CN107400516B - A kind of liquid-crystal compounds of cyclopropyl base class negative dielectric anisotropic and its application - Google Patents
A kind of liquid-crystal compounds of cyclopropyl base class negative dielectric anisotropic and its application Download PDFInfo
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Abstract
The invention discloses a kind of liquid-crystal compounds of cyclopropyl base class negative dielectric anisotropic and its applications, belong to liquid-crystal compounds and its application field, the liquid-crystal compounds of the cyclopropyl base class negative dielectric anisotropic has structure shown in formula I, wherein, R indicates the alkyl or alkoxy with 1-12 carbon atom；Ring A indicates the 1,4- phenylene that 1,4- phenylene, 1,4- cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms；Ring B indicates the 1,4- phenylene that 1,4- phenylene, 1,4- cyclohexylidene, 1,4- cyclohexadienylidene or 1-4 hydrogen atom are replaced by fluorine atoms；M is 0,1 or 2, and n is 0 or 1.Liquid-crystal compounds of the present invention has many advantages, such as good negative dielectric anisotropic, good liquid crystal intersolubility, relatively low rotary viscosity, it can be effectively reduced driving voltage, improve the response speed of liquid crystal display device, have the characteristics that optical anisotropy numerical value is moderate, charge conservation rate is high simultaneously, there is important application value.
Description
Technical field
The invention belongs to liquid-crystal compounds and its application fields, are related to a kind of novel cyclopropyl class negative dielectric anisotropic
Close object and the preparation method and application thereof.
Background technique
Liquid crystal display device development in recent years is more and more rapider, also develops different type, such as vehicle-mounted small-sized liquid crystal display
Device, portable liquid crystal device, ultrathin liquid crystal display device etc., this field exploitation is making progress, with TV
For, its main feature is that it is light-weight, take up space small, conveniently moving, there are also subnotebook PC, palm PC, mobile phones etc..
Liquid crystal material has pole as application of the environmentally conscious materials in the fields such as information display material, organic optoelectronic material
Big researching value and fine application prospect successfully solve visual angle, divide currently, TFT-LCD product technology is mature
The technical problems such as resolution, color saturation and brightness, large scale and small-medium size TFT-LCD display respective field gradually
Occupy the dominant position of flat-panel monitor.But the requirement to display technology is always in the continuous improvement, it is desirable that liquid crystal display
Realize faster response, reduce driving voltage to reduce power consumption etc., also require liquid crystal material have low voltage drive,
Quick response, wide temperature range and good low-temperature stability.
Liquid crystal material itself plays an important role to the performance for improving liquid crystal display, especially the rotation of reduction liquid crystal material
Turn viscosity and improves the dielectric anisotropy △ ε of liquid crystal material.New requirement is adapted it in order to improve the performance of material, it is novel
The synthesis of structure liquid-crystal compounds and the research of structure-performance relation become an important process of field of liquid crystals.
Summary of the invention
The first object of the present invention is to provide a kind of liquid-crystal compounds of novel cyclopropyl class negative dielectric anisotropic, the change
Closing object has many advantages, such as good negative dielectric anisotropic, good liquid crystal intersolubility, relatively low rotary viscosity, these are exactly
Required for improving liquid crystal material, there is important application value.
Liquid-crystal compounds of the present invention, has the following structure:
Wherein, R indicates the alkyl or alkoxy with 1-12 carbon atom；Ring A indicates 1,4- phenylene, the Asia 1,4- hexamethylene
The 1,4- phenylene that base or 1-4 hydrogen atom are replaced by fluorine atoms；Ring B indicates that 1,4- phenylene, 1,4- cyclohexylidene, 1,4- are sub-
The 1,4- phenylene that cyclohexenyl group or 1-4 hydrogen atom are replaced by fluorine atoms；
M is 0,1 or 2, and n is 0 or 1.
