CN105801414A - Bicyclo[3,3,0]octane polymerizable compound - Google Patents
Bicyclo[3,3,0]octane polymerizable compound Download PDFInfo
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- 0 *c(cc1)ccc1Br Chemical compound *c(cc1)ccc1Br 0.000 description 2
- DREIYIQPNMHCIL-UHFFFAOYSA-N OC(C1)CC(C2)C1CC2O Chemical compound OC(C1)CC(C2)C1CC2O DREIYIQPNMHCIL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a bicyclo[3,3,0]octane polymerizable compound. The general structural formula of the bicyclo[3,3,0]octane polymerizable compound is as shown in a formula I which is described in the specification. The compound as shown in the formula I has the advantages of good intersolubility with other monomers, good ultraviolet ray endurance capability, etc. As an RM, the bicyclo[3,3,0]octane polymerizable compound has the advantages of good intersolubility, a high voltage holding rate (VHR), high polymerization activity (few monomer residuals), etc., and is especially applicable as the RM to liquid crystal mixtures of a PSA (polymer-supported alignment) mode and a PS (polymer stabilization) mode. Meanwhile, the compound can be applied to a liquid crystal display including a polymer-stabilized blue phase and has good dissolvability and polymerisability; and a final product has no or tiny retardation effect.
Description
Technical field
The invention belongs to field of liquid crystals, relate to a kind of dicyclo [3,3,0] octane polymerizable compound.
Background technology
Polymerizable mesogenic unit (RMs) is currently the problem that display industry is very popular and important, the field of its possible application includes polymer-stabilized alignment (PSA) liquid crystal display, polymer stabilizing blue phase (PS-BP) liquid crystal display and graphical phase difference film (PatternRetarderFilm) etc..
PSA principle is just being used in different typical LC display, the liquid crystal display such as such as PSA-VA, PSA-OCB, PS-IPS/FFS and PS-TN.For presently the most wide variety of PSA-VA display, can being obtained the tilt angle of liquid crystal cell by PSA method, response time is had active influence by this tilt angle.For PSA-VA display, MVA or PVA pixel and the electrode design of standard can be used, it is that but if electrode design in side adopts special graph and do not adopt the design of projection at the other end, production can be simplified significantly, make display obtain extraordinary contrast and significantly high light transmission rate simultaneously.
Prior art has been found that LC mixture and the RMs application aspect in PSA display still suffer drawbacks that.First, up to the present it is not that each desired solvable RM is suitable for PSA display；Simultaneously, if it is desired to carry out being polymerized (this is likely to some application is advantageous for) by means of UV light without light trigger, then select to become less；Additionally, " material system " that LC mixture (hereinafter also referred to as " LC body mixture ") is formed with the combination of selected polymerizable components should have minimum rotary viscosity and best photoelectric properties, is used for strengthening " voltage retention " (VHR) to be effective.In PSA-VA, it is very important for adopting the high VHR after (UV) photoirradiation, otherwise can cause that the problems such as image retention occurs in final display.Up to the present, the combination that not all LC mixture forms with polymerizable components is adapted to PSA display.This is too short for UV sensitivity wavelength mainly due to polymerizable unit, or do not have inclination angle to occur after illumination or not enough inclination angle occurs, or homogeneity that polymerizable components is after illumination is poor, or because after UV VHR TFT display is applied for be the impact of the aspect such as relatively low.
Summary of the invention
It is an object of the invention to provide a kind of dicyclo [3,3,0] octane polymerizable compound.
