecting multiple and suitable monomer liquid crystal allotment mixing, can eutectic mixture be formed, effectively reduce the fusing point of liquid crystal; Simultaneously by adding the monomer liquid crystal of high clearing point, can improve the clearing point of mixed liquid crystal, thus modulate the mixed liquid crystal that nematic temperature range meets the demands, the clearing point of mixed liquid crystal and monomer liquid crystal and concentration meet following relational expression:
Tc＝∑X iT i
Wherein, Tc represents the clearing point of mixed liquid crystal, X irepresent the concentration of monomer liquid crystal in mixed liquid crystal, T irepresent the clearing point of monomer liquid crystal.
Embodiment 1 ~ 8 is the preparation embodiment of liquid crystalline cpd.Reaction process is generally by the process of TLC monitoring reaction, the aftertreatment that reaction terminates is generally washing, extract, merge dry after organic phase, the lower steaming of decompression desolventizes, and recrystallization, column chromatography, those skilled in the art can both realize the present invention according to description below.
Embodiment 1
Liquid crystal compound shown in preparation formula I-2-14, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) in an inert atmosphere, by 242.4g (2.4mol) raw material be dissolved in 1L tetrahydrofuran (THF), after being cooled to-30 DEG C, be added dropwise to 960ml n-Butyl Lithium, drip rear insulated and stirred 30 minutes, for subsequent use.In an inert atmosphere, by 386g (2mol) be dissolved in after being cooled to-80 DEG C in 1.5L tetrahydrofuran (THF), keep constant temperature to be added dropwise to the lithium diisopropylamine solution prepared, drip rear insulated and stirred 30 minutes, maintain the temperature in reaction system and pass into carbonic acid gas, react 1 hour, stop logical carbonic acid gas, naturally heat up, reaction solution is poured in the mixed solution of 1L water and 0.5L concentrated hydrochloric acid, separate organic layer, extraction, washing, steam neat solvent, the product re crystallization from toluene obtained, obtains 308g white crystal yield 64%.
B) by step a) gained 200g (0.83mol) product be dissolved in 1.5L toluene, add 108g (1mol) 1,3-dimercaptopropane, under stirring, be warming up to 60 DEG C, drip 150g (1mol) trifluoromethanesulfonic acid (CF 3sO 3h), be warming up to backflow after adding, point water, back flow reaction 12 hours, cooling, evaporate to dryness toluene, adds 1L methyl tertiary butyl ether and washes, suction strainer, obtain 220g product yield 58%.
C) by step b) gained 220g (0.48mol) product dissolve with 1L methylene dichloride, protection of inert gas borehole cooling, to-75 DEG C, drips 97g (0.96mol) triethylamine and 88g (0.5mol) 1L dichloromethane solution, add rear insulation reaction 1 hour, drip 161g (1.44mol) trihydrofluoride triethylamine, drip off insulation reaction 30 minutes, be added dropwise to 160g (1.44mol) Br2 again, drip off insulation reaction and be naturally warming up to-20 DEG C after 30 minutes, reaction solution is poured in the saturated solution of 1L sodium bisulfite, separatory, extraction, washing, crosses silicagel column, concentrated, obtain 42g product yield 13%.
D) by 164g (1mol) raw material 174g (1mol) m-bromofluorobenzene, 2L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product ethyl alcohol recrystallization, obtains product 193g, yield 90%.
E) by steps d) 214g (1mol) product that obtains be dissolved in 2L tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drip 443ml (1.1mol) n-Butyl Lithium lithium generation, obtain lithium reagent, the 500ml tetrahydrofuran solution dripping 125g (1.2mol) trimethyl borate after adding again replaces lithium, naturally after being warming up to 0 DEG C, pour in 2L water, add 200ml concentrated hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains 168g product yield 65%.
F) by step e) 258g (1mol) product that obtains with step c) 458g (1.1mol) product that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 467g yield 85%.
Embodiment 2
Liquid crystal compound shown in preparation formula I-2-16, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) reference example 1 step c) obtain
D) by 176g (1mol) raw material 174g (1mol) m-bromofluorobenzene, 2L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product ethyl alcohol recrystallization, obtains 203g product yield 90%.
E) by steps d) 226g (1mol) product that obtains be dissolved in 2L tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drip 443ml (1.1mol) n-Butyl Lithium lithium generation, obtain lithium reagent, the 500ml tetrahydrofuran solution dripping 125g (1.2mol) trimethyl borate after adding again replaces lithium, naturally after being warming up to 0 DEG C, pour in 2L water, add 200ml concentrated hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains 175g product yield 65%.
