CN103788039B - Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application - Google Patents

Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application Download PDF

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CN103788039B
CN103788039B CN201410088636.6A CN201410088636A CN103788039B CN 103788039 B CN103788039 B CN 103788039B CN 201410088636 A CN201410088636 A CN 201410088636A CN 103788039 B CN103788039 B CN 103788039B
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CN103788039A (en
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曹建华
王士波
贾磊磊
华瑞茂
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D309/06—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • 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
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked

Abstract

The invention discloses a kind of liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application.This compound is shown in formula I.In the compound of formula I molecular structure that the present invention provides, containing oxinane difluoromethylenedioconnecting linking groupLiquid-crystal compounds, not only there is higher dielectric anisotropy, it is often more important that there is the response speed being exceedingly fast and higher clearing point, and relatively low rotation viscosity simultaneously, for allotment liquid crystal compound for, this performance is extremely important.

Description

Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation thereof Method and application
Technical field
The invention belongs to liquid-crystal compounds and application, relate to a kind of containing cyclopenta and difluoromethylenedioconnecting linker Liquid-crystal compounds of group and preparation method and application.
Background technology
At present, it is increasingly wider that the range of application of liquid-crystal compounds is expanded, and it can be applicable to polytype display, electricity In optical device, sensor etc..Liquid-crystal compounds for above-mentioned display field of a great variety, wherein nematic liquid crystal application is For extensively.Nematic liquid crystal have been applied in passive TN, STN matrix display and there is tft active matrix system in.
For thin-film transistor technologies (TFT-LCD) application, although market is the hugest in recent years, technology is also Gradually ripe, but the requirement of Display Technique is also constantly being improved by people, is especially realizing quickly response, is reducing and drive electricity Press to reduce the aspects such as power consumption.Liquid crystal material is as one of important photoelectron material of liquid crystal display, to improving liquid crystal display The effect that the performance of device is important.
As liquid crystal material, need to there is good chemically and thermally stability and electric field and electromagnetic radiation are stablized Property.And as thin-film transistor technologies (TFT-LCD) liquid crystal material, do not need only have as outside upward stability, also should have Wider nematic temperature range, suitable birefringence anisotropy, the highest resistivity, good uviolresistance The performances such as energy, high electric charge conservation rate and low-steam pressure.
For dynamic menu display application, such as LCD TV, show to realize high-quality, eliminate display picture ghost with Hangover, it is desirable to liquid crystal has response speed quickly, therefore it is required that liquid crystal has relatively low rotary viscosity γ1；It addition, in order to drop Low equipment energy consumption, it is desirable to the driving voltage of liquid crystal is the lowest, so improving the dielectric anisotropy △ ε of liquid crystal to mixed liquid crystal Significant.
Numerous studies show, liquid crystal molecule introduces a difluoromethylenedioconnecting linking group (-CF2O-), after, liquid crystal can be made Rotary viscosity γ1Decrease.Additionally, due to difluoromethylenedioconnecting bridge (-CF2The contribution of dipole moment O-), end group fluorine atom Dipole moment be also improved to some extent, so that the dielectric anisotropy △ ε of liquid crystal molecule increased.Merck KGaA and What Chisso Corporation of Japan had been disclosed for that some have a different substituents has difluoromethylenedioconnecting linking group (-CF2O-) Liquid-crystal compounds (CN1717468A, CN101143808A, CN101157862A etc.).But the introducing of-CF2O-group can make liquid crystal Clearing point be greatly lowered.Need when allocating liquid crystal compound to add the bigger high clearing point compound of viscosity balance- The clearing point that CF2O-group is caused declines, thus constrains the space that liquid crystal compound response speed promotes.
Summary of the invention
It is an object of the invention to provide a kind of liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and Its preparation method and application.
The liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group that the present invention provides, its general structure is such as Shown in Formulas I,
Formulas I
In described Formulas I, at least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene of A, B At least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene；M is 0 or 1 or 2, and n is 0 or 1, R1Selected from C1-C20's Aliphatic hydrocarbon, R2、R3Be selected from H and F any one, Y be selected from H, F, Cl, CF3、CHF2、OCF3And OCHF2In any one Kind.
