CN106318402A - Negative liquid crystal compound, composition and applications thereof - Google Patents
Negative liquid crystal compound, composition and applications thereof Download PDFInfo
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Abstract
The present invention relates to a novel negative liquid crystal compound, which concurrently has an alkyl o-difluorobenzene unit structure and a cyclopentane/butane unit structure, and has the structure represented by a general formula I. The invention further relates to a preparation method of the liquid crystal compound, and a composition containing the liquid crystal compound. The invention further relates to applications of the liquid crystal compound and the composition in the liquid crystal display field. The liquid crystal compound and the composition of the present invention have advantages of negative dielectric anisotropy, stable structure, and good application prospect.
Description
Technical field
The present invention relates to liquid crystal display material field, be specifically related to a class negative liquid crystal compound and combinations thereof thing, and described compound and the application of compositions.
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 of liquid-crystal compounds significantly widened kinds of displays part, electro-optical device, electronic component, sensor etc..To this end, have been proposed that many different structures, particularly in nematic crystal field, nematic liquid crystal compound has the most obtained most commonly used application in flat faced display.Especially in the system of tft active matrix.
Liquid crystal display experienced by very long road for development with the discovery of liquid crystal.Within 1888, Austrian botanist Friedrich Reinitzer is found that the first liquid crystal material benzoic acid cholesterol (cholesteryl benzoate).Within 1917, Manguin has invented rubbing, in order to make single domain liquid crystal and research optical anisotropy.E.Bose in 1909 establishes and collects together (Swarm) theory, and obtains the experiment support (1918) of L.S.Ormstein and F.Zernike et al., is discussed as statistical fluctuation by De Gennes.G.W.Oseen and H.Zocher1933 foundes continuum theory, and obtains F.C.Frank perfect (1958).M.Born (1916) and K.Lichtennecker (nineteen twenty-six) finds and have studied the dielectric anisotropy of liquid crystal.1932, nematic phase was divided into the positive and negative big class of property two by W.Kast accordingly.Nineteen twenty-seven, V.Freedericksz and V.Zolinao finds that nematic liquid crystal, under electric field (or magnetic field) acts on, deforms upon and there is voltage threshold (Freederichsz transformation).This making being found to be liquid crystal display provides foundation.
Nineteen sixty-eight RCA Corp. of U.S. R.Williams finds that nematic liquid crystal forms striped farmland under electric field action, and has light scattering phenomenon.G.H.Heilmeir is with it developing into dynamic scattering display pattern, and makes first liquid crystal display (LCD) in the world.Early seventies, Helfrich and Schadt has invented TN principle, and people utilize TN photoelectric effect and integrated circuit to combine, and is made display device (TN-LCD), and wide prospect has been opened up in the application for liquid crystal.Since the seventies, due to large scale integrated circuit and the development of liquid crystal material, liquid crystal application in terms of display achieves breakthrough development, and T.Scheffer in 1983～1985 et al. successively proposes super-twist nematic (Super Twisred Nematic:STN) pattern and P.Brody and again used in active matrix (Active matrix:AM) mode that 1972 propose.Traditional TN-LCD technology has developed into STN-LCD and TFT-LCD technology, although the number of scanning lines of STN up to 768 row more than, but remain the problems such as response speed, visual angle and gray scale when the temperature increases, therefore large area, high information quantity,
Colored display uses Active Matrix LCD At mode mostly.TFT-LCD is widely used for direct viewing type TV, large-curtain projecting TV set, terminal shows and some military instrument shows, it is believed that TFT-LCD technology has the most wide application prospect.
Wherein " active matrix " includes two types: 1, as the OMS (metal-oxide semiconductor (MOS)) on the silicon wafer of substrate or other diode.2, as the thin film transistor (TFT) (TFT) on the glass plate of substrate.
Monocrystal silicon limits display size as substrate material, because each several part display device even module assembled many problems occurs in its junction.Thus, the second thin film transistor (TFT) is to have promising active matrix type, and the photoelectric effect utilized is typically TN effect.TFT includes compound semiconductor, such as Cdse, or the TFT based on polycrystalline or amorphous silicon.
