CN103788039A - Liquid crystal compound containing tetrahydropyrane difluoro methoxy-linking group and preparation method and application thereof - Google Patents
Liquid crystal compound containing tetrahydropyrane difluoro methoxy-linking group and preparation method and application thereof Download PDFInfo
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- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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Abstract
The invention discloses a liquid crystal compound containing a tetrahydropyrane difluoro methoxy-linking group and a preparation method and application thereof. The liquid crystal compound is represented by a formula I. In a molecular structure of the compound represented by the formula I, the liquid crystal compound containing the tetrahydropyrane difluoro methoxy-linking group (img file='DDA0000475765100000011. TIF' wi='384' he='112'/) has high dielectric anisotropy. What's more important is that the liquid crystal compound further has high response speed and clearing points and low rotational viscosity. Compared with blended liquid crystal compounds, the liquid crystal compound has very important significance. As the formula I, (img file='DDA0000475765100000012. TIF' wi='984' he='256'/).
Description
Technical field
The invention belongs to liquid crystalline cpd and Application Areas, relate to a kind of liquid crystalline cpd that contains cyclopentyl and the sub-methoxyl group linking group of difluoro 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.Of a great variety for the liquid crystalline cpd in above-mentioned demonstration 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 realize response fast, reducing driving voltage to reduce the aspects such as power consumption.Liquid crystal material, as one of important photoelectron material of liquid-crystal display, plays an important role to the performance of improving liquid-crystal display.
As liquid crystal material, need to there is good chemistry and thermostability and the stability to electric field and electromagnetic radiation.And as liquid crystal material for thin-film transistor technologies (TFT-LCD), not only need to have as outside upward stability, also should there is 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, show in order to realize high-quality, eliminate display frame ghost and hangover, require liquid crystal to there is very fast response speed, therefore require liquid crystal to there is 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 it is significant to mixed liquid crystal to improve the dielectric anisotropy △ ε of liquid crystal.
Large quantity research shows, the sub-methoxyl group linking group of difluoro of liquid crystal molecule introducing (CF
2o-), after, can make the rotary viscosity γ of liquid crystal
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, thereby the dielectric anisotropy △ ε of liquid crystal molecule is increased to some extent.What Merck KGaA and Japanese Chisso Corporation disclosed that some have a different substituents has the sub-methoxyl group linking group of a 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.In the time of allotment liquid crystal compound, need to add the high clearing point compound that viscosity is larger to carry out the clearing point decline that balance-CF2O-group causes, thereby restrict the space that liquid crystal compound response speed promotes.
Summary of the invention
The object of this invention is to provide a kind of liquid crystalline cpd that contains the sub-methoxyl group linking group of tetrahydropyrans difluoro and preparation method thereof and application.
The liquid crystalline cpd that contains the sub-methoxyl group linking group of tetrahydropyrans difluoro provided by the invention, its general structure is suc as formula shown in I,
Formula I
In described formula I, A is selected from least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene, and B is selected from least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene; M be 0 or 1 or 2, n be 0 or 1, R
1be selected from the aliphatic hydrocarbon of C1-C20, R
2, R
3all be selected from any one in H and F, Y is selected from H, F, Cl, CF
3, CHF
2, OCF
3and 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;
The method of compound shown in the described formula I of preparation provided by the invention, comprises following reaction scheme:
Above-mentioned reaction scheme is the synthesis step of compound shown in the described formula I of preparation, wherein R
1, R
2, R
3, A, B, Y, m and n definition identical with the definition of formula I, comprise following reactions steps:
1) oxysuccinic acid is mixed and reacted with the vitriol oil, react complete and obtain
2) by described step 1) gained
under the effect of Raney's nickel catalyst, carry out hydrogenation reaction with hydrogen, react complete and obtain
3) by described step 2) gained
react under triflic acid catalyzes with 1,3-dimercaptopropane, react complete and obtain
4) by described step 3) gained
with phenol
mix and react, react complete and react with hydrogen fluoride pyridine solution again, obtain after completion of the reaction
5) by described step 4) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) react, react complete and obtain
6) by described step 5) gained
react with triethyl silicane and boron trifluoride, react the complete compound shown in formula I that obtains
In above-mentioned reactions steps, described R
1, R
2, R
3, A, B, Y, m and n definition all identical with aforementioned definitions.