Concrete, compound shown in described Formulas I is chosen in particular from any one in Formulas I 1 to Formulas I 50:
In above-mentioned Formulas I 1-I50, R1Definition and Formulas I in R1Definition identical；
What the present invention provided prepares the method for compound shown in described Formulas I, including following reaction scheme:
Above-mentioned reaction scheme is to prepare the synthesis step of compound, wherein R shown in described Formulas I1、R2、R3, A, B, Y, m and n Definition identical with the definition of Formulas I, including following reactions steps:
1) malic acid is reacted with concentrated sulfuric acid mixing, react complete and obtain
2) by described step 1) gainedHydrogenation reaction is carried out with hydrogen under the effect of Raney's nickel catalyst, React complete obtaining
3) by described step 2) gainedWith 1,3-dimercaptopropane reacts under TFMS is catalyzed, React complete obtaining
4) by described step 3) gainedWith phenolMixing is reacted, reaction Complete react with hydrogen fluoride pyridine solution again, obtain after completion of the reaction
5) by described step 4) gainedWith RMgBr(Z=MgX, X= Cl, Br, I) or(Z=Li) react, react complete and obtain
6) by described step 5) gainedWith triethyl silicane and borontrifluoride Boron reacts, and reacts complete and obtains compound shown in Formulas I
In above-mentioned reactions steps, described R1、R2、R3, A, B, Y, m all identical with aforementioned definitions with the definition of n.
Described reactions steps 1) in, the charged material weight of described malic acid and the concentrated sulfuric acid is than for 1:1-2, specially 1:1；Temperature For 25-110 DEG C, specially 100 DEG C, the time is 1-5 hour, specially 2 hours；
Described reactions steps 2) in, described step 1) gainedCharged material weight with described Raney's nickel catalyst Ratio is 100:5-35, specially 100:20；In described hydrogenation reaction step, temperature is 0-100 DEG C, specially 30 DEG C, and the time is 1-10 hour, specially 6 hours；
Described reactions steps 3) in, described step 2) gainedWith 1,3-dimercaptopropane, TFMS The mole dosage that feeds intake is than for 1:1-2:1-2, specially 1:1.1:1.2, and temperature is 100-120 DEG C, specially 110 DEG C, and the time is 1-10 hour, specially 5 hours；
Described reactions steps 4) in, described step 3) gainedWithThree second Amine, pyridine hydrogen fluoride, bromine the mole dosage that feeds intake than for 1:1-2:1-2:1-5:1-5, specially 1:1.1:1.2:4:4；Described Carrying out in the step reacted with phenol, temperature is-100-30, is specially-80 DEG C, and the time is 1-5 hour, specially 1 hour, described With the reactions steps of pyridine hydrogen fluoride and bromine, temperature is-100-30 DEG C, is specially-80 DEG C, and the time is 0.5-3 hour, specifically It it is 2 hours；
Described reactions steps 5) in, described step 4) gainedWith RMgBr(Z=MgX, X=Cl, Br, I) or(Z=Li) the mole dosage that feeds intake than for 1:1-2, specially 1: 1.2；Temperature is-80-0 DEG C, is specially-10 DEG C, and the time is 1-10 hour, specially 2 hours；
Described reactions steps 6) in, described step 5) gainedWith triethyl group Silane, boron trifluoride the mole dosage that feeds intake than for 1:1-3:1-3, specially 1:2.1:2.1；In described reactions steps, temperature For-50-30 DEG C, being specially-30 DEG C, the time is 0.5-4 hour, specially 2 hours；
Above-mentioned reaction scheme reaction in steps carry out the most in a solvent；Described solvent is selected from oxolane, N, N- At least one in dimethylformamide, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, dichloromethane and toluene.
Compound shown in the Formulas I that the invention described above provides is preparing liquid crystal compound, liquid crystal display device material or electric light Learn the liquid crystal compound of compound, liquid crystal display device material or electric light described in the application in display device material and contained I Learn display device material, fall within protection scope of the present invention.