Negativity monomer liquid crystal containing alkyl is illustrated in patent JP10291945 as far back as Japanese Chisso Corporation in 1998.Liquid crystal monomer containing cyclopenta was reported in US61027230 by Jing Meisheng company in 2009.
At present, TFT-LCD product technology is the most ripe, successfully solves the technical barriers such as visual angle, resolution, color saturation and brightness, its display performance already close to or more than CRT display.Large scale and small-medium size TFT-LCD display the most gradually occupy the dominant position of flat faced display in respective field.Especially negative liquid crystal shows and shows fast response time that the characteristic that transmitance is high is developed rapidly in recent years.Therefore the negative liquid crystal finding photoelectric properties stable is extremely important.
Summary of the invention
It is an object of the invention to overcome defect of the prior art, it is provided that a kind of novel negative liquid crystal compound, this compound has alkyl o-difluoro-benzene and ring penta/butane cellular construction simultaneously.This compound has negative dielectric anisotropy and constitutionally stable feature,
Described compound has a structure as shown in formula I:
In described formula I, Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from H and the unsubstituted or substituted alkyl each containing 1～12 carbon atom；Wherein one or more CH2Group the most independently of one another can be by-C ≡ C-,-CF2O-,-CH=CH-or-O-replace, and wherein one or more H atom can be optionally substituted by halogen；
Rc is selected from the alkyl having 1～4 carbon atom；
A1And A2It is each independently selected from: singly-bound, 1,4-cyclohexyl, 1,4-cyclohexenyl group or 1,4-phenyl；In described 1,4-phenyl, H can be independently of one another by one or more halogen substiuted；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-(CH2)4-,-CH=CHCH2CH2-、-CH2CH2CH=CH-,-CF2O-、-OCF2-、-CF2CF2-,-CF=CF-,-CH2CF2-、-CF2CH2-、-OCF2CF2O-、-C2H4CF2O-、-CH2CF2OCH2-、-CH2OCF2CH2-、-OCF2C2H4-、-C3H6O-、-OC3H6-、-C2H4OCH2-、-CH2OC2H4-、-CH2O-、-OCH2-,-CH=CH-,-C ≡ C-or-COO-；
M and n is each independently selected from 0,1 or 2.
Liquid-crystal compounds of the present invention, due in structure have o-difluoro-benzene structure, therefore, have negative dielectric anisotropy advantage, beneficially liquid crystal indicator improve transmitance.
Liquid-crystal compounds of the present invention is preferably: in described formula I, and Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from the unsubstituted or substituted alkyl each containing 1～6 carbon atom；Wherein one or more CH2Group the most independently of one another can be by-CH=CH-, and-O-replaces, and wherein one or more H atom can be optionally substituted by halogen；
Rc is selected from the alkyl having 1～4 carbon atom；
A1It is selected from: singly-bound, 1,4-cyclohexyl, 1,4-cyclohexenyl group or 1,4-phenyl；H in described 1,4-phenyl can be independently of one another by one or more halogen substiuted；
A2It is selected from: singly-bound or 1,4-phenyl；H in described 1,4-phenyl can be independently of one another by one or more halogen substiuted；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-(CH2)4-、-CF2CF2-,-CF=CF-,-CH2CF2-、-CF2CH2-、-CH2O-、-OCH2-,-CH=CH-or-C ≡ C-；
M and n is each independently selected from 0,1 or 2.
Liquid-crystal compounds of the present invention is more preferably: in described formula I, and Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from the unsubstituted or substituted alkyl each containing 1-6 carbon atom；Wherein one or more CH2Group can be replaced by-O-the most independently of one another；
Rc is methyl；
A1Being selected from: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen of Isosorbide-5-Nitrae-phenyl can be independently of one another by one or more halogen substiuted；
A2Being selected from: singly-bound or Isosorbide-5-Nitrae-phenyl, wherein the hydrogen of Isosorbide-5-Nitrae-phenyl can be independently of one another by one or more halogen substiuted；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-CH2O-、-OCH2-；
M is 1 or 2；
N is 0 or 1.