Dicyclo provided by the invention [3,3,0] octane polymerizable compound, namely reactive mesogen " RMs ", its general structure shown in formula I,
In described Formulas I, R1And R2Identical or different, be selected from hydrogen, methyl, ethyl, chlorine, fluorine and trifluoromethyl any one；
Y1And Y2Identical or different, be selected from following group a, b or c any one:
A, any one in the alkylidene of singly-bound and C2-C20；
B, by-CH any in described group a2The group that-quilt-O-,-COO-,-OCO-,-CH=CH-or-C ≡ C-replace and obtain；
C, hydrogen any in described group a or b is replaced by fluorine or chlorine and the group that obtains；
Z1For-COO-,-CH=CH-COO-,-CH2CH2-COO-or singly-bound；
Z2For-OCO-,-OCO-CH=CH-,-OOC-CH2CH2-or singly-bound；
Z3And Z4Be selected from singly-bound and-O-any one；
A1And A2Identical or different, be selected from following group d, e or f any one:
D, any one in Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene and 1,3-phenylene；
E, the group that Isosorbide-5-Nitrae-phenylene in described group d or any hydrogen in 1,3-phenylene are replaced by fluorine, chlorine, cyano group, methyl, ethyl, methoxyl group, hydroxyl, difluoromethyl, trifluoromethyl, difluoro-methoxy or trifluoromethoxy and obtain；
F, by any one in Isosorbide-5-Nitrae-cyclohexylidene in described group d or disjunct two-CH2-replaced by O and the group that obtains；
M, n, o, p represent 0 or 1 all independently；
And when m and n is 1, o and p is 1；
Work as Z3And Z4When being-O-, o and p is 1.
Concrete, compound shown in Formulas I is any one in compound shown in Formulas I 1-Formulas I 18:
In described Formulas I 1 to Formulas I 18 ,-(F)-expression fluorine atom or hydrogen atom.
Compound shown in the Formulas I that the invention described above provides, can be prepared as follows and obtain:
When o, p represent 1,
X1Represent Cl or OH, X2Represent Cl, OH or Br；
Alcoholic compound (a-1) and acrylic acid derivative (a-2) mono-esterification is utilized to obtain single acrylic acid derivative ester (a-3) of alcoholic compound,
X1When representing Cl, alcoholic compound (a-1) is dissolved in solvent such as dichloromethane, dichloroethanes, toluene, benzene etc., under acid binding agent alkali such as triethylamine, pyridine, piperidines, diisopropylamine etc. exist, dropping acryloyl chloride derivant (a-2), then stoichiometric number hour, is conventionally treated single acrylic acid derivative ester (a-3).
X1When representing OH, alcoholic compound (a-1) is dissolved in solvent such as dichloromethane, dichloroethanes, toluene, benzene, ethyl acetate etc., under DCC, DMAP exist, dropping acrylic acid derivative (a-2), then stoichiometric number hour, is conventionally treated single acrylic acid derivative ester (a-3).
X2Represent OH, react with single acrylic acid derivative ester (a-3) of Triphosgene (a-4) with alcoholic compound, obtain chloroformate derivative (a-5).
Triphosgene (a-4) is dissolved in methylene chloride, dichloroethanes, toluene, benzene etc., at low temperatures dropping (a-3) (X2Represent OH), stoichiometric number hour under room temperature, it is conventionally treated chloroformate derivative (a-5).
Alcoholic compound (a-1) particular compound has: ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptandiol, 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecane, 1, 12-dodecanediol, 1, 14-tetradecane diols, ethylene chlorhydrin, 3-chloropropyl alcohol, 4-methaform, 5-chlorine amylalcohol, 6-Mecoral, 7-chlorine enanthol, 8-chlorine capryl alcohol, 9-chlorine nonyl alcohol, 10-chlorine decanol, ethylene bromohyrin, 3-bromopropyl alcohol, 4-bromobutanol, 5-bromine amylalcohol, 6-bromine hexanol, 7-bromine enanthol, 8-bromine capryl alcohol, 9-bromine nonyl alcohol, 10-bromine decanol.
The object lesson of acrylic acid derivative (a-2) has: acryloyl chloride, methacrylic chloride, α-fluoropropene acyl chlorides, α-trifluoromethyl acryloyl chloride, acrylic acid, methacrylic acid, α-perfluoroalkyl acrylate, α-trifluoromethyl acrylate.
Synthetic method 1:
Z1Represent-COO-,-CH=CH-COO-,-CH2CH2-COO-, Z2Represent-OCO-,-OCO-CH=CH-,-OOC-CH2CH2-, Z3、Z4Expression-O-, m, n, o, p represent that the synthetic route of 1 is
X3For singly-bound ,-CH2CH2-,-CH=CH-.Corresponding (b-1) is P-hydroxybenzoic acid, p-Coumaric Acid, para hydroxybenzene propanoic acid.