Liquid-crystal compounds is typically all deployed into what mixture used, generally mix with thing be desirable that have higher limpid Point and relatively low rotary viscosity, and the clearing point of mixture and rotary viscosity are the clearing points consisting of composition (monomer liquid crystal) Determine with rotary viscosity and content thereof.Containing difluoromethylenedioconnecting linking group (-CF2O-) although liquid-crystal compounds have relatively Low rotary viscosity, but its clearing point relatively contains other linking groups such as (-CH2O-,-C ≡ C-,-COO-,-CH2CH2-) liquid The clearing point of crystallization compound is low, and this is disadvantageous for allocating the mixture of higher clearing point, the inventors discovered that and will contain There is difluoromethylenedioconnecting linking group (-CF2The aromatic radical of liquid-crystal compounds O-) changes THP trtrahydropyranyl into, namely the present invention carries Compound shown in the Formulas I of confession, its rotary viscosity is lower compared with aromatic radical, and has the response speed being exceedingly fast, its synthetic method Also technique is simple, production cost is low, and liquid crystal compound allotment to relatively low rotary viscosity has very important reality Meaning.
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.Institute Method of stating is conventional method if no special instructions.Described raw material the most all can obtain from open commercial sources. In example below, GC represents that gas chromatographic purity, MP represent that fusing point, CP represent that clearing point, MS represent that mass spectrum, Δ ε represent dielectric Anisotropy, Δ n represents optical anisotropy.The method measuring GC, MP, CP, MS, Δ ε and Δ n is conventional method.
Compound I2(R shown in embodiment 1, Formulas I1=C3H7)
Step 1
Adding 500g (3.73mol) malic acid (I-0), the 500g concentrated sulfuric acid in 2L there-necked flask, stirring makes solid dissolve, slowly Dropping 300ml (20%) is fuming the concentrated sulfuric acid, within one hour, adds, and after adding, is warmed up to 100 DEG C of stirring reactions 2 hours, is cooled to room Temperature, pours in the trash ice of 2Kg, stirs suction filtration, washing.
The solids with methanol recrystallization obtained, obtains brown crystals (I-1) 287g, yield: 55%
Step 2
Addition 100g brown crystals (I-1) in 2L single port bottle, 200ml toluene, 100ml methyl alcohol, 20g Raney's nickel catalyst, Under normal temperature and pressure concussion hydrogenation 6 hours, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, under filtrate decompression steam neat solvent, Obtain 99.5g gray solid (I-2), yield: 96.8%
Step 3
2L there-necked flask adds 144g (1mol) (I-2), 118.8g (1.1mol) 1,3-dimercaptopropane, 180g (1.2mol) TFMS, 1500ml toluene, it is heated to reflux a point water, after 5 hours, after point water purification, cools to 90 DEG C, at 70-90 Add methyl tertiary butyl ether(MTBE) 100ml between DEG C in 45 minutes, continue cooling, separate out crystal, filter under nitrogen protection, obtain Crystal methyl tertiary butyl ether(MTBE) (25ml × 4) washs, and vacuum drying obtains orange crystal I-7, yield 100% step 4
5L there-necked flask adds 163g (1.1mol) 3,4,5-trifluoromethyl phenol, 131.5g (1.3mol) triethylamine, 1500ml Dichloromethane, is placed in cryostat, is cooled to-80 DEG C, is added dropwise to I-3 and 1000ml dichloromethane solution prepared by step, and 3 is little Time add, after 1 hour, still-80 DEG C drip 515ml hydrogen fluoride pyridine (70%, 4mol) solution, add half an hour, still-80 DEG C dropping 640g (4mol) bromine and the solution of 500ml dichloromethane, adds rear insulated and stirred and reacts 2 hours, remove cryostat, from So being raised to room temperature, add in sodium hydrate aqueous solution (regulation pH value to 5～8) and the 1000g ice of 32%, after separatory, aqueous phase is used 200ml dichloromethane extracts, and merges organic phase 100g diatomite and filters, washing, the lower solvent evaporated of decompression.The crude product obtained After column chromatography, petroleum ether recrystallization, obtains 183.5g light yellow solid (I-5), yield: 62%
