CN104046367A - Liquid crystal compound containing 2,6-dioxo-dicyclo-[2,2,1] heptanes structure as well as preparation method and application of liquid crystal compound - Google Patents
Liquid crystal compound containing 2,6-dioxo-dicyclo-[2,2,1] heptanes structure as well as preparation method and application of liquid crystal compound Download PDFInfo
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Abstract
The invention relates to a liquid crystal compound containing a 2,6-dioxo-dicyclo-[2,2,1] heptanes structure. The compound has a structural formula (I) as shown in the specification. The liquid crystal compound disclosed by the invention has characteristics of stable property, good intersolubility, good ultraviolet resistance, great dielectric anisotropy; by being applied to a liquid crystal composition, the compound disclosed by the invention has shorter response time, a moderate delta n value, and a higher charge retention rate, has low threshold value voltage, effectively improves comprehensive performances of the liquid crystal composition, and is wide in application prospect.
Description
Technical field
The present invention relates to a kind of novel liquid crystalline cpd containing 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure and its preparation method and application, belong to liquid crystal material technical field.
Background technology
In recent years, the Application Areas of liquid crystalline cpd is more and more wider, has been widely used in various types of display equipments, electrooptics device, sensor.Wherein, in display unit, nematic liquid crystal has the broadest purposes.Nematic liquid crystal has been widely used in passive TN or STN matrix display and has had in the system of tft active matrix.
Liquid crystal material requires to possess good chemistry and thermostability, the good stability to electric field and electromagnetic radiation, wider nematic temperature range, suitable specific refractory power, dielectric anisotropy, faster response speed and high voltage retention.
Along with the development of technique of display, liquid crystal material is also had higher requirement, especially in quick response, reduce driving voltage, reduce the aspects such as power consumption, be therefore necessary that development of new liquid crystalline cpd is to meet above-mentioned needs.
Summary of the invention
The object of this invention is to provide a kind of liquid crystalline cpd that contains 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, described compound has larger dielectric anisotropy, high clearing point, suitable high specific refractory power, and has good low-temperature stability.
For achieving the above object, the present invention adopts following technical scheme:
A kind of liquid crystalline cpd that contains 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, has following general structure (I):
In formula: R
1expression-H, has alkyl or the alkoxyl group of 1-12 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-replaces, but requires O atom directly not connect each other;
R
2expression-H ,-F ,-Cl ,-CN ,-NCS ,-CF
3,-OCF
3,-OCF
2cl, has alkyl or the alkoxyl group of 1-12 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-replaces, but requires O atom directly not connect each other;
A
1represent Isosorbide-5-Nitrae-phenylene, wherein, the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylidene or Isosorbide-5-Nitrae-phenylene; Wherein, 1-4 hydrogen atom in Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylidene can be replaced by fluorine atom; 1-4 in an Isosorbide-5-Nitrae-phenylene hydrogen atom can be replaced by fluorine atom or 1-2-CH-group can be replaced by nitrogen-atoms;
Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-O-CO-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CH
2cH
2-,-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-,-CH
2cHF-,-CHFCH
2-;
K, l, m are identical or different, represent independently of one another 0,1 or 2, and k+l+m≤3.
On this basis, the present invention has made preferred restriction to said structure:
In some preferred embodiments, described R
1expression-H, has alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-CH=CH-or-O-replaces, but requires O atom directly not connect each other;
R
2expression-H ,-F ,-Cl ,-CN ,-CF
3,-OCF
3,-OCF
2cl, has alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-CH=CH-or-O-replaces, but requires O atom directly not connect each other;
A
1represent Isosorbide-5-Nitrae-phenylene, wherein, the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene; Wherein, the 1-4 of an Isosorbide-5-Nitrae-cyclohexylidene hydrogen atom can be replaced by fluorine atom; 1-4 in an Isosorbide-5-Nitrae-phenylene hydrogen atom can be replaced by fluorine atom or 1-2-CH-group can be replaced by nitrogen-atoms;
Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2o-,-CH
2cH
2-,-C ≡ C-,-CH=CH-,-CF=CF-,-C
2f
4-;
K, l, m are identical or different, represent independently of one another 0,1 or 2, and k+l+m≤3.
