CN105238415A - Liquid crystal compound containing tetrahydropyran difluoro methylene oxygen group and preparation method and application thereof - Google Patents
Liquid crystal compound containing tetrahydropyran difluoro methylene oxygen group and preparation method and application thereof Download PDFInfo
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- CN105238415A CN105238415A CN201510755422.4A CN201510755422A CN105238415A CN 105238415 A CN105238415 A CN 105238415A CN 201510755422 A CN201510755422 A CN 201510755422A CN 105238415 A CN105238415 A CN 105238415A
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- 0 C*C(*)C(C*1)SC1C(CC1)OC(C2)C1C2C(CC1)CCC1C(C)C Chemical compound C*C(*)C(C*1)SC1C(CC1)OC(C2)C1C2C(CC1)CCC1C(C)C 0.000 description 4
- CHKBYOTYLXKLCN-UHFFFAOYSA-N CC(C1)C=CC(C)=C1F Chemical compound CC(C1)C=CC(C)=C1F CHKBYOTYLXKLCN-UHFFFAOYSA-N 0.000 description 1
- WLBUYXSHIYGEAO-UHFFFAOYSA-N CC(C1)CC(F)=C(C)C1F Chemical compound CC(C1)CC(F)=C(C)C1F WLBUYXSHIYGEAO-UHFFFAOYSA-N 0.000 description 1
- AULWVAYRLRBZKZ-UHFFFAOYSA-N CC(CCC1C)C(F)=C1F Chemical compound CC(CCC1C)C(F)=C1F AULWVAYRLRBZKZ-UHFFFAOYSA-N 0.000 description 1
- QFZFKXVGQIODJN-UHFFFAOYSA-N CC1C=CC(C)=CC1 Chemical compound CC1C=CC(C)=CC1 QFZFKXVGQIODJN-UHFFFAOYSA-N 0.000 description 1
- DHSKGTRREFTKAB-UHFFFAOYSA-N CC1C=CC(C)=CC1F Chemical compound CC1C=CC(C)=CC1F DHSKGTRREFTKAB-UHFFFAOYSA-N 0.000 description 1
- XAZKFISIRYLAEE-UHFFFAOYSA-N CC1CC(C)CC1 Chemical compound CC1CC(C)CC1 XAZKFISIRYLAEE-UHFFFAOYSA-N 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- DUOJVRWFIHNZTJ-UHFFFAOYSA-N CC1CNC(C)C1 Chemical compound CC1CNC(C)C1 DUOJVRWFIHNZTJ-UHFFFAOYSA-N 0.000 description 1
- YEJCHVFCLNKZPU-UHFFFAOYSA-N CC1COC(C)CC1 Chemical compound CC1COC(C)CC1 YEJCHVFCLNKZPU-UHFFFAOYSA-N 0.000 description 1
- RPMUDXVQHUECRE-UHFFFAOYSA-N CC1COC(C)OC1 Chemical compound CC1COC(C)OC1 RPMUDXVQHUECRE-UHFFFAOYSA-N 0.000 description 1
- QCZCRSKCSNLVJG-UHFFFAOYSA-N CCC(CCC(C)C=C)C(CC1)CCC1C=C Chemical compound CCC(CCC(C)C=C)C(CC1)CCC1C=C QCZCRSKCSNLVJG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a liquid crystal compound containing a tetrahydropyran difluoro methylene oxygen group and a preparation method and application thereof. The compound is shown as formula I. In a molecular structure of the compound shown as the formula I, the liquid crystal compound containing the tetrahydropyran difluoro methylene oxygen linking group is obtained, and higher dielectric anisotropy is achieved; more importantly, the fast response speed and the higher clearing point are achieved, lower rotary viscosity is achieved, and for blended liquid crystal mixture, the property has extremely important meanings.
Description
Technical field
The invention belongs to field of liquid crystals, relate to liquid crystalline cpd containing tetrahydropyrans difluoro methylene oxygen groups and preparation method thereof and application.
Background technology
At present, it is more and more wider that the range of application of liquid crystalline cpd is expanded, and it can be applicable in polytype indicating meter, electro-optical device, sensor.For liquid crystalline cpd of a great variety in above-mentioned display field, wherein nematic liquid crystal is most widely used.Nematic liquid crystal has been applied in passive TN, STN matrix display and has had in the system of tft active matrix.
For thin-film transistor technologies (TFT-LCD) Application Areas, although market is very huge in recent years, technology is also ripe gradually, people to the requirement of technique of display also in continuous raising, especially in realization response fast, driving voltage is reduced to reduce the aspects such as power consumption.Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.
As liquid crystal material, need to have good chemistry and thermostability and the stability to electric field and electromagnetic radiation.And as thin-film transistor technologies (TFT-LCD) liquid crystal material, not only need to have as outside upward stability, also should have the performances such as wider nematic temperature range, suitable degree of birefringence anisotropy, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate and low-steam pressure.
