CN106146251A - Compound and preparation method thereof - Google Patents
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- CN106146251A CN106146251A CN201510142844.4A CN201510142844A CN106146251A CN 106146251 A CN106146251 A CN 106146251A CN 201510142844 A CN201510142844 A CN 201510142844A CN 106146251 A CN106146251 A CN 106146251A
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Abstract
The invention discloses a kind of compound and preparation method thereof.This compound is shown in formula I:The preparation method of the present invention includes: coupling step: compound 1-a and compound 1-b coupling are converted into compound 2-a；Reduction step: it is compound 3-a that the ester group of compound 2-a is reduced to convert aldehyde groups；Alkenyl step: compound 3-a reacts with compound 3-b and is converted into compound 4-a；Wherein, 1-a, 1-b, 2-a, 3-a, 3-b and 4-a are as follows:According to the compound of the present invention, there is low rotary viscosity γ1With high dielectric anisotropy △ ε.The preparation method of the present invention, step is simple, mild condition, controllability are strong, yield is high, post-process simple and applicable industrialized production.
Description
Technical field
The present invention relates to liquid-crystal compounds field, particularly relate to a kind of compound and preparation method thereof.
Background technology
In recent years, the market of field of liquid crystal display is very huge, and technology also reaches its maturity, but the requirement to display quality also improves increasingly simultaneously, especially requires to realize quick response and reduces driving voltage to reduce power consumption.Liquid crystal material is one of important photoelectron material of liquid crystal display, play an important role to improving liquid crystal display performance, therefore liquid crystal material has obtained huge development and has occurred in that a large amount of liquid-crystal compounds, develop into cyclohexyl benzene class, phenylacetylene class, ethyl bridged bond class, end thiazolinyl liquid crystal and various fluorine-containing aromatic ring class liquid-crystal compounds etc. from biphenyl nitrile, esters, oxygen heterocycle class, pyrimidine ring class liquid-crystal compounds, constantly meet the display performance requirements such as TN, STN and TFT-LCD.
Liquid crystal material for display need to have proper temperature scope, wider liquid crystal state temperature, higher stability, be suitable for viscosity and have very fast response speed to electric field, additionally should also have the performances such as wider nematic phase, relatively low birefringence, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate and low-steam pressure.At present, there is no any liquid crystal monomer without applying in a liquid crystal display with the combination of other compounds；If two or more liquid crystal monomer mixes, then change the various types of properties of liquid crystal continuously.
The compound monomer of available liquid crystal material generally there are the defect with high rotary viscosity γ 1 and/or relatively low anisotropy △ ε, therefore can raise composition viscosity as the component in liquid-crystal composition and/or reduce composition response speed, thus affecting the display quality of liquid crystal material.The problems such as other available liquid crystal compou nd synthesis method there is also cumbersome, be difficult to that industrialized production, yield be low and production cost is high.
Content of the invention
The present invention provides a kind of compound to have high rotary viscosity γ in order to solve to there is liquid-crystal compounds in prior art1And/or the defect problem of relatively low anisotropy △ ε；There is provided the preparation method of a kind of compound in order to solving present in prior art that synthesis technique is numerous and diverse, be not suitable for industrialized production, the problem such as yield is low and production cost is high.
According to an aspect of the present invention, provide a kind of compound, this compound shown in formula I:
Wherein,
L1、L2And L3Be each independently selected from: singly-bound ,-CH=CH-,-COO-,-OOC-and
-CF=CF-；
R1And R2It is each independently selected from: hydrogen atom, there is the alkyl of 1-15 carbon atom and there is the alkoxyl of 1-15 carbon atom；
A1 、A2 、A3And A4The one being each independently selected from following radicals:
A, b and c are each independently selected from: the 0th, the 1st, 2 and 3, and a+b+c≤5.
Alternatively, the compound according to the present invention, one of described alkyl and/or alkoxyl and/or multiple-CH2-substituted by-CH=CH-,-C ≡ C-,-COO-,-OOC-, cyclobutane or-O-independently of one another.
