CN104744223B - A kind of containing three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, preparation method and application - Google Patents

A kind of containing three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, preparation method and application Download PDF

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CN104744223B
CN104744223B CN201510065153.9A CN201510065153A CN104744223B CN 104744223 B CN104744223 B CN 104744223B CN 201510065153 A CN201510065153 A CN 201510065153A CN 104744223 B CN104744223 B CN 104744223B
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oxolane
drip
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储士红
班全志
姜天孟
陈海光
谭小玉
田会强
苏学辉
高立龙
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Beijing Bayi Space LCD Technology Co Ltd
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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    • C07C17/00—Preparation of halogenated hydrocarbons
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    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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    • C09K19/00—Liquid crystal materials
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    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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Abstract

The present invention relates to liquid crystal material field, particularly to one containing three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, preparation method and application.The liquid-crystal compounds of the present invention, has below general formula structure: add the liquid-crystal composition of the compounds of this invention, and response time is short, Δ n numerical value is moderate, electric charge conservation rate high, and has relatively low threshold voltage, has a extensive future.

Description

A kind of containing three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, Preparation method and application
Technical field
The present invention relates to liquid crystal material field, particularly to one containing three ring [4.4.0.03,8] decyl and difluoromethyl The liquid-crystal compounds of ether, preparation method and application.
Background technology
At present, liquid crystal is used widely in field of information display, and the application in optical communication simultaneously also achieves necessarily Progress (S.T.Wu, D.K.Yang.Reflective Liquid Crystal Displays.Wiley, 2001).In recent years, The application of liquid-crystal compounds significantly widens kinds of displays part, electro-optical device, electronic component, sensor etc..For This, it has been suggested that many different structures, particularly in nematic crystal field, nematic liquid crystal compound is the most flat Panel display obtains most commonly used application.Especially in the system of tft active matrix.
Liquid crystal material requires possess good chemically and thermally stability, good to electric field and the stability of electromagnetic radiation, Wider nematic temperature range, suitable refractive index, dielectric anisotropy, response speed and high voltage keep faster Rate.
Along with the development of Display Technique, liquid crystal material be it is also proposed higher requirement, especially in quickly response, reduce Driving voltage, reduces the aspects such as power consumption.Accordingly, it would be desirable to develop the novel liquid crystal compound of more improvement performance.
Summary of the invention
It is an object of the invention to provide a kind of containing three ring [4.4.0.03,8] decyl and the LCD compound of difluoro methyl ether Thing.
It is a further object of the present invention to provide a kind of containing three ring [4.4.0.03,8] decyl and the liquid-crystalization of difluoro methyl ether The preparation method of compound.
Another object of the present invention is to provide a kind of containing three ring [4.4.0.03,8] decyl and the liquid crystal of difluoro methyl ether The application of compound.
For solving the problems referred to above, the present invention adopts the following technical scheme that
A kind of containing three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, there is below general formula structure:
In formula I, R represents the C1 that-H, the alkyl of C1～C12 or alkoxyl, one or more H atom are optionally substituted by halogen ～the alkyl of C12 or alkoxyl, one or more-CH2-independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF= The alkyl of C1～C12 that CH-,-CO-O-,-O-CO-or-O-replace and O atom is not directly connected to or alkoxyl；
Represent that 1,4-cyclohexylidene, 1,4-phenylene, 1～4 hydrogen are former independently of one another 1,4-cyclohexylidene that son is replaced by fluorine atoms or the 1,4-phenylene that 1～4 hydrogen atom is replaced by fluorine atoms；
L1、L2、L3And L4Represent H, F or Cl independently of one another；
X represents H, F, Cl, OCF2H、OCF3、CF3, the alkyl of C1～C6 or C1～C6 alkoxyl in one；
M represents 0,1 or 2；N represents 0,1 or 2.
On this basis, said structure is made that and preferably limits by the present invention, it is preferred that R represents-H, C1～C6Alkyl, One or more-CH2-replaced by-O-independently of one another and the C that is not joined directly together of oxygen atom1～C6Alkyl；It is highly preferred that R Expression-C3H7。
Represent that 1,4-phenylene or 1～2 hydrogen atom are taken by fluorine atom independently of one another The 1,4-phenylene in generation；
L1、L2、L3And L4Represent H or F independently of one another.