For dynamic menu display application, as LCD TV, in order to realize high-quality display, eliminating display frame ghost and hangover, requiring that liquid crystal has very fast response speed, therefore require that liquid crystal has lower rotary viscosity γ
1; In addition, in order to reduce equipment energy consumption, wish that the driving voltage of liquid crystal is low as far as possible, so the dielectric anisotropy △ ε improving liquid crystal is significant to mixed liquid crystal.
Large quantity research shows, liquid crystal molecule introduces the sub-methoxyl group linking group of a difluoro (-CF
2o-), after, the rotary viscosity γ of liquid crystal can be made
1decrease.In addition due to the sub-methoxyl group bridge of difluoro (-CF
2the contribution of moment of dipole O-), the moment of dipole of end group fluorine atom is also improved to some extent, thus the dielectric anisotropy △ ε of liquid crystal molecule is increased to some extent.What Merck KGaA and Japanese Chisso Corporation had disclosed that some have a different substituents has the sub-methoxyl group linking group of difluoro (-CF
2o-) liquid crystalline cpd (CN1717468A, CN101143808A, CN101157862A etc.).But the introducing of-CF2O-group can make the clearing point of liquid crystal significantly reduce.Need to add the larger high clearing point compound of viscosity to balance the clearing point that-CF2O-group causes decline when allocating liquid crystal compound, thus constrain the space that liquid crystal compound response speed promotes.
Summary of the invention
The object of this invention is to provide liquid crystalline cpd containing tetrahydropyrans difluoro methylene oxygen groups and preparation method thereof and application.
Liquid crystalline cpd containing tetrahydropyrans difluoro methylene oxygen groups provided by the invention, its general structure such as formula shown in I,
In described formula I,
be selected from least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;
be selected from least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;
M is 0 or 1 or 2;
N is 0 or 1;
R
1be selected from hydrogen, the total number of carbon atoms that normal olefine base that alkoxyl group that alkyl that fluorine, chlorine, cyano group, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C1-C25, fluorine replace is the alkyl of C1-C25, the total number of carbon atoms that fluorine replaces at least one that to be the total number of carbon atoms that the alkoxyl group of C1-C25 and fluorine replace be in the straight chain allylic alkylation of C1-C25;
R
2and R
3all be selected from H and F any one;
L is selected from least one in singly-bound, Sauerstoffatom, carbon atom, double bond and triple bond; X is the integer of 0-4, and when L is Sauerstoffatom, double bond and triple bond, x is 1;
Y is selected from H, F, Cl ,-CF
3,-CHF
2,-OCF
3with-OCHF
2in any one.
Concrete, compound shown in described formula I is specifically selected from formula I1 to any one in formula I50:
In above-mentioned formula I1-I50, R
1definition and formula I in R
1definition identical;
Shown in preparation formula I provided by the invention, the method for compound, comprises the steps:
Will
carry out condensation reaction with triethylamine mixing, react complete and carry out fluoridation with hydrogen fluoride pyridine and bromine again, obtain compound shown in described formula I after completion of the reaction;
Described
with
in, described R
1, R
2, R
3,
the definition of Y, m and n all with R in previously described formula I
1definition identical.
In aforesaid method,
the mole dosage that feeds intake of triethylamine, hydrogen fluoride pyridine, bromine, than being 1:1-2:1-2:1-5:1-5, is specially 1:1.1:1.2:4:4;
In described step of condensation, temperature is-100-30 DEG C, is specially-80 DEG C; Time is 1-5 hour, is specially 1 hour;
Describedly carry out in fluorination reaction step with hydrogen fluoride pyridine and bromine, temperature is-100-30 DEG C, is specially-80 DEG C; Time is 0.5-3 hour, is specially 2 hours;
Described reaction is carried out all in a solvent; Described solvent is specifically selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.
In aforesaid method, as initial action raw material
can prepare in accordance with the following steps and obtain:
1) 3,4-dihydropyrane-2-sodium formiate and iodoethane are mixed react, react complete and obtain
2) by described step 1) gained
carry out addition reaction with borine, the organic boron intermediate of generation carries out oxidizing reaction with hydrogen peroxide again, reacts complete and obtains
3) by described step 2) gained
carry out oxidizing reaction with Dai Si-Martin's oxygenant, react complete and obtain
4) by described step 3) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) react, react complete and obtain
5) by described step 4) gained
react with triethyl silicane and boron trifluoride, react complete and obtain
6) by described step 5) gained
be hydrolyzed with lithium hydroxide and react, react complete and obtain
7) by described step 6) gained
react under triflic acid catalyzes with 1,3-dimercaptopropane, react complete and obtain
In above-mentioned reactions steps, described R
1, R
2, R
3,
the definition of m with n is all identical with the definition in previously described formula I.