Liquid-crystal compounds of the present invention is more preferably: in described formula I, Ra is Pentamethylene. or Tetramethylene.；Rb is selected from the alkyl containing 1～6 carbon atom or alkoxyl；Rc is methyl；
A1For Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group or Isosorbide-5-Nitrae-phenyl, the one or more H in described Isosorbide-5-Nitrae-phenyl can be optionally substituted by halogen independently of one another；Z1For singly-bound or-CH2O-；M is 1 or 2；
A2For Isosorbide-5-Nitrae-phenyl, Z2For singly-bound, n is 0 or 1.
In general formula I of the present invention, when m is more than 1, represents and have many groups of-A1-Z1-construction unit；Wherein, each A1The concrete group represented can be the same or different, and each Z1The concrete group represented can be the same or different.
Liquid-crystal compounds of the present invention preferably has a compound of below general formula structure:
In described formula I-1～I-18, R is selected from the alkyl containing 1～5 carbon atom or alkoxyl.
Liquid-crystal compounds of the present invention most preferably has the compound of described formula I-1, I-2, I-3, I-4, I-9 and I-10, and wherein, R is selected from the alkyl containing 1～5 carbon atom or alkoxyl.Above-mentioned most preferred compound, while increasing dielectric anisotropy, improving clearing point, has lower viscosity and more preferable stability.
The second object of the present invention is to provide the preparation method of liquid-crystal compounds of the present invention.
There is formulaThe preparation method of compound as follows, in this structure, Ra is cyclobutyl or cyclopenta, m=1 or 2:
Synthetic route is:
Concretely comprise the following steps: (1) in an inert atmosphere ,-75～-65 DEG C with compoundFor initiation material, oxolane is solvent, adds n-BuLi and carries out Lithiation, obtains after insulation reaction 0.5-1hAddCarrying out the addition of lithium reagent and ketone, after stirring nature is risen again, be poured into water, separatory, separate organic facies, solvent is evaporated off after washing, add p-methyl benzenesulfonic acid and toluene, after the lower point of water that refluxes, cross silicagel column, toluene rushes post, and solvent is evaporated off, and to obtain final product
(2) by step (1) gainedIt is dissolved in toluene and ethanol, with palladium-carbon catalyst after normal temperature and pressure carries out hydrogenation 3h～5h, to obtain final product
There is formulaThe preparation method of compound as follows, in this structure, Ra is cyclobutyl or cyclopenta, n=0 or 1, m=1 or 2；A1For Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group or Isosorbide-5-Nitrae-phenyl, the one or more H in described Isosorbide-5-Nitrae-phenyl can be optionally substituted by halogen independently of one another；
Synthetic route is:
Concretely comprise the following steps: (1) in an inert atmosphere ,-75～-65 DEG C with compoundFor initiation material, oxolane is solvent, add n-BuLi and carry out lithium generation, obtain lithium after insulation reaction 0.5-1h for intermediate, add methyl borate. and carry out the addition of lithium reagent and boric acid, after stirring nature is risen again, pour in hydrochloric acid water, separatory, separate organic facies, solvent is evaporated off after washing, to obtain final product
(2) step (1) gained is takenWith toluene, ethanol, water as solvent, it is catalyst that four triphenylphosphines close palladiums, and sodium carbonate is alkali, and nitrogen is protected, backflow lower withThere is SUZUKI coupling reaction, to obtain final product
As the preferred version of this preparation method, as m=1,Represent phenyl or substituted-phenyl；
As m=2,RepresentDescribed A3For phenyl or substituted-phenyl.
There is formulaThe preparation method of compound as follows, in this structure, Ra is cyclobutyl or cyclopenta, m=1 or 2:
Synthetic route is:
Concretely comprise the following steps: (1) takesWith oxolane as solvent, in aqueous hydrogen peroxide solution, oxidation reaction generatesAfter adding ethyl acetate separatory, wash with sodium sulfite solution, solvent is evaporated off；
(2) step (1) gained is takenWithUnder the conditions of potassium carbonate, heating reflux reaction 3～5h is etherified, and toluene extracts, and washes organic facies, and solvent is evaporated off, and crosses silicagel column, solvent, ethyl alcohol recrystallization is again evaporated off, to obtain final product
In preparation method of the present invention, Rb is selected from H and the unsubstituted or substituted alkyl each containing 1～12 carbon atom；In the described substituted alkyl containing 1～12 carbon atom, one or more CH2Group can be independently of one another by-C ≡ C-,-CF2O-,-CH=CH-or-O-replace, and wherein one or more H atom can be optionally substituted by halogen independently of one another.Described Rb is preferably the alkyl containing 1～6 carbon atom or alkoxyl, more preferably contains alkyl or the alkoxyl of 1～5 carbon atom.