Preferably, in general formula I, R indicates that the alkyl or alkoxy with 1-5 carbon atom, ring A indicate Isosorbide-5-Nitrae-Asia benzene
The 1,4- phenylene that base, 1,4- cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms；Ring B indicates that 1,4- phenylene, 1,4- are sub-
The 1,4- phenylene that cyclohexyl, 1,4- cyclohexadienylidene or 1-4 hydrogen atom are replaced by fluorine atoms；
M is 0,1 or 2, and n is 0 or 1.
Technical solution more preferably, in general formula I, R indicate the alkyl or alkoxy with 1-5 carbon atom, ring A
Indicate the 1,4- phenylene that 1,4- phenylene, 1,4- cyclohexylidene or 1-2 hydrogen atom are replaced by fluorine atoms；And/or ring B table
Show the Asia the 1,4- benzene that 1,4- phenylene, 1,4- cyclohexylidene, 1,4- cyclohexadienylidene or 1-2 hydrogen atom are replaced by fluorine atoms
Base；
M is 0,1 or 2, and n is 0 or 1.
As further preferred technical solution, the liquid-crystal compounds is selected from one kind of following compound:
R indicates the alkyl or alkoxy with 1-5 carbon atom in I-1~I-48；
As preferred forms of the invention, the liquid-crystal compounds is selected from one kind of following compound:
The second object of the present invention is to provide the preparation method of the liquid-crystal compounds.
Liquid-crystal compounds of the present invention selects different synthetic routes according to the difference of ring B structure.
As a kind of technical solution, when n is 0 or 1, and ring B is that Isosorbide-5-Nitrae-phenylene or 1-4 hydrogen atom are replaced by fluorine atoms
Isosorbide-5-Nitrae-phenylene when, synthetic route is as follows:
Specifically includes the following steps:
(1)It reacts with organolithium reagent, then is reacted with borate, obtained
(2)WithIt is reacted by Suzuki
Synthesis
Wherein, X1Br or Cl is represented, R, m, n, ring A, ring B and gained liquid-crystal compounds in compound involved by each step
The group that R, m, n, ring A, ring B are represented in product is corresponding (see the restriction about each substituent group in general formula I).
In step 1) described in the above method,The molar ratio of organolithium reagent and borate be 1: 0.9~
1.8: 0.9~3.0.
Preferably, reaction temperature can be at -50~-100 DEG C；
Wherein, the organolithium reagent is selected from the one or more of n-BuLi, s-butyl lithium or tert-butyl lithium, described
Borate is selected from one or more of trimethylborate, three isobutyl ester of triisopropyl borate ester, butyl borate or boric acid.
In the step 2),WithThrowing
Expect that molar ratio is 1: 0.9~1.5.
Preferably, reaction temperature can be at 50~150 DEG C；
In above-mentioned courseSynthesis, can be according to n value and ring A structure
Difference, select different synthetic routes.
When n is 0 or 1, and ring A is Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1-4 hydrogen atom are replaced by fluorine atoms,
Synthetic route is as follows:
Specifically includes the following steps:
(1) withWithIt is raw material by Friedel-Crafts reaction, obtains
(2)By reduction reaction, obtain
Wherein, the group that m, the ring B in compound involved by each step are represented with m, ring B in gained liquid-crystal compounds product
Corresponding (see the restriction about each substituent group in general formula I).
In step described in the above method (1), Friedel-Crafts reaction used catalyst is alchlor；With the molar ratio of alchlor be 1: 1.0~3.0:1.0~
3.0；
Preferably, reaction temperature can be at -10~80 DEG C；
In the step (2), raw materials used reduction reaction includes triethylsilane and trifluoroacetic acid system；The molar ratio of triethylsilane and trifluoroacetic acid be 1: 1.0~
3.0:1.0~5.0；
Preferably, reaction temperature can be at -10~80 DEG C；
Work as n=1, and when ring A is 1 or 4 cyclohexylidene, i.e.,
Synthetic route is as follows:
Specifically includes the following steps:
(1)It reacts, obtains with triphenylphosphine
(2)WithIt is reacted, is obtained by wittig for raw material
It arrives
(3)Through catalytic hydrogenation, obtain
Wherein, the group that m, the ring B in compound involved by each step are represented with m, ring B in gained liquid-crystal compounds product
Corresponding (see the restriction about each substituent group in general formula I).
