CN104046366A - Liquid crystal compound containing 2-oxo-bicyclo[2, 2, 1] heptane structure, preparation method and application thereof - Google Patents
Liquid crystal compound containing 2-oxo-bicyclo[2, 2, 1] heptane structure, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a liquid crystal compound containing a 2-oxo-bicyclo[2, 2, 1] heptane structure. The compound has the structural formula (I) shown in the specification. The liquid crystal compound provided by the invention has the characteristics of short response time, moderate delta(n) numberic number and high charge retention rate, and has a low threshold voltage and a wide application prospect.
Description
Technical field
The present invention relates to a kind of liquid crystalline cpd, preparation method and application containing 2-oxygen-bicyclic group [2,2,1] heptane structure, 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.Therefore the novel liquid crystal compound that, needs the more improvement performances of exploitation.
Although there is very early the research report [EP0358290B1 of pair 2-oxygen-bicyclic group [2,2,1] heptane structure; Chem.zentralbl.1923, Vol 94, nb.III, p1012; Tedrahedron.1985, Vol 41, n.2, p.413-420; Tedrahedron.1985, Vol 41, n.23, p.5487-5494; EP 0358290 B1 etc.], but 2-oxygen-bicyclic group [2,2,1] iieptanes derivative is as liquid crystalline cpd, and especially the characteristic of nematic liquid crystal, there is not yet report.
Summary of the invention
The present invention's the first object is to provide a kind of liquid crystalline cpd containing 2-oxygen-bicyclic group [2,2,1] heptane structure.The liquid-crystal composition that contains 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 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 or 1-2-CH-group can be replaced by nitrogen-atoms;
A
2, A
3identical 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 or 1-2-CH
2-group can be replaced by Sauerstoffatom; 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
2identical 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-;
A, b are identical or different, represent independently of one another 0,1,2.
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 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
2, A
3identical or different, represent independently of one another
Z
1, Z
2identical 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-.
More preferably, in some embodiments, A
2, A
3identical or different, represent independently of one another
Z
1, Z
2identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2o-,-CH
2cH
2-,-C ≡ C-,-CH=CH-.
A, b are identical or different, represent independently of one another 0,1, and 1≤a+b≤2.
In some preferred embodiments, the compound of logical formula I is particularly preferably one or more of following compound:
R wherein
1expression-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, in alkyl or alkoxyl group one or more-CH
2-can be independently of one another by-CH=CH-, be replaced.
The synthetic route of the compound of said structure general formula (I) is as follows:
1)
under Catalyzed by p-Toluenesulfonic Acid, with glycol reaction, 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 hydrolysis generates under acidic conditions
4) by step 3) generate
react generation with Benzyl Chloride
after, under acidic conditions, be hydrolyzed deprotection and obtain
5) Br-A
1-(Z
1-A
2)
a-(Z
2-A
3)
b-R
2with
first carry out Ge Shi 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
it is the 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).
Described in aforesaid method each step feed intake and reaction conditions as follows:
Step 1) in,
with the molar ratio of ethylene glycol be 1: 2.0～4.0, the reaction times is 2～5 hours, 60～90 ℃ of temperature of reaction.
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 ℃, 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, 10～30 ℃ of temperature of reaction;
Step 4) in,
with the molar ratio of Benzyl Chloride be 1: 2.0～4.0, the reaction times is 2～5 hours, temperature of reaction is 60～90 ℃;
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, 0～20 ℃ of temperature of reaction; Add
after reaction times be 8～10 hours, 50～70 ℃ of temperature of reaction;
Step 6) in,
with the mass ratio that feeds intake of palladium charcoal be 1: 0.05～0.1,5～10 hours reaction times, 20～30 ℃ of temperature of reaction;
Step 7) in,
with the mass ratio that feeds intake of the vitriol oil be 1: 0.5～1,10～20 hours reaction times, 50～80 ℃ of temperature of reaction.
Above-mentioned
br-A
1-(Z
1-A
2)
a-(Z
2-A
3)
b-R
2, R
1-X
1,
all can obtain by method own known in open commercial sources or document is synthetic.
The invention provides at least one the liquid-crystal composition in a kind of compound that comprises general structure (I), the compound that it comprises the general formula that mass percent is 1-50% (I), the compound of the general formula that preferred mass per-cent is 3-30% (I).
