CN104046366B - A kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, preparation method and application thereof - Google Patents

A kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, preparation method and application thereof Download PDF

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CN104046366B
CN104046366B CN201410283560.2A CN201410283560A CN104046366B CN 104046366 B CN104046366 B CN 104046366B CN 201410283560 A CN201410283560 A CN 201410283560A CN 104046366 B CN104046366 B CN 104046366B
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CN104046366A (en
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姜天孟
班全志
田会强
储士红
陈海光
高立龙
梁现丽
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Beijing Bayi Space LCD Technology Co Ltd
Daxin Materials Corp
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Abstract

The present invention relates to a kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, there is following general structure (I):

Description

A kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, preparation method and application thereof
Technical field
The present invention relates to a kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, 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 equipment, Electrooptical devices, sensor.Wherein, nematic liquid crystal has the broadest purposes in a display device.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, higher requirement be it is also proposed to liquid crystal material, especially in quick response, reduce driving voltage, reduce the aspects such as power consumption.Therefore, the novel liquid crystal compound of the more improvement performances of exploitation is needed.
Although there is the research report [EP0358290B1 to 2-oxygen-bicyclic group [2,2,1] heptane structure very early; Chem.zentralbl.1923, Vol94, nb.III, p1012; Tedrahedron.1985, Vol41, n.2, p.413-420; Tedrahedron.1985, Vol41, n.23, p.5487-5494; EP0358290B1 etc.], but 2-oxygen-bicyclic group [2,2,1] iieptanes derivative is as liquid crystalline cpd, and the especially characteristic of nematic liquid crystal, there is not been reported.
Summary of the invention
The present invention first object is to provide a kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure.Liquid-crystal composition containing this liquid crystalline cpd, shows the characteristic that the time of response is short, Δ n numerical value is moderate, electric charge conservation rate is high, and has lower threshold voltage, has a extensive future.
For achieving the above object, the present invention adopts following technical scheme:
A kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure, described compound 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 optionally substituted by halogen, one or more-CH 2-can be replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another, but require that O atom does not directly 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 optionally substituted by halogen, one or more-CH 2-can be replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another, but require that O atom does not directly connect each other;
A 1represent Isosorbide-5-Nitrae-phenylene, wherein, 1-4 hydrogen atom in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms or 1-2-CH-group can be replaced by nitrogen-atoms;
A 2, A 3identical or different, represent Isosorbide-5-Nitrae-cyclohexylidene independently of one another, 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 atoms or 1-2-CH 2-group can be replaced by Sauerstoffatom; 1-4 hydrogen atom in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms or 1-2-CH-group can be replaced by nitrogen-atoms;
Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-O-CO-,-CF independently of one another 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-;
A, b are identical or different, represent 0,1,2 independently of one another.
In some preferred embodiments, R 1expression-H, has alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be optionally substituted by halogen, one or more-CH 2-can be replaced by-CH=CH-or-O-independently of one another, but require that O atom does not directly 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 optionally substituted by halogen, one or more-CH 2-can be replaced by-CH=CH-or-O-independently of one another, but require that O atom does not directly connect each other;
A 2, A 3identical or different, represent independently of one another
Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-CF independently of one another 2o-,-CH 2o-,-CH 2cH 2-,-C ≡ C-,-CH=CH-,-CF=CF-,-C 2f 4-.
More preferably, in some embodiments, A 2, A 3identical or different, represent independently of one another
Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-CF independently of one another 2o-,-CH 2o-,-CH 2cH 2-,-C ≡ C-,-CH=CH-.
A, b are identical or different, represent 0,1 independently of one another, and 1≤a+b≤2.
In some preferred embodiments, the compound of logical formula I is particularly preferably one or more of following compound:
Wherein R 1represent-H or there is the alkyl of 1-7 carbon atom; R 2expression-H ,-F ,-Cl ,-CN ,-CF 3,-OCF 3, there is alkyl or the alkoxyl group of 1-7 carbon atom; Wherein, the one or more-CH in alkyl or alkoxyl group 2-can be replaced by-CH=CH-independently of one another.