Chloroformate derivative (a-5) in solvent such as dichloromethane, dichloroethanes, toluene, benzene etc. under the catalysis of acid binding agent alkali such as triethylamine, pyridine, piperidines, diisopropylamine etc., esterification obtains the formic acid derivates (b-2) replaced, (b-2) in a solvent as dichloromethane, dichloroethanes, ethyl acetate etc. under dehydrant DCC, DMAP catalysis with 3,7-dihydroxy dicyclo [3,3,0] octane (b-3) esterification, conventional post processing obtains polymerizable compound (b-4).Synthetic method 2
Z1Represent-COO-,-CH=CH-COO-,-CH2CH2-COO-, Z2Represent-OCO-,-OCO-CH=CH-,-OOC-CH2CH2-, Z3、Z4Synthetic route when expression-O-, m and n represent 0, o, p represents 1 is
X2Represent Br or Cl, X3For singly-bound ,-CH2CH2-,-CH=CH-.
First halides (a-3) is in a solvent such as ethanol, methanol, toluene, n-butyl alcohol, dimethylformamide, dimethyl acetylamide etc. are at acid binding agent alkali such as sodium hydroxide, potassium hydroxide, Lithium hydrate, potassium carbonate, with phenol (b-1) etherificate replaced under the catalysis of sodium carbonate etc., obtain ether derivative (c-1), (c-1) in a solvent such as dichloromethane, dichloroethanes, ethyl acetate etc. are at dehydrant DCC, with 3 under DMAP catalysis, 7-dihydroxy dicyclo [3, 3, 0] octane (b-3) esterification, conventional post processing obtains polymerizable compound (c-2).
Synthetic method 3
Z1、Z2Represent singly-bound, Z3、Z4Expression-O-, o, p are 1, m, n, expression 0 or 1 time synthetic route as follows:
X2For Cl.
(d-1) in solvent such as oxolane, ether etc. with butyl lithium generation lithium halogen exchange reaction or react with magnesium chips, obtain lithium reagent or Grignard reagent (d-2), (d-2) of doubling dose and dicyclo [3,3,0] octane 3,7-diketone addition, through dehydration, obtaining alkene intermediate (d-4), the reaction condition of dehydration is in the catalysis of p-methyl benzenesulfonic acid fluxion hour next time in toluene.nullAlkene intermediate (d-4) is at ethanol、In toluene equal solvent，At catalyst such as Pd/C，Pt/C，Under Raney nickels etc. exist，Hydrogenation a few hours obtain saturated dicyclo [3,3,0] octane (bis ether) derivant (d-5)，Bis ether derivant (d-5) is at solvent such as dichloromethane、In dichloroethanes etc.，There is lower elimination methyl and obtain bisphenol derivative (d-6) in aluminum chloride or Boron tribromide，Bisphenol derivative (d-6) and (a-5) are at solvent such as dichloromethane、Dichloroethanes、Benzene、In acetone etc.，At acid binding agent triethylamine、Pyridine、There is lower esterification in diisopropylamine etc.，Or chloro thing (a-3) is in a solvent such as ethanol、Methanol、Toluene、N-butyl alcohol etc. are at alkali such as sodium hydroxide、Potassium hydroxide、Lithium hydrate、Potassium carbonate、With bisphenol derivative (d-6) etherificate under the catalysis of sodium carbonate etc.，Obtain polymerizable compound (d-7).
Synthetic method 4
Z1、Z2Represent singly-bound, Z3、Z4Representing singly-bound, synthetic route when m, n, o, p represent 0 is as follows:
X1Represent Cl.
Bisphenol derivative (d-6) and (a-5) are in solvent such as dichloromethane, dichloroethanes, benzene, acetone etc., esterification under acid binding agent triethylamine, pyridine, diisopropylamine etc. exist, conventional post processing obtains polymerizable compound (e-1).
It addition, any one comprising in the following product of component a, fall within protection scope of the present invention:
1) liquid-crystal composition；
2) optically anisotropic body of liquid-crystal composition；
Wherein, at least one in described component a compound shown in aforementioned Formulas I provided by the invention forms.