In step 1) described in the above method,Molar ratio with triphenylphosphine is 1.0:0.9
~1.5；
Preferably, reaction temperature can be at 50~150 DEG C；
In step (2) the wittig reaction, Molar ratio with potassium tert-butoxide is 1: 1.0~3.0:1.0~3.0；
Preferably, reaction temperature can be at -30~30 DEG C；
In the step 3),The mass ratio that feeds intake with catalyst is 1:
0.03~0.15；
Preferably, reaction temperature can be at 10~70 DEG C；
Wherein, the catalyst is selected from one or more of Pd/C, Raney's nickel, Pt/C, preferably Pt/C.
As second of technical solution, when n is 0 or 1, and ring B is Isosorbide-5-Nitrae-cyclohexadienylidene, i.e.,Synthetic route is as follows:
Specifically includes the following steps:
(1)With organolithium reagent carry out metallization reaction, then withReaction, obtains
(2)Through acid-catalyzed dehydration, obtain
Wherein, R, m, n, ring A generation in R, m in compound involved by each step, n, ring A and gained liquid-crystal compounds product
The group of table is corresponding (see the restriction about each substituent group in general formula I).
In step described in the above method (1)Organolithium reagent withMolar ratio be 1: 1.0~2.0:0.8~1.5；
Preferably, reaction temperature can be at -50~-100 DEG C；
Wherein, the organolithium reagent is selected from one or more of s-butyl lithium, tert-butyl lithium or n-BuLi.
In the step (2),Molar ratio with acid is 1:
0.02~0.2；
Preferably, reaction temperature can be at 50~120 DEG C；
Wherein, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-methyl benzenesulfonic acid, potassium acid sulfate,
Preferably p-methyl benzenesulfonic acid.
In above-mentioned courseSynthetic route it is preferably as follows:
Specifically includes the following steps:
(1)WithIt is reacted, is obtained by wittig for raw material
It arrives
(2)Through catalytic hydrogenation, obtain
(3)Through acid catalysis remove-insurance, obtain
Wherein, the group that n, the ring A in compound involved by each step are represented with n, ring A in gained liquid-crystal compounds product
Corresponding, more preferable n is 0 or 1, and ring A is 1 or 4 cyclohexylidene.
In the step of above method (1), With
The molar ratio of potassium tert-butoxide is 1: 1.0~3.0:1.0~3.0；
Preferably, reaction temperature can be at -30~30 DEG C；
In the step (2),The mass ratio that feeds intake with catalyst is
1:0.05~0.15；
Preferably, reaction temperature can be at 10~70 DEG C；
Wherein, the catalyst is selected from one or more of Pd/C, Raney's nickel, Pt/C, preferably Pd/C.
In the step (3),The mass ratio that feeds intake with acid is 1:
0.5~4.0；
Preferably, reaction temperature can be at 30~100 DEG C；
Wherein, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-methyl benzenesulfonic acid, preferably first
Acid.
As the third technical solution, when n is 0 or 1, and ring B is 1 or 4 cyclohexylidene, i.e.,Synthetic route is as follows:
Specifically includes the following steps:
Through catalytic hydrogenation, obtain
Wherein, the group phase that R, m in involved compound, ring A are represented with R, m, ring A in gained liquid-crystal compounds product
Corresponding (see the restriction about each substituent group in general formula I).
In step described in the above method,With catalyst
The mass ratio that feeds intake is 1:0.03~0.15；
Preferably, reaction temperature can be at 10~70 DEG C；
Wherein, the catalyst is selected from one or more of Pd/C, Raney's nickel, Pt/C, preferably Pd/C.
It is above-mentioned AndDisclosure can be passed through
Method known per se synthesizes to obtain in commercial sources or document.
Method of the present invention can be related to conventional post-processing if necessary, and the conventional post-processing is specific such as: using dichloro
Methane, ethyl acetate or toluene extraction, liquid separation are washed, dry, vacuum rotary evaporator evaporation, products therefrom vacuum distillation
Or recrystallization and/or chromatography purify.