Described reactions steps 1) in, the weight ratio that feeds intake of described oxysuccinic acid and the vitriol oil is 1:1-2, is specially 1:1; Temperature is 25-110 ℃, is specially 100 ℃, and the time is 1-5 hour, is specially 2 hours;
Described reactions steps 2) in, described step 1) gained
with the weight ratio that feeds intake of described Raney's nickel catalyst be 100:5-35, be specially 100:20; In described hydrogenation reaction step, temperature is 0-100 ℃, is specially 30 ℃, and the time is 1-10 hour, is specially 6 hours;
Described reactions steps 3) in, described step 2) gained
than for 1:1-2:1-2, be specially 1:1.1:1.2 with the mole dosage that feeds intake of 1,3-dimercaptopropane, trifluoromethanesulfonic acid, temperature is 100-120 ℃, is specially 110 ℃, and the time is 1-10 hour, is specially 5 hours;
Described reactions steps 4) in, described step 3) gained
with
the mole dosage that feeds intake of triethylamine, pyridine hydrogen fluoride, bromine, than for 1:1-2:1-2:1-5:1-5, is specially 1:1.1:1.2:4:4; In described step of reacting with phenol, temperature is-100-30, is specially-80 ℃, and the time is 1-5 hour, be specially 1 hour, in the reactions steps of described and pyridine hydrogen fluoride and bromine, temperature is-100-30 ℃, be specially-80 ℃, the time is 0.5-3 hour, is specially 2 hours;
Described reactions steps 5) in, described step 4) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) the mole dosage that feeds intake, than for 1:1-2, is specially 1:1.2; Temperature is-80-0 ℃, is specially-10 ℃, and the time is 1-10 hour, is specially 2 hours;
Described reactions steps 6) in, described step 5) gained
than for 1:1-3:1-3, be specially 1:2.1:2.1 with the mole dosage that feeds intake of triethyl silicane, boron trifluoride; In described reactions steps, temperature is-50-30 ℃, is specially-30 ℃, and the time is 0.5-4 hour, is specially 2 hours;
Above-mentioned reaction scheme reaction in steps all in solvent, carry out; Described solvent is selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.
Liquid crystal compound, liquid crystal display device material or the electro-optical display part material of the compound described in preparing application 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, also belong to protection scope of the present invention.
Liquid crystalline cpd is generally all deployed into mixture and uses, general mixture all requires to have higher clearing point and lower rotary viscosity, and the clearing point of mixture and rotary viscosity are to determine consisting of the clearing point of composition (monomer liquid crystal) and rotary viscosity and content thereof.Contain the sub-methoxyl group linking group of difluoro (CF
2o-) although liquid crystalline cpd have lower rotary viscosity, its clearing point contains other linking groups as (CH
2o-,-C ≡ C-,-COO-,-CH
2cH
2-) the clearing point of liquid crystalline cpd low, this mixture for the higher clearing point of allotment is disadvantageous, the inventor finds to contain the sub-methoxyl group linking group of difluoro (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 being exceedingly fast, also technique is simple, production cost is low for its synthetic method, and the liquid crystal compound for allotment with lower rotary viscosity has very important practical significance.
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 Δ ε represents dielectric anisotropy, and Δ n represents optical anisotropy.The method of measuring GC, MP, CP, MS, Δ ε and Δ n is ordinary method.
Compound I 2(R shown in embodiment 1, formula I
1=C
3h
7)
Step 1
In 2L there-necked flask, add 500g (3.73mol) oxysuccinic acid (I-0), the 500g vitriol oil, stirring makes dissolution of solid, slowly drips 300ml (20%) vitriol oil of being fuming, and within one hour, adds, after adding, be warmed up to 100 ℃ of stirring reactions 2 hours, cool to room temperature, pours in the trash ice of 2Kg, stir suction filtration, washing.