The synthetic route of the compound of said structure general formula (I) is as follows:
1) with glycol reaction under Catalyzed by p-Toluenesulfonic Acid, generate
2) by step 1) generate with lithium diisopropyl amido metallization reaction, then with R 1-X 1reaction, generates;
3) by step 2) generate react with POTASSIUM BOROHYDRIDE and lithium chloride, then be hydrolyzed generation in acid condition
4) by step 3) generate react with Benzyl Chloride and generate after, be hydrolyzed deprotection in acid condition and obtain
5) Br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2with first carry out grignard displacement, generate BrMg-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2after, with step 4) generate react, acidifying obtains
6) by step 5) generate under the catalysis of palladium charcoal, obtain with hydrogen reaction
7) by step 6) generate under sulphuric acid catalysis, etherificate cyclization generates the i.e. compound of above-mentioned general formula (I).
In above-mentioned steps 1) to step 7) in, described R1, R2, A1, A2, A3, Z 1, Z 2, a, b definition all identical with the definition in general structure (I).
Each step described in aforesaid method feed intake and reaction conditions as follows:
Step 1) in, be 1: 2.0 ~ 4.0 with the molar ratio of ethylene glycol, the reaction times is 2 ~ 5 hours, temperature of reaction 60 ~ 90 DEG C.
Step 2) in, lithium diisopropyl amido and R 1-X 1molar ratio be 1: 1.2 ~ 1.5: 1.4 ~ 2.0, temperature of reaction-30 ~ 20 DEG C, the reaction times is 4 ~ 8 hours.
Step 3) in, the molar ratio of POTASSIUM BOROHYDRIDE and lithium chloride is 1: 0.5 ~ 1.5: 0.5 ~ 1.5,3 ~ 5 hours reaction times, temperature of reaction 10 ~ 30 DEG C;
Step 4) in, be 1: 2.0 ~ 4.0 with the molar ratio of Benzyl Chloride, the reaction times is 2 ~ 5 hours, and temperature of reaction is 60 ~ 90 DEG C;
Step 5) in, Br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2 with molar ratio be 1.0: 1.0 ~ 3.0: 1.0, Br-A 1-(Z 1-A 3) a-(Z 2-A 3) b-R 2with reaction times be 4 ~ 6 hours, temperature of reaction 0 ~ 20 DEG C; Add after reaction times be 8 ~ 10 hours, temperature of reaction 50 ~ 70 DEG C;
Step 6) in, be 1: 0.05 ~ 0.1 with the mass ratio that feeds intake of palladium charcoal, 5 ~ 10 hours reaction times, temperature of reaction 20 ~ 30 DEG C;
Step 7) in, be 1: 0.5 ~ 1 with the mass ratio that feeds intake of the vitriol oil, 10 ~ 20 hours reaction times, temperature of reaction 50 ~ 80 DEG C.
Above-mentioned br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2, R 1-X 1, all can be obtained by itself known method synthesis in open commercial sources or document.
The invention provides the liquid-crystal composition that one comprises at least one in the compound of general structure (I), it comprises the compound of the general formula (I) that mass percent is 1-50%, and preferred mass per-cent is the compound of the general formula (I) of 3-30%.
The present invention also provides the application of above-mentioned liquid-crystal composition in the indicating meter of TN, IPS, FFS, ADS-TFT pattern.
Beneficial effect of the present invention is as follows: the liquid-crystal composition adding the compounds of this invention, and the time of response is short, Δ n numerical value is moderate, electric charge conservation rate is high, and has lower threshold voltage, has a extensive future.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.Following embodiment for explaining the present invention, and is not used for limiting the present invention.
Described starting material if no special instructions, all can obtain from open commercial sources.