X represents H, F, OCF2H、OCF3Or CH3。
M represents that 0,1 or 2, n represent 0,1 or 2, and m+n≤3.
In some preferred embodiments, the compound of formula I is particularly preferably one or more of following compound:
In I1～I18, R represents alkyl or the alkoxyl of H, C1～C6；Wherein, the H in alkyl or alkoxyl can be by Halogen substiuted, one or more-CH2-can be replaced by-O-, but require that O atom is not directly connected to.
As the preferred forms of the present invention, the compound of formula I is selected from one or more of following compound:
It is a further object of the present invention to provide described containing three ring [4.4.0.03,8] decyl and the liquid-crystalization of difluoro methyl ether The preparation method of compound, specifically includes following steps:
Step 1):Generate with magnesium chips generation grignard reaction
Step 2):With Br2Reaction generates
Step 3):Under the catalysis of copper chloride lithium, generate
Step 4):Generation is reacted with difluorodibromomethane
Step 5):Warp Williamson Synthesis reaction obtains compounds of formula I,
In above-mentioned steps 1) to step 5) in, R in described structural formula,L1、L2、L3、L4、 The definition of X, m, n is all identical with the definition in claim 1 general structure (I).
Synthetic route is as follows:
Concrete,
Step 1) in(I-1) is 1:1～3 with the mol ratio of magnesium chips, concretely comprises the following steps and protects at nitrogen Protect down, will(I-1) is dissolved in oxolane, takes(I-1) and oxolane The 5%-10% of mixed solution and magnesium chips stirring cause grignard reaction, backflow, drip remaining(Ⅰ-1) With the mixed solution of oxolane, drip and finish, back flow reaction 1h～6h；
Step 2) it is with dichloromethane as solvent, mol ratio is the Br of 1:1～32With triphenylphosphine 0～5 DEG C reaction 1～ 3h, rear temperature control 0～5 DEG C of droppingsThe mixed solution of (I-3) and dichloromethane (dichloromethane withVolume mass ratio be 3～5:1, unit is mL/g), drip finish, temperature control-5～10 DEG C reaction 2～3h；
Step 3) it is with oxolane as solvent, mol ratio is 1～3:1(I-2) with(I-4) react under the catalysis of copper chloride lithium, and feed way is to add in reaction vessel(I-2), then drip under conditions of temperature is 10-20 DEG C(I-4) and tetrahydrochysene The mixed solution of furan, drips and finishes, back flow reaction 3～6h or addition in reaction vesselThen in temperature it is Drip under conditions of 40～50 degreeWith the mixed solution of oxolane, drip and finish, back flow reaction 3～6h；
Step 4): in molar ratio(I-5): n-Buli:CF2Br2=1:1～2: 2～4, under nitrogen protection, will in low-temperature reactorIt is dissolved in oxolane In, it being cooled to-75 DEG C～-85 DEG C after opening stirring, start to drip n-Buli, after dropping, temperature control reaction 2～4h, drips afterwards CF2Br2, drip complete, natural temperature reaction is to-30 DEG C～-10 DEG C；
Step 5): making solvent with water, do consisting of phase-transferring agent with tetrabutyl ammonium bromide, adding mol ratio is 1:1's～3(I-6) with(I-7), are warming up to backflow, Reaction 5～10h.
Concrete, step 5) in molar ratio, tetrabutyl ammonium bromide is 5%～10%.
Preferably, step 1) inWith the mixed solution of oxolane drip finish after, back flow reaction 1h～ 3h。
Step 3) in back flow reaction 4～5h；
Step 5) in back flow reaction 6～7h.
Above-mentionedN-BuLi, difluorodibromomethane, bromine etc. all can lead to Cross method synthesis known per se in open commercial sources or document to obtain.
The present invention also provides for a kind of liquid-crystal composition, wherein comprises the compounds of formula I that mass percent is 1-50%, Preferred mass percentage ratio is the compounds of formula I of 3-25%.
The liquid-crystal compounds of the present invention and liquid-crystal composition can be applicable in TN, IPS, FFS, ADS-TFT pattern.
Beneficial effects of the present invention is as follows: add the liquid-crystal composition of the compounds of this invention, and response time is short, Δ n number It is worth moderate, electric charge conservation rate height, and there is relatively low threshold voltage, have a extensive future.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Described raw material if no special instructions, all can be either commercially available from open.