The solid recrystallizing methanol obtaining, obtains brown crystal (I-1) 287g, yield: 55%
Step 2
In 2L single port bottle, add 100g brown crystal (I-1), 200ml toluene, 100ml methyl alcohol, 20g Raney's nickel catalyst, shakes hydrogenation 6 hours under normal temperature and pressure, inhale hydrogen to theoretical amount, remove by filter carefully catalyzer, under filtrate decompression, steam neat solvent, obtain 99.5g gray solid (I-2), yield: 96.8%
Step 3
In 2L there-necked flask, add 144g (1mol) (I-2); 118.8g (1.1mol) 1; 3-dimercaptopropane; 180g (1.2mol) trifluoromethanesulfonic acid; 1500ml toluene; reflux is divided water, after 5 hours, after point water purification; cool to 90 ℃; between 70-90 ℃, in 45 minutes, add methyl tertiary butyl ether 100ml, continue cooling, crystallize out; under nitrogen protection, filter; methyl tertiary butyl ether for crystal (25ml × 4) washing obtaining, vacuum-drying obtains orange crystal I-7, yield 100% step 4
In 5L there-necked flask, add 163g (1.1mol) 3, 4, 5-trifluoromethyl phenol, 131.5g (1.3mol) triethylamine, 1500ml methylene dichloride, be placed in cryostat, be cooled to-80 ℃, be added dropwise to I-3 and 1000ml dichloromethane solution prepared by step, within 3 hours, add, after 1 hour, still drip 515ml hydrogen fluoride pyridine (70% at-80 ℃, 4mol) solution, add half an hour, still at-80 ℃ of solution that drip 640g (4mol) bromines and 500ml methylene dichloride, add rear insulated and stirred reaction 2 hours, remove cryostat, naturally be raised to room temperature, add in 32% aqueous sodium hydroxide solution (regulating pH value to 5～8) and 1000g ice, water 200ml dichloromethane extraction after separatory, merge organic phase 100g diatomite filtration, washing, the lower solvent evaporated of decompression.Sherwood oil recrystallization after the crude product column chromatography obtaining, obtains 183.5g light yellow solid (I-5), yield: 62%
Step 5
In 1L there-necked flask, add 45g (0.16mol) 4-(4-propyl group-trans cyclohexyl) bromobenzene, 450ml tetrahydrofuran (THF), under nitrogen atmosphere, be placed in cryostat,, be cooled to-80 ℃, drip 70.5ml (2.5M, 0.176mol) n-Butyl Lithium hexane solution, within 1 hour, add, after 1 hour, move to constant pressure funnel;
In 1L there-necked flask, add 39.5g (0.13mol) (I-5), 200ml tetrahydrofuran solution, stirring and dissolving is limpid, under nitrogen atmosphere, be placed in cryostat, be cooled to-10 ℃, be added dropwise to 4-(4-propyl group-trans cyclohexyl) the benzene lithium tetrahydrofuran solution of above-mentioned preparation, within 2 hours, add, after 1 hour, remove cryostat, naturally be raised to room temperature, add 100ml saturated aqueous ammonium chloride, separatory, 200ml dichloromethane extraction secondary for water, merge organic layer, the lower neat solvent that steams of decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, obtain 56.8g white solid (I-6), yield: 84.6%
Step 6
In 1L there-necked flask, add 45g (0.09mol) (I-6), 450ml methylene dichloride, under nitrogen atmosphere, be placed in cryostat, be cooled to-30 ℃, drip 31.5ml (0.198mol) triethyl silicane, add half an hour, after half an hour, be added dropwise to 60.5g (46.5%, 0.198mol) Eorontrifluoride etherate solution, stirring reaction 2 hours, remove cryostat, naturally be raised to room temperature, slowly be added dropwise to 200ml saturated sodium bicarbonate aqueous solution, separatory, water is used 100ml dichloromethane extraction once, merge organic layer, the lower neat solvent that steams of decompression, obtain colourless liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, use again ethyl alcohol recrystallization, obtain 29g white solid (I2, R
1=C
3h
7), yield: 67%
Gc：99.92%
MP：49℃
CP:22℃
Δn[589nm,20℃]：0.142
Δε[KHz,20℃]:20.1
This embodiment is prepared to compound (I2, R shown in gained formula I
1=C
3h
7) carry out liquid crystal property test, concrete steps comprise: this embodiment is prepared to compound (I2, R shown in gained formula I
1=C
3h
7) be dissolved in clearing point CP in the parent of 80 ℃ take 10% ratio, the clearing point CP of test gained liquid crystal compound, acquired results CP is 82.4 ℃;
And known compound take clearing point CP as 0 ℃
replace aforesaid compound (I2, R
1=C
3h
7), as above test, in contrast, the clearing point CP of the liquid crystal compound that this known compound of gained and parent are obtained by mixing is 78.8 ℃.