" conventional aftertreatment " refers to, in aqueous, mixed solution methylene dichloride, ethyl acetate or toluene extract, separatory, washing, dry and vacuum rotary evaporator evaporation, then product underpressure distillation or recrystallization and/or chromatography purification.
Embodiment 1
The synthetic line preparing compd B YLC-01 is as follows:
The synthesis of step 1-1 compound 2
Add 100.0g compound 1,127.6g ethylene glycol in 1L there-necked flask, 5g tosic acid, 300ml toluene, be heated to 80 DEG C of reaction 3h, carry out conventional aftertreatment, obtain 112g light yellow liquid compound 2, GC:96.2%, yield: 87%.
The synthesis of step 1-2 compound 3
Under nitrogen protection, in 2L there-necked flask, add 81.0g Diisopropylamine, 300ml tetrahydrofuran (THF); temperature control-20 DEG C drips 0.6mol n-Butyl Lithium, insulation reaction 0.5h, drips 88.0g compound 2; insulation reaction 0.5h, drips 91.2g N-PROPYLE BROMIDE, naturally rises to room temperature reaction 5h.Carry out conventional aftertreatment, obtain 96.0g light yellow liquid compound 2, GC:97%, yield: 100%.
The synthesis of step 1-3 compound 4
Under nitrogen protection; add POTASSIUM BOROHYDRIDE, lithium chloride and 300ml tetrahydrofuran (THF), temperature control 0 DEG C drips the mixing solutions of compound 3 and THF; drip and finish; temperature control 20 DEG C, reaction 5h, carries out conventional aftertreatment; sherwood oil recrystallization; obtain 28.4g colourless transparent liquid compound 4, GC:98.0%, yield: 82%.
The synthesis of step 1-4 compound 5
Under nitrogen protection, add 120.0g compound 4,117.6g carbonating potassium, 1000mlDMF in 2L there-necked flask, temperature control 60 DEG C drips Benzyl Chloride, and rear temperature control 60 degree reaction 5h, carries out conventional aftertreatment, obtain 86.4g compound 5, GC:94.8%, yield: 72%.
The synthesis of step 1-5 compound 8
Add 28.7g compound 6 (0.1mol) in 2L there-necked flask, 300ml tetrahydrofuran (THF), be cooled to 0 degree, temperature control 0 degree drips 50g the tetrahydrofuran solution of (0.1mol, 2mol/L), rear temperature control 0 degree reaction 4h obtains compound 7;
Rear temperature control 10-30 degree drips 24.6g compound 5 (0.1mol), drips and finishes, be warming up to 50 degree, and temperature control reaction 10h, rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 36.3g compound 8, GC:96.2%, yield: 80%.
The synthesis of step 1-6 compound 9
22.7g compound 8 (0.05mol) is added in 2L there-necked flask, 500ml tetrahydrofuran (THF), the palladium carbon of 1.1g water content 10% is added under stirring, pump drainage hydrogen three times, temperature control 20 DEG C reaction 10h, carries out conventional aftertreatment, sherwood oil recrystallization, obtain 16.8g compound 9, GC:94.6%, yield: 92%.
The synthesis of step 1-7 compd B YLC-01
Under nitrogen protection, in 500ml there-necked flask, add 14.6g compound 9 (0.04mol), the 7g vitriol oil, 100ml toluene, temperature control 50 DEG C, reaction 20h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, with Rotary Evaporators except desolventizing.Thick product is through chromatogram purification, and PE/EA wash-out, EtOH/EA recrystallization obtains 9.2g compound as white solid BYLC-01, GC:99.9%, yield: 66%.
GC-MS：m/z：346.2(M +)；
1H-NMR(300MHz,CDCl 3):0.83-1.26(m,9H)，1.51-1.62(m,6H)，6.20-7.22(m,2H),7.32-7.65(m,4H)。
Embodiment 2
The synthetic line preparing compd B YLC-03 is as follows:
The synthesis of compound 5 and purification condition are with described in embodiment 1.