Concrete, described component a weight/mass percentage composition in liquid-crystal composition is 0.05-30%, is specially 0.1-0.5%, more specifically 0.35%；
Described optically anisotropic body is optical anisotropic film.
Additionally; application in preparing liquid crystal display material or electrooptics display material or liquid crystal display of liquid-crystal compounds or the said goods shown in the Formulas I that the invention described above provides and comprise liquid-crystal compounds shown in described Formulas I or at least one liquid crystal display material in the said goods or electrooptics display material or liquid crystal display, falls within protection scope of the present invention.Wherein, described liquid crystal display is the 3D display of PSA-VA, PSA-OCB, PS-IPS, PS-TN, PS-BP or FPR material type.
In these display, compound shown in Formulas I is joined in LC medium, and after being incorporated in LC box, apply between electrode under voltage by UV photo polymerization or crosslinking, it is possible to form the pre-tilt of liquid crystal molecule.This is advantageous for for simplifying LCD Making programme, raising response speed, reducing threshold voltage.
The advantage such as that compound shown in Formulas I provided by the invention has is good with other monomer intersolubilities, ultraviolet tolerance is good.There is the advantages such as intersolubility is good, electric charge conservation rate (VHR) is high, polymerization activity high (monomer residue is few) as RM, it is very suitable for as the RM liquid crystal compound for PSA (orientation that polymer is supported), PS (polymer stabilizing) pattern formula, particularly in PSA-VA situation.R1Being particularly suitable as RM for compound shown in methyl and Formulas I that end group is methacrylate, this forms more preferably tilt angle after being conducive to polymerization, keeps higher electric charge conservation rate (VHR).Compound shown in this Formulas I is for, in PSA display, can enable PSA display set up stable tilt angle, and preferably have very high resistivity value, low threshold voltage and short response time simultaneously.Meanwhile, this kind of material can also be applied and include polymer stabilizing blue phase liquid crystal display, the dissolubility having had and polymerizability, and final products do not have or minimum hesitation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Compound shown in embodiment 1, preparation Formulas I 1
Step 1
13g (0.54mol) magnesium chips is added in 1L there-necked flask, 100mlTHF, inflated with nitrogen displaced air, heating is to refluxing, drip the 350mlTHF solution of a small amount of 91g (0.486) mol para-bromoanisole, after initiation reaction, added with one hour, reflux half an hour again, obtain black grignard reagent solution.
Grignard reagent solution is cooled to 20 DEG C, the 100ml toluene solution of dropping 28g (0.2mol) dicyclo [3,3,0] octane 3,7-diketone, precipitates out a lot of solid, heat release, within one hour, adds, then 60 DEG C of stirring reactions 4 hours.
Reactant liquor pours hydrolysis in the 1L frozen water of 50ml hydrochloric acid into, separates aqueous phase, uses 200ml methylbenzene extraction, merges organic facies, washes 2 times, steam neat solvent, obtain dope under decompression.
Above-mentioned dope is dissolved in 200ml toluene, adds 1g p-methyl benzenesulfonic acid, under backflow, separate the water that reaction generates.Reaction in 2 hours terminates.Directly cross silicagel column, obtain orange solution, be cooled to 0 DEG C, precipitate out crystal.It is filtrated to get pale yellow crystals 15g.
Gc:72.82%26.58%.Yield: 31%.MS analyzes, and molecular ion peak is all 318, for two products (1-a) of double-bond isomerism
Step 2
The 15g product 100ml toluene that step 1 is obtained, 50ml ethanol is heating for dissolving in 1L single port bottle, add Raney nickel catalyst 2g, hydrogenate 24 hours under atmospheric agitation, inhaling hydrogen to theoretical amount, careful is filtered to remove Raney nickel, steams neat solvent under decompression, with toluene alcohol mixed solvent recrystallization, obtain beautiful white crystal 13g.Gc:99.486%
Step 3
7.2g (0.022mol) step 2 product (1-b) is added in 250ml there-necked flask, 100ml dichloromethane, CL, it is cooled to 0 DEG C, drip the 10ml dichloromethane solution of 5.5g (0.022mol) Boron tribromide under stirring, add rear reactant liquor and become brown by colourless.At room temperature stir 20 hours again.