In above-mentioned test, in parent used, the structural formula of each component composition and parts by weight thereof are as follows:
As from the foregoing, utilize this embodiment 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, can significantly improve the clearing point CP of gained liquid crystal compound, and in field of liquid crystal display, require the clearing point of liquid crystal display device material used or electro-optical display part material high as far as possible, compound shown in visible formula I provided by the invention is being prepared liquid crystal display device material or electro-optical display part Material Field has important using value.
Compound I 45(R shown in embodiment 2, preparation formula I
1=C
3h
7)
Step 1
In 5L there-necked flask, add 286g (1.1mol) 2, 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 ℃, be added dropwise to I-3 and 1000ml dichloromethane solution prepared by embodiment 1 step 3, within 3 hours, add, after 1 hour, still drip 515ml hydrogen fluoride pyridine (70% at-80 ℃, 4mol) solution, add half an hour, still at-80 ℃ of solution that drip 640g (4mol) bromines and 500ml methylene dichloride, add rear insulated and stirred reaction 2 hours, remove cryostat, naturally be raised to room temperature, add in 32% aqueous sodium hydroxide solution (regulating pH value to 5～8) and 1000g ice, water 200ml dichloromethane extraction after separatory, merge organic phase 100g diatomite filtration, washing, the lower solvent evaporated of decompression.Sherwood oil recrystallization after the crude product column chromatography obtaining, ethyl alcohol recrystallization twice, obtains 269g light yellow solid (I-5), yield: 66%
Step 5
In 500ml there-necked flask, add 5.8g (0.24mol) magnesium chips, 100ml tetrahydrofuran (THF), with an iodine, under nitrogen atmosphere, reflux to the color of iodine disappears, and slowly drips the solution of 45g (0.16mol) 4-propyl group bromobenzene and 150ml tetrahydrofuran (THF), and add half an hour, after back flow reaction 1 hour, move to constant pressure funnel;
In 1L there-necked flask, add 53g (0.13mol) (I-5), 200ml tetrahydrofuran solution, stirring and dissolving is limpid, under nitrogen atmosphere, be placed in cryostat, be cooled to-10 ℃, 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 be raised to room temperature, add the 2N diluted hydrochloric acid aqueous solution of 100ml, separatory, 200ml dichloromethane extraction secondary for water, merge organic layer, the lower neat solvent that steams of decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, obtain 50g white solid (I-6), yield: 72.8%
Step 6
In 1L there-necked flask, add 47.5g (0.09mol) (I-6), 470ml methylene dichloride, under nitrogen atmosphere, be placed in cryostat, be cooled to-30 ℃, drip 31.5ml (0.198mol) triethyl silicane, add half an hour, after half an hour, be added dropwise to 60.5g (46.5%, 0.198mol) Eorontrifluoride etherate solution, stirring reaction 2 hours, remove cryostat, naturally be raised to room temperature, slowly be added dropwise to 200ml saturated sodium bicarbonate aqueous solution, separatory, water is used 100ml dichloromethane extraction once, merge organic layer, the lower neat solvent that steams of decompression, obtain colourless liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, use again ethyl alcohol recrystallization, obtain 29.7g white solid (I45, R
1=C
3h
7), yield: 64.5%
Gc：99.95%
MP：68℃
CP：21℃
Δn[589nm,20℃]：0.18
Δε[KHz,20℃]:17
This embodiment is prepared to compound (I45, R shown in gained formula I
1=C
3h
7) carry out liquid crystal property test, concrete steps comprise: this embodiment is prepared to compound (I45, R shown in gained formula I
1=C
3h
7) be dissolved in clearing point CP in the parent of 80 ℃ take 10% ratio, the clearing point CP of test gained liquid crystal compound, acquired results CP is 86 ℃;
And known compound take clearing point CP as 0 ℃
replace aforesaid compound (I45, R
1=C
3h
7), as above test, in contrast, the clearing point CP of the liquid crystal compound that this known compound of gained and parent are obtained by mixing is 78.8 ℃.
