CN106146243A - Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels - Google Patents
Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels Download PDFInfo
- Publication number
- CN106146243A CN106146243A CN201510175958.9A CN201510175958A CN106146243A CN 106146243 A CN106146243 A CN 106146243A CN 201510175958 A CN201510175958 A CN 201510175958A CN 106146243 A CN106146243 A CN 106146243A
- Authority
- CN
- China
- Prior art keywords
- compound
- liquid
- mass fraction
- crystal
- crystal composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CCCCc(cc1)ccc1-c1ccc(-c2cc(F)c(*Oc(cc3I)cc(F)c3F)c(F)c2)c(F)c1 Chemical compound CCCCc(cc1)ccc1-c1ccc(-c2cc(F)c(*Oc(cc3I)cc(F)c3F)c(F)c2)c(F)c1 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
The present invention relates to technical field of liquid crystal display, disclose a kind of liquid-crystal compounds and preparation method thereof, a kind of liquid-crystal composition and a kind of display panels.The structural formula of described liquid-crystal compounds is shown in formula I, this liquid-crystal compounds is the compound of 7-hydrogen benzo [de] anthracene class, this compounds has preferable physics and chemical stability, and there is higher clearing point, make the compositions containing this liquid-crystal compounds have wider nematic phase range, greatly widen the application of liquid-crystal composition.
Description
Technical field
The present invention relates to technical field of liquid crystal display, particularly relate to a kind of liquid-crystal compounds and preparation side thereof
Method, a kind of liquid-crystal composition and a kind of display panels.
Background technology
In panel display apparatus, Thin Film Transistor-LCD (Thin Film Transistor Liquid
Crystal Display, is called for short TFT-LCD) have that volume is little, low in energy consumption, manufacturing cost is relatively low and
The feature such as radiationless, occupies leading position in current flat panel display market.
Liquid crystal display has been widely used the various aspects in social life, and lcd technology is developed so far,
Various liquid-crystal compoundss are on the actual application.Some general requirements to liquid-crystal compounds, bag
Include the phase transition temperature of liquid-crystal compounds, optical anisotropy, dielectric anisotropy, viscosity, resistivity etc.,
All the application that liquid crystal material is final there is the biggest impact.The exploitation of new liquid-crystal compounds and its composition
Compositions, improve the various character of liquid crystal, the application effect improving liquid crystal display is of crucial importance.And liquid
Crystal composite is to use various of monomer liquid-crystal compounds to want according to technology such as the electric light physical properties of liquid crystal display
Ask and be compounded into.The liquid-crystal composition of excellent properties to be obtained must be with the monomer liquid crystal chemical combination of function admirable
Thing, people need the synthesis compound containing different liquid crystal structures to realize the different electric light physical properties of mixed liquid crystal
Energy.
According to its display mode, LCD can be divided into the type that dynamically shines, distortion type (TN), supertwist type (STN)
With plane conversion type (IPS), although the liquid-crystal composition display characteristic used by these LCD is different,
But there is following general character: driving voltage is low, liquid crystal operating temperature range width, suitable photoanisotropy and good
Good heat stability, light stability and chemical stability.In the allocation process of mixed liquid crystal compositions, past
Toward adding some monomer liquid crystal compounds with a certain property, improve the limpid of liquid-crystal composition
The performances such as point, it is desired that the monomer liquid crystal compound of this property is always researcher.
Summary of the invention
The invention provides a kind of liquid-crystal compounds and preparation method thereof, a kind of liquid-crystal composition and a kind of liquid crystal
Display floater, in order to improve the clearing point of liquid-crystal composition, and then widens the range of application of display panels.
First the embodiment of the present invention provides a kind of liquid-crystal compounds, the structural formula of described liquid-crystal compounds such as Formulas I
Shown in:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6.
In this technical scheme, this liquid-crystal compounds is the compound of 7-hydrogen benzo [de] anthracene class, such chemical combination
Thing has preferable physics and chemical stability, and has higher clearing point so that containing this LCD compound
The compositions of thing has wider nematic phase range, has greatly widened the application of liquid-crystal composition.
Preferably, R is the alkyl of 1 to 7 selected from carbon number；R1It is 1 to 7 selected from hydrogen, carbon number
Alkyl；N is 0,1 or 2.