More preferably, in some embodiments, R
1represent to have alkyl or the alkoxyl group of 1-7 carbon atom; Wherein, in alkyl or alkoxyl group one or more-CH
2-can be independently of one another by-CH=CH-, be replaced;
R
2expression-H ,-F ,-Cl ,-CN ,-CF
3,-OCF
3, there is alkyl or the alkoxyl group of 1-7 carbon atom; Wherein, in alkyl or alkoxyl group one or more-CH
2-can be independently of one another by-CH=CH-, be replaced;
A
1represent Isosorbide-5-Nitrae-phenylene, wherein, the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene; Wherein the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2cH
2-,-C ≡ C-;
K, l, m are identical or different, represent independently of one another 0,1,2, and k+l+m≤2.
In some preferred embodiments, the compound of logical formula I is particularly preferably one or more of following compound:
Above-claimed cpd textural property is stable, has the advantages that mutual solubility is good, uvioresistant performance is good, electric charge conservation rate is high and dielectric anisotropy is large.
Another object of the present invention is to provide the above-mentioned preparation method who contains the liquid crystalline cpd of 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, and for realizing this purpose, the present invention adopts following technical scheme:
A kind of preparation method who contains the liquid crystalline cpd of 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, comprises the steps:
Step 1:
with
under Catalyzed by p-Toluenesulfonic Acid, react generation
Step 2:
under pyridine effect, react generation with Tosyl chloride
Step 3:
react with sodium iodide, generate
Step 4:
with
reaction generates
Step 5:
through potassium permanganate oxidation, generate
Step 6:
closed loop under hydrochloric acid catalysis, generates
Step 7:
with
reaction generates the compound of said structure general formula (I).
The concrete synthetic route of the compound of said structure general formula (I) can be as follows:
In above-mentioned steps 1) to step 7) in, X in described structural formula
1represent H or Br, R
1, R
2, A
1, A
2, A
3, A
4, Z
1, Z
2, Z
3, k, l, m definition all identical with the definition in general structure (I).
Preparation method of the present invention, described step 1) in,
with
molar ratio be 1: 1～3,0 ℃～30 ℃ of temperature of reaction, the reaction times is 6～18 hours;
Preparation method of the present invention, described step 2) in,
the molar ratio of Tosyl chloride and pyridine is 1: 1～1.5: 1～2,0 ℃～30 ℃ of temperature of reaction, and the reaction times is 6～18 hours;
Preparation method of the present invention, described step 3) in,
with the molar ratio of sodium iodide be 1: 1.0～3.0,10 ℃～50 ℃ of temperature of reaction, the reaction times is 6～12 hours;
Preparation method of the present invention, described step 4) in,
with
molar ratio be 1: 0.9～1.1, temperature of reaction-10 ℃～30 ℃, the reaction times is 2～12 hours;
Preparation method of the present invention, described step 5) in,
with the molar ratio of potassium permanganate be 1: 1.0～2.0,0 ℃～30 ℃ of temperature of reaction, the reaction times is 1～4 hour.
Preparation method of the present invention, described step 6) in,
with the molar ratio of hydrochloric acid be 1: 2.0～4.0,0 ℃～30 ℃ of temperature of reaction, the reaction times is 1～4 hour.
Preparation method of the present invention, described step 7) in,
with
molar ratio be 1: 0.9～1.2,60 ℃～120 ℃ of temperature of reaction, the reaction times is 4～12 hours.
Further, preparation method of the present invention, preferably:
Step 1) in,
with
molar ratio be 1: 2.0;
Step 2) in,
the molar ratio of Tosyl chloride and pyridine is 1: 1.1: 1.3;
Step 3) in,
with the molar ratio of sodium iodide be 1: 2.5;
Step 4) in,
with
the molar ratio that feeds intake be 1: 1.0;
Step 5) in,
with the molar ratio of potassium permanganate be 1: 1.2;
Step 6) in,
with the molar ratio of hydrochloric acid be 1: 3.0;
Step 7) in,
with
molar ratio be 1: 1.0;
Wherein, more preferably described step 1) in, temperature of reaction is 15 ℃～25 ℃, the time is 8～12 hours;
Described step 2) in, temperature of reaction is 15 ℃～25 ℃, and the time is 8～12 hours;
Described step 3) in, temperature of reaction is 40 ℃～50 ℃, and the time is 8～10 hours;
Described step 4) in, temperature of reaction is 5 ℃～15 ℃, and the reaction times is 8～10 hours;
Mentioned in technical solution of the present invention
all can obtain by method own known in open commercial sources or document is synthetic.