F) by step e) 270g (1mol) product that obtains with step c) 458g (1.1mol) that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 477g product yield 85%.
Embodiment 3
Liquid crystal compound shown in preparation formula I-2-18, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) reference example 1 step c) obtain
D) by 190g (1mol) raw material 174g (1mol) m-bromofluorobenzene, 2L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product ethyl alcohol recrystallization, obtains 216g product yield 90%.
E) by steps d) 240g (1mol) product that obtains be dissolved in 2L tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drip 443ml (1.1mol) n-Butyl Lithium lithium generation, obtain lithium reagent, the 500ml tetrahydrofuran solution dripping 125g (1.2mol) trimethyl borate after adding again replaces lithium, naturally after being warming up to 0 DEG C, pour in 2L water, add 200ml concentrated hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains 184g product yield 65%.
F) by step e) 184g (1mol) product that obtains with step c) 458g (1.1mol) that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 489g product yield 85%.
Embodiment 4
Liquid crystal compound shown in preparation formula I-2-15, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) reference example 1 step c) obtain
D) by 176g (1mol) raw material 174g (1mol) m-bromofluorobenzene, 2L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product ethyl alcohol recrystallization, obtains 203g product yield 90%.
E) by steps d) 226g (1mol) product that obtains be dissolved in 2L tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drip 443ml (1.1mol) n-Butyl Lithium lithium generation, obtain lithium reagent, the 500ml tetrahydrofuran solution dripping 125g (1.2mol) trimethyl borate after adding again replaces lithium, naturally after being warming up to 0 DEG C, pour in 2L water, add 200ml concentrated hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains product 175g, yield 65%.
F) by step e) 270g (1mol) product that obtains with step c) 458g (1.1mol) that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 477g product yield 85%.
Embodiment 5
Liquid crystal compound shown in preparation formula I-2-1-1, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) reference example 1 step c) obtain
D) by 170g (1mol) raw material 174g (1mol) m-bromofluorobenzene, 2L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product ethyl alcohol recrystallization, obtains 198g product yield 90%.
E) by steps d) 220g (1mol) product that obtains be dissolved in 2L tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drip 443ml (1.1mol) n-Butyl Lithium lithium generation, obtain lithium reagent, the 500ml tetrahydrofuran solution dripping 125g (1.2mol) trimethyl borate after adding again replaces lithium, naturally after being warming up to 0 DEG C, pour in 2L water, add 200ml concentrated hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains 171g product yield 65%.
F) by step e) 264g (1mol) product that obtains with step c) 458g (1.1mol) product that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 472g product yield 85%.
Embodiment 6
Liquid crystal compound shown in preparation formula I-2-5-1, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) by step 2) gained 220g (0.48mol) product dissolve with 1L methylene dichloride, protection of inert gas borehole cooling, to-75 DEG C, drips 97g (0.96mol) triethylamine and 121g (0.5mol) 1L dichloromethane solution, add rear insulation reaction 1 hour, drip 161g (1.44mol) trihydrofluoride triethylamine, drip off insulation reaction 30 minutes, then be added dropwise to 160g (1.44mol) Br 2, drip off insulation reaction and be naturally warming up to-20 DEG C after 30 minutes, reaction solution is poured in the saturated solution of 1L sodium bisulfite, separatory, extraction, and silicagel column is crossed in washing, concentrated, obtains product (6-a) 44g, yield 19%.
D) reference example 1 steps d) obtain
E) reference example 1 step e) obtain
F) by step e) 258g (1mol) product that obtains with step c) 530g (1.1mol) product (6-a), 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and the catalyzer 3g tetra-triphenylphosphine palladium that obtain mixing reflux carries out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 524g product yield 85%.
Embodiment 7
Liquid crystal compound shown in preparation formula I-2-7-1, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) by step b) gained 220g (0.48mol) product dissolve with 1L methylene dichloride, protection of inert gas borehole cooling, to-75 DEG C, drips 97g (0.96mol) triethylamine and 113g (0.5mol) 1L dichloromethane solution, add rear insulation reaction 1 hour, drip 161g (1.44mol) trihydrofluoride triethylamine, drip off insulation reaction 30 minutes, then be added dropwise to 160g (1.44mol) Br 2, drip off insulation reaction and naturally heat up-20 DEG C after 30 minutes, reaction solution is poured in the saturated solution of 1L sodium bisulfite, separatory, extraction, and silicagel column is crossed in washing, concentrated, obtains 38g product yield 17%.