Use above-mentioned preparation method to stablize, be efficiently obtained by liquid-crystal compounds of the present invention.
The third object of the present invention is the protection compositions containing described liquid-crystal compounds.Described liquid-crystal compounds mass percent in the composition is 1～80%, preferably 3～50%.
It is contemplated that, addition based on above-mentioned liquid-crystal compounds, it is possible to significantly improve dielectric anisotropy and the clearing point of existing customary liquid-crystal compositions.
The fourth object of the present invention is to protect described liquid-crystal compounds and the compositions containing described liquid-crystal compounds in the application of field of liquid crystal display.Liquid-crystal compounds of the present invention and liquid-crystal composition can be applicable in liquid crystal indicator, and described liquid crystal indicator includes and is not limited to VA, FFS or IPS liquid crystal display.By liquid-crystal composition application to after liquid crystal indicator, have dielectric constant big and for negative, clearing point is high, intersolubility is good and the technique effect of the feature of stable performance.
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.
In each embodiment, described raw material if no special instructions, is all either commercially available from open.
Embodiment 1
1, negative liquid crystal compound is: 2-(4-Pentamethylene .-hexamethylene) the fluoro-1-methylbenzene of-5-ethyoxyl-3,4-two；The structure of described compound is as follows:
2, according to following route and the step described compound of synthesis:
Concretely comprise the following steps: in the there-necked flask of 1000ml clean dried, add 0.10mol'sWith 150ml oxolane, being cooled to-70 DEG C under nitrogen protection, temperature control-65～-70 DEG C of dropping 0.11mol concentration are the n-BuLi hexane solution of 2.5mol/L, and temperature control reacts 1.0 hours；Temperature control-65～-70 DEG C, drip 0.1molWith the solution of 50ml oxolane composition, drip complete temperature control and react process in 1 hour；Reactant liquor is poured slowly in the beaker equipped with trash ice and 50ml concentrated hydrochloric acid, acidification hydrolization, separatory after stirring, aqueous phase methylbenzene extraction twice, use toluene 50ml, merging organic facies, solvent evaporated every time；Add 400ml toluene and 2g p-methyl benzenesulfonic acid, be dehydrated 4 hours；It is down to room temperature, washes twice, solvent is evaporated off；After crossing silica gel column chromatography, toluene and ethyl alcohol recrystallization purify, and dry, and add after the palladium carbon of 5% mass is hydrogenated with 4h under an atmosphere of hydrogen, are filtered to remove palladium carbon, evaporated under reduced pressure solvent, to obtain final product.
After testing, the yield of products therefrom is 60%, and gas phase purity is 99.5%；GC-MS testing result is: m/z:322.2 (M+)；H-NMR nuclear magnetic spectrogram (CDCl3, 300MHz): δ H:1.40-1.73 (m, 21H), 2.35-3.98 (m, 6H), 6.24 (m, 1H).