In addition, it should be noted that in preparation method of the present invention, part does not make each step solvent for use and consumption, the separating-purifying of product being particularly limited, the rate of addition of reactant etc. are those skilled in the art understands and grasp.In the present invention, except make special instruction, the 5-15 that the volumetric usage of solvent is generally reactant quality doubly, can suitably adjust according to the size of reaction substrate consumption and selected reaction flask by concrete consumption; The rate of addition of reactant is conventionally in conjunction with concrete speed of response Comprehensive Control etc.On basis disclosed by the invention, those skilled in the art can according to practical situation correspondingly select any can with technical scheme realize the present invention.
Preparation method of the present invention is scientific and reasonable, easy and simple to handle, be easy to amplify produce, and prepared liquid crystalline cpd yield is up to 75%.
The 3rd object of the present invention is to provide a kind of liquid-crystal composition that contains above-mentioned liquid crystalline cpd.Wherein, the 1-50% that the consumption of above-mentioned liquid crystalline cpd is liquid-crystal composition, preferably 3-30%.In liquid-crystal composition, the those skilled in the art that are defined as of other compositional selectings and consumption thereof grasp.Predictably, add above-mentioned liquid crystalline cpd can reduce threshold voltage, the Δ n numerical value of regulation system, and can improve or improve the over-all properties of liquid-crystal composition.
In addition, the present invention is the further application of claimed above-mentioned liquid crystalline cpd in manufacturing display unit also, the specifically application in the indicating meter of TN, IPS, FFS-TFT pattern.
The novel liquid crystal compound that adopts technique scheme to obtain has stable in properties, mutual solubility is good, uvioresistant performance is good, the feature that dielectric anisotropy is large, described compound applies in liquid-crystal composition, has that the time of response is shorter, Δ n numerical value is moderate, electric charge conservation rate is higher, and has lower threshold voltage, the over-all properties that effectively improves or improved liquid-crystal composition, has a extensive future.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Described starting material if no special instructions, all can obtain from open commercial sources.
" conventional aftertreatment " refers to, in the aqueous solution, for mixed solution, methylene dichloride, ethyl acetate or toluene extract, separatory, washing, dry and vacuum rotary evaporator evaporation, then underpressure distillation or recrystallization and/or chromatography purification for product.
Embodiment 1
The synthetic line of preparing compd B YLC-01 is as follows:
Synthesizing of step 1-1 compound 3
In the there-necked flask of 500ml with division box, add 40g (0.298mol) compound 1,62g (0.597mol) compound 2,0.5g tosic acid, 0.2L methylene dichloride, open and stir, room temperature (20 ℃ of left and right), after clock reaction 8h, pours reaction solution in 500ml water into, stir, separatory, water extracts by ethyl acetate, and organic phase washes with water three times, separatory, merge all organic phases anhydrous sodium sulfate drying 0.5h, suction filtration, merging filtrate, the concentrated solvent of doing to obtain, obtain 38.8g light yellow liquid, GC:97.56%, yield: 75%.
Synthesizing of step 1-2 compound 4
In 500ml there-necked flask, add 38.8g (0.223mol) compound 3,80ml methylene dichloride, 23g (0.289mol) pyridine, room temperature (20 ℃ of left and right) stirs, slowly add 46.6g (0.245mol) Tosyl chloride, reaction 8h, water cancellation, dichloromethane extraction, concentrated dry rear use (30%EA/HEX) crosses silicagel column, concentrated 62g light yellow solid, the yield: 85%, GC:95% done to obtain.