Step 5
Addition 45g (0.16mol) 4-(4-bromo-trans cyclohexyl) bromobenzene in 1L there-necked flask, 450ml oxolane, Under nitrogen atmosphere, being placed in cryostat, be cooled to-80 DEG C, dropping 70.5ml (2.5M, 0.176mol) n-butyl lithium hexane is molten Liquid, adds, after 1 hour, moves to constant pressure funnel for 1 hour；
Adding 39.5g (0.13mol) (I-5) in 1L there-necked flask, 200ml tetrahydrofuran solution, stirring and dissolving is limpid, at nitrogen Under gas atmosphere, it is placed in cryostat, is cooled to-10 DEG C, be added dropwise to 4-(4-bromo-trans cyclohexyl) the benzene lithium four of above-mentioned preparation Hydrogen tetrahydrofuran solution, adds, after 1 hour, removes cryostat, for 2 hours, is naturally raised to room temperature, adds 100ml saturated ammonium chloride water-soluble Liquid, separatory, aqueous phase 200ml dichloromethane extracts secondary, merges organic layer, steam neat solvent, obtain yellow liquid, stone under decompression Oil ether heating for dissolving, crosses silicagel column, and petroleum ether is cleaned, and steams neat solvent, obtain 56.8g white solid (I-6), yield under decompression: 84.6%
Step 6
1L there-necked flask adds 45g (0.09mol) (I-6), 450ml dichloromethane, in a nitrogen atmosphere, is placed in cryostat, In, it is cooled to-30 DEG C, drips 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, be naturally raised to room temperature, slowly Being added dropwise to 200ml saturated sodium bicarbonate aqueous solution, separatory, aqueous phase 100ml dichloromethane extracts once, merges organic layer, subtracts Neat solvent is steamed in pressure, obtains colourless liquid, petroleum ether heating for dissolving, crosses silicagel column, and petroleum ether is cleaned, and steams neat solvent under decompression, Again with ethyl alcohol recrystallization, obtain 29g white solid (I2, R1=C3H7), yield: 67%
Gc:99.92%
MP:49 DEG C
CP:22℃
Δ n [589nm, 20 DEG C]: 0.142
Δε[KHz,20℃]:20.1
Compound (I2, R shown in gained Formulas I are prepared by this embodiment1=C3H7) carry out liquid crystal property test, concrete steps bag Include: compound (I2, R shown in gained Formulas I are prepared by this embodiment1=C3H7) to be dissolved in clearing point CP with the ratio of 10% be 80 DEG C In parent, the clearing point CP, acquired results CP of test gained liquid crystal compound are 82.4 DEG C；
And with known compound that clearing point CP is 0 DEG CReplace aforesaid compound (I2, R1=C3H7), as above test, as comparison, the liquid crystal compound that this known compound of gained is obtained by mixing with parent Clearing point CP be 78.8 DEG C.
In above-mentioned test, in parent used, structural formula and the parts by weight thereof of each component composition are as follows:
From the foregoing, it will be observed that utilize this embodiment to prepare the allotment parent liquid-crystal compounds of compound shown in gained Formulas I, with existing The liquid-crystal compounds of similar structures used by field is compared, and is remarkably improved the clearing point CP of gained liquid crystal compound, and at liquid crystal Display field, it is desirable to the clearing point of liquid crystal display device material used or electro-optical display part material is the highest, it is seen that this Shown in the Formulas I that invention provides, compound is preparing liquid crystal display device material or electro-optical display part Material Field has important Using value.