Inventor is it has furthermore been found that described liquid-crystal compounds is selected from following chemical structural formula:
The present invention also provides for a kind of method preparing above-mentioned liquid-crystal compounds, comprises the following steps:
Step a, compound I-1 is carried out bromo-reaction with N-bromo-succinimide in oxolane,
Obtain compound I-2；Reaction equation is as follows:
Step b, compound I-2 and butyl lithium are reacted after, andCarry out addition anti-
Should, then it is dehydrated, obtains compound I-3；Reaction equation is as follows:
Step c, compound I-3 is carried out in ethanol and ethyl acetate hydrogenation, obtain compound I-4；
Reaction equation is as follows:
Step d, compound I-4 is carried out in dichloromethane bromo-reaction, obtain compound I-5；Reaction
Formula is as follows:
Step e, by compound I-5 and R1Base magnesium bromide carries out coupling reaction, obtains compound I-6；Reaction
Formula is as follows:
Step f, compound I-6 is obtained compound I-7 with formic acid hydrolysis in toluene；The following institute of reaction equation
Show:
Step g, compound I-7 and methoxyl methyl benzyltriphenylphosphonium chloride are carried out Wittig reaction after, use salt
Acid hydrolysis, obtains compound I-8；Reaction equation is as follows:
Step h, compound I-8 is carried out reduction reaction with sodium borohydride in oxolane, obtain chemical combination
Thing I-9；Reaction equation is as follows:
Step i, compound I-9 paratoluensulfonyl chloride is carried out hydroxyl protection reaction, obtain compound I-10；
Reaction equation is as follows:
Step j, compound I-10 and allylic bromination magnesium being carried out coupling reaction, product is separated, obtains
Trans product, i.e. compound I；Reaction equation is as follows:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6；Ts represents p-toluenesulfonyl.
The present invention also provides for a kind of liquid-crystal composition, including the LCD compound shown in the Formulas I that at least one is above-mentioned
Thing.
In this technical scheme, owing to have employed the liquid-crystal compounds shown in Formulas I in liquid-crystal composition, because of
This, be beneficial to improve the clearing point of liquid-crystal composition, and the cryogenic property of liquid-crystal composition is the most preferable.In liquid crystal group
In compound the liquid-crystal compounds shown in Formulas I can add one, two kinds, three kinds the most multiple.
Inventor finds, it is preferred that in described liquid-crystal composition, the quality of the liquid-crystal compounds shown in Formulas I is divided
Number is 10%～60%, preferably 15%～40%, more preferably 20%～40%.Such as mass fraction is 15%,
17%, 19%, 20%, 23%, 25%, 26%, 28%, 29%, 30%, 35% or 40%.
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 18%:
Mass fraction is the liquid-crystal compounds of 24%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 26%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 11%:
Mass fraction is the liquid-crystal compounds of 19%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 10%:
The embodiment of the present invention also provides for the preparation method of a kind of any of the above-described kind of described liquid-crystal composition, described system
Preparation Method includes: each component in liquid-crystal composition be mixed to get.
The embodiment of the present invention also provides for a kind of display panels, and the liquid crystal layer of described display panels uses
Any of the above-described kind of liquid-crystal composition obtains.
In this technical scheme, owing to liquid-crystal composition has higher clearing point, there is wider nematic phase
Scope, therefore, uses this liquid-crystal composition as liquid crystal layer, is conducive to improving the aobvious of display panels
Show performance.
Accompanying drawing explanation
The general structure of the liquid-crystal compounds that Fig. 1 provides for the embodiment of the present invention；
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the compound P1 of the embodiment of the present invention 1 preparation；
Fig. 3 is the hydrogen nuclear magnetic spectrogram of the compound P2 of the embodiment of the present invention 2 preparation.
Detailed description of the invention
In order to improve the clearing point of liquid-crystal compounds, embodiments provide a kind of liquid-crystal compounds and
Preparation method, a kind of liquid-crystal composition and a kind of display panels.In this technical scheme, this LCD compound
Thing is the compound of 7-hydrogen benzo [de] anthracene class, and this compounds has preferable physics and chemical stability,
And there is higher clearing point so that the compositions containing this liquid-crystal compounds has wider nematic phase model
Enclose, greatly widened the application of liquid-crystal composition.For making the purpose of the present invention, technical scheme and excellent
Point is clearer, below lifts specific embodiment and is described in further detail the present invention.