The synthesis of step 2-5 compound 8
Add 28.7g compound 6 (0.1mol) in 2L there-necked flask, 300ml tetrahydrofuran (THF), be cooled to 0 degree, temperature control 0 degree drips 100g the tetrahydrofuran solution of (0.2mol, 2mol/L), rear temperature control 10 degree reaction 4h obtains compound 7 (molecular weight: 311); Rear dropping 31.2g compound 5 (0.1mol), is warming up to 60 degree, and temperature control reaction 9h, rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 40.6g compound 8, GC:96.2%, yield: 78%.
The synthesis of step 2-6 compound 9
31.2g compound 8 (0.06mol) is added in 2L there-necked flask, 500ml tetrahydrofuran (THF), the palladium carbon of 2.5g water content 10% is added under stirring, pump drainage hydrogen three times, temperature control 30 DEG C reaction 8h, carries out conventional aftertreatment, sherwood oil recrystallization, obtain 23.5g compound 9, GC:94.6%, yield: 91%.
The synthesis of step 2-7 compd B YLC-02
Under nitrogen protection, in 500ml there-necked flask, add 21.5g compound 9 (0.05mol), the 17g vitriol oil, 100ml toluene, temperature control 70 DEG C, reaction 15h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, with Rotary Evaporators except desolventizing.Thick product is through chromatogram purification, and PE/EA wash-out, EtOH/EA recrystallization obtains 14g compound as white solid BYLC-02, GC:99.9%, yield: 68%.
GC-MS：m/z：412(M +)；
1H-NMR(300MHz,CDCl 3):0.91-1.34(m,9H)，1.62-1.82(m,6H)，6.10-7.02(m,2H),7.12-7.65(m,4H)。
Embodiment 3
The synthetic line preparing compd B YLC-03 is as follows:
The synthesis of compound 5 and purification condition are with described in embodiment 1.
The synthesis of step 3-5 compound 8
Add 45.6g compound 6 (0.1mol) in 2L there-necked flask, 300ml tetrahydrofuran (THF), be cooled to 0 degree, temperature control 0 degree drips 150g the tetrahydrofuran solution of (0.3mol, 2mol/L), rear temperature control reaction 6h obtains compound 7; Rear dropping 24.6g compound 5, is warming up to 70 degree, and temperature control reaction 8h, rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 49.3g compound 8, GC:96.2%, yield: 78%.
The synthesis of step 3-6 compound 9
38g compound 8 (0.06mol) is added in 2L there-necked flask, 500ml tetrahydrofuran (THF), the palladium carbon of 3.8g water content 10% is added under stirring, pump drainage hydrogen three times, temperature control 40 DEG C reaction 5h, carries out conventional aftertreatment, sherwood oil recrystallization, obtain 30g compound 9, GC:94.6%, yield: 93%.
The synthesis of step 3-7 compd B YLC-03
Under nitrogen protection, in 500ml there-necked flask, add 21.6g compound 9 (0.04mol), the 21.6g vitriol oil, 100ml toluene, temperature control 80 DEG C, reaction 10h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, with Rotary Evaporators except desolventizing.Thick product is through chromatogram purification, and PE/EA wash-out, EtOH/EA recrystallization obtains 14g compound as white solid BYLC-03, GC:99.9%, yield: 68%.
GC-MS：m/z：524(M +)；
1H-NMR(300MHz,CDCl 3):0.92-1.35(m,9H)，1.51-1.62(m,6H)，6.20-7.02(m,2H),7.32-7.65(m,4H)。
Above-mentioned br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2, R 1-X 1with all can be obtained by itself known method synthesis in open commercial sources or document.