D) reference example 1 steps d) obtain
E) reference example 1 step e) obtain
F) by step e) 258g (1mol) that obtains with step c) 512g (1.1mol) product that obtains 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 510g product yield 85%.
Embodiment 8
Liquid crystal compound shown in preparation formula I-1-2-1, structural formula is as follows,
Synthetic route is,
Specifically comprise the following steps a ~ step f totally six steps,
A) reference example 1 step a) obtains
B) reference example 1 step b) obtain
C) reference example 1 step c) obtain
F) by step c) 458g (1.0mol) product that obtains 180g (1.1mol) 3L toluene, 500ml ethanol, 1.5L water, 159g (1.5mol) sodium carbonate and catalyzer 3g tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, reaction solution is poured in 2L water, separatory, extraction, washing, crosses silicagel column, concentrated, product re crystallization from toluene, obtains 387g product yield 85%.
The performance perameter of the liquid crystalline cpd that embodiment 1 ~ 8 is prepared is as shown in the table.
Embodiment 9
According to the mass ratio of following ingredients, prepare liquid-crystal composition M1.
According to the mass ratio 25: 75 between B component and component C, with the composition of liquid crystalline cpd shown in 25 parts of general formula I I B component, with the composition of compound shown in the general formula III of following mass fraction component C, prepare liquid-crystal composition M1.
Embodiment 10
According to the mass ratio of following ingredients, prepare liquid-crystal composition a.
Embodiment 11
According to the mass ratio of following ingredients, prepare liquid-crystal composition b
The performance test results of the liquid-crystal composition in embodiment 9 ~ 11 is as shown in the table.
Liquid-crystal composition Δn Δε Cp γ 1
M1 0.100 10.6 95 130
a 0.102 11.1 100 125
b 0.101 11.0 101 123
As can be seen from embodiment 9 ~ 11, compound shown in general formula I adds in liquid-crystal composition, has and strengthens liquid-crystal composition dielectric anisotropy Δ ε, reduction mixture rotary viscosity γ 1, contrast gradient change is less under low temperature feature.

Claims (9)

1. the liquid crystalline cpd containing the sub-methoxyl group linking group of dimethyl benzene and difluoro, is characterized in that: the structural formula of described compound as shown in general formula I,
Wherein,
be selected from any one in group;
X 1, X 2, X 3be selected from H, F, Cl, CF 3, CHF 2, OCF 3and OCHF 2in any one;
R 1be selected from carbon atom be 1 ~ 6 straight chained alkyl, carbonatoms be 2 ~ 6 straight-chain alkenyl, carbonatoms be any one in the cycloalkyl of 3 ~ 6;
M is selected from 0 or 1;
N is selected from 1 or 2.
2. the liquid crystalline cpd containing dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 1, is characterized in that: shown in described general formula I, compound is specially the compound shown in formula I-1 to I-4,
3. the liquid crystalline cpd containing dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 1, is characterized in that:
Shown in described general formula I, compound is specially the compound shown in formula I-1-1 to I-4-2,
4. contain the preparation method of the liquid crystalline cpd of dimethyl benzene and the sub-methoxyl group linking group of difluoro, it is characterized in that:
The synthetic route of compound shown in described general formula I is,
Specifically comprise the following steps a ~ step f totally six steps,
A) in an inert atmosphere, will be dissolved in after being cooled to-30 DEG C in tetrahydrofuran (THF) and add n-Butyl Lithium, drip rear insulated and stirred 30 minutes, obtain lithium diisopropylamine, for subsequent use.In an inert atmosphere, will be dissolved in tetrahydrofuran (THF) the lithium diisopropylamine being cooled to and keeping constant temperature to be added dropwise to after-80 DEG C preparing, drip rear insulated and stirred 30 minutes, maintain the temperature in reaction system and pass into carbonic acid gas, react 1 hour, stop logical carbonic acid gas, naturally heat up, reaction solution is poured in the mixed solution of water and hydrochloric acid, separate organic layer, extraction, washing, steams neat solvent, the product re crystallization from toluene obtained, obtains white crystal
B) by step a) gained be dissolved in toluene, add 1,3-dimercaptopropane, be warming up to 60 DEG C under stirring, drip trifluoromethanesulfonic acid, be warming up to backflow after adding, point water, back flow reaction 12 hours, cooling, evaporate to dryness toluene, adds methyl tertiary butyl ether and washes, suction strainer, obtain product