First the embodiment of the present invention provides a kind of liquid-crystal compounds, as it is shown in figure 1, described liquid-crystal compounds
Structural formula is shown in formula I:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6.
In this technical scheme, this liquid-crystal compounds is the compound of 7-hydrogen benzo [de] anthracene class, such chemical combination
Thing has preferable physics and chemical stability, and has higher clearing point so that containing this LCD compound
The compositions of thing has wider nematic phase range, has greatly widened the application of liquid-crystal composition.
Wherein, carbon number be the alkyl of 1 to 10 can be the carbon number of straight or branched be 1 to 10
Alkyl, or the ring-type or substituted ring-type carbon number of alkyl is the alkyl of 1-10, such as first
Base, ethyl, n-pro-pyl, 1-Methylethyl, normal-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-diformazan
Base propyl group, n-pentyl, isopentyl, hexyl, heptyl, octyl group, cyclopropyl, cyclobutyl, cyclopenta, ring
Hexyl, suberyl, ring octyl group, and straight chain or the substituted carbon number of branched alkyl be the cycloalkanes of 3-8
Base etc.；N can be 0,1,2,3,4,5 or 6.
Here it should be noted that in Formulas I square brackets can include current cyclohexyl, it is also possible to include separately
On one cyclohexyl, the compound that i.e. following formula also represents for Formulas I, the two equivalent, all represent this LCD compound
Thing has a n+1 cyclohexyl:
Preferably, R is the alkyl of 1 to 7 selected from carbon number；R1It is 1 to 7 selected from hydrogen, carbon number
Alkyl；N is 0,1 or 2.
Inventor is it has furthermore been found that described liquid-crystal compounds is selected from following chemical structural formula:
The present invention also provides for a kind of method preparing above-mentioned liquid-crystal compounds, comprises the following steps:
Step a, compound I-1 is carried out bromo-reaction with N-bromo-succinimide in oxolane,
Obtain compound I-2；Reaction equation is as follows:
Step b, compound I-2 and butyl lithium are reacted after, andCarry out addition anti-
Should, then it is dehydrated, obtains compound I-3；Reaction equation is as follows:
Step c, compound I-3 is carried out in ethanol and ethyl acetate hydrogenation, obtain compound I-4；
Reaction equation is as follows:
Step d, compound I-4 is carried out in dichloromethane bromo-reaction, obtain compound I-5；Reaction
Formula is as follows:
Step e, by compound I-5 and R1Base magnesium bromide carries out coupling reaction, obtains compound I-6；Reaction
Formula is as follows:
Step f, compound I-6 is obtained compound I-7 with formic acid hydrolysis in toluene；The following institute of reaction equation
Show:
Step g, compound I-7 and methoxyl methyl benzyltriphenylphosphonium chloride are carried out Wittig (witting) reaction
After, hydrolyze with hydrochloric acid, obtain compound I-8；Reaction equation is as follows:
Step h, compound I-8 is carried out reduction reaction with sodium borohydride in oxolane, obtain chemical combination
Thing I-9；Reaction equation is as follows:
Step i, compound I-9 paratoluensulfonyl chloride is carried out hydroxyl protection reaction, obtain compound I-10；
Reaction equation is as follows:
Step j, compound I-10 and allylic bromination magnesium being carried out coupling reaction, product is separated, obtains
Trans product, i.e. compound I；Reaction equation is as follows:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6；Ts represents p-toluenesulfonyl.
The present invention also provides for a kind of liquid-crystal composition, including the LCD compound shown in the Formulas I that at least one is above-mentioned
Thing.
In this technical scheme, owing to have employed the liquid-crystal compounds shown in Formulas I in liquid-crystal composition, because of
This, be beneficial to improve the clearing point of liquid-crystal composition, and the cryogenic property of liquid-crystal composition is the most preferable.In liquid crystal group
In compound the liquid-crystal compounds shown in Formulas I can add one, two kinds, three kinds the most multiple.
Inventor finds, it is preferred that in described liquid-crystal composition, the quality of the liquid-crystal compounds shown in Formulas I is divided
Number is 10%～60%, preferably 15%～25%.Such as mass fraction is 15%, 17%, 20%, 23%,
25%, 28%, 32%, 35% or 39%.