Described reactions steps 1) in, the mole dosage that feeds intake of described 3,4-dihydropyrane-2-sodium formiates, iodoethane, sodium carbonate, than being 1:1-2:0.01-0.1, is specially 1:1.2:0.09; Temperature is 25-110 DEG C, is specially 105-110 DEG C, and the time is 1-5 hour, is specially 5 hours;
Described reactions steps 2) in, described step 1) gained
compare for 1:0.4-1:0.5-1:1-2 with the mole dosage that feeds intake of described borine, sodium acetate, hydrogen peroxide, be specially 1:0.46:0.88:1; In described borine addition reaction step, temperature is-40-40 DEG C, is specially-10-0 DEG C, and the time is 1-10 hour, is specially 10 hours; In described hydrogen peroxide oxidation reactions steps, temperature is-40-40 DEG C, is specially-10-30 DEG C, and the time is 1-10 hour, is specially 2 hours;
Described reactions steps 3) in, described step 2) gained
compare for 1:1-2 with the mole dosage that feeds intake of Dai Si-Martin's oxygenant, be specially 1:1.5, temperature is 10-30 DEG C, is specially 25 DEG C, and the time is 1-10 hour, is specially 2 hours;
Described reactions steps 4) in, described step 3) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) the mole dosage that feeds intake, than being 1:1-2, is specially 1:1; Temperature is-80-0 DEG C, is specially-10 DEG C, and the time is 1-10 hour, is specially 2 hours;
Described reactions steps 5) in, described step 4) gained
compare for 1:1-3:1-3 with the mole dosage that feeds intake of triethyl silicane, boron trifluoride, be specially 1:2.1:2.1; In described reactions steps, temperature is-50-30 DEG C, is specially-30 DEG C, and the time is 0.5-4 hour, is specially 2 hours;
Described reactions steps 6) in, described step 5) gained
compare for 1:5 with the mole dosage that feeds intake of lithium hydroxide, be specially 1:2, temperature is 10-40 DEG C, and the time is 1-18 hour, is specially 10 hours;
Described reactions steps 7) in, described step 6) gained
compare for 1:1-2:1-2 with the mole dosage that feeds intake of 1,3-dimercaptopropane, trifluoromethanesulfonic acid, be specially 1:1.1:1.2, temperature is 100-120 DEG C, is specially 110 DEG C, and the time is 1-10 hour, is specially 5 hours;
Shown in above-mentioned synthesis type I, compound reaction scheme as shown in Figure 1.
In addition, comprise the liquid crystal compound of the formula I that the invention described above provides, also belong to protection scope of the present invention.
Present invention also offers a kind of liquid crystal compound, shown in the contained I of this mixture shown in compound, formula II to formula IV at least one:
Described formula II in formula IV, R
1, R
2and R
3all be selected from least one in the fluoroalkyl of hydrogen, halogen ,-CN, the alkyl of C1-C7, the alkoxyl group of C1-C7, the thiazolinyl of C2-C7 and C1-C5;
Z is all selected from singly-bound ,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-OCH
2-,-CH
2o-,-CF
2o-and-OCF
2-at least one;
all be selected from least one in singly-bound and following radicals:
Y1 and Y2 is all selected from least one in H and F;
P is the integer of 0-2;
When P is 2, A2-Z is identical or different.
Above-mentioned liquid crystal compound also can be made up of at least one in compound shown in described formula I, formula II to formula IV.
Described liquid crystal compound is specially following liquid crystal compound a, b, c, d, e or f:
Described liquid crystal compound a comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound a specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound b comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound b specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound c comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound c specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound d comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound d specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound e comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound e specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound f comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound f specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
The mass fraction of compound shown in described formula I is 2-40 part, is specially 4-20 part, more specifically can be 14,26,26.5,29,42 parts;
The mass parts of compound shown in described formula II is 4-50 part, is specially 10-40 part, more specifically can be 20,23,24,36 parts;
The mass parts of compound shown in described formula III is 5-50 part, is specially 20-50 part, more specifically can be 14,17,21.5,22,50 parts;
The mass parts of compound shown in described formula IV is 3-45 part, is specially 10-40 part, more specifically can be 13,16,17,32,33 parts.
The liquid crystal compound of the compound described in the application prepared in liquid crystal compound, liquid crystal display device material or electro-optical display part material and contained I of compound shown in the formula I that the invention described above provides, liquid crystal display device material or electro-optical display part material, also belong to protection scope of the present invention.