" conventional post processing " refers to, in aqueous, mixed liquor dichloromethane, ethyl acetate or toluene extraction, separatory, Washing, is dried and vacuum rotary evaporator evaporates, and then product decompression distillation or recrystallization and/or chromatography purifies.
Embodiment 1
The synthetic line preparing compound L C-01 is as follows:
1, the synthesis of compound 4
There-necked flask is sequentially added into 0.24 mole of Br2, 0.24 mole of triphenylphosphine, 0.2L dichloromethane stirring and dissolving, after It is cooled to 0～5 DEG C, temperature control 0～5 DEG C of reaction 1h, rear temperature control 0～5 DEG C of droppings compound 3 and 0.2L oxolane of 0.2 mole Mixed solution, drip and finish, temperature control stirring 2h, rear add 0.4L water, stir 5 minutes, stand 10 minutes, separatory, upper strata is aqueous phase, Lower floor is product phase.Product is washed three times with (0.4L × 3) mutually, and 20g anhydrous magnesium sulfate is dried 1 hour.Filtration drying agent, with rotation Turn evaporimeter and remove solvent, obtain 0.16 mole of light yellow liquid compound 4, GC:99.1%, yield: 80%.
2, the synthesis of compound 5
In there-necked flask add 0.16 mole of magnesium chips, 200ml oxolane, inflated with nitrogen displaced air three times, add 10ml by The mixed solution of 0.16 mole compound 1 and 200ml oxolane, stirring causes grignard reaction, the remaining compound 1 of rear dropping (magnesium is 1:1 with total mol ratio of compound 1, and simply the mixed solution of compound 1 and oxolane adds at twice, first Add 5%-10% volume to be used for causing, remaining drip addition again) and the mixed solution of oxolane, back flow reaction 1h, Obtain Grignard reagent compound 2, after be cooled to 10-20 DEG C, add the copper chloride lithium solution of 0.01 mole, temperature control 10-20 DEG C drip Add the mixed solution of 0.16 mole compound 4 and 100ml oxolane, drip and finish, be warming up to back flow reaction 4h.
Post processing: adding 0.5L water, 0.5L toluene in there-necked flask, stir 5 minutes, stand 10 minutes, separatory, upper strata is for having Machine phase, lower floor is aqueous phase.Organic facies is washed three times with (0.5L × 3), and anhydrous sodium sulfate is dried, sucking filtration, and filtrate crosses silicagel column, and 3 Times post height toluene rushes post, and concentrating under reduced pressure is spin-dried for solvent, adds 200ml ethanol, freezes case (-30 DEG C) 6h, sucking filtration, dry 0.14 Mole compound 5, GC:99%, yield: 86%.
3, the synthesis of compound 6
2L low-temperature reactor, nitrogen is protected, and is added thereto to 0.14mol compound 5,0.3L THF, after opening stirring Liquid nitrogen cooling to-75 DEG C～-85 DEG C, starts to drip 0.14mol n-Buli (n-BuLi), process temperature control-75 DEG C～-85 DEG C, After dropping, temperature control reaction 1h, drips 0.16molCF afterwards2Br2, process temperature control-75 DEG C～-85 DEG C, drip complete, naturally rise Temperature reaction is to-30 DEG C of direct post processings.
Post processing: to the mixed solution (PH < 5) of reactant liquor dropping 140g dense HCl+0.5L water, stir 0.5h, separatory, water Use (0.5L × 2) methylbenzene extraction twice mutually, merge organic facies and be washed to neutrality (2L/ time, about 2 times), organic facies anhydrous slufuric acid Sodium is dried, sucking filtration, and filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, merged post liquid and concentrates, and obtained 0.14mol compound 6, G/C content 70% (main peak), yield 100%.
4, the synthesis of compound 8
The reaction unit of 2L there-necked flask, addition 0.5L water, 0.007mol tetrabutyl ammonium bromide, 0.14mol compound 6, 0.14mol compound 7, is warming up to backflow under stirring, reflux 6h, controls GC (raw material) < 2%, start post processing in rear sampling.