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 18%:
Mass fraction is the liquid-crystal compounds of 24%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 26%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 11%:
Mass fraction is the liquid-crystal compounds of 19%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 10%:
The embodiment of the present invention also provides for the preparation method of a kind of any of the above-described kind of described liquid-crystal composition, described system
Preparation Method includes: each component in liquid-crystal composition be mixed to get.
The embodiment of the present invention also provides for a kind of display panels, and described liquid crystal layer comprises any of the above-described kind of liquid
Crystal composite, such as, display panels includes first substrate and the second substrate putting box, Yi Jiwei
Liquid crystal layer between first substrate and second substrate, this liquid crystal layer can use any of the above-described kind of liquid crystal combination
Thing obtains.
In this technical scheme, owing to liquid-crystal composition has higher clearing point, there is wider nematic phase
Scope, therefore, uses this liquid-crystal composition as liquid crystal layer, is conducive to improving the aobvious of display panels
Show performance.
Several specific embodiment is set forth below, but the present invention is not limited by these embodiments.
One, the preparation of the liquid-crystal compounds shown in Formulas I
Enumerating the preparation process of the liquid-crystal compounds shown in several specific embodiment formula I, the present invention is also
Being not limited to following embodiment, specifically, the preparation process of this liquid-crystal compounds is as follows:
Embodiment 1
A kind of concrete compound P1 of the liquid-crystal compounds shown in Formulas I:
The synthetic route of P1 is as follows:
Step a, compound P1-1 is carried out bromo-reaction with N-bromo-succinimide in oxolane,
Obtain compound P1-2, particularly as follows:
In 250ml there-necked flask, 2.5 grams are had the compound 7 of formula P1-1,7-dimethyl-7H-benzo [de]
Anthracene (preparing according to patent WO2011/115378) is dissolved in 50ml oxolane, under agitation adds
Enter 1.8 grams of N-bromo-succinimides, be warming up to 35 DEG C and react 1 hour, then, add 80 milliliters of water,
Separate out yellow solid, filter, be dried, product mass spectrum (m/e): 324, obtain the compound of formula P1-2；
Step b-c, compound P1-2 and butyl lithium are reacted after, then andCarry out additive reaction,
Then it is dehydrated, then hydrogenates, obtain compound P1-4, particularly as follows:
In 250ml there-necked flask, add 50 milliliters of oxolanes, 3.23 g of compound P1-2, protect at nitrogen
Protect borehole cooling to-78 DEG C, be slowly added dropwise the hexane solution of the butyl lithium that 6.3 milliliters of concentration is 1.6M, add
-78 DEG C of insulation reaction of Bi Yu 1 hour, are added thereto to 1.8 gramsWith 10 milliliters of oxolanes
The solution being made into, finishes, and warms naturally to 25 DEG C, stirring reaction 2 hours.Add ammonium chloride solution hydrolysis.
Then separatory, washing, in organic layer, then add 100 milliliters of toluene, 1 gram of ethylene glycol, 1 gram of single water
Closing p-methyl benzenesulfonic acid reflux water-dividing 15 hours, cooling, washing, organic layer is concentrated to dryness and obtains compound P1-3.