C) by step b) gained dissolve with methylene dichloride, protection of inert gas borehole cooling to-75 DEG C, drip triethylamine and dichloromethane solution, add rear insulation reaction 1 hour, drip trihydrofluoride triethylamine, drip off insulation reaction 30 minutes, then be added dropwise to Br 2, drip off insulation reaction and be naturally warming up to-20 DEG C after 30 minutes, reaction solution is poured in the saturated solution of sodium bisulfite, separatory, extraction, and silicagel column is crossed in washing, concentrated, obtains
D) will m-bromofluorobenzene, toluene, ethanol, water, sodium carbonate and catalyzer tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, and reaction solution is poured into water, separatory, extraction, and silicagel column is crossed in washing, and concentrated, product ethyl alcohol recrystallization, obtains
E) by steps d) gained be dissolved in tetrahydrofuran (THF), inflated with nitrogen displaced air, is cooled to-80 DEG C, drips n-Butyl Lithium lithium generation, obtains lithium reagent, the tetrahydrofuran solution dripping trimethyl borate after adding again replaces lithium, after being naturally warming up to 0 DEG C, is poured into water, adds hydrochloric acid, separatory, extraction, washing, evaporate to dryness, obtains
F) by step e) gained with step c) gained toluene, ethanol, water, sodium carbonate and catalyzer tetra-triphenylphosphine palladium mixing reflux is carried out after SUZUKI reacts 4 hours, and reaction solution is poured into water, separatory, extraction, and silicagel column is crossed in washing, and concentrated, product re crystallization from toluene, obtains
5. contain the liquid-crystal composition of the liquid crystalline cpd composition of dimethyl benzene and the sub-methoxyl group linking group of difluoro, it is characterized in that: described liquid-crystal composition comprises the component A be made up of compound shown in general formula I, the B component be made up of one or both compounds shown in general formula I I, the component C be made up of three to ten kinds of compounds shown in general formula III, the mass ratio of described component A, B component, component C is 1 ~ 40: 5 ~ 40: 5 ~ 80
Wherein,
R 1, R 2be selected from carbonatoms be 1 ~ 6 straight chained alkyl, carbonatoms be any one in the straight-chain alkenyl of 2 ~ 6;
R 3be selected from H, F, carbonatoms is any one in the straight chained alkyl of 1 ~ 6;
be selected from Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene any one;
P is 2 or 3;
(F) H or F is represented.
6. the liquid-crystal composition containing the liquid crystalline cpd composition of dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 5, is characterized in that: the compound shown in described general formula I I is specially the compound shown in formula II-1 to formula II-9,
7. the liquid-crystal composition containing the liquid crystalline cpd composition of dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 5, is characterized in that: the compound shown in described general formula III is specially the compound shown in formula III-1 to formula III-10,
8. the liquid-crystal composition containing the liquid crystalline cpd composition of dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 5, is characterized in that: in described liquid-crystal composition, the mass ratio of component A, B component, component C is 10 ~ 35: 15 ~ 35: 25 ~ 75.
9. the liquid-crystal composition containing the liquid crystalline cpd composition of dimethyl benzene and the sub-methoxyl group linking group of difluoro according to claim 8, it is characterized in that: also comprise the additive that the weight percentage accounting for liquid-crystal composition is not more than 0.05% in described liquid-crystal composition, described additive is at least one in antioxidant, anti ultraviolet agent, chiral agent.
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CN107760316A (en) * 2017-09-30 2018-03-06 烟台显华化工科技有限公司 Liquid-crystal compounds containing the methyl substituents benzene of 3 fluorine 5 and difluoromethylenedioconnecting linking group and preparation method and application
CN108717239A (en) * 2017-11-20 2018-10-30 山东蓝贝易书信息科技有限公司 Easy hot erasing type liquid crystal film board and preparation method
CN113897202A (en) * 2021-11-17 2022-01-07 浙江工业大学 Difluoromethyleneoxy liquid crystal compound and synthesis method thereof
CN114507159A (en) * 2022-04-06 2022-05-17 中节能万润股份有限公司 Preparation method of 4- [3(E) -penten-1-yl ] benzoate liquid crystal monomer
CN114507159B (en) * 2022-04-06 2024-05-03 中节能万润股份有限公司 Preparation method of 4- [3 (E) -pentene-1-yl ] benzoate liquid crystal monomer

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