Liquid crystalline cpd generally is all deployed into mixture to use, general mixture all requires to have higher clearing point and lower rotary viscosity, and the clearing point of mixture and rotary viscosity determine consisting of the clearing point of composition (monomer liquid crystal) and rotary viscosity and content thereof.Containing the sub-methoxyl group linking group of difluoro (-CF
2o-) although liquid crystalline cpd have lower rotary viscosity, its clearing point comparatively containing other linking groups as (-CH
2o-,-C ≡ C-,-COO-,-CH
2cH
2-) the clearing point of liquid crystalline cpd low, this for the higher clearing point of allotment mixture be disadvantageous, the present inventor finds will containing difluoro Asia methoxyl group linking group (-CF
2the aromatic base of liquid crystalline cpd O-) changes THP trtrahydropyranyl into, also be compound shown in formula I provided by the invention, its rotary viscosity is lower compared with aromatic base, and there is the response speed be exceedingly fast, also technique is simple, production cost is low for its synthetic method, and liquid crystal compound allotment to lower rotary viscosity has very important practical significance.
Accompanying drawing explanation
Fig. 1 is the synthetic route of compound shown in formula I.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.In embodiment, GC represents gas chromatographic purity below, and MP represents fusing point, and CP represents clearing point, and MS represents mass spectrum, and △ ε represents dielectric anisotropy, and △ n represents optical anisotropy.The method measuring GC, MP, CP, MS, △ ε and △ n is ordinary method.
(the R of Compound I 2 shown in embodiment 1, formula I
1=C
3h
7)
Step 1
150g (1mol) 3 is added in 2L is withstand voltage reaction flask, 4-dihydropyrane-2-sodium formiate (I-0), 192.3g (1.2mol) iodoethane, 10g anhydrous sodium carbonate, 500mlN, dinethylformamide, stirs and is warmed up to 105-110 DEG C of stirring reaction 5 hours, cool to room temperature, pour in the frozen water of 2Kg, 200ml toluene extracts four times, merges organic phases washed with water four times, evaporated under reduced pressure solvent, obtain oily matter underpressure distillation, collection boiling point is: 75-80 DEG C/8mmHg fraction, obtains 135.2g (I-1), yield: 87%
Step 2
40g (0.26mol) colorless oil (I-1) is added in 1L there-necked flask, 350ml dry tetrahydrofuran, be placed in cryostat, be cooled to-10 DEG C, be added dropwise to 100ml borine (0.12mol) tetrahydrofuran solution, react after 1 hour, be warmed up to 0 DEG C of stirring reaction 10 hours, be cooled to-10 DEG C again, be added dropwise to the solution of 30.4g (0.23mol) sodium acetate and 45ml water, temperature control is slowly added dropwise to 30ml (0.26mol) 30% hydrogen peroxide solution below 30 DEG C, room temperature reaction is after 2 hours, separate organic phase, aqueous phase is extracted with ethyl acetate four times, merge organic phase, neat solvent is steamed under decompression, 100ml anhydrous diethyl ether is added in resistates, suction filtration, filtrate decompression is distilled, collection boiling point is: 98-107 DEG C/0.4mmHg fraction, obtain 28.4g (I-2), light yellow oil, yield: 71%
Step 3
Add in 2L there-necked flask 20g (0.115mol) (I-2), 1000ml methylene dichloride, stirring at room temperature is dissolved, add 72.8g (0.172mol) Dai Si-Martin reagent, after 2 hours, add the aqueous solution containing 10% dithionous acid sodium that 500ml sodium bicarbonate is saturated, separate organic phase, aqueous phase dichloromethane extraction twice, merge organic phase, wash with water, saturated salt is washed, neat solvent is steamed under decompression, residue over silica gel post decolours, clean with 50% ethyl acetate and sherwood oil, neat solvent is steamed under decompression, obtain 17.6g (I-3), colorless oil, yield 89%
Step 4
Add in 2L there-necked flask 20g (0.115mol) (I-2), 1000ml methylene dichloride, stirring at room temperature is dissolved, add 72.8g (0.172mol) Dai Si-Martin reagent, after 2 hours, add the aqueous solution containing 10% dithionous acid sodium that 500ml sodium bicarbonate is saturated, separate organic phase, aqueous phase dichloromethane extraction twice, merge organic phase, wash with water, saturated salt is washed, neat solvent is steamed under decompression, residue over silica gel post decolours, clean with 50% ethyl acetate and sherwood oil, neat solvent is steamed under decompression, obtain 17.6g (I-3), colorless oil, yield 89%
Step 4
24.6g (87.5mmol) 4-(4-bromo-trans cyclohexyl) bromobenzene is added in 1L there-necked flask, 150ml tetrahydrofuran (THF), in a nitrogen atmosphere, be placed in cryostat, be cooled to 0 DEG C, drip 44ml (2M, 88mmol) isopropyl magnesium bromide tetrahydrofuran solution, after 1 hour, move to constant pressure funnel;