Gained compound P1-3 is transferred in reactor, adds 15 milliliters of ethanol, 10 milliliters of ethyl acetate, 0.1
Palladium/the carbon of gram 5%, with reactor described in hydrogen purge, carries out hydrogenation under Hydrogen Vapor Pressure 0.1MPa
2 hours, after reactant liquor is removed catalyst, it is concentrated to dryness, silica gel column chromatography, petroleum ether: dichloromethane
=10:1 eluting, obtains product, i.e. obtains the compound of formula P1-4；
Step d, compound P1-4 is carried out in dichloromethane bromo-reaction, obtain compound P1-5, tool
Body is:
In 250ml there-necked flask, by 4.0 grams of compound dissolutions with formula P1-4 obtained in step b-c
In 50ml dichloromethane, add 1 gram of pyridine, control reaction temperature and be maintained at 25 DEG C, drip 1.9g bromine
5 milliliters of dichloromethane solutions.Finishing maintenance 25 DEG C to react 2 hours, add water, separatory, organic layer is sub-
Sodium bisulphate solution washs, washing, and magnesium sulfate is dried, silica gel column chromatography, petroleum ether: dichloromethane=10:
1 eluting, obtains the compound of formula P1-5；
Step e, compound P1-5 and propyl group magnesium bromide are carried out coupling reaction, obtain compound P1-6, tool
Body is:
In 250ml there-necked flask, by 4.6 grams of compound dissolutions with formula P1-5 obtained in step d
In 50ml toluene, it is subsequently adding four (triphenyl phosphorus) palladium catalyst of catalytic amount (about 0.1g), stirs
Mix down in the tetrahydrofuran solution 20 milliliters of propyl group magnesium bromide of 30 DEG C of dropping 1.5M, then insulation is anti-
Answer 3 hours, add water, separatory, after organic layer washing, magnesium sulfate is dried, silica gel column chromatography, petroleum ether:
Dichloromethane=10:1 eluting, obtains product, obtains the compound of formula P1-6；
Step f, compound P1-6 is obtained compound P1-7 with formic acid hydrolysis in toluene, particularly as follows:
In 250ml there-necked flask, by 3.1 grams of compound dissolutions with formula P1-6 obtained in step e at 50ml
In toluene, in stirring simultaneously, 1.2 gram of 80% formic acid solution, back flow reaction 2 hours, cooling, water are added
Washing, organic layer is concentrated to dryness, petroleum ether/re crystallization from toluene, i.e. obtains the compound shown in formula P1-7；
Step g, compound P1-7 and methoxyl methyl benzyltriphenylphosphonium chloride are carried out Wittig reaction after, use salt
Acid hydrolysis, obtains compound P1-8, particularly as follows:
In 500ml there-necked flask, add 2.87 grams of methoxymethyl triphenylphosphonium chlorinations and 20 milliliters of tetrahydrochysenes
Furan, is cooled to-10 DEG C, is dividedly in some parts 0.95 gram of potassium tert-butoxide, then, obtains 3.1 grams in step f
The compound of formula P1-7 is dissolved in 10ml oxolane, is added dropwise to above-mentioned 500 milliliters of there-necked flasks, then will
Reaction temperature is slowly increased to 25 DEG C, reacts 40 minutes.Add water, separatory, after organic layer is concentrated to dryness, add
Enter 30 milliliters of petroleum ether and the mixed solvent of ethanol, be sufficiently stirred for, separate out solid, sucking filtration, obtain mother solution,
By mother liquor concentrations to dry, add 50 milliliters of dichloromethane, hydrochloric acid of 10 milliliter of 35% concentration, back flow reaction
30 minutes, cooling, separatory, it is washed to neutrality.After organic layer washing, magnesium sulfate is dried, silica gel column chromatography,
Petroleum ether: dichloromethane=10:1 eluting, obtains the compound shown in formula P1-8；
Step h, compound P1-8 is carried out reduction reaction with sodium borohydride in oxolane, obtain chemical combination
Thing P1-9；Particularly as follows:
In 500 milliliters of there-necked flasks, adding 200 milliliters of oxolanes, 4.0 grams obtain formula P1-8 in step g
Compound, be dividedly in some parts 3.9 grams of sodium borohydrides in 30 DEG C, finish stirring 4 hours, add water, separate out solid
Body, filters, product mass spectrum (m/e): 398, obtains the compound shown in P1-9.
Step i, compound P1-9 paratoluensulfonyl chloride is carried out hydroxyl protection reaction, obtain compound
P1-10；Particularly as follows:
500 milliliters of there-necked flasks, add 300 milliliters of dichloromethane, 1 gram of pyridine, and 3.5 grams of rapid h obtain formula P1-9
Compound, control temperature 20～25 DEG C and be dividedly in some parts 1.9 grams of paratoluensulfonyl chlorides, finish in 20～25 DEG C
Stirring 8 hours, add water separatory, and organic layer is concentrated to dryness, toluene/petroleum ether mixed solvent recrystallization, obtains
Compound shown in P1-10.
