CN104059674A - Liquid crystal composition containing difluoromethoxy bridged bond and application thereof - Google Patents
Liquid crystal composition containing difluoromethoxy bridged bond and application thereof Download PDFInfo
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Abstract
The invention provides a liquid crystal composition containing a difluoromethoxy bridged bond and a -O(CH2)nF unit structure. The liquid crystal compound has a structure shown in a formula I as follows: R-Al-Z1-A2-Z2-A3-CF2O-A4-Z3-A5-O(CH2)n-CH2F(I); the compound has the characteristics of being low in rotary viscosity and great in dielectric anisotropy; after the liquid crystal composition is applied, the dielectric anisotropy of the existing idiomatic liquid crystal composition can be further improved, and therefore, the liquid crystal composition has technical effect of lowering drive voltage of an apparatus.
Description
Technical field
The present invention relates to liquid crystal display material field, be specifically related to a kind of contain difluoro-methoxy bridged bond and-O (CH
2) liquid crystalline cpd and the application thereof of nF modular construction.
Background technology
At present, liquid crystal is used widely in field of information display, and the application in optical communication simultaneously also makes some progress (S.T.Wu, D.K.Yang.Reflective Liquid Crystal Displays.Wiley, 2001).In recent years, the Application Areas of liquid crystalline cpd had significantly been widened kinds of displays part, electro-optical device, electronic component, sensor.For this reason, proposed many different structures, particularly in nematic liquid crystal field, nematic liquid crystal compound has obtained applying the most widely so far in flat-panel monitor.In system especially for tft active matrix.
Liquid-crystal display follows the discovery of liquid crystal to experience very long road for development.Within 1888, Austrian botanist Friedrich Reinitzer has found the first liquid crystal material M-nitro benzoic acid cholesterol (cholesteryl benzoate).Within 1917, Manguin has invented friction Directional Method, in order to make single domain liquid crystal and Optical anisotropy.E.Bose in 1909 has set up and has collected together (Swarm) theory, and obtains the people's such as L.S.Ormstein and F.Zernike experiment support (1918), by De Gennes, is discussed as statistical fluctuation.G.W.Oseen and H.Zocher1933 found continuum theory, and obtain F.C.Frank perfect (1958).M.Born (1916) and K.Lichtennecker (nineteen twenty-six) have found and have studied the dielectric anisotropy of liquid crystal.1932, W.Kast was divided into nematic phase the large class of positive and negative property two accordingly.Nineteen twenty-seven, V.Freedericksz and V.Zolinao find that nematic liquid crystal, under electric field (or magnetic field) effect, deformation occurs and have voltage threshold (Freederichsz transformation).This making that is found to be liquid-crystal display provides foundation.
The nineteen sixty-eight R.Williams of U.S. RCA Corp. finds that nematic liquid crystal forms striped farmland under electric field action, and has light scattering phenomenon.G.H.Heilmeir develops into dynamic scattering display format with being about to it, and makes first liquid-crystal display (LCD) in the world.Early seventies, Helfrich and Schadt have invented TN principle, and people utilize TN photovoltaic effect and unicircuit to combine, and are made display device (TN-LCD), for wide prospect has been opened up in the application of liquid crystal.Since the seventies, development due to large-scale integrated circuit and liquid crystal material, the application of liquid crystal aspect demonstration obtained breakthrough development, and the people such as 1983～1985 years T.Scheffer successively propose supertwist nematic phase (Super Twisred Nematic:STN) pattern and P.Brody is adopted again in active matrix (Active matrix:AM) mode of proposition in 1972.Traditional TN-LCD technology has developed into STN-LCD and TFT-LCD technology, although more than the number of scanning lines of STN can reach 768 row, still exist the problems such as response speed, visual angle and gray scale when temperature raises, so big area, high information quantity,
The colored Active Matrix LCD At mode that mostly adopts that shows.TFT-LCD has been widely used in direct viewing type TV, large-curtain projecting TV set, terminal shows and some military instrument shows, believes that TFT-LCD technology has more wide application prospect.
Wherein " active matrix " comprises two types: 1, the OMS on the silicon wafer as substrate (metal-oxide semiconductor (MOS)) or other diode.2, the thin film transistor on the sheet glass as substrate (TFT).