Add in 1L there-necked flask 15g (87.2mmol) (I-3), 200ml tetrahydrofuran solution, stirring and dissolving is limpid, in a nitrogen atmosphere, be placed in cryostat, be cooled to-10 DEG C, be added dropwise to 4-(4-bromo-trans cyclohexyl) the phenyl-magnesium-bromide tetrahydrofuran solution of above-mentioned preparation, within 2 hours, add, after 1 hour, remove cryostat, naturally room temperature is raised to, add in 100ml saturated ammonium chloride containing 2M salt aqueous acid, separatory, aqueous phase 200ml dichloromethane extraction secondary, merge organic layer, neat solvent is steamed under decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, neat solvent is steamed under decompression, obtain 28g colorless oil (I-4), yield: 86%
Step 5
Add in 1L there-necked flask 26g (69.4mmol) (I-4), 250ml methylene dichloride, in a nitrogen atmosphere, be placed in cryostat, be cooled to-30 DEG C, drip 24.3ml (0.152mol) triethyl silicane, half an hour adds, after half an hour, be added dropwise to 46.5g (46.5%, 0.152mol) Eorontrifluoride etherate solution, stirring reaction 2 hours, remove cryostat, naturally room temperature is raised to, slowly be added dropwise to 200ml saturated sodium bicarbonate aqueous solution, separatory, aqueous phase with 100ml dichloromethane extraction once, merge organic layer, neat solvent is steamed under decompression, obtain colourless liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, neat solvent is steamed under decompression, use ethyl alcohol recrystallization again, obtain 16.4g white solid, yield: 66%
Step 6
Add in 500mL there-necked flask 16g (44.6mmol) (I-5), 150ml tetrahydrofuran (THF), 150ml water, adds 3.8g (90mmol) lithium hydroxide, stirring at room temperature reacts 10 hours, decompression is lower steams except tetrahydrofuran solvent, drips 2M dilute hydrochloric acid and is adjusted to acidity, suction filtration, filter cake washes with water, vacuum-drying, obtains 14.4g white solid (I-6), yield: 98%
Step 7
Add in 1L there-necked flask 14g (42.4mmol) (I-6); 5g (46.6mmol) 1; 3-dimercaptopropane; 7.65g (51mmol) trifluoromethanesulfonic acid; 500ml toluene; reflux divides water, after 5 hours, after point water purification; cool to 90 DEG C; between 70-90 DEG C, add methyl tertiary butyl ether 100ml in 45 minutes, continue cooling, crystallize out; filter under nitrogen protection; crystal methyl tertiary butyl ether (25ml × 4) washing obtained, vacuum-drying obtains orange crystal I-7, yield 100%
Step 8
6.9g (46.6mmol) 3 is added in 2L there-necked flask, 4, 5-trifluoromethyl phenol, 55.5g (55mmol) triethylamine, 500ml methylene dichloride, be placed in cryostat, be cooled to-80 DEG C, be added dropwise to I-7 and 200ml dichloromethane solution prepared by step, within 1 hour, add, after 1 hour, still drip 24ml hydrogen fluoride pyridine (70% at-80 DEG C, 0.186mol) solution, half an hour adds, the solution of 30g (0.186mol) bromine and 100ml methylene dichloride is still dripped at-80 DEG C, add rear insulated and stirred and react 2 hours, remove cryostat, naturally room temperature is raised to, in the aqueous sodium hydroxide solution (adjust ph to 5 ~ 8) adding 32% and 300g ice, aqueous phase 100ml dichloromethane extraction after separatory, merge organic phase 4g diatomite filtration, washing, the lower solvent evaporated of decompression.Sherwood oil recrystallization after the crude product column chromatography obtained, obtains white crystal product, then uses ethyl alcohol recrystallization twice, obtains 13.7g, white solid (I2, R
1=C
3h
7), yield: 67%
Gc：99.92％
MP：52℃
CP:21℃
Δn[589nm,20℃]：0.145
Δε[KHz,20℃]:21.3
Prepared by compound (I2, R shown in gained formula I to this embodiment
1=C
3h
7) carry out liquid crystal property test, concrete steps comprise: compound (I2, R shown in gained formula I prepared by this embodiment
1=C
3h
7) to be dissolved in clearing point CP be in the parent of 80 DEG C for ratio with 10%, the clearing point CP of test gained liquid crystal compound, acquired results CP is 83.4 DEG C;
As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.(the R of Compound I 45 shown in embodiment 2, preparation formula I
1=C
3h
7)
Step 1
5.8g (0.24mol) magnesium chips is added in 500ml there-necked flask, 100ml tetrahydrofuran (THF), with an iodine, in a nitrogen atmosphere, reflux disappears to the color of iodine, and slowly drip the solution of 45g (0.16mol) 4-propyl group bromobenzene and 150ml tetrahydrofuran (THF), half an hour adds, back flow reaction, after 1 hour, moves to constant pressure funnel;