Post processing: adding toluene 1L, stirring, separatory in reactant liquor, aqueous phase is used (0.5L × 2) methylbenzene extraction twice, merged Organic facies (0.5L × 2) is washed 2 times, and organic facies anhydrous sodium sulfate is dried, sucking filtration, and filtrate crosses silicon gel column, 3 times of post height toluene Rinsing pillar, cross post liquid concentrating under reduced pressure, 500ml ethanol 80 DEG C is put in refrigerator-freezer recrystallization (freezing 3h), rear sucking filtration after dissolving, dry Obtain 0.05mol compound 8 (LC-01), G/C content 99%, yield: 50%.
GC-MS:562 (molecular ion peak), 495 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.5-6.2 (m, 8H), 1.8-0.8 (m, 21H).
Embodiment 2
The synthetic line preparing compound BYLC-02 is as follows:
1, the synthesis of compound 4
There-necked flask is sequentially added into the Br of 0.08 mole2, 0.24 mole of triphenylphosphine, 0.2L dichloromethane stirring and dissolving, After be cooled to 0～5 DEG C, temperature control 0～5 DEG C of reaction 3h, rear temperature control 0～5 DEG C of droppings compound 3 and 0.3L tetrahydrochysene of 0.0.08 mole The mixed solution of furan, drips and finishes, temperature control stirring 3h, rear addition 0.4L water, stirs 5 minutes, stands 10 minutes, and separatory, upper strata is Aqueous phase, lower floor is product phase.Product is washed three times with (0.4L × 3) mutually, and 20g anhydrous magnesium sulfate is dried 1 hour.Filtration drying Agent, removes solvent with Rotary Evaporators, obtains 0.164 mole of light yellow liquid compound 4, GC:99.5%, yield: 82%.
2, the synthesis of compound 5
In there-necked flask add 0.48 mole of magnesium chips, 200ml oxolane, inflated with nitrogen displaced air three times, add 20ml by The mixed solution of 0.16 mole compound 1 and 200ml oxolane, stirring causes grignard reaction, the remaining compound 1 of rear dropping With oxolane mixed solution, back flow reaction 3h, obtain Grignard reagent compound 2, after be cooled to 10-20 DEG C, add and 0.01 rub Your copper chloride lithium solution, the mixed solution of temperature control 10-20 DEG C dropping 0.05 mole compound 4 and 100ml oxolane, drips Finish, be warming up to back flow reaction 5h.
Post processing: adding 0.5L water, 0.5L toluene in there-necked flask, stir 5 minutes, stand 10 minutes, separatory, upper strata is for having Machine phase, lower floor is aqueous phase.Organic facies is washed three times with (0.5L × 3), and anhydrous sodium sulfate is dried, sucking filtration, and filtrate crosses silicagel column, and 3 Times post height toluene rushes post, and concentrating under reduced pressure is spin-dried for solvent, adds 200ml ethanol, freezes case (-30 DEG C) 6h, sucking filtration, dry 0.13 Mole compound 5, GC:98%, yield: 80%.
3, the synthesis of compound 6
2L low-temperature reactor, nitrogen is protected, and is added thereto to 0.13mol compound 5,0.3L THF, after opening stirring Liquid nitrogen cooling to-75 DEG C～-85 DEG C, starts to drip 0.26moln-Buli (n-BuLi), process temperature control-75 DEG C～-85 DEG C, Temperature control reaction 4h after dropping, rear dropping 0.15mol mass fraction is the CF of 51%2Br2With the mixed solution of oxolane, Process temperature control-75 DEG C～-85 DEG C, drips complete, and natural temperature reaction is to-10 DEG C of direct post processings.
Post processing: to the mixed solution (PH < 5) of reactant liquor dropping 120g dense HCl+0.5L water, stir 0.5h, separatory, water Use (0.5L × 2) methylbenzene extraction twice mutually, merge organic facies and be washed to neutrality (2L/ time, about 2 times), organic facies anhydrous slufuric acid Sodium is dried, sucking filtration, and filtrate crosses silicon gel column, 3 times of post height toluene rinse pillars, merged post liquid and concentrates, and obtained 0.13mol compound 6, G/C content 66% (main peak), yield 100%.
3, the synthesis of compound 8
The reaction unit of 2L there-necked flask, addition 0.4L water, 0.013mol tetrabutyl ammonium bromide, 0.13mol compound 6, 0.39mol compound 7, is warming up to backflow under stirring, reflux 7h, controls GC (raw material) < 2%, start post processing in rear sampling.