Synthesizing of step 1-3 compound 5
In 500ml there-necked flask, add 62g (0.189mol) compound 4,300ml acetone, 70.8g (0.472mol) sodium iodide, slowly be heated to reflux (45 ℃ of left and right), reaction 8h, water cancellation, ethyl acetate is extracted, Sulfothiorine washes with water after washing one time to nearly neutrality, rear concentrating done, and with (10%EA/HEX), crosses silicagel column, and concentrated doing to obtain 38.6g light yellow liquid, yield: 72%, GC:95%.
Synthesizing of step 1-4 compound 7
In 500ml there-necked flask, add 38.6g (0.136mol) compound 5,100ml tetrahydrofuran (THF), nitrogen punching row three times, 5 ℃-10 ℃ of temperature controls, drip 15ml (0.149mol) LDA solution, drip and finish, 5 ℃-10 ℃ reaction 1h of temperature control, drip 25g (0.136mol) compound 6, drip and finish, reaction 8h, TLC follows the tracks of and reacts completely, water cancellation, and ethyl acetate is extracted, dry, concentrate and do, with (EA/HEX=1/9), cross silicagel column, concentrated doing to obtain 32.6g light yellow liquid, yield: 70%, GC:88.6%.
Synthesizing of step 1-5 compound 8
In 500ml there-necked flask, add 32.6g (0.095mol) compound 7,100ml acetone, 5 ℃-10 ℃ of temperature controls, add 18g (0.114mol) potassium permanganate in batches, finish, 10 ℃-20 ℃ reaction 3h of temperature control, TLC follows the tracks of and reacts completely, water cancellation, and ethyl acetate is extracted, dry, concentrate and do, with (EA/HEX=1/9), cross silicagel column, concentrated doing to obtain 29g light yellow liquid, yield: 90%, GC:90.8%.
Synthesizing of step 1-6 compound 9
In 500ml there-necked flask, add 29g (0.085mol) compound 8,100ml tetrahydrofuran (THF), room temperature (20 ℃ of left and right) stirs, slowly add 9.5g (0.255mol) concentrated hydrochloric acid, finish room temperature reaction 2h, TLC follows the tracks of and reacts completely, water cancellation, and ethyl acetate is extracted, dry, concentrated dry, with (EA/HEX=1/9), cross silicagel column, concentrated dry, alcohol crystal obtains 22.8g white solid, yield: 95%, GC:99.3%.
Step 1-7BYLC-01's is synthetic
In 500ml there-necked flask, add 22.8g (0.08mol) compound 9,14g (0.08mol) compound 10,17g (0.16mol) sodium carbonate, 80m toluene, 80ml water, 60ml ethanol, 0.4g zeroth order palladium, start stirring, be heated to reflux (85 ℃ of left and right), reaction 8h, separatory, with methylbenzene extraction, dry, concentrated dry, with (EA/HEX=1/9), cross silicagel column, concentrated dry, alcohol crystal obtains 19.2g white solid, yield: 72%, GC:99.5%.
After testing: GC-MS:m/z:334.1 (M
+);
1H-NMR(300MHz,CDCl
3):0.92-1.52(m,5H)，2.11-2.95(m,2H),3.65-4.53(m,4H),6.53-7.12(m,2H),7.21-7.53(m,4H)。
Embodiment 2
The synthetic line of preparing compd B YLC-02 is as follows:
In 500ml there-necked flask, add 20g (0.07mol) compound 9,22.3g (0.063mol) compound 11,14.8g (0.14mol) sodium carbonate, 80m toluene, 80ml water, 60ml ethanol, 0.3g zeroth order palladium, start stirring, be heated to 65 ℃-75 ℃, reaction 8h, separatory, with methylbenzene extraction, dry, concentrated dry, with (EA/HEX=1/9), cross silicagel column, concentrated dry, alcohol crystal obtains 24.4g white solid, yield: 68.3%, GC:99.7%.