Silicon single crystal has limited display size as substrate material because each several part display device even module assembled in its junction, there are many problems.Thereby the second thin film transistor is the promising active matrix type of tool, the photovoltaic effect of utilizing is TN effect normally.TFT comprises compound semiconductor, and as Cdse, or to take polycrystalline or amorphous silicon be basic TFT.
At present, TFT-LCD product technology is ripe, has successfully solved the technical barriers such as visual angle, resolving power, fullness of shade and brightness, and its display performance has approached or surpassed CRT monitor.Large size and small-medium size TFT-LCD indicating meter occupy the dominant position of flat-panel monitor gradually in field separately.But because being subject to the restriction of liquid crystal material itself, it is fast not that TFT-LCD still exists response, and voltage is low not, the high not many defects of electric charge conservation rate.Therefore the single crystal compound of finding low viscosity, high dielectric anisotropy is particularly important.
The monomer liquid crystal that is-O (CH2) nF to end in patent DE4222371 as far back as Merck KGaA company in 1992 is set forth, but does not obtain desirable respective compound.
Summary of the invention
For above-mentioned background, the invention provides a kind of novel liquid crystalline cpd, this compound have simultaneously difluoro-methoxy bridged bond and-O (CH
2) nF modular construction.This compound has the low and large feature of dielectric anisotropy of rotary viscosity, have suc as formula shown in structure I:
R-A
1-Z
1-A
2-Z
2-A
3-CF
2O-A
4-Z
3-A
5-O(CH
2)n-CH
2F
(Ⅰ)
Wherein, R is selected from H and does not replace or replace the alkyl that contains separately 1-12 carbon atom or alkoxyl group; One or more CH in the alkyl that contains separately 1-12 carbon atom replacing or alkoxyl group
2group is separately independently of one another by-C ≡ C-,-CF
2o-,-CH=CH-,-O-,-CO-O-or-O-CO-with O atom each other not directly the mode of keyed jointing replace, and wherein one or more H atoms can be replaced by halogen;
A
1, A
2and A
3be selected from independently of one another: singly-bound, 1,3-cyclopentyl, Isosorbide-5-Nitrae-cyclohexyl, 1,4-cyclohexenyl, piperidines-Isosorbide-5-Nitrae-bis-base, Isosorbide-5-Nitrae-Ya bis-rings [2,2,2] octyl group, Isosorbide-5-Nitrae-phenyl, naphthalene-2,6-bis-bases, trans naphthane-2,6-bis-bases, tetraline-2,6-bis-bases, 1,2-indane, indenes, phenanthryl or diphenylene-oxide, a CH in Isosorbide-5-Nitrae-cyclohexyl wherein
2or two not direct-connected CH
2can be replaced by O or S; In Isosorbide-5-Nitrae-phenyl, a CH or two not direct-connected CH can be replaced by N.Hydrogen in above-mentioned arbitrary situation in structure can be replaced by one or more halogens (arbitrary situation general reference A herein independently of one another
1, A
2and A
3be selected from arbitrary substituting group);
A
4and A
5be selected from independently of one another: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or more halogens independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-,-(CH
2)
4-,-CH=CHCH
2cH
2-,-CH
2cH
2cH=CH-, CF
2o, OCF
2, CF
2cF
2, CF=CF, CH
2cF
2, CF
2cH
2, OCF
2cF
2o, C
2h
4cF
2o, CH
2cF
2oCH
2, CH
2oCF
2cH
2, OCF
2c
2h
4, C
3h
6o, OC
3h
6, C
2h
4oCH
2, CH
2oC
2h
4, CH
2o, OCH
2,-CH=CH-,-C ≡ C-or COO.
N is 1,2 or 3.
Halogen described in the present invention is preferably F.