Trash ice and dilute hydrochloric acid hydrolysis is added in reactant liquor.Filter the violet solid precipitated out, wash post-drying, with toluene alcohol mixed solvent recrystallization, obtain 5.3g product (1-c).Yield 81%Gc:98.86%
Step 4
100ml there-necked flask adds step 3 product (1-c) 4.7g (0.016mol), 60ml dichloromethane, 8ml triethylamine, solid is entirely molten, the 10ml dichloromethane solution of 4.2g (0.04mol) methacrylic chloride is dripped, at room temperature stirring reaction 4 hours again after adding under ice-water bath.Precipitate out solid salt.
Add water 50ml, dissolved solid salt, separates organic layer, washing, steams neat solvent under decompression, and petroleum ether dissolution crosses silicagel column, evaporates neat solvent, ethyl alcohol recrystallization 2 times, obtains white crystal 5.0g.Yield 73%.Gc:99.8%
MP:90.5 DEG C
MS:m/z%430 (8.7M+)360(4.2)69(100)41(23.2)
By compound shown in this embodiment 1 gained Formulas I 1Join in precursor compositions, it is possible to obtain the liquid-crystal composition of favorable dispersibility.Wherein, the consumption of compound shown in Formulas I 1 is the 0.35% of precursor compositions gross mass.
It can be seen that compound shown in this embodiment gained Formulas I 1 has good dispersibility in liquid-crystal composition, it is adaptable to as the liquid crystal monomer of PSVA display.
Precursor compositions is made up of the monomer of following each mass parts:
Monomer mass number
Similar synthetic method can synthesize following compounds
MP:84 DEG C
MS:m/z%466 (15.2M+)396(1.6)69(100)41(20.9)
MP:76 DEG C
MS:m/z%502 (5.2M+)432(0.2)69(100)41(18.3)
Compound shown in embodiment 2, preparation Formulas I 5
Step 1
94.5g (1mol) 3-chloropropyl alcohol is put in 1L there-necked flask, add dichloromethane 300ml, triethylamine 121g (1.2mol), polymerization inhibitor 0.2g, dropping acryloyl chloride 99.5g (1.1mol), adds stirring reaction 13 hours under room temperature.
Being filtered to remove the salt of precipitation, organic facies is washed twice, steams neat solvent under decompression, residue decompression distillation, collects 92-96 DEG C/35mmHg fraction.Obtain 96.2g.Gc:99.08%.Yield: 65%
Step 2
250ml there-necked flask adds embodiment 1 step 3 product (1-c) 3.0g (0.017mol), 5.37g (0.0363mol) (2-a), 3.38g (0.0408mol) Anhydrous potassium carbonate, 0.1g potassium iodide, 50mlDMF, 90 DEG C of isothermal reactions 7 hours in oil bath pan.
Being cooled to room temperature, add water 100ml, 50ml dichloromethane, dissolving salt, separates organic facies, and 30ml dichloromethane extraction aqueous phase once, merges organic facies and washes 2 times.Anhydrous sodium sulfate dries.Steam neat solvent under decompression, cross silicagel column, petroleum ether, toluene Mixed Solvent recrystallization with petroleum ether dissolution, obtain white crystal 4.9g.Yield 56%.HPLC:99.8%.DSC:79 DEG C
Similar synthetic method can synthesize following compounds
Compound shown in embodiment 3, preparation Formulas I 8
Step 1
90g (1mol) BDO is put in 1L there-necked flask, adds dichloromethane 600ml, triethylamine 121g (1.2mol), polymerization inhibitor 0.2g, dropping acryloyl chloride 99.5g (1.1mol), add stirring reaction 13 hours under room temperature.