After testing: GC-MS:m/z:512.3 (M
+), 365.1 (M
+) (fracture of difluoro-methoxy bridged bond);
1H-NMR(300MHz,CDCl
3):0.91-1.43(m,5H)，2.10-2.93(m,2H)，3.53-4.51(m,4H)，6.15-6.99(m,4H)，7.11-7.55(m,4H)。
Embodiment 3
The synthetic line of preparing compd B YLC-03 is as follows:
In 500ml there-necked flask, add 18g (0.063mol) compound 9,17.8g (0.0756mol) compound 12,13.3g (0.126mol) sodium carbonate, 70m toluene, 70ml water, 55ml ethanol, 0.2g zeroth order palladium, start stirring, be heated to 100 ℃-105 ℃, reaction 8h, separatory, with methylbenzene extraction, dry, concentrated dry, with (EA/HEX=1/9), cross silicagel column, concentrated dry, alcohol crystal obtains 17.5g white solid, yield: 70.5%, GC:99.5%.
After testing: GC-MS:m/z:394.1 (M
+);
1H-NMR(300MHz,CDCl
3):0.92-1.93(m,21H)，2.10-2.95(m,3H)，3.53-4.51(m,4H)，7.11-7.53(m,8H)。
According to the method for previous embodiment 1, only the substituting group in reactant is carried out to corresponding replacement according to the substituting group in target product, can obtain belonging to as follows the compound of general structure (I):
Embodiment 4
Comparative example 1,
replace
get final product
Embodiment 5
Comparative example 1, will
replace with
can obtain
Embodiment 6
Comparative example 1, will
replace with
can obtain
The application of embodiment 7 liquid crystalline cpd of the present invention in liquid-crystal composition
The liquid crystalline cpd 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.
In the present invention, each performance test parameter abbreviation is as follows:
△ n is optical anisotropy, n
ofor specific refractory power (589nm, 20 ℃);
V
10for threshold voltage, it is the character voltage (V, 20 ℃) when transmitance changes 10%;
Cp be liquid-crystal composition clearing point (℃);
τ on is for until the time while reaching transmitance 90%, and τ off is for until the time when reaching transmitance 10% and cutting off, τ be τ on+ τ off (time of response) (ms).
VHR electric charge conservation rate (%): mixed liquid crystal is injected in liquid crystal cell, put into thermostat container, after temperature ℃ is stablized, 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.
Get the liquid crystalline cpd of following parts by weight and prepare liquid-crystal composition, the performance perameter of concrete proportioning and gained liquid-crystal composition is by shown in following table.
The application of liquid crystalline cpd of the present invention in TN, IPS, FFS-TFT mode display, result is as following table:
The weight percent of each component performance perameter when in table 1. liquid-crystal composition
The weight percent of each component performance perameter when in table 2. liquid-crystal composition
The weight percent of each component performance perameter when in table 3. liquid-crystal composition
Comparative example:
Table 4. does not add the weight percent performance perameter when of each component of liquid-crystal composition of the compounds of this invention
By table, 1-4 can find out, add compound provided by the present invention, composition viscosity is lower, time of response is fast, and there is larger polarity and lower threshold voltage, significant for the quick response that realizes indicating meter, be suitable for very much allocating liquid crystal compound.
The add-on of compound is advisable with 1-50%, more preferably 3-30%.
Except the composition that test example exemplifies, the liquid-crystal composition that adds other compound composition provided by the invention has same good optical property.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, 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. the liquid crystalline cpd containing 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, is characterized in that having following general structure (I):
In formula: R
1expression-H, has alkyl or the alkoxyl group of 1-12 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-replaces, but requires O atom directly not connect each other;
R
2expression-H ,-F ,-Cl ,-CN ,-NCS ,-CF
3,-OCF
3,-OCF
2cl, has alkyl or the alkoxyl group of 1-12 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-replaces, but requires O atom directly not connect each other;
A
1represent Isosorbide-5-Nitrae-phenylene, wherein, the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylidene or Isosorbide-5-Nitrae-phenylene; Wherein, 1-4 hydrogen atom in Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylidene can be replaced by fluorine atom; 1-4 in an Isosorbide-5-Nitrae-phenylene hydrogen atom can be replaced by fluorine atom or 1-2-CH-group can be replaced by nitrogen-atoms;
Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-O-CO-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CH
2cH
2-,-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-,-CH
2cHF-,-CHFCH
2-;
K, l, m are identical or different, represent independently of one another 0,1 or 2, and k+l+m≤3.