It can be stablized using above-mentioned preparation method, be efficiently obtained liquid-crystal compounds of the present invention.
The third object of the present invention is the composition that protection contains the liquid-crystal compounds.The liquid-crystal compounds is combining
Mass percent in object is 1~60%, preferably 3~50%, further preferably 5~25%.
The fourth object of the present invention is that the protection liquid-crystal compounds and the composition containing the liquid-crystal compounds exist
The application of field of liquid crystal display, the application preferably in liquid crystal display device.The liquid crystal display device includes but not
It is limited to TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.It has used the liquid-crystal compounds or has contained the LCD compound
The composition of object has good negative dielectric anisotropic, and rotary viscosity is low, so that driving voltage be effectively reduced, improves liquid crystal
The response speed of display device, while having the characteristics that optical anisotropy numerical value is moderate, charge conservation rate is high.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The raw material unless otherwise instructed, can be obtained from public commercial source.
According to the common detection methods of this field, the various performance parameters of liquid-crystal compounds are obtained by linear fit,
In, the concrete meaning of each performance parameter is as follows:
△ n represents optical anisotropy (25 DEG C)；△ ε represents dielectric anisotropy (25 DEG C, 1000Hz)；γ 1 represents rotation
Turn viscosity (mPa.s, 25 DEG C).
Embodiment 1
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-01 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-01-1:
Under nitrogen protection, 37.5g 1, the fluoro- 4- methyl -3- propoxyl group benzene of 2- bis-, the 26.5g tert-butyl alcohol are added into reaction flask
The hexane solution of 0.24mol n-BuLi is added dropwise in potassium, 200ml tetrahydrofuran, temperature control -70~-80 DEG C, drips and finishes insulation reaction 1
Hour, 32.5g trimethylborate is added dropwise in temperature control -70~-80 DEG C, then rises again naturally to -30 DEG C.2M aqueous hydrochloric acid solution is added
300ml is acidified, and conventional post-processing is carried out, and petroleum ether is recrystallized to give light yellow solid (compound BYLC-01-1)
41.0g, HPLC:99.4%, yield 88.5%；
(2) synthesis of compound BYLC-01-2:
22.5g chlorobenzene, 32.0g alchlor are added in reaction flask, 27.5g Cyclopropyl carbonyl chloride is added dropwise in temperature control -5~5 DEG C,
It drips and finishes insulation reaction 30min, then return and warm to room temperature naturally, be stirred to react 6h, with cryosel aqueous acid quenching reaction, carry out normal
Rule post-processing, obtains light yellow liquid (compound BYLC-01-2) 31.6g, GC:95.8%, yield 87.5%；
(3) synthesis of compound BYLC-01-3:
27.5g BYLC-01-2,50ml triethylsilane are added in reaction flask, reaction is stirred at room temperature in 50ml trifluoroacetic acid
Overnight, add water quenching to go out, carry out conventional post-processing, be spin-dried for solvent and obtain colourless liquid (compound BYLC-01-3) 19.6g, GC:
98.5%, yield 78.2%；
(4) synthesis of compound BYLC-01:
Under nitrogen protection, 23.0g compound BYLC-01-1,16.6g BYLC-01-3,150ml are added into reaction flask
N,N-Dimethylformamide, 50ml deionized water, 13.8g Anhydrous potassium carbonate, 0.4g 1,1- bis- (diphenylphosphine) ferrocene dichloro
Change palladium (II), heating reflux reaction 3 hours.Conventional post-processing is carried out, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization is obtained
To white solid (compound BYLC-01) 27.0g, GC:99.7%, yield: 85.7%.
Gained white solid BYLC-01 is analyzed using GC-MS, the m/z of product is 316.1 (M+).
1H-NMR(300MHz,CDCl3): 0.15-1.85 (m, 10H), 1.95-2.75 (m, 5H), 3.53-4.15 (m, 2H),
6.91-7.75(m,5H)。
Technical solution according to embodiment 1, it is only necessary to the corresponding raw material of simple replacement does not change any substantive operations,
Following liquid-crystal compounds can be synthesized.