Wherein, liquid crystalline cpd of the present invention is preferred:
The alkyl that contains separately 1-5 carbon atom or alkoxyl group that R is selected from H and does not replace or replace, one or more CH in the alkyl that contains separately 1-5 carbon atom of replacement or alkoxyl group
2group separately independently of one another by-CH=CH-or-O-replaces, and wherein one or more H atoms can be replaced by halogen;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl; Isosorbide-5-Nitrae-cyclohexyl wherein, a CH
2or two not direct-connected CH
2can be replaced by O.Hydrogen in above-mentioned arbitrary situation in structure can be replaced by one or more halogens independently of one another;
A
4and A
5be selected from independently of one another: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2;
N is 1,2 or 3.
Further preferably:
R is selected from H and does not replace the alkyl that contains 1-5 carbon atom;
A
1and A
2be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl; Isosorbide-5-Nitrae-cyclohexyl wherein, a CH
2or two not direct-connected CH
2can be replaced by O.Hydrogen in above-mentioned arbitrary situation in structure independently of one another cocoa is replaced by one or more fluorine elements;
A
3for Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or two fluorine element independently of one another;
A
4and A
5be selected from: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or two fluorine element independently of one another;
Z
1and Z
2be selected from: singly-bound or-(CH
2)
2-;
N is 1,2 or 3.
And more preferably described liquid crystalline cpd is selected from following formula compound:
R is selected from the alkyl that contains 2-5 carbon atom;
N is 1,2 or 3.
As best mode for carrying out the invention, described liquid crystalline cpd is:
Above-claimed cpd has higher dielectric anisotropy, is applied to the driving voltage that can reduce device after composition.
The second object of the present invention is to provide a kind of preparation method who contains difluoro-methoxy bridged bond liquid crystalline cpd, and described preparation method's synthetic route is as follows:
Comprise the steps:
(1) starting material compound II-1, take Tetrabutyl amonium bromide as catalyzer, and DMF is solvent, at 65～72 ℃ and Br (CH
2) nCH
2f reaction, obtains compound ii-2;
(2) take and draw Buddhist nun's nickel as catalyzer in compound ii-2, under room temperature, obtains compound ii-3 with hydrogen reaction;
(3) trifluoromethane sulfonic acid be take as catalyzer in compound ii-4, and toluene and octane-iso are solvent, with 1,3-dimercaptopropane reflux dewatering, filters and obtains compound ii-5;
(4) compound ii-3 and compound ii-5, take hydrogen fluoride triethylamine as dewatering agent, and bromine is catalyzer ,-75 ℃ of following reactions, obtains target compound I;
Wherein, R, A
1, A
2, A
3, A
4, A
5, Z
1, Z
2, Z
3and n refer to the same.
Adopt that above-mentioned preparation method is can mass stable obtains containing difluoro-methoxy bridged bond liquid crystalline cpd, there is the advantage that dielectric anisotropy is large.
The 3rd object of the present invention is to protect the above-mentioned difluoro-methoxy bridged bond liquid crystalline cpd that contains in the application of field of liquid crystal display.
Particularly, the claimed liquid-crystal composition that contains difluoro-methoxy bridged bond liquid crystalline cpd of the present invention.Wherein contain difluoro-methoxy bridged bond liquid crystalline cpd and add with reasonable manner, add-on is advisable with 1-80%, more preferably 3-50%.Those skilled in the art will envision that, based on adding of above-mentioned liquid crystalline cpd, can further improve the dielectric anisotropy of existing habitual liquid-crystal composition, there is the technique effect of the driving voltage that reduces device.
The present invention further asks for protection the application of above-mentioned composition in liquid crystal indicator, and described liquid crystal indicator includes, but are not limited to TN, ADS, FFS or IPS liquid-crystal display.Liquid-crystal composition is applied to after liquid crystal indicator, there is the driving voltage of reduction.
In the present invention, each performance test parameter abbreviation is as follows:
Δ ε is illustrated in the dielectric anisotropy under 25 ℃ and 1kHz;
γ 1 is illustrated in the rotary viscosity (mPas) at 25 ℃.
△ n is optical anisotropy, and no is specific refractory power (589nm, 25 ℃);
C.p be liquid-crystal composition clearing point (℃);
VHR electric charge conservation rate (%): mixed liquid crystal is injected in liquid crystal cell, put into thermostat container, after temperature-stable, enter test procedure, manually get and a little obtain electric charge conservation rate numerical value.Measuring voltage is 5V, and power-up time is 5ms, and Holding Time is 500ms.