Step j, compound P1-10 and allylic bromination magnesium are carried out coupling reaction, obtain compound P1；
Particularly as follows:
In 250ml there-necked flask, by molten for 2.8 grams of compounds with formula P1-10 obtained in step i
Solution is in 50ml oxolane, and the oxolane of four chloro keto acid two lithiums being subsequently adding 2 milliliters of 2M is molten
Liquid, in the tetrahydrofuran solution 10 milliliters of allylic bromination magnesium of 10 DEG C of dropping 1.0M under stirring, so
Rear insulation reaction 3 hours, adds water, separatory, and after organic layer washing, magnesium sulfate is dried, silica gel column chromatography,
Petroleum ether: dichloromethane=10:1 eluting, eluent is concentrated to dryness, and toluene/ethanol/petroleum ether mixing is molten
Agent recrystallization, removes cis-product, obtains trans product, as shown in P1；Product mass spectrum: (m/e):
422, product hydrogen nuclear magnetic spectrogram is as shown in Figure 2.
Through nuclear magnetic resonance analyser and mass spectrograph etc. detect, determine the structural formula of this liquid-crystal compounds as shown in P1,
The named 3-of liquid-crystal compounds P1 ((1r, 4s)-4-(butyl-3-alkene-1-base) cyclohexyl)-7,7-dimethyl-9-propyl group-7H-
Benzo [de] anthracene, its English name is: 3-((1r, 4s)-4-(but-3-en-1-yl) cyclohexyl)-7,7-dimethyl-
9-propyl-7H-benzo[de]anthracene。
The character of compound P1 is as follows:
Clearing point: 266 DEG C
Embodiment 2
The compound P2 that the another kind of the liquid-crystal compounds shown in Formulas I is concrete
P2 synthetic route is with reference to the synthetic route of P1, only by step bChange into?.Product mass spectrum: (m/e): 504, product hydrogen nuclear magnetic spectrogram is as shown in Figure 3.
Through nuclear magnetic resonance analyser and mass spectrograph etc. detect, determine the structural formula of this liquid-crystal compounds as shown in P2,
The named 3-of liquid-crystal compounds P2 ((1s, 1 ' r, 4S, 4 ' S)-4 '-(butyl-3-alkene-1-base)-[1,1 '-two (hexamethylene)]-4-
Base)-7,7-dimethyl-9-propyl group-7H-benzo [de] anthracene, its English name is: 3-((1s, 1'r, 4S, 4'S)-4'-
(but-3-en-1-yl)-[1,1'-bi(cyclohexan)]-4-yl)-7,7-dimethyl-9-propyl-7H-benzo[de]ant
hracene。
The character of compound P2 is as follows:
Clearing point: 265 DEG C
By changing other chemical combination that different reactants can be limited by similar method synthesis type I
Thing, for example:
Two, the preparation of the liquid-crystal composition of above-mentioned liquid-crystal compounds is included
Only choose several preferred embodiment at this and illustrate that the compositions comprising above-mentioned liquid-crystal compounds has
Preferably performance, the present invention is not limited to these embodiments restrictions.
In the liquid-crystal composition of following embodiment, in addition to the liquid-crystal compounds shown in Formulas I, other is each
Component is by commercially available.
The liquid-crystal composition of embodiment 3～5 is prepared by each component being mixed to get.
Embodiment 3
Each component of liquid-crystal composition A and content (percetage by weight) thereof are as shown in table 1:
Each component of table 1 liquid-crystal composition A and percetage by weight table thereof
The method of testing of the clearing point (Cp) of liquid-crystal composition A: by People's Republic of China's information industry
The test side of liquid crystal material clearing point in the liquid crystal material performance test methods (SJ 20746-1999) that portion issues
Method is measured.Each liquid-crystal composition following is also tested according to this method of testing, follow-up the most one by one
Repeat.
After testing, the clearing point of liquid-crystal composition A is 156 DEG C.This liquid-crystal composition A has high limpid
Point, therefore can widen the range of application of liquid-crystal composition.
Embodiment 4
Each component of liquid-crystal composition B and content (percetage by weight) thereof are as shown in table 2:
Each component of table 2 liquid-crystal composition B and percetage by weight table thereof
The clearing point of liquid-crystal composition B is 177 DEG C.This liquid-crystal composition B has high clearing point, can expand
In the range of application of wide liquid-crystal composition.
Embodiment 5
Each component of liquid-crystal composition C and content (percetage by weight %) thereof are as shown in table 3:
Each component of table 3 liquid-crystal composition C and percetage by weight table thereof
After testing, the clearing point of liquid-crystal composition C is 190 DEG C.This liquid-crystal composition C has high limpid
Point, can widen the range of application of liquid-crystal composition significantly.