The synthesis path provided according to embodiment 1, it is not necessary to preparation process carries out essence adjustment, raw material only changes into the raw material of corresponding group, can synthesize the compound of following structure:
Embodiment 2
1, negative liquid crystal compound is: 4 '-cyclobutyl-2,3-two fluoro-6-methyl-4-pentylbiphenyl；The structure of described compound is as follows:
2, according to following route and the step described compound of synthesis:
Concretely comprise the following steps: in the there-necked flask of 1000ml clean dried, add 0.1mol'sWith 150ml oxolane, being cooled to-70 DEG C under nitrogen protection, temperature control-65～-70 DEG C of dropping 0.11mol concentration are the n-BuLi hexane solution of 2.5mol/L, and temperature control reacts 1.0 hours；Temperature control-65～-70 DEG C, dropping 0.12mol methyl borate. stirring nature temperature reaction, to after-30 degrees Celsius, adds the acidifying of 1M hydrochloric acid, separating organic facies, aqueous phase 100ml ethyl acetate extracts once, after merging organic facies washes twice, solvent is evaporated off, adds 0.1molAdd 400ml toluene, 200ml water and the potassium carbonate of 0.2mol and four/triphenyl palladium, back flow reaction 3h；Separating organic facies, aqueous phase 100ml toluene extracts once, after merging organic facies washes twice, crosses silica gel column chromatography, and toluene rushes post 1 time, solvent, toluene and ethyl alcohol recrystallization is evaporated off and purifies, dry, to obtain final product.
After testing, the yield of products therefrom is 60%, gas phase purity 99.0%；The testing result of GC-MS is: m/z:300.1 (M+)；H-NMR nuclear magnetic spectrogram (CDCl3, 300MHz): δ H:0.96-1.96 (m, 7H), 2.25-3.24 (m, 10H), 6.73-7.40 (m, 5H).
The synthesis path provided according to embodiment 2, it is not necessary to preparation process carries out essence adjustment, raw material only changes into the raw material of corresponding group, can synthesize the compound of following structure:
Embodiment 3
1, negative liquid crystal compound is: 2-(4-cyclopenta-cyclohexyl methoxy)-3,4-two fluoro-1-methyl-5-butyl benzene；The structure of described compound is as follows:
2, according to following route and the step described compound of synthesis:
Concretely comprise the following steps:
(1) in the clean there-necked flask of 1000ml, synthesis in embodiment 2 is addedThe oxolane of 0.1mol, 200ml, is heated to 60 DEG C, and dropping 0.4mol concentration is the aqueous hydrogen peroxide solution of 30%, drip after finishing, back flow reaction 3h, separatory, aqueous phase 100ml ethyl acetate is extracted twice, merge organic facies, add 100ml water and the washing of 5g sodium sulfite solution, solvent is evaporated off；With the petroleum ether recrystallization of 50ml toluene and 50ml, obtain faint yellow solid 15g；The gas phase purity of gained faint yellow solid is 90%, and yield is 70%；After testing, its structure is
(2) adding 9.4g step (1) gained faint yellow solid in the there-necked flask of clean 250ml, 8.3g potassium carbonate, the ethanol mixing of 60ml is heated with stirring to backflow, dropping 0.5mol'sEthanol solution, refluxes after adding 4 hours again and is etherified, and pours in 200ml water, and ether extracts, and washes organic facies, steams neat solvent, petroleum ether dissolution, crosses silicagel column, again steam neat solvent, ethyl alcohol recrystallization, obtain 10.5g white crystal, to obtain final product.
After testing, the yield of products therefrom is 60%, and gas phase purity is 99.9%；GC-MS testing result is: m/z:350.2 (M+)；H-NMR nuclear magnetic spectrogram (CDCl3, 300MHz): δ H:0.96-2.55 (m, 29H), 3.90 (m, 2H), 6.56 (m, 1H).
The synthesis path provided according to embodiment 3, it is not necessary to preparation process carries out essence adjustment, raw material only changes into the raw material of corresponding group, can synthesize the compound of following structure:
Embodiment 4
Containing the compositions of liquid-crystal compounds of the present invention, particular make-up is as shown in table 1.
Table 1: the composition of compositions and consumption
Embodiment 5
Containing the compositions of liquid-crystal compounds of the present invention, particular make-up is as shown in table 2.
Table 2: the composition of compositions and consumption
Embodiment 6
Containing the compositions of liquid-crystal compounds of the present invention, particular make-up is as shown in table 3.
Table 3: the composition of compositions and consumption
Comparative example
Compared with Example 6, differ only in: useWithReplace liquid-crystal compounds of the present invention；Compositions particular make-up is as shown in table 4.