Compound I45(R shown in embodiment 2, formula I1=C3H7)
Step 1
5L there-necked flask adds 286g (1.1mol) 2,3', 4', 5', 6-five fluoro-[1,1'-biphenyl]-4-phenol, 131.5g (1.3mol) triethylamine, 1500ml dichloromethane, it is placed in cryostat, is cooled to-80 DEG C, be added dropwise to embodiment 1 step 3 and prepare I-3 and 1000ml dichloromethane solution, within 3 hours, add, after 1 hour, still-80 DEG C drip 515ml hydrogen fluoride pyridine (70%, 4mol) solution, adds half an hour, still at-80 DEG C of dropping 640g (4mol) bromines and the solution of 500ml dichloromethane, protects after adding Temperature stirring reaction 2 hours, removes cryostat, naturally is raised to room temperature, add 32% sodium hydrate aqueous solution (regulate pH value to 5～ 8) and in 1000g ice, after separatory, aqueous phase 200ml dichloromethane extracts, and merges organic phase 100g diatomite and filters, washing, The lower solvent evaporated of decompression.After the crude product column chromatography obtained, petroleum ether recrystallization, ethyl alcohol recrystallization twice, obtain 269g light yellow Solid (I-5), yield: 66%
Step 5
Adding 5.8g (0.24mol) magnesium chips in 500ml there-necked flask, 100ml oxolane, and an iodine, at nitrogen atmosphere Under, it is heated to reflux to the color of iodine disappearing, is slowly added dropwise the molten of 45g (0.16mol) 4-propyl group bromobenzene and 150ml oxolane Liquid, adds half an hour, and back flow reaction, after 1 hour, moves to constant pressure funnel；
Adding 53g (0.13mol) (I-5) in 1L there-necked flask, 200ml tetrahydrofuran solution, stirring and dissolving is limpid, at nitrogen Under atmosphere, it is placed in cryostat, is cooled to-10 DEG C, be added dropwise to the 4-propylbenzene magnesium bromide tetrahydrofuran solution of above-mentioned preparation, 1 Hour add, after 1 hour, remove cryostat, be naturally raised to room temperature, add the 2N diluted hydrochloric acid aqueous solution of 100ml, separatory, aqueous phase Extracting secondary with 200ml dichloromethane, merge organic layer, steam neat solvent, obtain yellow liquid under decompression, petroleum ether adds thermosol Solving, cross silicagel column, petroleum ether is cleaned, and steams neat solvent, obtain 50g white solid (I-6), yield: 72.8% under decompression
Step 6
1L there-necked flask adds 47.5g (0.09mol) (I-6), 470ml dichloromethane, in a nitrogen atmosphere, is placed in low temperature In groove, it is cooled to-30 DEG C, drips 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, be naturally raised to room temperature, Being slowly added dropwise into 200ml saturated sodium bicarbonate aqueous solution, separatory, aqueous phase 100ml dichloromethane extracts once, merges organic Layer, steams neat solvent under decompression, obtains colourless liquid, petroleum ether heating for dissolving, crosses silicagel column, and petroleum ether is cleaned, and steams clean under decompression Solvent, then with ethyl alcohol recrystallization, obtain 29.7g white solid (I45, R1=C3H7), yield: 64.5%
Gc:99.95%
MP:68 DEG C
CP:21 DEG C
Δ n [589nm, 20 DEG C]: 0.18
Δε[KHz,20℃]:17
Compound (I45, R shown in gained Formulas I are prepared by this embodiment1=C3H7) carry out liquid crystal property test, concrete steps Including: compound (I45, R shown in gained Formulas I are prepared by this embodiment1=C3H7) to be dissolved in clearing point CP with the ratio of 10% be 80 DEG C Parent in, test gained liquid crystal compound clearing point CP, acquired results CP be 86 DEG C；
And with known compound that clearing point CP is 0 DEG CReplace aforementionedization Compound (I45, R1=C3H7), as above test, as comparison, the liquid crystal that this known compound of gained and parent are obtained by mixing mixes The clearing point CP of compound is 78.8 DEG C.
In above-mentioned test, in parent used, structural formula and the parts by weight thereof of each component composition are as follows:
From the foregoing, it will be observed that utilize this embodiment to prepare the allotment parent liquid-crystal compounds of compound shown in gained Formulas I, with existing The liquid-crystal compounds of similar structures used by field is compared, and is remarkably improved the clearing point CP of gained liquid crystal compound, and at liquid crystal Display field, it is desirable to the clearing point of liquid crystal display device material used or electro-optical display part material is the highest, it is seen that this Shown in the Formulas I that invention provides, compound is preparing liquid crystal display device material or electro-optical display part Material Field has important Using value.