Post processing: adding toluene 1L, stirring, separatory in reactant liquor, aqueous phase is used (0.5L × 2) methylbenzene extraction twice, merged Organic facies (0.5L × 2) is washed 2 times, and organic facies anhydrous sodium sulfate is dried, sucking filtration, and filtrate crosses silicon gel column, 3 times of post height toluene Rinsing pillar, cross post liquid concentrating under reduced pressure, 300ml ethanol 80 DEG C is put in refrigerator-freezer recrystallization (freezing 3h), rear sucking filtration after dissolving, dry in the air Do to obtain 0.038mol compound 8 (LC-02), G/C content 99%, yield: 44%.
GC-MS:674 (molecular ion peak), 513 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.0-6.5 (m, 10H), 1.8-0.9 (m, 21H).
Embodiment 3
WithReplaceAccording to the method for embodiment 1 it is Available compound L C-07:
After testing, G/C content 99.8%, it is etherified yield 40%.
GC-MS:656 (molecular ion peak), 589 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.0-6.5 (m, 11H), 1.8-0.9 (m, 21H).
Following compound is equally synthesized by the method for embodiment 1～embodiment 3:
GC-MS:580 (molecular ion peak), 513 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.2-6.2 (m, 7H), 1.8-0.8 (m, 21H).
GC-MS:544 (molecular ion peak), 495 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.4-6.1 (m, 9H), 1.8-0.8 (m, 21H).
GC-MS:562 (molecular ion peak), 513 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.2-6.4 (m, 8H), 1.8-0.8 (m, 21H).
GC-MS:544 (molecular ion peak), 477 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.4-6.2 (m, 9H), 1.8-0.8 (m, 21H).
GC-MS:562 (molecular ion peak), 495 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.5-6.2 (m, 8H), 1.8-0.8 (m, 21H).
GC-MS:674 (molecular ion peak), 607 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.4-6.2 (m, 10H), 1.8-0.9 (m, 21H).
GC-MS:638 (molecular ion peak), 589 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.4-6.5 (m, 12H), 1.8-0.9 (m, 21H).
GC-MS:656 (molecular ion peak), 607 (losing 3,4,5-trifluoro-benzene epoxides)；
1H-NMR(300MHz,CDCl3): 7.4-6.4 (m, 11H), 1.8-0.9 (m, 21H).
GC-MS:656 (molecular ion peak), 495 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.4-6.5 (m, 10H), 1.8-0.9 (m, 21H).
GC-MS:638 (molecular ion peak), 495 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.4-6.8 (m, 10H), 1.8-0.9 (m, 21H).
GC-MS:656 (molecular ion peak), 513 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.0-6.5 (m, 10H), 1.8-0.9 (m, 21H).
GC-MS:674 (molecular ion peak), 419 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.6-6.5 (m, 10H), 1.7-0.9 (m, 21H).
GC-MS:656 (molecular ion peak), 401 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.6-6.8 (m, 11H), 1.8-0.8 (m, 21H).
GC-MS:704 (molecular ion peak), 589 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.5-6.4 (m, 12H), 1.7-0.9 (m, 21H).
GC-MS:722 (molecular ion peak), 607 (fractures of difluoro-methoxy bridged bond)；
1H-NMR(300MHz,CDCl3): 7.4-6.3 (m, 11H), 1.8-0.9 (m, 21H).
Embodiment 4:
The liquid-crystal compounds used in following compositions is all carried by Beijing Bayi Space LCD Materials Technology Co., Ltd. Supply.In addition to specified otherwise, in embodiment, the content of each component all represents mass percent.
In the present invention, each performance test parameter shorthand is as follows:
△ n is optical anisotropy, noFor refractive index (589nm, 20 DEG C)；
V10For threshold voltage, it is the character voltage (V, 20 DEG C) when transmitance changes 10%, V90For saturation voltage, it is Character voltage when transmitance changes 90% (V, 20 DEG C)；Liquid crystal comprehensive parameter tester EOT-5016.Just set polarizing axis The polaroid handed over, is attached to be marked with testing cassete (4.0 μm) top and bottom of liquid crystal by polaroid.To liquid crystal cell making alive, when light is from entirely Voltage when saturating original state is reduced to 10% transmitance is saturation voltage.Light source is halogen light, liquid crystal cell 64HZ Square wave drive.