Table 4: the composition of compositions and consumption
Experimental example
According to the common detection methods of this area, detection embodiment 4～6 and the performance of comparative example resulting composition.Testing result is as shown in table 5；Wherein, the concrete meaning of each performance parameter is as follows:
△ n is optical anisotropy (25 DEG C)；
△ ε is to represent the dielectric anisotropy under 25 DEG C and 1kHz；
C.p is clearing point (DEG C)；
γ 1 is the rotary viscosity (mPa s) at 25 DEG C.
Table 5: the performance test results of compositions
| △n | △ε | C.p | γ1 | |
| Embodiment 4 | 0.089 | -3.3 | 70 | 82 |
| Embodiment 5 | 0.080 | -3.4 | 72 | 82 |
| Embodiment 6 | 0.080 | -3.4 | 71 | 82 |
| Comparative example | 0.080 | -3.0 | 68 | 82 |
As can be seen from Table 5, the liquid-crystal composition containing liquid-crystal compounds of the present invention has big dielectric anisotropy, can effectively reduce the use of polar monomer in liquid-crystal composition, the purpose reaching to improve response time with this.It addition, liquid-crystal composition provided by the present invention has higher clearing point performance, the use for high clearing point monocrystalline in liquid-crystal composition can be reduced, increase low viscosity component and use, effectively reduce the viscosity characteristics of liquid-crystal composition.
In addition to the compositions that embodiment is enumerated, other liquid-crystal compositions adding other liquid-crystal compounds with alkyl o-difluoro-benzene and ring penta/butane cellular construction that the present invention provides can obtain the most excellent optically and electrically performance.
Although, use general explanation, detailed description of the invention and test, the present invention is described in detail, but on the 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 without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (10)
1. a negative liquid crystal compound, it is characterised in that described compound has a structure as shown in formula I:
In described formula I, Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from H and the unsubstituted or substituted alkyl each containing 1～12 carbon atom；In the described substituted alkyl containing 1～12 carbon atom, one or more CH2Group can be independently of one another by-C ≡ C-,-CF2O-,-CH=CH-or-O-replace, and wherein one or more H atom can be optionally substituted by halogen independently of one another；
Rc is selected from the alkyl having 1～4 carbon atom；
A1And A2It is each independently selected from: singly-bound, 1,4-cyclohexyl, 1,4-cyclohexenyl group or 1,4-phenyl；In described 1,4-phenyl, one or more H can be optionally substituted by halogen independently of one another；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-(CH2)4-,-CH=CHCH2CH2-、-CH2CH2CH=CH-,-CF2O-、-OCF2-、-CF2CF2-,-CF=CF-,-CH2CF2-、-CF2CH2-、-OCF2CF2O-、-C2H4CF2O-、-CH2CF2OCH2-、-CH2OCF2CH2-、-OCF2C2H4-、-C3H6O-、-OC3H6-、-C2H4OCH2-、-CH2OC2H4-、-CH2O-、-OCH2-,-CH=CH-,-C ≡ C-or-COO-；
M and n is each independently selected from 0,1 or 2.
Liquid-crystal compounds the most according to claim 1, it is characterised in that in described formula I, Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from the unsubstituted or substituted alkyl each containing 1～6 carbon atom；In the described substituted alkyl containing 1～6 carbon atom, one or more CH2Group can be replaced by-CH=CH-or-O-independently of one another, and wherein one or more H atom can be optionally substituted by halogen independently of one another；
Rc is selected from the alkyl having 1～4 carbon atom；
A1It is selected from: singly-bound, 1,4-cyclohexyl, 1,4-cyclohexenyl group or 1,4-phenyl；One or more H in described 1,4-phenyl can be optionally substituted by halogen independently of one another；
A2It is selected from: singly-bound or 1,4-phenyl；One or more H in described 1,4-phenyl can be optionally substituted by halogen independently of one another；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-(CH2)4-、-CF2CF2-,-CF=CF-,-CH2CF2-、-CF2CH2-、-CH2O-、-OCH2-,-CH=CH-or-C ≡ C-；
M and n is each independently selected from 0,1 or 2.