Compound I29(R shown in embodiment 3, formula I1=C5H11)
Step 1
Addition 38.7g (0.16mol) 3-fluoro-4'-amyl group-1 in 500ml there-necked flask, 1'-biphenyl, 250ml oxolane, In a nitrogen atmosphere, being placed in cryostat, be cooled to-80 DEG C, dropping 70.5ml (2.5M, 0.176mol) n-butyl lithium hexane is molten Liquid, adds, after 1 hour, moves to constant pressure funnel for 1 hour；
Adding (I-5) of the preparation of 39.5g (0.13mol) embodiment 2 step 1 in 1L there-necked flask, 200ml oxolane is molten Liquid, stirring and dissolving is limpid, in a nitrogen atmosphere, is placed in cryostat, is cooled to-10 DEG C, is added dropwise to the fluoro-4-of 2-of above-mentioned preparation (4 '-amyl-phenyl) benzene lithium tetrahydrofuran solution, adds, after 1 hour, removes cryostat, be naturally raised to room temperature for 2 hours, adds 100ml saturated aqueous ammonium chloride, separatory, aqueous phase 200ml dichloromethane extracts secondary, merges organic layer, and the lower steaming of decompression is clean Solvent, obtains yellow liquid, petroleum ether heating for dissolving, crosses silicagel column, and petroleum ether is cleaned, and steams neat solvent, obtain 73g white under decompression Look solid (I-6), yield: 86.5%
Step 2
1L there-necked flask adds 32.5g (0.05mol) (I-6), 320ml dichloromethane, in a nitrogen atmosphere, is placed in low temperature In groove, it is cooled to-30 DEG C, drips 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, be naturally raised to room temperature, Being slowly added dropwise into 150ml saturated sodium bicarbonate aqueous solution, separatory, aqueous phase 100ml dichloromethane extracts once, merges organic Layer, steams neat solvent under decompression, obtains colourless liquid, petroleum ether heating for dissolving, crosses silicagel column, and petroleum ether is cleaned, and steams clean under decompression Solvent, then with ethyl alcohol recrystallization, obtain 18.6g white solid (I29, R1=C5H11), yield: 58.6%
Gc:99.95%
MP:71 DEG C
CP:39 DEG C
Δ n [589nm, 20 DEG C]: 0.13
Δε[KHz,20℃]:17.
From the foregoing, it will be observed that compound shown in the Formulas I that provides of the present invention is preparing liquid crystal display device material or electrooptics shows Device material field has important using value.
This embodiment prepares liquid crystal property test and the previous embodiment 1 gained LCD compound of compound shown in gained Formulas I Thing (I45, R1=C3H7), test result without substantive difference, here is omitted.

Claims (8)

1. compound shown in Formulas I,
In described Formulas I, at least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene of A, B is selected from Fluoro Isosorbide-5-Nitrae-phenylene；M is 2, and n is 0 or 1, R1Selected from the aliphatic hydrocarbon of C1-C20, R2、R3It is F, Y selected from F.
2. compound shown in Formulas I 5, I27, I38, I45-I50
Wherein, R1Aliphatic hydrocarbon selected from C1-C20.
Compound the most according to claim 1, it is characterised in that: during shown in described Formulas I, compound is following compound Any one:
In above-claimed cpd, R1Definition and Formulas I in R1Definition identical.
4. prepare the method for arbitrary described compound in claims 1 to 3 for one kind, it is characterised in that the method comprises following synthesis Step 1 is to 6:
1) malic acid is reacted with concentrated sulfuric acid mixing, react complete and obtain
2) by described step 1) gainedHydrogenation reaction is carried out with hydrogen, reaction under the effect of Raney's nickel catalyst Complete obtain
3) by described step 2) gainedWith 1,3-dimercaptopropane reacts under TFMS is catalyzed, reaction Complete obtain
4) by described step 3) gainedWith phenolMixing is reacted, and reacts complete React with hydrogen fluoride pyridine solution again, obtain after completion of the reaction
5) by described step 4) gainedWith RMgBr(Z=MgX, X=Cl, Br, I) or(Z=Li) react, react complete and obtain
6) by described step 5) gainedEnter with triethyl silicane and boron trifluoride Row reaction, reacts complete and obtains compound shown in Formulas I
In above-mentioned reactions steps, described R1、R2、R3, A, B, Y, m all identical with aforementioned definitions with the definition of n.