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: added the liquid-crystal composition of the compounds of this invention, 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 are used for illustrating the present invention, but are not used for limiting the scope of the invention.Following embodiment is used 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 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 2
In 1L there-necked flask, add 100.0g compound 1,127.6g ethylene glycol, 5g tosic acid, 300ml toluene, is heated to 80 ℃ of reaction 3h, carries out conventional aftertreatment, obtains 112g light yellow liquid compound 2, GC:96.2%, yield: 87%.
Synthesizing of step 1-2 compound 3
Under nitrogen protection, in 2L there-necked flask, add 81.0g Diisopropylamine, 300ml tetrahydrofuran (THF); temperature control-20 ℃ drip 0.6mol n-Butyl Lithium, and 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%.
Synthesizing of step 1-3 compound 4
Under nitrogen protection; add POTASSIUM BOROHYDRIDE, lithium chloride and 300ml tetrahydrofuran (THF), 0 ℃ of mixing solutions that drips compound 3 and THF of temperature control; drip and finish; 20 ℃ of temperature controls, reaction 5h, carries out conventional aftertreatment; sherwood oil recrystallization; obtain 28.4g colourless transparent liquid compound 4, GC:98.0%, yield: 82%.
Synthesizing of step 1-4 compound 5
Under nitrogen protection, in 2L there-necked flask, add 120.0g compound 4,117.6g carbonating potassium, 1000ml DMF, 60 ℃ of dropping Benzyl Chlorides of temperature control, rear temperature control 60 degree reaction 5h, carry out conventional aftertreatment, obtain 86.4g compound 5, GC:94.8%, yield: 72%.
Synthesizing of step 1-5 compound 8
In 2L there-necked flask, add 28.7g compound 6 (0.1mol), 300ml tetrahydrofuran (THF), is cooled to 0 degree, and 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, and is warming up to 50 degree, temperature control reaction 10h, and rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 36.3g compound 8, GC:96.2%, yield: 80%.
Synthesizing of step 1-6 compound 9
In 2L there-necked flask, add 22.7g compound 8 (0.05mol), 500ml tetrahydrofuran (THF), the palladium carbon that adds 1.1g water content 10% under stirring, pump drainage hydrogen three times, 20 ℃ of reaction 10h of temperature control, carry out conventional aftertreatment, sherwood oil recrystallization, obtain 16.8g compound 9, GC:94.6%, yield: 92%.
Step 1-7 compd B YLC-01's is synthetic
Under nitrogen protection, in 500ml there-necked flask, add 14.6g compound 9 (0.04mol), the 7g vitriol oil, 100ml toluene, 50 ℃ of temperature controls, reaction 20h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, removes desolventizing with Rotary Evaporators.Thick product is through chromatogram purification, PE/EA wash-out, and EtOH/EA recrystallization obtains 9.2g white solid compd B YLC-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 of preparing compd B YLC-03 is as follows:
Synthetic and the purification condition of compound 5 is with described in embodiment 1.
Synthesizing of step 2-5 compound 8
In 2L there-necked flask, add 28.7g compound 6 (0.1mol), 300ml tetrahydrofuran (THF), is cooled to 0 degree, and temperature control 0 degree drips 100g
the tetrahydrofuran solution of (0.2mol, 2mol/L), rear temperature control 10 degree reaction 4h obtain compound 7 (molecular weight: 311); Rear dropping 31.2g compound 5 (0.1mol), are warming up to 60 degree, temperature control reaction 9h, and rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 40.6g compound 8, GC:96.2%, yield: 78%.
Synthesizing of step 2-6 compound 9
In 2L there-necked flask, add 31.2g compound 8 (0.06mol), 500ml tetrahydrofuran (THF), the palladium carbon that adds 2.5g water content 10% under stirring, pump drainage hydrogen three times, 30 ℃ of reaction 8h of temperature control, carry out conventional aftertreatment, sherwood oil recrystallization, obtain 23.5g compound 9, GC:94.6%, yield: 91%.