Liquid-crystal compounds the most according to claim 1, it is characterised in that in described formula I, Ra is selected from Pentamethylene. or Tetramethylene.；
Rb is selected from the unsubstituted or substituted alkyl each containing 1-6 carbon atom；In the described substituted alkyl containing 1～6 carbon atom, one or more CH2Group can be replaced by-O-independently of one another；
Rc is methyl；
A1It is selected from: singly-bound, Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group, Isosorbide-5-Nitrae-phenyl；One or more H in described 1,4-phenyl can be optionally substituted by halogen independently of one another；
A2It is selected from: singly-bound or Isosorbide-5-Nitrae-phenyl；One or more H in described 1,4-phenyl can be optionally substituted by halogen independently of one another；
Z1And Z2It is each independently selected from: singly-bound ,-(CH2)2-、-CH2O-、-OCH2-；
M is 1 or 2；
N is 0 or 1.
Liquid-crystal compounds the most according to claim 1, it is characterised in that in described formula I: Ra is Pentamethylene. or Tetramethylene.；Rb is selected from the alkyl containing 1～6 carbon atom or alkoxyl；Rc is methyl；
A1For Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group or Isosorbide-5-Nitrae-phenyl, the one or more H in described Isosorbide-5-Nitrae-phenyl can be optionally substituted by halogen independently of one another；Z1For singly-bound or-CH2O-；M is 1 or 2；
A2For Isosorbide-5-Nitrae-phenyl, Z2For singly-bound, n is 0 or 1.
Liquid-crystal compounds the most according to claim 1, it is characterised in that described compound is selected from the compound with below general formula structure:
In described formula I-1～I-18, R is selected from the alkyl containing 1～5 carbon atom or alkoxyl.
6. prepare the method for negative liquid crystal compound described in Claims 1 to 5 any one for one kind, it is characterised in that said method comprising the steps of:
(1) in an inert atmosphere, with compoundFor initiation material, oxolane is solvent, adds n-BuLi and carries out Lithiation, obtainsAddCarry out the addition of lithium reagent and ketone, products therefrom adds p-methyl benzenesulfonic acid and toluene reacts, after purification, to obtain final product
(2) by step (1) gainedIt is dissolved in toluene and ethanol, carries out hydrogenation with palladium-carbon catalyst in normal temperature and pressure, to obtain final product
In raw material described in each step and product, Ra is cyclobutyl or cyclopenta, m=1 or 2.
7. prepare the method for negative liquid crystal compound described in Claims 1 to 5 any one for one kind, it is characterised in that said method comprising the steps of:
(1) in an inert atmosphere, with compoundFor initiation material, oxolane is solvent, adds n-BuLi and carries out lithium generation, obtains lithium for intermediate, adds methyl borate. and carries out the additive reaction of lithium reagent and boric acid and generate
(2) step (1) gained is takenWith toluene, ethanol, water as solvent, it is catalyst that four triphenylphosphines close palladium, and sodium carbonate is alkali, and nitrogen is protected, withThere is SUZUKI coupling reaction, to obtain final product
In raw material described in each step and product, Ra is cyclobutyl or cyclopenta, n=0 or 1, m=1 or 2；A1For Isosorbide-5-Nitrae-cyclohexyl, Isosorbide-5-Nitrae-cyclohexenyl group or Isosorbide-5-Nitrae-phenyl, the one or more H in described Isosorbide-5-Nitrae-phenyl can be optionally substituted by halogen independently of one another.
8. prepare the method for negative liquid crystal compound described in Claims 1 to 5 any one for one kind, it is characterised in that said method comprising the steps of:
(1) takeWith oxolane as solvent, in aqueous hydrogen peroxide solution, oxidation reaction generates
(2) step (1) gained is takenWithUnder the conditions of potassium carbonate, carry out etherification reaction, after purification, to obtain final product
In raw material described in each step and product, Ra is cyclobutyl or cyclopenta, m=1 or 2.
9. the compositions containing negative liquid crystal compound described in Claims 1 to 5 any one, it is characterised in that in the composition, the percentage by weight of liquid-crystal compounds is 1～80%.
10. compositions described in negative liquid crystal compound described in Claims 1 to 5 any one or claim 9 is in the application of field of liquid crystal display.
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