Embodiment
Embodiment 1:
4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3, the fluoro-4'-propyl group of 5-bis-biphenyl (compound 6) synthetic
1) 5-benzyloxy-1, the fluoro-2-of 3-bis-(3-fluorine propoxy-)-benzene (compound 2) synthetic
In 50mL reaction flask, add 22mL DMF, start stirring, add 5.9g2, the fluoro-4-bromophenol of 3-bis-(compound 1), after solid dissolves completely, then adds 10mL water, 0.25g Tetrabutyl amonium bromide, 4.0g Anhydrous potassium carbonate.Heat temperature raising, 65～72 ℃ of dropping 4.0g3-fluorine N-PROPYLE BROMIDEs of temperature control, stirring reaction 4 hours, adds 10mL toluene and 15mL water, stirs 10 minutes, standing separatory, twice of 5mL for water * 2 methylbenzene extraction (stirring standing 5 minutes 2 minutes), this water is abandoned it.Merge all organic phases, with 10mL * 3 water washing three times.Be spin-dried for solvent, obtain white solid, theoretical yield: 7.4g, actual output 6.0g, yield: 81.1%.Gas phase purity (GC) 98.3%.
2) 3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenol (compound 3) synthetic
In 1L there-necked flask, add 65.0g5-benzyloxy-1, the fluoro-2-of 3-bis-(3-fluorine propoxy-)-benzene (compound 2), 200mL toluene, 13g Raney's nickel clean with 450ml alcohol flushing, hydrogen pump drainage 3 times.Logical hydrogen, is warming up to 35 ℃, stops heating, hydrogenation 4 hours.Concentrated solvent, underpressure distillation, obtains product, theoretical yield: 45.2g, actual output 34.0g, yield: 75.2%.Gas phase purity (GC) 98.0%.
Same method can be prepared:
The fluoro-4-of 3-(3-fluorine propoxy-)-phenol
3) trifluoromethyl sulfonic acid (compound 5) is synthetic
In 1L there-necked flask, add 102g4 '-propyl group-2,6-DfBP formic acid (compound 4), 47mL1,3-dimercaptopropane, 42mL trifluoromethane sulfonic acid, 145mL toluene and 145mL octane-iso, one side mouth is installed water trap, be warming up to backflow, react 0 ℃ of Slow cooling 6 hours, suction filtration, obtains solid.After dry, carrying out next step feeds intake.
4) 4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3, the fluoro-4'-propyl group of 5-bis-biphenyl (compound 6) synthetic
In 2L there-necked flask, add 200mL methylene dichloride, 39mL triethylamine and 57.7g3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenol (compound 3), be cooled to 20 ℃, add the solution being formed by 117g trifluoromethyl sulfonic acid (compound 5) and 200mL methylene dichloride, stir 1 hour.Below temperature control-75 ℃, drip 77g hydrogen fluoride triethylamine, continue to stir 1 hour.Below temperature control-75 ℃, the solution being comprised of 15mL bromine and 30mL methylene dichloride, rises again and carry out aftertreatment after-10 ℃.In 10L bucket, add 1L water, start stirring, pour reaction solution into, stirring minute, slowly add sodium bicarbonate solid (producing a large amount of gas) closely neutral to solution PH, standing separatory, water is with 500ml dichloromethane extraction once, merge organic phase, 70 ℃ are spin-dried for solvent and obtain thick material, and with 2 times of ethanol and 0.5 times of sherwood oil recrystallization three times, suction filtration dries white solid.Theoretical yield: 116.6g, actual output: 86.1g, yield 73.8%.Gas phase purity (GC) 99.9%,
Fusing point: 48.7 ℃
Δ n is 0.130,
Δ ε is 15.1,
γ 1 is 150mPas.
Mass spectroscopy fragment: 252,281,486 (molecular ion peaks);
H-NMR nuclear magnetic spectrogram (CDCl
3, 300mhZ): δ H:0.90-2.60 (m, 9H), 3.90-4.10 (m, 4H), 6.10-7.30 (m, 8H).