Being filtered to remove the salt of precipitation, organic facies is washed twice, steams neat solvent under decompression, residue decompression distillation, collects 98-101 DEG C/33mmHg fraction.Obtain 46.2g.Gc:90.08%.Yield: 32%
Step 2
0.96g (0.00324mol) triphosgene is put in 100ml there-necked flask, 20ml dichloromethane, Dropping funnel adds the product (3-a) of 1.27g (0.00884mol) step 1 and the 5ml dichloromethane solution of 0.77g (0.00972mol) pyridine, inflated with nitrogen displaced air, in time being cooled to-5 DEG C, the lower dropping of stirring, adds, stir 1 hour at 0-5 DEG C after adding again half an hour.
Adding the hydrolysis of 20ml frozen water, separatory, aqueous phase 10ml dichloromethane extraction, merge organic facies, wash 2 times, anhydrous sodium sulfate dries.Obtain the dichloromethane solution of (3-b).
Step 3
100ml there-necked flask adds 1.0g (0.0034mol) bis-phenol (1-c), 20ml dimethylformamide, 0.34g (0.0034mol) triethylamine, 1.03g (0.0075mol) potassium carbonate, inflated with nitrogen displaced air, the dichloromethane solution of (3-b) that agitation and dropping step 2 obtains under room temperature, then at room temperature stirring reaction 1 hour again.
Adding 40ml water, separatory, organic phases washed with water 2 times in reactant liquor, then with the hydrochloric acid washing that 40mlPH is 1, be washed with water to neutrality, anhydrous sodium sulfate dries.
Dissolve with petroleum ether toluene Mixed Solvent, cross silicagel column, steam solvent under decompression, then with petroleum ether toluene Mixed Solvent recrystallization, obtain 0.8g white crystal.Gc:99.18%.Yield: 38%DSC:75 DEG C
Compound 20 mass parts shown in this embodiment gained Formulas I 8 and compound 13 mass parts shown in Formulas I 18 are joined in precursor compositions 67 mass parts, it is possible to obtain the liquid-crystal composition of favorable dispersibility.
It can be seen that compound shown in this embodiment gained Formulas I 8 and Formulas I 18 has good dispersibility in liquid-crystal composition, with other liquid crystal, there is good intersolubility.
Wherein, precursor compositions is made up of the monomer of following each mass parts:
Monomer mass number
Similar synthetic method can synthesize following compounds
Compound shown in embodiment 4, preparation Formulas I 12
Step 1
100ml there-necked flask adds 1.38g (0.01mol) P-hydroxybenzoic acid, 20ml dimethylformamide, 1.11g (0.011mol) triethylamine, 1.52g (0.011mol) potassium carbonate, inflated with nitrogen displaced air, the mole that under room temperature, agitation and dropping step 2 obtains is (3-b) dichloromethane solution of 0.01mol, then at room temperature stirring reaction 1 hour again.
Adding 40ml water, separatory, organic phases washed with water 2 times in reactant liquor, then with the hydrochloric acid washing that 40mlPH is 1, be washed with water to neutrality, anhydrous sodium sulfate dries.
Dissolve with petroleum ether toluene Mixed Solvent, recrystallization, obtain 1.38g white crystal (4-a).Gc:99.18%.Yield: 45%
Step 2
Step 1 is obtained 1.38g (0.0045mol) white crystal (4-a) and joins in 100ml there-necked flask, 10ml dichloromethane, 10ml ethyl acetate, 1.15g (0.0055mol) N, N-dicyclohexylcarbodiimide (DCC), 0.2gDMAP, 0.32g (0.0023mol) 3 is dripped at 0 DEG C, the 5ml dichloromethane solution of 7-dihydroxy dicyclo [3,3,0] octane.At room temperature stirring reaction 4 hours again after adding.
Filter the solid DCU precipitated out, solvent, residue petroleum ether dissolution are evaporated off under decompression, cross silicagel column, with petroleum ether toluene Mixed Solvent recrystallization, obtain white crystal 0.91g, yield 55%.DSC:62.5 DEG C
Similar synthetic method can synthesize following compounds
Compound shown in embodiment 5, preparation Formulas I 11
Step 1
74g (0.5mol) oily liquids (2-a) is put in 1L there-necked flask, adds 138g (1mol) Anhydrous potassium carbonate, 400ml ethanol, 138g (1mol) P-hydroxybenzoic acid, be heated to reflux 4 hours together.