Embodiment 2
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-03 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-03-1:
40.3g cyclopropylmethyl bromide, 78.5g triphenylphosphine, 150ml n,N-Dimethylformamide, control are added in reaction flask
105~110 DEG C of reaction 6h of temperature are cooled to 80 DEG C hereinafter, addition 300ml toluene, is refrigerated to -10 DEG C or so, and suction filtration obtains white
Solid (compound BYLC-03-1) 106.3g, yield 89.5%；
(2) synthesis of compound BYLC-03-2:
Under nitrogen protection, 77.6g compound BYLC-03-1 and 300ml tetrahydrofuran, temperature control -10 are added into reaction flask
~5 DEG C of addition 25.5g potassium tert-butoxides react 30min, and 31.5g 4- (4- chlorobenzene)-cyclohexanone is added dropwise in temperature control -10~5 DEG C, then
Naturally it returns and warms to room temperature, react 3h, 200ml water quenching reaction is added, carry out conventional post-processing, obtain white solid (compound
BYLC-03-2): 31.4g, GC:97.5%, yield: 85%；
(3) synthesis of compound BYLC-03-3:
24.6g compound BYLC-03-2,1.2g platinum carbon, 30ml toluene, 50ml ethyl alcohol, hydrogen displacement are added in reaction flask
Twice, 10~20 DEG C of hydrogenation reaction 6h of temperature control carry out conventional post-processing, obtain white solid (compound BYLC-03-3):
23.6g, GC:99.2%, yield: 95.5%；
(4) synthesis of compound BYLC-03:
Under nitrogen protection, 20.5g compound BYLC-01-1,22.1g BYLC-03-3,120ml are added into reaction flask
N,N-Dimethylformamide, 40ml deionized water, 12.3g Anhydrous potassium carbonate, 0.3g 1,1- bis- (diphenylphosphine) ferrocene dichloro
Change palladium (II), heating reflux reaction 3 hours.Conventional post-processing is carried out, through chromatogram purification, n-hexane elution, ethyl alcohol recrystallization is obtained
To white solid (compound BYLC-03) 30.4g, GC:99.7%, yield: 85.7%.
Gained white solid BYLC-03 is analyzed using GC-MS, the m/z of product is 398.1 (M+).
1H-NMR(300MHz,CDCl3):0.15-1.85(m,21H1.95-2.75(m,4H),3.53-4.15(m,2H),
6.91-7.75(m,5H)。
Technical solution according to embodiment 2, it is only necessary to the corresponding raw material of simple replacement does not change any substantive operations,
Following liquid-crystal compounds can be synthesized.
Embodiment 3
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-05 is as follows:
Specific step is as follows:
(1) synthesis of compound BYLC-05-1:
Under nitrogen protection, 77.5g BYLC-03-1 and 300ml tetrahydrofuran is added into reaction flask, temperature control -5~5 DEG C add
Enter 25.5g potassium tert-butoxide, react 30min, 23.2g Isosorbide-5-Nitrae-cyclohexanedione monoethylene acetal is added dropwise in temperature control -5~5 DEG C, then
Naturally it returns and warms to room temperature, react 3h, 200ml water quenching reaction is added, carry out conventional post-processing, obtain white solid (compound
BYLC-05-1): 24.2g, GC:96.5%, yield: 83.5%；
(2) synthesis of compound BYLC-05-2:
20.0g compound BYLC-05-1,1.8g palladium carbon, 20ml toluene, 40ml ethyl alcohol, hydrogen displacement are added in reaction flask
Twice, 10~30 DEG C of hydrogenation reaction 6h of temperature control carry out conventional post-processing, obtain white solid (compound BYLC-05-2):
19.8g, GC:99.5%, yield: 97.8%；
(3) synthesis of compound BYLC-05-3:
18.3g BYLC-05-2,30ml formic acid, 60ml toluene, 50~60 DEG C of reaction 4h of temperature control, progress are added in reaction flask