Method the most according to claim 4, it is characterised in that: described reactions steps 1) in, described malic acid and the concentrated sulfuric acid Charged material weight than for 1:1-2；Temperature is 25-110 DEG C, and the time is 1-5 hour；
Described reactions steps 2) in, described step 1) gainedWith the charged material weight ratio of described Raney's nickel catalyst it is 100:5-35；In described hydrogenation reaction step, temperature is 0-100 DEG C, and the time is 1-10 hour；
Described reactions steps 3) in, described step 2) gainedWith 1,3-dimercaptopropane, throwing to TFMS Material mole dosage ratio is for 1:1-2:1-2, and temperature is 100-120 DEG C, and the time is 1-10 hour；
Described reactions steps 4) in, add triethylamine and bromine, described step 3) gainedWithTriethylamine, pyridine hydrogen fluoride, bromine the mole dosage that feeds intake than for 1:1-2:1-2:1-5:1-5；Described Carrying out in the step reacted with phenol, temperature is-100-30 DEG C, and the time is 1-5 hour, described and pyridine hydrogen fluoride and the reaction of bromine In step, temperature is-100-30 DEG C, and the time is 0.5-3 hour；
Described reactions steps 5) in, described step 4) gainedWith RMgBr(Z=MgX, X=Cl, Br, I) or(Z=Li) the mole dosage that feeds intake than for 1:1-2,；Temperature For-80-0 DEG C, the time is 1-10 hour；
Described reactions steps 6) in, described step 5) gainedWith triethyl group silicon Alkane, boron trifluoride the mole dosage that feeds intake than for 1:1-3:1-3；In described reactions steps, temperature is-50-30 DEG C, and the time is 0.5-4 hour；
Above-mentioned reaction scheme reaction in steps carry out the most in a solvent；Described solvent is selected from oxolane, N, N-diformazan At least one in base formamide, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, dichloromethane and toluene.
6. method as claimed in claim 5, it is characterised in that: described reactions steps 1) in, described malic acid and the concentrated sulfuric acid Charged material weight is than for 1:1；Temperature is 100 DEG C, and the time is 2 hours；
Described reactions steps 2) in, described step 1) gainedWith the charged material weight ratio of described Raney's nickel catalyst it is For 100:20；In described hydrogenation reaction step, temperature is 30 DEG C, and the time is 6 hours；
Described reactions steps 3) in, described step 2) gainedWith 1,3-dimercaptopropane, the feeding intake of TFMS Mole dosage is than for 1:1.1:1.2, and temperature is 110 DEG C, and the time is 5 hours；
Described reactions steps 4) in, described step 3) gainedWithTriethylamine, pyrrole Pyridine hydrogen fluoride, bromine the mole dosage that feeds intake than for 1:1.1:1.2:4:4；Described and phenol carries out in the step reacted, and temperature is-80 DEG C, the time is 1 hour, and described with the reactions steps of pyridine hydrogen fluoride and bromine, temperature is-80 DEG C, and the time is 2 hours；
Described reactions steps 5) in, described step 4) gainedWith RMgBr(Z=MgX, X=Cl, Br, I) or(Z=Li) the mole dosage that feeds intake is than for 1:1.2；Temperature For-10 DEG C, the time is 2 hours；
Described reactions steps 6) in, described step 5) gainedWith triethyl group silicon Alkane, boron trifluoride the mole dosage that feeds intake than for 1:2.1:2.1；In described reactions steps, temperature is-30 DEG C, and the time is 2 little Time.
7. claim 1-3 arbitrary described compound application in preparing electro-optical display part material.
8. comprise the electro-optical display part material of the arbitrary described compound of claim 1-3.
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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
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Citations (9)

* Cited by examiner, † Cited by third party
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
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

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