Putting in 1L water, it is acid for regulating PH with dilute hydrochloric acid, and toluene extracts 2 times, and combining methylbenzene phase is washed 2 times, steamed neat solvent under decompression.With toluene pet ether mixed solvent recrystallization, obtain white solid 39g, yield 31%.Gc:96.1%
Step 2
Step 1 is obtained 39g (0.156mol) white solid (5-a) and joins in 1000ml there-necked flask, 200ml dichloromethane, 200ml ethyl acetate, 38.5g (0.187mol) N, N-dicyclohexylcarbodiimide (DCC), 1gDMAP, 11g (0.078mol) 3 is dripped at 0 DEG C, the 35ml dichloromethane solution of 7-dihydroxy dicyclo [3,3,0] octane.At room temperature stirring reaction 4 hours again after adding.
Filter the solid DCU precipitated out, solvent, residue petroleum ether dissolution are evaporated off under decompression, cross silicagel column, with petroleum ether toluene Mixed Solvent recrystallization, obtain white crystal 24.5g, yield 52%.DSC:76 DEG C
Similar synthetic method can synthesize following compounds
。
Claims (8)
1. compound shown in Formulas I,
In described Formulas I, R1And R2Identical or different, be selected from hydrogen, methyl, ethyl, chlorine, fluorine and trifluoromethyl any one；
Y1And Y2Identical or different, be selected from following group a, b or c any one:
A, any one in the alkylidene of singly-bound and C2-C20；
B, by-CH any in described group a2The group that-quilt-O-,-COO-,-OCO-,-CH=CH-or-C ≡ C-replace and obtain；
C, hydrogen any in described group a or b is replaced by fluorine or chlorine and the group that obtains；
Z1For-COO-,-CH=CH-COO-,-CH2CH2-COO-or singly-bound；
Z2For-OCO-,-OCO-CH=CH-,-OOC-CH2CH2-or singly-bound；
Z3And Z4Be selected from singly-bound and-O-any one；
A1And A2Identical or different, be selected from following group d, e or f any one:
D, any one in Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene and 1,3-phenylene；
E, the group that Isosorbide-5-Nitrae-phenylene in described group d or any hydrogen in 1,3-phenylene are replaced by fluorine, chlorine, cyano group, methyl, ethyl, methoxyl group, hydroxyl, difluoromethyl, trifluoromethyl, difluoro-methoxy or trifluoromethoxy and obtain；
F, by any one in Isosorbide-5-Nitrae-cyclohexylidene in described group d or disjunct two-CH2-replaced by O and the group that obtains；
M, n, o, p represent 0 or 1 all independently；
And when m and n is 1, o and p is 1；
Work as Z3And Z4When being-O-, o and p is 1.
2. compound according to claim 1, it is characterised in that: compound shown in described Formulas I is any one in compound shown in Formulas I 1-Formulas I 18:
In described Formulas I 1 to Formulas I 18 ,-(F)-expression fluorine atom or hydrogen atom.
3. comprise in the following product of component a any one:
1) liquid-crystal composition；
2) optically anisotropic body of described liquid-crystal composition；
Wherein, at least one in described component a compound shown in the arbitrary described Formulas I of claim 1 or 2 forms.
4. liquid-crystal composition according to claim 3, it is characterised in that: described component a weight/mass percentage composition in described liquid-crystal composition is 0.05%-30%；
Described optically anisotropic body is optical anisotropic film.
5. compound shown in Formulas I described in claim 1 or 2 or the application in preparing liquid crystal display material or electrooptics display material or liquid crystal display of the product described in claim 3 or 4.
6. application according to claim 5, it is characterised in that: described liquid crystal display is the 3D display of PSA-VA, PSA-OCB, PS-IPS, PS-TN, PS-BP or FPR material type.
7. comprise compound shown in Formulas I described in claim 1 or 2 and at least one liquid crystal display material in product described in claim 3 or 4 or electrooptics display material or liquid crystal display.
8. application according to claim 7, it is characterised in that: described liquid crystal display is the 3D display of PSA-VA, PSA-OCB, PS-IPS, PS-TN, PS-BP or FPR material type.
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