Alternatively, the compound according to the present invention, one or more of described alkyl or alkoxyl hydrogen is independently of one another by Cl, F, CN, OCN, OCF3、CF3、CHF2、OCHF2, SCN, NCS or SF5Replace.
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention, this compound is:
Alternatively, the compound according to the present invention,
R1It is selected from: hydrogen, carbon number are the straight chained alkyl of 1-10 or the unbranched alkoxy that carbon number is 1-10；
R2It is selected from: hydrogen, Cl, F, CN, OCF3、CF3,、SCN、CHF2、OCHF2, carbon number be the straight chained alkyl of 1-10 or the unbranched alkoxy that carbon number is 1-10；
-(F) represents there is fluorine atom substituent on phenyl ring or is hydrogen.
According to a further aspect in the invention, providing the preparation method of a kind of compound, the method includes:
Coupling step: compound 1-a and compound 1-b coupling are converted into compound 2-a；
Reduction step: it is compound 3-a that the ester group of described compound 2-a is reduced to convert aldehyde groups；
Alkenyl step (S1300): described compound 3-a reacts with compound 3-b and is converted into compound 4-a；
Wherein, described 1-a, 1-b, 2-a, 3-a, 3-b and 4-a are as follows:
Alternatively, preparation in accordance with the present invention, described coupling step is:
Adding 1eq compound 1-a, 1～1.2eq compound 1-b and 1～3eq sodium acid carbonate in solvent, nitrogen protection adds catalytic amount tetrakis triphenylphosphine palladium, purifies to obtain compound 2-a after back flow reaction 2～4h.
Alternatively, preparation in accordance with the present invention, described reduction step is:
Adding 1eq compound 2-a in solvent, nitrogen protection drips DIBAL-H at-10 DEG C～0 DEG C, purifies to obtain compound 3-a after reacting 3～5 hours at 20 DEG C～25 DEG C.
Alternatively, preparation in accordance with the present invention, alkenyl step is:
Dissolving 1eq compound 3-a in a solvent, the compound 3-b of-5 DEG C～0 DEG C dropping 1～5eq, room temperature reaction purifies to obtain compound 4-a after 4～6 hours.
The present invention has the beneficial effect that:
According to the compound of the present invention, there is low rotary viscosity γ1With the characteristic of high dielectric anisotropy △ ε, the compound of the present invention is used for seasoning liquid crystal composite, low rotary viscosity γ can be obtained1With high dielectric anisotropy △ ε, make composition have appropriate viscosity and quick response speed, so that liquid crystal material obtains good display performance, liquid crystal material is used for liquid crystal indicator to realize quickly responding and reduce driving voltage to reduce power consumption.
According to the compounds process for production thereof of the present invention, synthetic route is simple, reaction condition is gentle, controllability is strong, post-processing step is simple, and yield is high and applicable industrialized production.
Brief description
Fig. 1 is the flow chart according to the compounds of this invention preparation method；
Fig. 2 is the GC collection of illustrative plates that embodiment 3 prepares compound.
Detailed description of the invention
Specific embodiment is only the description of the invention, and does not constitute the restriction to present invention, is further described the present invention below in conjunction with accompanying drawing and specific embodiment and describes.
According to an aspect of the present invention, provide a kind of compound, this compound shown in formula I:
Wherein, L1、L2And L3It is each independently selected from: singly-bound ,-CH=CH-,-COO-,-OOC-and-CF=CF-；R1And R2It is each independently selected from: hydrogen atom, there is the alkyl of 1-15 carbon atom and there is the alkoxyl of 1-15 carbon atom；A1 、A2 、A3And A4The one being each independently selected from following radicals:
A, b and c are each independently selected from: the 0th, the 1st, 2 and 3, and a+b+c≤5.