In above-mentioned test, in parent used, the structural formula of each component composition and parts by weight thereof are as follows:
As from the foregoing, utilize this embodiment 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, can significantly improve the clearing point CP of gained liquid crystal compound, and in field of liquid crystal display, require the clearing point of liquid crystal display device material used or electro-optical display part material high as far as possible, compound shown in visible formula I provided by the invention is being prepared liquid crystal display device material or electro-optical display part Material Field has important using value.
Compound I 29(R shown in embodiment 3, preparation formula I
1=C
5h
11)
Step 1
In 500ml there-necked flask, add the fluoro-4'-of 38.7g (0.16mol) 3-amyl group-1,1'-biphenyl, 250ml tetrahydrofuran (THF), under nitrogen atmosphere, is placed in cryostat,, be cooled to-80 ℃, drip 70.5ml (2.5M, 0.176mol) n-Butyl Lithium hexane solution, within 1 hour, add, after 1 hour, move to constant pressure funnel;
(I-5) that adds 39.5g (0.13mol) embodiment 2 steps 1 to prepare in 1L there-necked flask, 200ml tetrahydrofuran solution, stirring and dissolving is limpid, under nitrogen atmosphere, be placed in cryostat, be cooled to-10 ℃, be added dropwise to the fluoro-4-of 2-(4 '-amyl group-phenyl) the benzene lithium tetrahydrofuran solution of above-mentioned preparation, within 2 hours, add, after 1 hour, remove cryostat, naturally be raised to room temperature, add 100ml saturated aqueous ammonium chloride, separatory, 200ml dichloromethane extraction secondary for water, merge organic layer, the lower neat solvent that steams of decompression, obtain yellow liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, obtain 73g white solid (I-6), yield: 86.5%
Step 2
In 1L there-necked flask, add 32.5g (0.05mol) (I-6), 320ml methylene dichloride, under nitrogen atmosphere, be placed in cryostat, be cooled to-30 ℃, drip 17.5ml (0.11mol) triethyl silicane, add half an hour, after half an hour, be added dropwise to 33.6g (46.5%, 0.11mol) Eorontrifluoride etherate solution, stirring reaction 2 hours, remove cryostat, naturally be raised to room temperature, slowly be added dropwise to 150ml saturated sodium bicarbonate aqueous solution, separatory, water is used 100ml dichloromethane extraction once, merge organic layer, the lower neat solvent that steams of decompression, obtain colourless liquid, sherwood oil heating for dissolving, cross silicagel column, sherwood oil is cleaned, the lower neat solvent that steams of decompression, use again ethyl alcohol recrystallization, obtain 18.6g white solid (I29, R
1=C
5h
11), yield: 58.6%
Gc：99.95%
MP：71℃
CP：39℃
Δn[589nm,20℃]：0.13
Δε[KHz,20℃]:17.
As from the foregoing, compound shown in formula I provided by the invention is being prepared liquid crystal display device material or electro-optical display part Material Field has important using value.
This embodiment prepares the liquid crystal property test and previous embodiment 1 gained liquid crystalline cpd (I45, R of compound shown in gained formula I
1=C
3h
7), test result without substantive difference, repeat no more herein.