Embodiment 2:
2-(4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3,5-difluorophenyl)-5-propyl group-[1,3] diox (compound 9) synthetic
1) trifluoromethyl sulfonic acid (compound 8) is synthetic
In 1L there-necked flask, add 106g2,6-dioxy-4-(5-propyl group-[1,3] dioxo hexanaphthene-2-yl)-phenylformic acid (compound 7), 47mL1,3-dimercaptopropane, 42mL trifluoromethane sulfonic acid, 145mL toluene and 145mL octane-iso, a side mouth is installed water trap, is warming up to backflow, react 6 hours, 0 ℃ of Slow cooling, suction filtration, obtains solid.After dry, carrying out next step feeds intake.
2) 4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3, the fluoro-4'-propyl group of 5-bis-biphenyl (compound 9) synthetic
In 2L there-necked flask, add 200mL methylene dichloride, 39mL triethylamine and 57.7g3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenol (compound 3), be cooled to 20 ℃, add the solution being formed by 120g trifluoromethyl sulfonic acid (compound 8) and 200mL methylene dichloride, stir 1 hour.Below temperature control-75 ℃, drip 77g hydrogen fluoride triethylamine, continue to stir 1 hour.Below temperature control-75 ℃, the solution being comprised of 15mL bromine and 30mL methylene dichloride, rises again and carry out aftertreatment after-10 ℃.In 10L bucket, add 1L water, start stirring, pour reaction solution into, stirring minute, slowly add sodium bicarbonate solid (producing a large amount of gas) closely neutral to solution PH, standing separatory, water is with 500ml dichloromethane extraction once, merge organic phase, 70 ℃ are spin-dried for solvent and obtain thick material, and with 3 times of ethyl alcohol recrystallizations three times, suction filtration dries white solid.Theoretical yield: 119.0g, actual output: 71.0g, yield 59.6%
Gas phase purity (GC) 99.9%,
Fusing point: 72.8 ℃
Δ n is 0.076,
Δ ε is 20.3,
γ 1 is 106mPas.
Mass spectroscopy fragment: 163,191,291,496 (molecular ion peaks);
H-NMR nuclear magnetic spectrogram (CDCl
3, 300mhZ): δ H:0.90-2.60 (m, 10H), 3.70-4.10 (m, 8H), 5.98 (m, 1H) 6.10-6.50 (m, 4H).
Embodiment 3:
4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3,5, fluoro-4''-propyl group-[1, the 1' of 2'-tri-; 4', 1''] terphenyl (compound 12) synthetic
1) trifluoromethyl sulfonic acid (compound 11) is synthetic
In 1L there-necked flask, add 137g3, fluoro-4''-propyl group-[1, the 1' of 5,2'-tri-; 4', 1''] terphenyl-4-formic acid (compound 10), 47mL1,3-dimercaptopropane, 42mL trifluoromethane sulfonic acid, 145mL toluene and 145mL octane-iso, one side mouth is installed water trap, is warming up to backflow, reacts 6 hours, 0 ℃ of Slow cooling, suction filtration, obtains solid.After dry, carrying out next step feeds intake.
2) 4-{[3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenoxy group]-difluoromethyl }-3, the fluoro-4'-propyl group of 5-bis-biphenyl (compound 12) synthetic
In 2L there-necked flask, add 200mL methylene dichloride, 39mL triethylamine and 57.7g3, the fluoro-4-of 5-bis-(3-fluorine propoxy-)-phenol (compound 3), be cooled to 20 ℃, add the solution being formed by 142g trifluoromethyl sulfonic acid (compound 11) and 400mL methylene dichloride, stir 1 hour.Below temperature control-75 ℃, drip 77g hydrogen fluoride triethylamine, continue to stir 1 hour.Below temperature control-75 ℃, the solution being comprised of 15mL bromine and 30mL methylene dichloride, rises again and carry out aftertreatment after-10 ℃.In 10L bucket, add 1L water, start stirring, pour reaction solution into, stirring minute, slowly add sodium bicarbonate solid (producing a large amount of gas) closely neutral to solution PH, standing separatory, water is with 500ml dichloromethane extraction once, merge organic phase, 70 ℃ are spin-dried for solvent and obtain solid, and with 2 times of ethanol and 1 times of toluene recrystallization three times, suction filtration dries white solid.Theoretical yield: 139.2g, actual output: 144.1g, yield 82.0%
Gas phase purity (GC) 99.9%,
Fusing point: 80.2 ℃, clearing point: 170.2 ℃
Δ n is 0.200,
Δ ε is 21.0,
γ 1 is 245mPas.