Compound according to the present invention, containing ptfe ring hexadiene structure, this structure has asymmetric carbon atom, induction can produce big spontaneous polarization value, improve the dielectric anisotropy △ ε of this compound, composition is made to have fast-response speed when it is as a kind of component of composition, it is easy to produce good phase sequence.The Stability Analysis of Structures of this compound, has wide liquid crystal state temperature range, has preferable low temperature intersolubility, when it is applied to optics as composition, makes optics realize relatively low threshold voltage.This compound other has low rotary viscosity γ1Liquid-crystal composition material and display performance can be improved, significant to the quick response realizing display.It is low that liquid-crystal composition containing this compounds can be applicable to prepare driving voltage, wide temperature range, the liquid crystal indicator of fast response time.Wherein a+b+c≤5, are the numbers in order to limit group, and group number is too many, and molecular weight increases so that it is be difficult to mixing, are difficult to form composition with other monomers, are unfavorable for application.
According to one embodiment of the present invention, one of alkyl and/or alkoxyl and/or multiple-CH2-substituted by-CH=CH-,-C ≡ C-,-COO-,-OOC-, cyclobutane or-O-independently of one another.
According to one embodiment of the present invention, one or more of alkyl or alkoxyl hydrogen is independently of one another by Cl, F, CN, OCN, OCF3、CF3、CHF2、OCHF2, SCN, NCS or SF5Replace.
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, this compound is:
According to one embodiment of the present invention, R1It is selected from: hydrogen, carbon number are the straight chained alkyl of 1-10 or the unbranched alkoxy that carbon number is 1-10；R2It is selected from: hydrogen, Cl, F, CN, OCF3、CF3,、SCN、CHF2、OCHF2, carbon number be the straight chained alkyl of 1-10 or the unbranched alkoxy that carbon number is 1-10；-(F) represents there is fluorine atom substituent on phenyl ring or is hydrogen.
According to the compound of the present invention, there is low rotary viscosity γ1With the characteristic of high dielectric anisotropy △ ε, the compound of the present invention is used for seasoning liquid crystal composite, low rotary viscosity γ can be obtained1With high dielectric anisotropy △ ε, composition is made to have appropriate viscosity and quick response speed, so that liquid crystal material obtains good display performance.
Preparation in accordance with the present invention, the method includes:
Coupling step S1100: compound 1-a is converted into compound 2-a with compound 1-b coupling；
Reduction step S1200: it is compound 3-a that the ester group of compound 2-a is reduced to convert aldehyde groups；
Alkenyl step S1300: compound 3-a reacts with compound 3-b and is converted into compound 4-a；
Wherein, 1-a, 1-b, 2-a, 3-a, 3-b and 4-a are as follows:
The synthetic route of method produced according to the present invention is shown below:
Preparation in accordance with the present invention; coupling step S1100 is: add 1eq compound 1-a, 1～1.2eq compound 1-b and 1～3eq sodium acid carbonate in solvent; nitrogen protection adds catalytic amount tetrakis triphenylphosphine palladium, purifies to obtain compound 2-a after back flow reaction 2～4h.
Preparation in accordance with the present invention, in this step, the preferred toluene of solvent, the mixed solvent of second alcohol and water, the preferred 1:1:1 of its volume ratio, add the amount of solvent to be generally the mixed solvent of the corresponding 10ml of 1g reactant 1-a；Tetrakis triphenylphosphine palladium addition is catalytic amount, in general, 0.1mol reactant 1-a adds the tetrakis triphenylphosphine palladium of 0.1-1g, after reaction completes, near room temperature can be extracted by toluene, and organic phase merging is washed to neutrality, after solvent evaporated, toluene is added to dissolve, cross silicagel column to decolour, elute with toluene, after collecting eluent and being evaporated, obtain solid 2-a.Yield can reach more than 90%, and purity can reach more than 98%.The reaction occurring in this step is suzuki reaction, and reaction condition is gentle, and controllability is strong, and post processing is simple and yield is high.
Preparation in accordance with the present invention, described reduction step S1200 is: add 1eq compound 2-a in solvent, and nitrogen protection drips DIBAL-H at-10 DEG C～0 DEG C, purifies to obtain compound 3-a after reacting 3～5 hours at 20 DEG C～25 DEG C.