Comparative example does not include that the liquid-crystal composition of the liquid-crystal compounds shown in Formulas I is as shown in table 4:
Each component of table 4 liquid-crystal composition D and percetage by weight table thereof
After testing, the clearing point of liquid-crystal composition D is 87 DEG C.This liquid-crystal composition D has relatively low clear
Bright spot, it is seen that use the liquid-crystal composition including compound shown in Formulas I, due to the compound shown in Formulas I originally
Body has higher clearing point, can obtain higher clear when it mixes with suitably other liquid-crystal compounds
Bright spot, has widened the range of application of liquid-crystal composition significantly.
Obviously, those skilled in the art can carry out various change and modification without deviating from this to the present invention
Bright spirit and scope.So, if the present invention these amendment and modification belong to the claims in the present invention and
Within the scope of its equivalent technologies, then the present invention is also intended to comprise these change and modification.
Claims (11)
1. a liquid-crystal compounds, it is characterised in that the structural formula of described liquid-crystal compounds shown in formula I:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6.
2. liquid-crystal compounds as claimed in claim 1, it is characterised in that R is 1 selected from carbon number
To the alkyl of 7；R1It is the alkyl of 1 to 7 selected from hydrogen, carbon number；N is 0,1 or 2.
3. liquid-crystal compounds as claimed in claim 1, it is characterised in that described liquid-crystal compounds is concrete
Selected from following chemical structural formula:
4. the method preparing liquid-crystal compounds as claimed in claim 1, it is characterised in that include
Following steps:
Step a, compound I-1 is carried out bromo-reaction with N-bromo-succinimide in oxolane,
Obtain compound I-2；Reaction equation is as follows:
Step b, compound I-2 and butyl lithium are reacted after, andCarry out addition anti-
Should, then it is dehydrated, obtains compound I-3；Reaction equation is as follows:
Step c, compound I-3 is carried out in ethanol and ethyl acetate hydrogenation, obtain compound I-4；
Reaction equation is as follows:
Step d, compound I-4 is carried out in dichloromethane bromo-reaction, obtain compound I-5；Reaction
Formula is as follows:
Step e, by compound I-5 and R1Base magnesium bromide carries out coupling reaction, obtains compound I-6；Reaction
Formula is as follows:
Step f, compound I-6 is obtained compound I-7 with formic acid hydrolysis in toluene；The following institute of reaction equation
Show:
Step g, compound I-7 and methoxyl methyl benzyltriphenylphosphonium chloride are carried out Wittig reaction after, use salt
Acid hydrolysis, obtains compound I-8；Reaction equation is as follows:
Step h, compound I-8 is carried out reduction reaction with sodium borohydride in oxolane, obtain chemical combination
Thing I-9；Reaction equation is as follows:
Step i, compound I-9 paratoluensulfonyl chloride is carried out hydroxyl protection reaction, obtain compound I-10；
Reaction equation is as follows:
Step j, compound I-10 and allylic bromination magnesium being carried out coupling reaction, product is separated, obtains
Trans product, i.e. compound I；Reaction equation is as follows:
Wherein, R is the alkyl of 1 to 10 selected from carbon number；R1It is 1 to 10 selected from hydrogen, carbon number
Alkyl；N any integer in 0 to 6；Ts represents p-toluenesulfonyl.
5. a liquid-crystal composition, it is characterised in that include that at least one is as described in claim 1
The liquid-crystal compounds shown in Formulas I in liquid-crystal compounds.
6. liquid-crystal composition as claimed in claim 5, it is characterised in that in described liquid-crystal composition,
The mass fraction of the liquid-crystal compounds shown in Formulas I is 10%～60%.
7. liquid-crystal composition as claimed in claim 6, it is characterised in that in described liquid-crystal composition,
The mass fraction of the liquid-crystal compounds shown in Formulas I is 20%～40%.