Add in 1L there-necked flask 22g (0.13mol) (I-3), 200ml tetrahydrofuran solution, stirring and dissolving is limpid, in a nitrogen atmosphere, be placed in cryostat, be cooled to-10 DEG C, be added dropwise to the 4-propylbenzene magnesium bromide tetrahydrofuran solution of above-mentioned preparation, within 1 hour, add, after 1 hour, remove cryostat, naturally room temperature is raised to, add the 2N diluted hydrochloric acid aqueous solution of 100ml, separatory, aqueous phase 200ml dichloromethane extraction secondary, merge organic layer, neat solvent is steamed under decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, neat solvent is steamed under decompression, obtain 29g colourless liquid (I-4), yield: 77.5%
Step 2
The synthetic operation of Compound I-5 is same as the step 5 of embodiment 1, yield 72%
Step 3
The synthetic operation of Compound I-6 is same as the step 6 of embodiment 1, yield 99%
Step 4
The synthetic operation of Compound I-7 is same as the step 7 of embodiment 1, obtains orange crystal 1-7, yield 100%
Step 5
286g (1.1mol) 2 is added in 5L there-necked flask, 3', 4', 5', 6-five fluoro-[1, 1'-biphenyl]-4-phenol, 131.5g (1.3mol) triethylamine, 1500ml methylene dichloride, be placed in cryostat, be cooled to-80 DEG C, be added dropwise to I-7 (1mol) and the 1500ml dichloromethane solution of step 4 preparation, within 3 hours, add, after 1 hour, still drip 515ml hydrogen fluoride pyridine (70% at-80 DEG C, 4mol) solution, half an hour adds, the solution of 640g (4mol) bromine and 500ml methylene dichloride is still dripped at-80 DEG C, add rear insulated and stirred and react 2 hours, remove cryostat, naturally room temperature is raised to, in the aqueous sodium hydroxide solution (adjust ph to 5 ~ 8) adding 32% and 1000g ice, aqueous phase 100ml dichloromethane extraction after separatory, merge organic phase 50g diatomite filtration, washing, the lower solvent evaporated of decompression.Sherwood oil recrystallization after the crude product column chromatography obtained, obtains white crystal product, then uses ethyl alcohol recrystallization twice, ethyl alcohol recrystallization twice, obtains 330g white crystal (I45, R
1=C
3h
7), yield: 64.5%
Gc：99.91％
MP：70℃
CP：26℃
Δn[589nm,20℃]：0.15
Δε[KHz,20℃]：21
Prepared by compound (I45, R shown in gained formula I to this embodiment
1=C
3h
7) carry out liquid crystal property test, concrete steps comprise: compound (I45, R shown in gained formula I prepared by this embodiment
1=C
3h
7) to be dissolved in clearing point CP be in the parent of 80 DEG C for ratio with 10%, the clearing point CP of test gained liquid crystal compound, acquired results CP is 81.6 DEG C;
As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.
(the R of Compound I 29 shown in embodiment 3, preparation formula I
1=C
5h
11)
Step 1
The fluoro-4'-amyl group-1 of 38.7g (0.16mol) 3-is added in 500ml there-necked flask, 1'-biphenyl, 250ml tetrahydrofuran (THF), in a nitrogen atmosphere, is placed in cryostat, be cooled to-80 DEG C, drip 68ml (2.5M, 0.17mol) lithium hexane solution, half an hour adds, after 1 hour, move to constant pressure funnel;
Add in 1L there-necked flask 27.5g (0.16mol) (I-3), 250ml tetrahydrofuran solution, stirring and dissolving is limpid, in a nitrogen atmosphere, be placed in cryostat, be cooled to-10 DEG C, be added dropwise to the fluoro-4-of 2-(4 '-amyl-phenyl) the benzene lithium tetrahydrofuran solution of above-mentioned preparation, within 2 hours, add, after 1 hour, remove cryostat, naturally room temperature is raised to, add 100ml saturated aqueous ammonium chloride, separatory, aqueous phase 200ml dichloromethane extraction secondary, merge organic layer, neat solvent is steamed under decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, neat solvent is steamed under decompression, obtain 55g white solid (I-4), yield: 83.5%
Step 2
Add in 1L there-necked flask 20.7g (0.05mol) (I-4), 320ml methylene dichloride, in a nitrogen atmosphere, be placed in cryostat, be cooled to-30 DEG C, drip 17.5ml (0.11mol) triethyl silicane, half an hour adds, after half an hour, be added dropwise to 33.6g (46.5%, 0.11mol) Eorontrifluoride etherate solution, stirring reaction 2 hours, remove cryostat, naturally room temperature is raised to, slowly be added dropwise to 150ml saturated sodium bicarbonate aqueous solution, separatory, aqueous phase with 100ml dichloromethane extraction once, merge organic layer, neat solvent is steamed under decompression, obtain colourless liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, neat solvent is steamed under decompression, use ethyl alcohol recrystallization again, obtain 11.5g white solid (I-5), yield: 57.5%
Step 3
The synthetic operation of Compound I-6 is same as the step 6 of embodiment 1, yield 99%
Step 4
The synthetic operation of Compound I-7 is same as the step 7 of embodiment 1, obtains brown crystals 1-7, yield 100%
Step 5
Compound I 29 (R
1=C
5h
11) synthetic operation be same as the step 5 of embodiment 2, ethyl alcohol recrystallization for several times, obtains white crystal, yield 68.8%
Gc：99.95％
MP：77℃
CP：35℃
Δn[589nm,20℃]：0.14
Δε[KHz,20℃]：19