Conventional post-processing, obtains white solid (compound BYLC-05-3): 12.5g, GC:96.8%, yield: 88.7%；
(4) synthesis of compound BYLC-05-4:
Addition 19.5g 1 in reaction flask, the fluoro- 4- methyl -3- propoxyl group benzene of 2- bis-, 130ml tetrahydrofuran, temperature control -70~-
The hexane solution of 80 DEG C of dropwise addition 0.12mol n-BuLis drips and finishes insulation reaction 1 hour, and 15.2g is added dropwise in temperature control -70~-80 DEG C
The solution of BYLC-05-3 and 30ml tetrahydrofuran composition, then rises again naturally to -30 DEG C.Be added 2M aqueous hydrochloric acid solution 100ml into
Row acidification carries out conventional post-processing, is spin-dried for solvent and obtains light yellow liquid (compound BYLC-05-4) 31.3g, GC:94.8%
(suitable+anti-), yield 95.5%；
(5) synthesis of compound BYLC-05:
28.0g BYLC-05-4,0.3g p-methyl benzenesulfonic acid, 120ml toluene, reflux dewatering 4h, progress are added in reaction flask
Conventional post-processing, obtains white solid (compound BYLC-05): 22.2g, GC:99.8%, yield: 83.6%；
Gained white solid BYLC-05 is analyzed using GC-MS, the m/z of product is 320.2 (M+).
1H-NMR(300MHz,CDCl3):0.15-1.85(m,15H),1.90-2.75(m,7H),3.53-4.15(m,2H),
5.53-5.95(m,1H),6.65-7.55(m,1H)。
Technical solution according to embodiment 3, it is only necessary to the corresponding raw material of simple replacement does not change any substantive operations,
Following liquid-crystal compounds can be synthesized.
Embodiment 4
The structural formula of liquid-crystal compounds are as follows:
The synthetic line of prepare compound BYLC-07 is as follows:
Specific step is as follows:
The synthesis of compound BYLC-07:
30.0g compound BYLC-05,2.1g palladium carbon, 40ml toluene, 70ml ethyl alcohol, hydrogen displacement two are added in reaction flask
Secondary, 10~30 DEG C of hydrogenation reaction 6h of temperature control carry out conventional post-processing, obtain white solid (compound BYLC-07): 27.7g,
GC:99.8%, yield: 92.5%；
Gained white solid BYLC-07 is analyzed using GC-MS, the m/z of product is 322.2 (M+).
1H-NMR(300MHz,CDCl3):0.15-1.85(m,21H)1.95-2.75(m,4H),3.53-4.15(m,2H),
6.51-7.35(m,1H)。
Technical solution according to embodiment 4, it is only necessary to the corresponding raw material of simple replacement does not change any substantive operations,
Following liquid-crystal compounds can be synthesized.
Experimental example 1
By compound obtained by compound BYLC-01 obtained by embodiment 1 and the technical solution according to embodiment 1
The liquid-crystal compounds performance parameter data of BYLC-02 and comparative example 1 (known common another like liquid-crystal compounds) carry out pair
Than arranging, testing result is as shown in table 1:
Table 1: the performance test results of liquid-crystal compounds
By the testing result of table 1, it is apparent that liquid-crystal compounds provided by the invention and traditional chemistry similar knot
Structure compound is compared, and rotary viscosity is suitable, has bigger negative dielectric anisotropic and high clearing point, for promoting liquid crystal group
The dielectric anisotropy for closing object has positive effect, is further reduced polar monomer use, has good low temperature intersolubility, have
The reduction liquid-crystal composition rotary viscosity of effect is to promote the response time.