Mass spectroscopy fragment: 173,346,375,580 (molecular ion peaks);
H-NMR nuclear magnetic spectrogram (CDCl
3, 300mhZ): δ H:0.90-2.60 (m, 9H), 3.90-4.10 (m, 4H), 6.10-7.30 (m, 11H).
According to the technical scheme of embodiment 1-3, provide for simple replacement of the raw material that contains corresponding group and can synthesize following compound:
Embodiment 4 mixed crystal compositions
The liquid crystal monomer using in following composition is all provided by Beijing Bayi Space LCD Materials Technology Co., Ltd..Except specified otherwise, in embodiment, the content of each component all represents mass percent.
Get the liquid crystalline cpd of following parts by weight and prepare liquid-crystal composition, the performance perameter of concrete proportioning and the liquid-crystal composition of gained is by shown in following table.
Have difluoro methyl ether bridged bond and-application in TN, IPS, FFS, ADS-TFT pattern of the liquid crystalline cpd of O (CH2) nF structure, the results are shown in Table 1-table 3.
The parts by weight of each component and performance perameter in table 1, liquid-crystal composition
The parts by weight of each component and performance perameter in table 2, liquid-crystal composition
The performance perameter of the liquid-crystal composition of table 3, liquid crystalline cpd
Table 4, the performance perameter of not adding the liquid-crystal composition of the compounds of this invention
By table, 1-4 can find out: added the liquid-crystal composition of the compounds of this invention, rotary viscosity is moderate, Δ n numerical value is moderate, electric charge conservation rate is high, especially has very large dielectric anisotropy.The add-on of compound is advisable with 1-80%, more preferably 3-50%.
Except the composition that test example exemplifies, add provided by the invention other have difluoro methyl ether bridged bond and-O (CH
2) other liquid-crystal compositions of liquid crystalline cpd of nF structure can obtain same good optics and electric property.
Although, above used general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a liquid crystalline cpd that contains difluoro-methoxy bridged bond, is characterized in that: described liquid crystalline cpd has suc as formula structure shown in I:
R-A
1-Z
1-A
2-Z
2-A
3-CF
2O-A
4-Z
3-A
5-O(CH
2)n-CH
2F
(Ⅰ)
Wherein, R is selected from H and does not replace or replace the alkyl that contains separately 1-12 carbon atom or alkoxyl group; One or more CH in the alkyl that contains separately 1-12 carbon atom replacing or alkoxyl group
2group is separately independently of one another by-C ≡ C-,-CF
2o-,-CH=CH-,-O-,-CO-O-or-O-CO-with O atom each other not directly the mode of keyed jointing replace, and wherein one or more H atoms can be replaced by halogen;
A
1, A
2and A
3be selected from independently of one another: singly-bound, 1,3-cyclopentyl, Isosorbide-5-Nitrae-cyclohexyl, 1,4-cyclohexenyl, piperidines-Isosorbide-5-Nitrae-bis-base, Isosorbide-5-Nitrae-Ya bis-rings [2,2,2] octyl group, Isosorbide-5-Nitrae-phenyl, naphthalene-2,6-bis-bases, trans naphthane-2,6-bis-bases, tetraline-2,6-bis-bases, 1,2-indane, indenes, phenanthryl or diphenylene-oxide, a CH in Isosorbide-5-Nitrae-cyclohexyl wherein
2or two not direct-connected CH
2can be replaced by O or S; In Isosorbide-5-Nitrae-phenyl, a CH or two not direct-connected CH can be replaced by N; Hydrogen in above-mentioned arbitrary situation in structure can be replaced by one or more halogens independently of one another;
A
4and A
5be selected from independently of one another: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or more halogens independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-,-(CH
2)
4-,-CH=CHCH
2cH
2-,-CH
2cH
2cH=CH-, CF
2o, OCF
2, CF
2cF
2, CF=CF, CH
2cF
2, CF
2cH
2, OCF
2cF
2o, C
2h
4cF
2o, CH
2cF
2oCH
2, CH
2oCF
2cH
2, OCF
2c
2h
4, C
3h
6o, OC
3h
6, C
2h
4oCH
2, CH
2oC
2h
4, CH
2o, OCH
2,-CH=CH-,-C ≡ C-or COO.