8. liquid-crystal composition as claimed in claim 7, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 16%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 18%:
Mass fraction is the liquid-crystal compounds of 24%:
9. liquid-crystal composition as claimed in claim 7, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 26%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 11%:
Mass fraction is the liquid-crystal compounds of 19%:
10. liquid-crystal composition as claimed in claim 7, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 17%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 10%:
11. 1 kinds of display panels, it is characterised in that the liquid crystal layer of described display panels comprise as
The arbitrary described liquid-crystal composition of claim 5～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510175958.9A CN106146243A (en) | 2015-04-14 | 2015-04-14 | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510175958.9A CN106146243A (en) | 2015-04-14 | 2015-04-14 | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106146243A true CN106146243A (en) | 2016-11-23 |
Family
ID=57336130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510175958.9A Pending CN106146243A (en) | 2015-04-14 | 2015-04-14 | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106146243A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992801A (en) * | 2014-05-23 | 2014-08-20 | 京东方科技集团股份有限公司 | 7-hydrobenzo (de) anthracene liquid crystal compound and liquid crystal composition thereof |
| CN104017585A (en) * | 2014-05-29 | 2014-09-03 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel |
| CN104045504A (en) * | 2014-05-30 | 2014-09-17 | 京东方科技集团股份有限公司 | Compound, preparation method of compound, liquid crystal composition and preparation method of composition |
| CN104163748A (en) * | 2014-05-30 | 2014-11-26 | 京东方科技集团股份有限公司 | Compound and preparation method thereof, liquid crystal composition and preparation method thereof |
| CN104496742A (en) * | 2014-12-30 | 2015-04-08 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition and application of liquid crystal compound and liquid crystal composition |
-
2015
- 2015-04-14 CN CN201510175958.9A patent/CN106146243A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992801A (en) * | 2014-05-23 | 2014-08-20 | 京东方科技集团股份有限公司 | 7-hydrobenzo (de) anthracene liquid crystal compound and liquid crystal composition thereof |
| CN104017585A (en) * | 2014-05-29 | 2014-09-03 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel |
| CN104045504A (en) * | 2014-05-30 | 2014-09-17 | 京东方科技集团股份有限公司 | Compound, preparation method of compound, liquid crystal composition and preparation method of composition |
| CN104163748A (en) * | 2014-05-30 | 2014-11-26 | 京东方科技集团股份有限公司 | Compound and preparation method thereof, liquid crystal composition and preparation method thereof |
| CN104496742A (en) * | 2014-12-30 | 2015-04-08 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition and application of liquid crystal compound and liquid crystal composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI639686B (en) | Liquid crystal compound containing cyclopentyl group and difluoromethyleneoxy linking group and its preparation Preparation method and application | |
| CN104496742B (en) | A kind of liquid crystalline cpd, composition and application thereof | |
| CN109423296B (en) | Dibenzothiophene negative dielectric anisotropy compound and preparation method and application thereof | |
| CN109423297B (en) | Dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| CN106699710A (en) | Laterally tetrafluoro-substituted dibenzoheterocyclic compound and preparation method thereof | |
| TWI507511B (en) | Liquid crystal compound with negative dielectric anisotropy, liquid crystal display, and optoelectronic device | |
| CN102875339B (en) | Liquid crystal compound and preparation method and application thereof | |
| CN102659533B (en) | Indene derivative used as component of liquid crystal medium, preparation method thereof and application thereof | |
| CN104387388A (en) | Novel method for synthetizing gulf-site n-heterocyclic 3,4:9,10-perylene tetracarboxylic acid diimide | |
| CN108690636B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN110229679B (en) | Self-alignment additive for liquid crystal medium and preparation method and application thereof | |
| CN107345141B (en) | Liquid crystal compound with negative dielectric anisotropy of isoamyl and application thereof | |
| CN106146243A (en) | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels | |
| CN106632440B (en) | A kind of preparation method of aryl-boric acid ester and ene boric acid ester | |
| CN103788039B (en) | Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application | |
| CN107345140B (en) | Liquid crystal compound with isobutyl negative dielectric anisotropy and application thereof | |
| CN102898413B (en) | Novel liquid crystal compound with dioxa saturated indene ring and composition thereof | |
| CN106147784A (en) | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels | |
| CN104744187A (en) | Method for preparing alkene compound in microchannel reactor through aldehyde compound | |
| CN102827615A (en) | Biphenyl acetylene blue phase liquid crystal composite material and production method | |
| CN106147783A (en) | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels | |
| CN109423298B (en) | Novel dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| CN114105919A (en) | Liquid crystal compound and preparation method and application thereof | |
| CN107345138B (en) | Isobutyl liquid crystal compound, preparation method and application | |
| CN106146242A (en) | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161123 |