Cp is the clearing point (DEG C) of liquid-crystal composition；
τonFor until time when reaching transmitance 90%, τoffFor until reaching time when transmitance 10% is cut off, τ For τon+τoff(response time) (ms).
VHR is electric charge conservation rate (%): injected by mixed liquid crystal in liquid crystal cell, puts in calorstat, after temperature DEG C is stable, Enter test program, manually take and a little obtain electric charge conservation rate numerical value.Measurement voltage is 5V, and power-up time is 5ms, Holding Time is 500ms.
Take the liquid-crystal compounds of following parts by weight and prepare liquid-crystal composition, concrete proportioning and the liquid crystal combination of gained The performance parameter of thing is by shown in following table.
The liquid-crystal compounds of the present invention application in IPS, FFS, ADS-TFT pattern, result such as following table:
Table 1.1 adds the percentage by weight of each component in the liquid-crystal composition 1 of the compounds of this invention
The performance parameter of table 1.2 liquid-crystal composition 1
Performance parameter Parameter value
△n 0.101
Δε +9.6
V10 1.11
η 11
Cp 112
τ 10
VHR 99%
Table 2.1 adds the percentage by weight of each component in the liquid-crystal composition 2 of the compounds of this invention
The performance parameter of table 2.2 liquid-crystal composition 2
Performance parameter Parameter value
△n 0.112
Δε +10.1
V10 1.05
η 16
Cp 120
τ 8
VHR 99%
Table 3.1 is not added with the percentage by weight of each component of liquid-crystal composition 3 of the compounds of this invention
The performance parameter of table 3.2 liquid-crystal composition 3
Performance parameter Parameter value
△n 0.098
Δε +9.3
V10 1.15
η 21
Cp 100
τ 15
VHR 97%
Table 4.1 is not added with the percentage by weight of liquid-crystal composition 4 component of the compounds of this invention
Table 4.2 liquid-crystal composition 4 performance parameter
Performance parameter Parameter value
△n 0.096
Δε +9.0
V10 1.20
η 23
Cp 96
τ 16
VHR 96%
By adding the liquid-crystal composition 1 (table 1.1) of the compounds of this invention, liquid-crystal composition 2 (table 2.1) is compared and is not added with The liquid-crystal composition 3 (table 3.1) of the compounds of this invention and the performance parameter of liquid-crystal composition 4 (table 4.1) understand, and add this The liquid-crystal composition response time of bright compound is shorter, Δ n numerical value is moderate, electric charge conservation rate is higher, and has relatively low threshold Threshold voltage, is particularly suited for the TFT display mode of fast-response.Present configuration leads to the addition of the compound of formula (I) with 1- 50% is advisable, more preferably 3-25%.
In addition to the compositions that test example is enumerated, add the liquid-crystal composition of other compound composition that the present invention provides also The most excellent optical property can be obtained.
Although, the present invention is described in detail the most with a general description of the specific embodiments, but On the basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Cause This, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.

Claims (11)

1. one kind contains three ring [4.4.0.03,8] decyl and the liquid-crystal compounds of difluoro methyl ether, it is characterised in that have following Formula:
In formula I: R represent C1 that-H, the alkyl of C1～C12 or alkoxyl, one or more H atom be optionally substituted by halogen～ The alkyl of C12 or alkoxyl, one or more-CH2-independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF= The alkyl of C1～C12 that CH-,-CO-O-,-O-CO-or-O-replace and O atom is not directly connected to or alkoxyl；
Represent 1,4-cyclohexylidene, 1,4-phenylene, 1～4 hydrogen atom quilt independently of one another The 1,4-phenylene that fluorine atom substituted 1,4-cyclohexylidene or 1～4 hydrogen atom are replaced by fluorine atoms；
L1、L2、L3And L4Represent H, F or Cl independently of one another；
X represents H, F, Cl, OCF2H、OCF3、CF3, the alkyl of C1～C6 or C1～C6 alkoxyl in one；
M represents 0,1 or 2；N represents 0,1 or 2.