Embodiment 4
The liquid crystalline cpd used 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 shorthand is as follows:
△ n is optical anisotropy, n ofor specific refractory power (589nm, 20 DEG C);
V 10for threshold voltage, be the character voltage (V, 20 DEG C) when transmitance changes 10%, V 90for saturation voltage, be character voltage when transmitance changes 90% (V, 20 DEG C); Liquid crystal comprehensive parameter tester EOT-5016.The polaroid that setting polarizing axis is orthogonal, is attached to testing cassete (4.0 μm) top and bottom being marked with liquid crystal by polaroid.To liquid crystal cell making alive, the voltage when light is reduced to 10% transmitance from the original state of full impregnated is saturation voltage.Light source is halogen light, and the square wave of liquid crystal cell 64HZ drives.
Cp is the clearing point (DEG C) of liquid-crystal composition;
τ on is that τ off is until reach time when transmitance 10% is cut off, and τ is τ on+ τ off (time of response) (ms) until time when reaching transmitance 90%.
VHR electric charge conservation rate (%): injected by mixed liquid crystal in liquid crystal cell, put into thermostat container, after temperature DEG C is stablized, enters test procedure, manually gets and a little obtain electric charge conservation rate numerical value.Measuring voltage is 5V, and power-up time is 5ms, HoldingTime is 500ms.
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.
The weight percent of each component of table 1 embodiment 4 liquid-crystal composition
The performance perameter of table 2 embodiment 4 liquid-crystal composition
Performance perameter Parameter value
△n 0.1020
Δε +7.5
V 10 1.25
η 15
Cp 82
τ 13
Comparative example:
Table 3 does not add the weight percent of each component of liquid-crystal composition of liquid crystalline cpd of the present invention
Table 4 does not add the performance perameter of the liquid-crystal composition of liquid crystalline cpd of the present invention
Performance perameter Parameter value
△n 0.1020
Δε +6.6
V 10 1.41
η 18
Cp 81
τ 17
As can be seen from table 2 and table 4, add compound provided by the present invention, composition viscosity is lower, and the time of response is fast, and has larger polarity and lower threshold voltage.
The add-on of compound is advisable with 1-50%, more preferably 3-30%.
Except exemplified composition, the liquid-crystal composition adding other compound provided by the invention composition has optical property excellent equally.
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 without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.

Claims (11)

1. one kind contains the liquid crystalline cpd of 2-oxygen-bicyclic group [2,2,1] heptane structure, it 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 optionally substituted by halogen, one or more-CH 2-can be replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another, but require that O atom does not directly connect each other;
R 2expression-H ,-F ,-Cl ,-CN ,-NCS-, have alkyl or the alkoxyl group of 1-12 carbon atom; Wherein, the H in alkyl or alkoxyl group can be optionally substituted by halogen, one or more-CH 2-can be replaced by-C ≡ C-,-CH=CH-,-CF=CF-,-CF=CH-,-CO-O-,-O-CO-or-O-independently of one another, but require that O atom does not directly connect each other;
A 1represent Isosorbide-5-Nitrae-phenylene, wherein, 1-4 hydrogen atom in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms or 1-2-CH-group can be replaced by nitrogen-atoms;
A 2, A 3identical or different, represent Isosorbide-5-Nitrae-cyclohexylidene independently of one another, 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 atoms or 1-2-CH 2-group can be replaced by Sauerstoffatom; 1-4 hydrogen atom in Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms or 1-2-CH-group can be replaced by nitrogen-atoms;
Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-O-CO-,-CF independently of one another 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-;
A, b are identical or different, represent 0,1,2 independently of one another.
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 optionally substituted by halogen, one or more-CH 2-can be replaced by-CH=CH-or-O-independently of one another, but require that O atom does not directly connect each other.
3. liquid crystalline cpd according to claim 1, is characterized in that, described R 2expression-H ,-F ,-Cl ,-CN-, have alkyl or the alkoxyl group of 1-8 carbon atom; Wherein, the H in alkyl or alkoxyl group can be optionally substituted by halogen, one or more-CH 2-can be replaced by-CH=CH-or-O-independently of one another, but require that O atom does not directly connect each other.