Claims (7)
1. compound shown in formula I,
Formula I
In described formula I, A is selected from least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene, and B is selected from least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene; M be 0 or 1 or 2, n be 0 or 1, R
1be selected from the aliphatic hydrocarbon of C1-C20, R
2, R
3all be selected from any one in H and F, Y is selected from H, F, Cl, CF
3, CHF
2, OCF
3and OCHF
2in any one.
2. compound according to claim 1, is characterized in that: 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.
3. a method of preparing compound described in claim 1 or 2, is characterized in that the method comprises following synthesis step 1 to 6:
1) oxysuccinic acid is mixed and reacted with the vitriol oil, react complete and obtain
2) by described step 1) gained
under the effect of Raney's nickel catalyst, carry out hydrogenation reaction with hydrogen, react complete and obtain
3) by described step 2) gained
react under triflic acid catalyzes with 1,3-dimercaptopropane, react complete and obtain
4) by described step 3) gained
with phenol
mix and react, react complete and react with hydrogen fluoride pyridine solution again, obtain after completion of the reaction
5) by described step 4) gained
with Grignard reagent
x=Cl, Br, I) or
(Z=Li) react, react complete and obtain
6) by described step 5) gained
react with triethyl silicane and boron trifluoride, react the complete compound shown in formula I that obtains
In above-mentioned reactions steps, described R
1, R
2, R
3, A, B, Y, m and n definition all identical with aforementioned definitions.
4. method according to claim 3, is characterized in that: described reactions steps 1) in, the weight ratio that feeds intake of described oxysuccinic acid and the vitriol oil is 1:1-2; Temperature is 25-110 ℃, and the time is 1-5 hour;
Described reactions steps 2) in, described step 1) gained
with the weight ratio that feeds intake of described Raney's nickel catalyst be 100:5-35; In described hydrogenation reaction step, temperature is 0-100 ℃, and the time is 1-10 hour;
Described reactions steps 3) in, described step 2) gained
be 1:1-2:1-2 with 1,3-dimercaptopropane, to the mole dosage ratio that feeds intake of trifluoromethanesulfonic acid, temperature is 100-120 ℃, and the time is 1-10 hour;
Described reactions steps 4) in, described step 3) gained
with
the mole dosage ratio that feeds intake of triethylamine, pyridine hydrogen fluoride, bromine is 1:1-2:1-2:1-5:1-5; In described step of reacting with phenol, temperature is-100-30, and the time is 1-5 hour, and in the reactions steps of described and pyridine hydrogen fluoride and bromine, temperature is-100-30 ℃ that the time is 0.5-3 hour;
Described reactions steps 5) in, described step 4) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) the mole dosage ratio that feeds intake is 1:1-2; Temperature is-80-0 ℃ that the time is 1-10 hour;
Described reactions steps 6) in, described step 5) gained
compare for 1:1-3:1-3 with the mole dosage that feeds intake of triethyl silicane, boron trifluoride; In described reactions steps, temperature is-50-30 ℃ that the time is 0.5-4 hour;
Above-mentioned reaction scheme reaction in steps all in solvent, carry out; Described solvent is selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.
5. method as claimed in claim 4, is characterized in that: described reactions steps 1) in, the weight ratio that feeds intake of described oxysuccinic acid and the vitriol oil is 1:1; Temperature is 100 ℃, and the time is 2 hours;
Described reactions steps 2) in, described step 1) gained
with the weight ratio that feeds intake of described Raney's nickel catalyst for for 100:20; In described hydrogenation reaction step, temperature is 30 ℃, and the time is 6 hours;
Described reactions steps 3) in, described step 2) gained
with the mole dosage ratio that feeds intake of 1,3-dimercaptopropane, trifluoromethanesulfonic acid be 1: 1.1: 1.2, temperature is 110 ℃, the time is 5 hours;
Described reactions steps 4) in, described step 3) gained
with
the mole dosage ratio that feeds intake of triethylamine, pyridine hydrogen fluoride, bromine is 1: 1.1: 1.2: 4: 4; In described step of reacting with phenol, temperature is-80 ℃, and the time is for being 1 hour, and in the reactions steps of described and pyridine hydrogen fluoride and bromine, temperature is-80 ℃, and the time is 2 hours;
Described reactions steps 5) in, described step 4) gained
with Grignard reagent
(Z=MgX, X=Cl, Br, I) or
(Z=Li) the mole dosage ratio that feeds intake is 1: 1.2; Temperature is-10 ℃, and the time is 2 hours;
Described reactions steps 6) in, described step 5) gained
with the mole dosage ratio that feeds intake of triethyl silicane, boron trifluoride be 1: 2.1: 2.1; In described reactions steps, temperature is-30 ℃, and the time is 2 hours.