Prepared by compound (I29, R shown in gained formula I to this embodiment
1=C
5h
11) carry out liquid crystal property test, concrete steps comprise: compound (I29, R shown in gained formula I prepared by this embodiment
1=C
5h
11) to be dissolved in clearing point CP be in the parent of 80 DEG C for ratio with 10%, the clearing point CP of test gained liquid crystal compound, acquired results CP is 84.3 DEG C;
As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.
Embodiment 4
According to component each shown in table 1 and weight percentage mixing, obtain liquid crystal compound a provided by the invention;
The composition of table 1, liquid crystal compound a
The performance test results of this liquid crystal compound a is as shown in table 2:
The performance test results of table 2, liquid crystal compound a
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display.
Embodiment 5
According to component each shown in table 3 and weight percentage mixing, obtain liquid crystal compound b provided by the invention;
The composition of table 3, liquid crystal compound b
The performance test results of this liquid crystal compound b is as shown in table 4:
The performance test results of table 4, liquid crystal compound b
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display
Embodiment 6
According to component each shown in table 5 and weight percentage mixing, obtain liquid crystal compound c provided by the invention;
The composition of table 5, liquid crystal compound c
The performance test results of this liquid crystal compound c is as shown in table 6:
The performance test results of table 6, liquid crystal compound c
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display
Embodiment 7
According to component each shown in table 7 and weight percentage mixing, obtain liquid crystal compound d provided by the invention;
The composition of table 7, liquid crystal compound d
The performance test results of this liquid crystal compound d is as shown in table 8:
The performance test results of table 8, liquid crystal compound d
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display.
Embodiment 8
According to component each shown in table 9 and weight percentage mixing, obtain liquid crystal compound e provided by the invention;
The composition of table 9, liquid crystal compound e
The performance test results of this liquid crystal compound e is as shown in table 10:
The performance test results of table 10, liquid crystal compound e
| Cp | 87℃ |
| Δn | 0.110 |
| Δε | 6.9 |
| γ1 | 63 |
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display.
Embodiment 9
According to component each shown in table 11 and weight percentage mixing, obtain liquid crystal compound f provided by the invention;
The composition of table 11, liquid crystal compound f
The performance test results of this liquid crystal compound f is as shown in table 12:
The performance test results of table 12, liquid crystal compound f
| Cp | 87℃ |
| Δn | 0.110 |
| Δε | 7.2 |
| γ1 | 63 |
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, be applicable in liquid-crystal display.
Comparative example 1
In order to the characteristic of compound shown in display type I, prepared liquid crystal compound g, the component in this liquid crystal compound g, compared with the component of liquid crystal compound a, does not add I-10, I-1, and other components do not become.
The composition of table 13, liquid crystal compound g
The performance test results of liquid crystal compound a is as shown in table 2:
The performance test results of table 2, liquid crystal compound a
The performance test results of table 14, liquid crystal compound g
Embodiment 4 and embodiment 10 contrast and find, if do not add Compound I-10, I-1, then the specific inductivity of liquid crystal compound can reduce greatly.
Claims (10)
1. compound shown in formula I,
In described formula I,
be selected from least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;
be selected from least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;
M is 0 or 1 or 2;
N is 0 or 1;
R
1be selected from hydrogen, the total number of carbon atoms that normal olefine base that alkoxyl group that alkyl that fluorine, chlorine, cyano group, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C1-C25, fluorine replace is the alkyl of C1-C25, the total number of carbon atoms that fluorine replaces at least one that to be the total number of carbon atoms that the alkoxyl group of C1-C25 and fluorine replace be in the straight chain allylic alkylation of C1-C25;
R
2and R
3all be selected from H and F any one;
L is selected from least one in singly-bound, Sauerstoffatom, carbon atom, double bond and triple bond; X is the integer of 0-4, and when L is Sauerstoffatom, double bond and triple bond, x is 1;
Y is selected from H, F, Cl ,-CF
3,-CHF
2,-OCF
3with-OCHF
2in any one.