Step 2-7 compd B YLC-02's is synthetic
Under nitrogen protection, in 500ml there-necked flask, add 21.5g compound 9 (0.05mol), the 17g vitriol oil, 100ml toluene, 70 ℃ of temperature controls, reaction 15h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, removes desolventizing with Rotary Evaporators.Thick product is through chromatogram purification, PE/EA wash-out, and EtOH/EA recrystallization obtains 14g white solid compd B YLC-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 of preparing compd B YLC-03 is as follows:
Synthetic and the purification condition of compound 5 is with described in embodiment 1.
Synthesizing of step 3-5 compound 8
In 2L there-necked flask, add 45.6g compound 6 (0.1mol), 300ml tetrahydrofuran (THF), is cooled to 0 degree, and 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, temperature control reaction 8h, and rear hcl acidifying is less than 7 to PH, carries out conventional aftertreatment, obtains 49.3g compound 8, GC:96.2%, yield: 78%.
Synthesizing of step 3-6 compound 9
In 2L there-necked flask, add 38g compound 8 (0.06mol), 500ml tetrahydrofuran (THF), adds the palladium carbon of 3.8g water content 10%, pump drainage hydrogen three times under stirring, 40 ℃ of reaction 5h of temperature control, carry out conventional aftertreatment, sherwood oil recrystallization, obtain 30g compound 9, GC:94.6%, yield: 93%.
Step 3-7 compd B YLC-03's is synthetic
Under nitrogen protection, in 500ml there-necked flask, add 21.6g compound 9 (0.04mol), the 21.6g vitriol oil, 100ml toluene, 80 ℃ of temperature controls, reaction 10h, dichloromethane extraction, washing, anhydrous sodium sulfate drying, removes desolventizing with Rotary Evaporators.Thick product is through chromatogram purification, PE/EA wash-out, and EtOH/EA recrystallization obtains 14g white solid compd B YLC-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 obtain by method own known in open commercial sources or document is synthetic.
Embodiment 4
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, be the character voltage (V, 20 ℃) when transmitance changes 10%, V
90for saturation voltage, be character voltage when transmitance changes 90% (V, 20 ℃); Liquid crystal comprehensive parameter tester EOT-5016.The polaroid of setting polarizing axis quadrature, is attached to polaroid testing cassete (the 4.0 μ m) top and bottom that are marked with liquid crystal.Give 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 liquid crystal cell drives with the square wave of 64HZ.
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 the liquid-crystal composition of gained is by shown in following table.
The weight percent of table 1 embodiment 4 each components of liquid-crystal composition
The performance perameter of table 2 embodiment 4 liquid-crystal compositions
| 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 |
By table 2 and table 4, can be found out, 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 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-oxygen-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 or 1-2-CH-group can be replaced by nitrogen-atoms;
A
2, A
3identical 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 or 1-2-CH
2-group can be replaced by Sauerstoffatom; 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
2identical 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-;
A, b are identical or different, represent independently of one another 0,1,2.
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
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 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
3identical or different, represent independently of one another
Z
1, Z
2identical or different, represent independently of one another carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2o-,-CH
2cH
2-,-C ≡ C-,-CH=CH-;
A, b are identical or different, represent independently of one another 0,1, and 1≤a+b≤2.
7. the preparation method containing the liquid crystalline cpd of 2-oxygen-bicyclic group [2,2,1] heptane structure, is characterized in that, comprises the steps:
1)
under Catalyzed by p-Toluenesulfonic Acid, with glycol reaction, 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 hydrolysis generates under acidic conditions
4) by step 3) generate
react generation with Benzyl Chloride
after, under acidic conditions, be hydrolyzed deprotection and obtain
5) Br-A
1-(Z
1-A
2)
a-(Z
2-A
3)
b-R
2with
first carry out Ge Shi 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
it is the 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,
with the molar ratio of ethylene glycol be 1: 2.0～4.0, the reaction times is 2～5 hours, 60～90 ℃ of temperature of reaction;
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 ℃, 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, 10～30 ℃ of temperature of reaction;
Step 4) in,
with the molar ratio of Benzyl Chloride be 1: 2.0～4.0, the reaction times is 2～5 hours, temperature of reaction is 60～90 ℃;
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, 0～20 ℃ of temperature of reaction; Add
after reaction times be 8～10 hours, 50～70 ℃ of temperature of reaction;
Step 6) in,
with the mass ratio that feeds intake of palladium charcoal be 1: 0.05～0.1,5～10 hours reaction times, 20～30 ℃ of temperature of reaction;
Step 7) in,
with the mass ratio that feeds intake of the vitriol oil be 1: 0.5～1,10～20 hours reaction times, 50～80 ℃ of temperature of reaction.