Liquid-crystal compounds the most according to claim 1, it is characterised in that R represents-H, C1～C6Alkyl, one or many Individual-CH2-replaced by-O-independently of one another and the C that is not joined directly together of oxygen atom1～C6Alkyl；
Represent that 1,4-phenylene or 1～2 hydrogen atom are replaced by fluorine atoms independently of one another 1, 4-phenylene；
L1、L2、L3And L4Represent H or F independently of one another；
X represents H, F, OCF2H、OCF3Or CH3；
M represents that 0,1 or 2, n represent 0,1 or 2, and m+n≤3.
Liquid-crystal compounds the most according to claim 1 and 2, it is characterised in that the compound of formula I is selected from following compound One or more:
In I1～I18, R represents the alkyl of H, C1～C6, one or more CH2Group is replaced by-O-independently of one another and oxygen is former The alkyl of C1～C6 that son is not joined directly together.
4. containing three ring [4.4.0.0 described in any one of claim 1-33,8] liquid-crystal compounds of decyl and difluoro methyl ether Preparation method, it is characterised in that
Step 1):Generate with magnesium generation grignard reaction
Step 2):With Br2Reaction generates
Step 3):WithUnder the catalysis of copper chloride lithium, generate
Step 4):Generation is reacted with difluorodibromomethane
Step 5):WithThrough Williamson Synthesis reaction obtains compounds of formula I,
In above-mentioned steps 1) to step 5) in, R in described structural formula,L1、L2、L3、L4、X、m、n Definition all identical with the definition in claim 1-3 formula I.
The most according to claim 4 containing three ring [4.4.0.03,8] preparation of liquid-crystal compounds of decyl and difluoro methyl ether Method, it is characterised in that
Step 1) inIt is 1:1～3 with the mol ratio of magnesium chips, under nitrogen protection, willIt is dissolved in oxolane, takes5%-10% with oxolane mixed solution Cause grignard reaction, backflow with magnesium chips stirring, drip remainingWith the mixed solution of oxolane, drip Finish, back flow reaction 1h～6h；
Step 2) it is with dichloromethane as reaction dissolvent, mol ratio is the Br of 1:1～32With triphenylphosphine 0～5 DEG C reaction 1～ 3h, rear temperature control 0～5 DEG C of droppingsWith the mixed solution of dichloromethane, drip finish, temperature control-5～10 DEG C reaction 2～ 3h；
Step 3) it is with oxolane as reaction dissolvent, mol ratio is 1～3:1WithReacting under the catalysis of copper chloride lithium, feed way is to add in reaction vesselThen drip under conditions of temperature is 10-20 DEG CMixing with oxolane Solution or addition in reaction vesselThen drip under conditions of temperature is 40～50 degreeWith the mixed solution of oxolane, drip and finish, back flow reaction 3～6h；
Step 4) in molar ratio Under nitrogen protection, will in low-temperature reactorIt is dissolved in oxolane, opens Being cooled to-75 DEG C～-85 DEG C after stirring, start to drip n-Buli, after dropping, temperature control reaction 2～4h, drips CF afterwards2Br2, Dripping complete, natural temperature reaction is to-30 DEG C～-10 DEG C；
Step 5): making solvent with water, do consisting of phase-transferring agent with tetrabutyl ammonium bromide, adding mol ratio is 1:1's～3WithIt is warming up to backflow, reacts 5～10h.
The preparation method of liquid-crystal compounds the most according to claim 5, it is characterised in that step 1) inDrip after finishing with the mixed solution of oxolane, back flow reaction 1h～3h.
The preparation method of liquid-crystal compounds the most according to claim 5, it is characterised in that step 3) in back flow reaction 4～ 5h；Step 5) in back flow reaction 6～7h.
8. comprise described in any one of claim 1-3 containing three ring [4.4.0.03,8] decyl and the liquid-crystalization of difluoro methyl ether The liquid-crystal composition of compound.
Liquid-crystal composition the most according to claim 8, it is characterised in that containing three ring [4.4.0.03,8] decyl and difluoro The weight/mass percentage composition of the liquid-crystal compounds of methyl ether is 1～50%.
Liquid-crystal composition the most according to claim 9, it is characterised in that: containing three ring [4.4.0.03,8] decyl and difluoro The weight/mass percentage composition of the liquid-crystal compounds of methyl ether is 3～25%.
Liquid-crystal compounds described in 11. any one of claim 1-3 or the liquid-crystal composition described in claim 8 or 9 or 10 exist Application in TN, IPS, FFS, ADS-TFT mode LCD.
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