2. liquid crystalline cpd according to claim 1, is characterized in that, described R
1expression-H, has alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-CH=CH-or-O-replaces, but requires O atom directly not connect each other.
3. liquid crystalline cpd according to claim 1, is characterized in that, described R
2expression-H ,-F ,-Cl ,-CN ,-CF
3,-OCF
3,-OCF
2cl, has alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be replaced by halogen, one or more-CH
2-can be independently of one another by-CH=CH-or-O-replaces, but requires O atom directly not connect each other.
4. liquid crystalline cpd according to claim 1, is characterized in that, described A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene; Wherein, the 1-4 of an Isosorbide-5-Nitrae-cyclohexylidene hydrogen atom can be replaced by fluorine atom; 1-4 in an Isosorbide-5-Nitrae-phenylene hydrogen atom can be replaced by fluorine atom or 1-2-CH-group can be replaced by nitrogen-atoms.
5. liquid crystalline cpd according to claim 1, is characterized in that, described Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2o-,-CH
2cH
2-,-C ≡ C-,-CH=CH-,-CF=CF-,-C
2f
4-.
6. liquid crystalline cpd according to claim 1, is characterized in that, described A
2, A
3, A
4identical or different, represent independently of one another Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene; Wherein the hydrogen atom of the 1-4 in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atom;
Described Z
1, Z
2, Z
3identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2cH
2-,-C ≡ C-;
K, l, m are identical or different, represent independently of one another 0,1,2, and k+l+m≤2.
7. the preparation method containing the liquid crystalline cpd of 2,6-dioxygen generation-bicyclic group-[2.2.1] heptane structure, is characterized in that, comprises the steps:
Step 1:
with
under Catalyzed by p-Toluenesulfonic Acid, react generation
Step 2:
under pyridine effect, react generation with Tosyl chloride
Step 3:
react with sodium iodide, generate
Step 4:
with
reaction generates
Step 5:
through potassium permanganate oxidation, generate
Step 6:
closed loop under hydrochloric acid catalysis, generates
Step 7:
with
reaction generates the compound of said structure general formula (I);
Wherein, X
1represent H or Br, R
1, R
2, A
1, A
2, A
3, A
4, Z
1, Z
2, Z
3, k, l, m definition all identical with the definition in general structure (I).
8. preparation method according to claim 7, is characterized in that, described step 1) in,
with
molar ratio be 1: 1～3,0 ℃～30 ℃ of temperature of reaction, the reaction times is 6～18 hours;
Described step 2) in,
the molar ratio of Tosyl chloride and pyridine is 1: 1～1.5: 1～2,0 ℃～30 ℃ of temperature of reaction, and the reaction times is 6～18 hours;
Described step 3) in,
with the molar ratio of sodium iodide be 1: 1.0～3.0,10 ℃～50 ℃ of temperature of reaction, the reaction times is 6～12 hours;
Described step 4) in,
with
molar ratio be 1: 0.9～1.1, temperature of reaction-10 ℃～30 ℃, the reaction times is 2～12 hours;
Described step 5) in,
with the molar ratio of potassium permanganate be 1: 1.0～2.0,0 ℃～30 ℃ of temperature of reaction, the reaction times is 1～4 hour.
Described step 6) in,
with the molar ratio of hydrochloric acid be 1: 2.0～4.0,0 ℃～30 ℃ of temperature of reaction, the reaction times is 1～4 hour;
Described step 7) in,
with
molar ratio be 1: 0.9～1.2,60 ℃～120 ℃ of temperature of reaction, the reaction times is 4～12 hours.
9. the application of the arbitrary described liquid crystalline cpd of claim 1-6 in display unit, the specifically application in the indicating meter of TN, IPS, FFS-TFT pattern.
10. a liquid-crystal composition that contains the arbitrary described liquid crystalline cpd of claim 1-6, is characterized in that, the 1-50% that the consumption of described liquid crystalline cpd is liquid-crystal composition, preferably 3-30%.
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