4. liquid crystalline cpd according to claim 1, is characterized in that, described A 2, A 3identical or different, represent independently of one another
5. liquid crystalline cpd according to claim 1, is characterized in that, described Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-CF independently of one another 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 3identical or different, represent independently of one another
Z 1, Z 2identical or different, represent carbon-carbon single bond ,-CO-O-,-CF independently of one another 2o-,-CH 2o-,-CH 2cH 2-,-C ≡ C-,-CH=CH-;
A, b are identical or different, represent 0,1 independently of one another, and 1≤a+b≤2.
7. one kind contains the preparation method of the liquid crystalline cpd of 2-oxygen-bicyclic group [2,2,1] heptane structure, it is characterized in that, comprises the steps:
1) with glycol reaction under Catalyzed by p-Toluenesulfonic Acid, generate
2) by step 1) generate with lithium diisopropyl amido metallization reaction, then with R 1-X 1reaction, generates;
3) by step 2) generate react with POTASSIUM BOROHYDRIDE and lithium chloride, then be hydrolyzed generation in acid condition
4) by step 3) generate react with Benzyl Chloride and generate after, be hydrolyzed deprotection in acid condition and obtain
5) Br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2with first carry out grignard displacement, generate BrMg-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2after, with step 4) generate react, acidifying obtains
6) by step 5) generate under the catalysis of palladium charcoal, obtain with hydrogen reaction
7) by step 6) generate under sulphuric acid catalysis, etherificate cyclization generates the i.e. compound of above-mentioned general formula (I);
Wherein, described R1, R2, A1, A2, A3, Z 1, Z 2, a, b definition all identical with the definition in general structure (I).
8. preparation method according to claim 7, is characterized in that,
Step 1) in, be 1: 2.0 ~ 4.0 with the molar ratio of ethylene glycol, the reaction times is 2 ~ 5 hours, temperature of reaction 60 ~ 90 DEG C;
Step 2) in, the molar ratio of lithium diisopropyl amido and R1-X1 is 1: 1.2 ~ 1.5: 1.4 ~ 2.0, temperature of reaction-30 ~ 20 DEG C, and the reaction times is 4 ~ 8 hours;
Step 3) in, the molar ratio of POTASSIUM BOROHYDRIDE and lithium chloride is 1: 0.5 ~ 1.5: 0.5 ~ 1.5,3 ~ 5 hours reaction times, temperature of reaction 10 ~ 30 DEG C;
Step 4) in, be 1: 2.0 ~ 4.0 with the molar ratio of Benzyl Chloride, the reaction times is 2 ~ 5 hours, and temperature of reaction is 60 ~ 90 DEG C;
Step 5) in, Br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2 with molar ratio be 1.0: 1.0 ~ 3.0: 1.0, Br-A 1-(Z 1-A 2) a-(Z 2-A 3) b-R 2with reaction times be 4 ~ 6 hours, temperature of reaction 0 ~ 20 DEG C; Add after reaction times be 8 ~ 10 hours, temperature of reaction 50 ~ 70 DEG C;
Step 6) in, be 1: 0.05 ~ 0.1 with the mass ratio that feeds intake of palladium charcoal, 5 ~ 10 hours reaction times, temperature of reaction 20 ~ 30 DEG C;
Step 7) in, be 1: 0.5 ~ 1 with the mass ratio that feeds intake of the vitriol oil, 10 ~ 20 hours reaction times, temperature of reaction 50 ~ 80 DEG C.
9. comprise a liquid-crystal composition at least one in general structure (I) compound described in any one of claim 1-6, it is characterized in that, comprise the compound of the general formula (I) that mass percent is 1-50%.
10. liquid-crystal composition according to claim 9, is characterized in that, comprises the compound of the general formula (I) that mass percent is 3-30%.
The application of liquid-crystal composition described in 11. claims 9 or 10 in the indicating meter of TN, IPS, FFS, ADS-TFT pattern.
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