Experimental example 2
By compound obtained by compound BYLC-03 obtained by embodiment 2 and the technical solution according to embodiment 2
The liquid-crystal compounds performance parameter data of BYLC-04 and comparative example 2 (known common another like liquid-crystal compounds) carry out pair
Than arranging, testing result is as shown in table 2:
Table 2: the performance test results of liquid-crystal compounds
By the testing result of table 2, it is apparent that liquid-crystal compounds provided by the invention and traditional chemistry similar knot
The negative dielectric anisotropic compound of structure is compared, and has bigger negative dielectric anisotropic and higher clearing point performance, for
The dielectric anisotropy for promoting liquid-crystal composition has positive effect, is further reduced polar monomer use, has good low
Warm intersolubility reduces liquid-crystal composition rotary viscosity to promote the response time.
Experimental example 3
By compound BYLC-05 obtained by embodiment 3 and comparative example 3 (known common another like liquid-crystal compounds)
Liquid-crystal compounds performance parameter data compare arrangement, testing result is as shown in table 3:
Table 3: the performance test results of liquid-crystal compounds
By the testing result of table 3, it is apparent that liquid-crystal compounds provided by the invention and traditional chemistry similar knot
The negative dielectric anisotropic compound of structure is compared, and has bigger negative dielectric anisotropic and higher clearing point performance, for
The dielectric anisotropy for promoting liquid-crystal composition has positive effect, is further reduced polar monomer use, has good low
Warm intersolubility reduces liquid-crystal composition rotary viscosity to promote the response time.
Experimental example 4
By compound BYLC-07 obtained by embodiment 4 and comparative example 4 (known common another like liquid-crystal compounds)
Liquid-crystal compounds performance parameter data compare arrangement, testing result is as shown in table 4:
Table 4: the performance test results of liquid-crystal compounds
By the testing result of table 4, it is apparent that liquid-crystal compounds provided by the invention and traditional chemistry similar knot
The negative dielectric anisotropic compound of structure is compared, and has bigger negative dielectric anisotropic and higher clearing point performance, for
The dielectric anisotropy for promoting liquid-crystal composition has positive effect, is further reduced polar monomer use, has good low
Warm intersolubility reduces liquid-crystal composition rotary viscosity to promote the response time.
In addition, discovery after herein described compound is particularly applicable in the liquid-crystal composition of conventional system, it can be with
The dielectric anisotropy △ ε of liquid-crystal composition is improved, while keeping rotary viscosity γ 1 appropriate and refractive index appropriate respectively to different
Property △ n, gained liquid-crystal composition have the characteristics that significant quick response and low voltage drive feature.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, 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 are fallen within the scope of the claimed invention.
Claims (16)
1. a kind of negative dielectric anisotropic liquid crystal compound, which is characterized in that have structure shown in formula I:
Wherein, R indicates the alkyl or alkoxy with 1-12 carbon atom；Ring A indicate 1,4- phenylene, 1,4- cyclohexylidene or
The 1,4- phenylene that 1-4 hydrogen atom is replaced by fluorine atoms；Ring B indicates 1,4- phenylene, 1,4- cyclohexylidene, the Asia 1,4- hexamethylene
The 1,4- phenylene that alkenyl or 1-4 hydrogen atom are replaced by fluorine atoms；
M is 0,1 or 2, and n is 0 or 1.
2. liquid-crystal compounds according to claim 1, which is characterized in that in general formula I, R indicates there is 1-5 carbon atom
Alkyl or alkoxy, ring A indicates the Isosorbide-5-Nitrae-that Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-4 hydrogen atom are replaced by fluorine atoms
Phenylene；Ring B indicates that 1,4- phenylene, 1,4- cyclohexylidene, 1,4- cyclohexadienylidene or 1-4 hydrogen atom are replaced by fluorine atoms
1,4- phenylene；
M is 0,1 or 2, and n is 0 or 1.
3. liquid-crystal compounds according to claim 2, which is characterized in that the R indicates the alkyl with 1-5 carbon atom
Or alkoxy, ring A indicate Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 1-2 hydrogen atom are replaced by fluorine atoms；
And/or ring B indicates that Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene or 1-2 hydrogen atom are replaced by fluorine atoms
1,4- phenylene；
M is 0,1 or 2, and n is 0 or 1.