6. the arbitrary described compound of claim 1-2 is in the application of preparing in liquid crystal compound, liquid crystal display device material or electro-optical display part material.
7. comprise liquid crystal compound, liquid crystal display device material or the electro-optical display part material of the arbitrary described compound of claim 1-2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922373A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Synthesis method of methyl platinolate |
| CN113736476A (en) * | 2020-05-27 | 2021-12-03 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display component |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10318420A1 (en) * | 2003-04-24 | 2004-11-11 | Merck Patent Gmbh | Liquid crystalline compounds for use in media for electro-optical displays, e.g. in cars or aircraft, comprise compounds with tetrahydropyran-3,6- diyl and oxydifluoromethylene linking groups |
| CN101294079A (en) * | 2002-11-27 | 2008-10-29 | 默克专利股份有限公司 | Liquid crystalline compounds |
| US20100276635A1 (en) * | 2009-04-30 | 2010-11-04 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display |
| US20100294991A1 (en) * | 2009-05-20 | 2010-11-25 | Chisso Corporation | Liquid Crystal Composition and Liquid Crystal Display Device |
| US20100309402A1 (en) * | 2007-09-06 | 2010-12-09 | Chisso Corporation | Four- or five-ring liquid crystal compound having lateral fluorine, liquid crystal composition, and liquid crystal display device |
| US20100328600A1 (en) * | 2007-09-10 | 2010-12-30 | Chisso Corporation | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| CN103275735A (en) * | 2013-05-13 | 2013-09-04 | 石家庄诚志永华显示材料有限公司 | Dielectric positive liquid crystal composition |
| CN103289708A (en) * | 2013-06-09 | 2013-09-11 | 石家庄诚志永华显示材料有限公司 | Positive dielectric anisotropic liquid crystal composition |
| 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 |
-
2014
- 2014-03-12 CN CN201410088636.6A patent/CN103788039B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101294079A (en) * | 2002-11-27 | 2008-10-29 | 默克专利股份有限公司 | Liquid crystalline compounds |
| DE10318420A1 (en) * | 2003-04-24 | 2004-11-11 | Merck Patent Gmbh | Liquid crystalline compounds for use in media for electro-optical displays, e.g. in cars or aircraft, comprise compounds with tetrahydropyran-3,6- diyl and oxydifluoromethylene linking groups |
| US20100309402A1 (en) * | 2007-09-06 | 2010-12-09 | Chisso Corporation | Four- or five-ring liquid crystal compound having lateral fluorine, liquid crystal composition, and liquid crystal display device |
| US20100328600A1 (en) * | 2007-09-10 | 2010-12-30 | Chisso Corporation | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| US20100276635A1 (en) * | 2009-04-30 | 2010-11-04 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display |
| 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 |
| CN103275735A (en) * | 2013-05-13 | 2013-09-04 | 石家庄诚志永华显示材料有限公司 | Dielectric positive liquid crystal composition |
| CN103289708A (en) * | 2013-06-09 | 2013-09-11 | 石家庄诚志永华显示材料有限公司 | Positive dielectric anisotropic liquid crystal composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922373A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Synthesis method of methyl platinolate |
| CN110922373B (en) * | 2018-09-19 | 2023-09-12 | 张家港九力新材料科技有限公司 | Synthesis method of methyl broad maleate |
| CN113736476A (en) * | 2020-05-27 | 2021-12-03 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display component |
| CN113736476B (en) * | 2020-05-27 | 2023-04-07 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display component |
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