N is 1,2 or 3.
2. liquid crystalline cpd according to claim 1, is characterized in that: the alkyl that contains separately 1-5 carbon atom or alkoxyl group that R is selected from H and does not replace or replace, one or more CH in the alkyl that contains separately 1-5 carbon atom of replacement or alkoxyl group
2group separately independently of one another by-CH=CH-or-O-replaces, and wherein one or more H atoms can be replaced by halogen;
A
1, A
2and A
3be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl; Isosorbide-5-Nitrae-cyclohexyl wherein, a CH
2or two not direct-connected CH
2can be replaced by O.Hydrogen in above-mentioned arbitrary situation in structure can be replaced by one or more halogens independently of one another;
A
4and A
5be selected from independently of one another: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or more fluorine elements independently of one another;
Z
1, Z
2and Z
3be selected from independently of one another: singly-bound ,-(CH
2)
2-, CF
2o, OCF
2, CH
2o or OCH
2;
N is 1,2 or 3.
3. liquid crystalline cpd according to claim 1, is characterized in that: R is selected from H and does not replace the alkyl that contains 1-5 carbon atom;
A
1and A
2be selected from independently of one another: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-phenyl; Isosorbide-5-Nitrae-cyclohexyl wherein, a CH
2or two not direct-connected CH
2can be replaced by O.Hydrogen in above-mentioned arbitrary situation in structure can be replaced by one or more fluorine elements independently of one another;
A
3for Isosorbide-5-Nitrae-phenyl, wherein hydrogen can be replaced by one or two fluorine element independently of one another;
A
4and A
5be selected from: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen in Isosorbide-5-Nitrae-phenyl can be replaced by one or two fluorine element independently of one another;
Z
1and Z
2be selected from: singly-bound or-(CH
2)
2-;
N is 1,2 or 3.
4. liquid crystalline cpd according to claim 1, is characterized in that: described liquid crystalline cpd is selected from following formula compound:
R is selected from the alkyl that contains 2-5 carbon atom;
N is 1,2 or 3.
5. liquid crystalline cpd according to claim 4, is characterized in that: described liquid crystalline cpd is:
6. the preparation method who contains the liquid crystalline cpd of difluoro-methoxy bridged bond, is characterized in that: comprise the steps:
(1) starting material compound II-1, take Tetrabutyl amonium bromide as catalyzer, and DMF is solvent, at 65～72 ℃ and Br (CH
2) nCH
2f reaction, obtains compound ii-2;
(2) take and draw Buddhist nun's nickel as catalyzer in compound ii-2, under room temperature, obtains compound ii-3 with hydrogen reaction;
(3) trifluoromethane sulfonic acid be take as catalyzer in compound ii-4, and toluene and octane-iso are solvent, with 1,3-dimercaptopropane reflux dewatering, filters and obtains compound ii-5;
(4) compound ii-3 and compound ii-5, take hydrogen fluoride triethylamine as dewatering agent, and bromine is catalyzer ,-75 ℃ of following reactions, obtains target compound I;
Wherein, R, A
1, A
2, A
3, A
4, A
5, Z
1, Z
2, Z
3and n refer to same claim 1-5 any one.
7. the application of liquid crystalline cpd in field of liquid crystal display described in claim 1-5 any one.
8. the liquid-crystal composition that contains liquid crystalline cpd described in claim 1-5 any one.
9. the application of composition in manufacturing liquid crystal indicator described in claim 8.
10. application according to claim 9, is characterized in that: described liquid crystal indicator is TN, ADS, FFS or IPS liquid-crystal display.
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| CN115806466A (en) * | 2022-12-28 | 2023-03-17 | 北京燕化集联光电技术有限公司 | Negative liquid crystal compound and application thereof |
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