9. at least one the liquid-crystal composition comprising in the arbitrary described general structure of claim 1-6 (I) compound, it is characterized in that, the compound that comprises the general formula that mass percent is 1-50% (I), the compound of the general formula that preferred mass per-cent is 3-30% (I).
10. the application of liquid-crystal composition in the indicating meter of TN, IPS, FFS, ADS-TFT pattern described in claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543178A (en) * | 2015-09-16 | 2017-03-29 | 阜阳欣奕华材料科技有限公司 | A kind of compound, liquid-crystal composition and liquid crystal display |
| CN107728355A (en) * | 2016-08-11 | 2018-02-23 | 三星显示有限公司 | Display |
| CN112342034A (en) * | 2019-08-09 | 2021-02-09 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251631A (en) * | 1997-03-12 | 1998-09-22 | Dainippon Printing Co Ltd | Liquid crystal photochromic material and recording medium comprising the same |
| CN1249736A (en) * | 1997-01-22 | 2000-04-05 | 智索公司 | Liquid-crystal compounds, liquid-crystal composition contg. same, and liquid-crystal display element contg. same |
| CN101421375A (en) * | 2006-04-15 | 2009-04-29 | 默克专利股份有限公司 | Liquid-crystalline mixtures and liquid-crystal displays |
| US20100216986A1 (en) * | 2007-09-06 | 2010-08-26 | Merck Patent Gesellschaft | 2, 5-selenophene derivatives and 2, 5-tellurophene derivatives |
| CN103289708A (en) * | 2013-06-09 | 2013-09-11 | 石家庄诚志永华显示材料有限公司 | Positive dielectric anisotropic liquid crystal composition |
| CN103553872A (en) * | 2013-10-31 | 2014-02-05 | 北京八亿时空液晶科技股份有限公司 | Bicyclo[2,2,1]heptane-containing compounds and application thereof |
-
2014
- 2014-06-23 CN CN201410283560.2A patent/CN104046366B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249736A (en) * | 1997-01-22 | 2000-04-05 | 智索公司 | Liquid-crystal compounds, liquid-crystal composition contg. same, and liquid-crystal display element contg. same |
| JPH10251631A (en) * | 1997-03-12 | 1998-09-22 | Dainippon Printing Co Ltd | Liquid crystal photochromic material and recording medium comprising the same |
| CN101421375A (en) * | 2006-04-15 | 2009-04-29 | 默克专利股份有限公司 | Liquid-crystalline mixtures and liquid-crystal displays |
| US20100216986A1 (en) * | 2007-09-06 | 2010-08-26 | Merck Patent Gesellschaft | 2, 5-selenophene derivatives and 2, 5-tellurophene derivatives |
| CN103289708A (en) * | 2013-06-09 | 2013-09-11 | 石家庄诚志永华显示材料有限公司 | Positive dielectric anisotropic liquid crystal composition |
| CN103553872A (en) * | 2013-10-31 | 2014-02-05 | 北京八亿时空液晶科技股份有限公司 | Bicyclo[2,2,1]heptane-containing compounds and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543178A (en) * | 2015-09-16 | 2017-03-29 | 阜阳欣奕华材料科技有限公司 | A kind of compound, liquid-crystal composition and liquid crystal display |
| CN107728355A (en) * | 2016-08-11 | 2018-02-23 | 三星显示有限公司 | Display |
| CN107728355B (en) * | 2016-08-11 | 2022-04-19 | 三星显示有限公司 | Display device |
| CN112342034A (en) * | 2019-08-09 | 2021-02-09 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition and application thereof |
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Effective date of registration: 20161221 Address after: 102500 Beijing City, Fangshan District Yanshan Gang Nan Lu Dong Yi Xiang C No. 6 room 218 Patentee after: Beijing Bayi Space LCD Materials Technology Co., Ltd. Patentee after: Daxin Materials Corp. Address before: 102500 Beijing City, Fangshan District Yanshan Gang Nan Lu Dong Yi Xiang C No. 6 room 218 Patentee before: Beijing Bayi Space LCD Materials Technology Co., Ltd. |