4. liquid-crystal compounds according to claim 1-3, which is characterized in that the liquid-crystal compounds is selected from as follows
One kind of compound:
Wherein, R indicates the alkyl or alkoxy with 1-5 carbon atom.
5. liquid-crystal compounds according to claim 1, which is characterized in that the liquid-crystal compounds is selected from following compound
It is a kind of:
6. the preparation method of any one of the claim 1-5 liquid-crystal compounds, which is characterized in that when n is 0 or 1, and ring B is
When Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1-4 hydrogen atom are replaced by fluorine atoms, the synthetic route of the liquid-crystal compounds is such as
Under:
Specifically includes the following steps:
(1)It reacts with organolithium reagent, then is reacted with borate, obtained
(2)WithIt is reacted and is synthesized by Suzuki
Wherein, X1Br or Cl is represented, the R, m, n, ring A, ring B in compound involved by each step are the same as any one of claim 1-5 institute
It states.
7. preparation method according to claim 6, which is characterized in that describedIt is prepared by following methods:
When n is 0 or 1, and ring A is Isosorbide-5-Nitrae-phenylene that Isosorbide-5-Nitrae-phenylene or 1-4 hydrogen atom are replaced by fluorine atoms, synthesis
Route is as follows:
Specifically includes the following steps:
(1) withWithIt is raw material by Friedel-Crafts reaction, obtains
(2)By reduction reaction, obtain
Work as n=1, and when ring A is 1 or 4 cyclohexylidene, i.e.,Synthesis
Route is as follows:
Specifically includes the following steps:
(1)It reacts, obtains with triphenylphosphine
(2)WithIt is reacted, is obtained by wittig for raw material
(3)Through catalytic hydrogenation, obtain
8. the preparation method of any one of the claim 1-5 liquid-crystal compounds, which is characterized in that when n is 0 or 1, and ring B is
When Isosorbide-5-Nitrae-cyclohexadienylidene, i.e.,Synthetic route is as follows:
Specifically includes the following steps:
(1)With organolithium reagent carry out metallization reaction, then withReaction, obtains
(2)Through acid-catalyzed dehydration, obtain
Wherein, R, m in compound involved by each step, n, ring A are the same as described in claim any one of 1-5.
9. preparation method according to claim 8, which is characterized in that
It is describedSynthetic route it is as follows:
Specifically includes the following steps:
(1)WithIt is reacted, is obtained by wittig for raw material
(2)Through catalytic hydrogenation, obtain
(3)Through acid catalysis remove-insurance, obtain
Wherein, m, n, the ring A in compound involved by each step are the same as described in claim any one of 1-5.
10. preparation method according to claim 9, which is characterized in that the m is with described in claim any one of 1-5, n
It is 0 or 1, and ring A is 1 or 4 cyclohexylidene.
11. the preparation method of any one of the claim 1-5 liquid-crystal compounds, which is characterized in that when n is 0 or 1, and ring B is
When 1 or 4 cyclohexylidene, i.e.,Synthetic route is as follows:
Specifically includes the following steps:
Through catalytic hydrogenation, obtain
Wherein, R, m in involved compound, ring A are the same as described in claim any one of 1-5.
12. a kind of liquid-crystal composition, which is characterized in that comprising mass percent be any one of the claim 1-5 of 1-60% institute
State compound.
13. liquid-crystal composition according to claim 12, it is characterised in that: the right for being 3-50% comprising mass percent
It is required that any one of 1-5 compound.
14. liquid-crystal composition according to claim 13, it is characterised in that: the power for being 5~25% comprising mass percent
Benefit requires any one of 1-5 compound.
15. any one of any one of the claim 1-5 compound or claim 12-14 composition is filled in liquid crystal display
Application in setting.
16. application according to claim 15, it is characterised in that: the liquid crystal display device be TN, ADS, VA,
PSVA, FFS or IPS liquid crystal display.
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| CN111440053A (en) * | 2020-04-07 | 2020-07-24 | 西安瑞联新材料股份有限公司 | Industrial production method of cyclopropylmethyl cyclohexyl difluorobiphenyl compounds |
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