2. compound according to claim 1, is characterized in that: shown in described formula I, compound is selected from formula I1 to any one in formula I50:
In described formula I1-I50, R
1definition and claim 1 in R
1definition identical.
3. prepare a method for compound shown in the arbitrary described formula I of claim 1 or 2, comprise the steps:
Will
carry out condensation reaction with triethylamine mixing, react complete and carry out fluoridation with hydrogen fluoride pyridine and bromine again, obtain compound shown in described formula I after completion of the reaction;
Described
with
in, described R
1, R
2, R
3, A, B, Y, m and n definition all with R in claim 1
1definition identical.
4. method according to claim 3, is characterized in that: described in
the mole dosage that feeds intake of triethylamine, hydrogen fluoride pyridine, bromine, than being 1:1-2:1-2:1-5:1-5, is specially 1:1.1:1.2:4:4;
In described step of condensation, temperature is-100-30 DEG C, is specially-80 DEG C; Time is 1-5 hour, is specially 1 hour;
Describedly carry out in fluorination reaction step with hydrogen fluoride pyridine and bromine, temperature is-100-30 DEG C, is specially-80 DEG C; Time is 0.5-3 hour, is specially 2 hours;
Described reaction is carried out all in a solvent; Described solvent is specifically selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.
5. the liquid crystal compound containing compound shown in the arbitrary described formula I of claim 1 or 2.
6. liquid crystal compound according to claim 5, is characterized in that: at least one of described liquid crystal compound also in compound shown in contained II to formula IV:
Described formula II in formula IV, R
1, R
2and R
3all be selected from least one in the fluoroalkyl of hydrogen, halogen ,-CN, the alkyl of C1-C7, the alkoxyl group of C1-C7, the thiazolinyl of C2-C7 and C1-C5;
Z is all selected from singly-bound ,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-OCH
2-,-CH
2o-,-CF
2o-and-OCF
2-at least one;
all be selected from least one in singly-bound and following radicals:
Y
1and Y
2all be selected from least one in H and F;
P is the integer of 0-2;
When P is 2,
identical or different.
7. liquid crystal compound according to claim 6, is characterized in that: described liquid crystal compound is made up of compound described in described formula I to formula IV;
Described liquid crystal compound is specially following liquid crystal compound a, b, c, d, e or f:
Described liquid crystal compound a comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound a specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound b comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound b specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound c comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound c specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound d comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound d specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound e comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound e specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound f comprises the component of following each mass parts or is made up of the component of following each mass parts:
Described liquid crystal compound f specifically comprises the component of following each mass parts or is made up of the component of following each mass parts:
8. the liquid crystal compound according to claim 6 or 7, is characterized in that: the mass fraction of compound shown in described formula I is 2-40 part, is specially 4-20 part;
The mass parts of compound shown in described formula II is 4-50 part, is specially 10-40 part;
The mass parts of compound shown in described formula III is 5-50 part, is specially 20-50 part;
The mass parts of compound shown in described formula IV is 3-45 part, is specially 10-40 part.
9. the application in liquid crystal compound, liquid crystal display device material or electro-optical display part material prepared by compound shown in the arbitrary described formula I of claim 1-2 or the arbitrary described liquid crystal compound of claim 5-8.
10. comprise liquid crystal display device material or the electro-optical display part material of compound or the arbitrary described liquid crystal compound of claim 5-8 shown in the arbitrary described formula I of claim 1-2.
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| JP2014152181A (en) * | 2013-02-04 | 2014-08-25 | Dic Corp | Liquid crystal composition and liquid crystal display element using the same |
| CN104093815A (en) * | 2013-03-25 | 2014-10-08 | Dic株式会社 | Liquid crystal composition and liquid crystal display element employing same |
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|---|---|---|---|---|
| US20100294991A1 (en) * | 2009-05-20 | 2010-11-25 | Chisso Corporation | Liquid Crystal Composition and Liquid Crystal Display Device |
| US20140034876A1 (en) * | 2012-07-26 | 2014-02-06 | Jnc Petrochemical Corporation | Compound having 2,2-difluorovinyloxy group or 1,2,2-trifluorovinyloxy group, liquid crystal composition and liquid crystal display device |
| JP2014152181A (en) * | 2013-02-04 | 2014-08-25 | Dic Corp | Liquid crystal composition and liquid crystal display element using the same |
| CN104093815A (en) * | 2013-03-25 | 2014-10-08 | Dic株式会社 | Liquid crystal composition and liquid crystal display element employing same |
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