The method according to the invention, in reduction step, the preferred oxolane of solvent, also other solvents such as dichloromethane can be selected, reaction uses saturated aqueous ammonium chloride cancellation after completing, and carries out separatory, extract aqueous phase ethyl acetate after layering, extraction finishes merging organic phase, is dried and is concentrated to give solid 3-a.Yield can reach more than 70%, and purity can reach more than 90%.The reaction condition of this step is gentle, controllability is strong and product is single, post-processes simple yield high.
Preparation in accordance with the present invention, alkenyl step S1300 is: dissolving 1eq compound 3-a in a solvent, the compound 3-b of-5 DEG C～0 DEG C dropping 1～5eq, room temperature reaction purifies to obtain compound 4-a after 4～6 hours.
Preparation in accordance with the present invention, this preferred oxolane of step solvent, it is also possible to select other solvents such as dichloromethane, reaction adds water after completing cancellation, and aqueous phase is extracted with ethyl acetate by layering separatory, merges organic phase, is dried and is concentrated to give crude product.Being dissolved in crude product in toluene solvant, crossing silicagel column decolouring, elute with toluene solvant, collect eluent and solvent is evaporated off, gains absolute ethyl alcohol is recrystallized to give end-product 4-a.Yield is more than 70%, and gas chromatographic detection purity is more than 99.5%.
According to the preparation method of the compounds of this invention, synthetic route is simple, reaction condition is gentle, controllability is strong, post-processing step is simple and yield is high, be suitable for industrialized production and reduce production cost.
In sum, the optional many factors of compound according to the present invention and preparation method thereof, can be combined into different embodiments according to claim.Embodiment is only used for that the present invention will be described, does not limit the invention.Below in conjunction with accompanying drawing, the present invention is described further.Due to the diversity according to the substituent in the compounds of this invention, the combined result of claim is also numerous, therefore selects the synthetic method of a kind of particular compound to illustrate as the preparation method to the present invention for the embodiment.
This chemical formula specifically synthesizing compound is:
The coupling step S1100 reaction equation preparing this compound is as follows:
The reduction step S1200 reaction equation preparing this compound is as follows:
The reaction equation preparing this compound alkenyl step S1300 is as follows:
Embodiment 1
nullPreparation method flow chart according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1eq reactant 1-b-1 is dissolved in a solvent，Add 1eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 2h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The volume ratio of second alcohol and water selects 1:3:3，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，The corresponding 10ml solvent of generally 1g reactant 1-a-1，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 90%，Gas chromatographic purity is 98.0%；
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to-10 DEG C; insulation dropping DIBAL-H under nitrogen protection, dropping is warming up to 20 DEG C after finishing, insulation reaction 3 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent, selects ethyl acetate to extract after cancellation, and merging organic phase, drying are concentrated to give white solid 3-a-1; yield is 70%, and chromatography of gases purity is 90%；
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of-5 DEG C of dropping 1eq, drip to finish and be warmed to room temperature, react 4～6 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a-1, yield is 70%, gas chromatographic purity is 99.5%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 1 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
Embodiment 2
nullThe flow chart of preparation method is shown according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1.2eq reactant 1-b-1 is dissolved in a solvent，Add 3eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 4h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The volume ratio of second alcohol and water selects 4:3:3，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，Generally 1 gram reactant 1-a-1 correspondence 10ml solvent，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 93%，Gas chromatographic purity is 98.2%；
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to 0 DEG C; insulation dropping DIBAL-H under nitrogen protection, dropping is warming up to 25 DEG C after finishing, insulation reaction 5 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent, selects ethyl acetate to extract after cancellation, and merging organic phase, drying are concentrated to give white solid 3-a-1; yield is 72%, and chromatography of gases purity is 93%；
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of 0 DEG C of dropping 5eq, drip to finish and be warmed to room temperature, react 6 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a-1, yield is 73%, gas chromatographic purity is 99.7%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 2 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
Embodiment 3
nullPreparation method flow chart according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1.1eq reactant 1-b-1 is dissolved in a solvent，Add 1.5eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 3h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The volume ratio of second alcohol and water selects 4:3:3，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，Generally 1 gram reactant 1-a-1 correspondence 10ml solvent，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 90%，Gas chromatographic purity is 98.2%；
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to-5 DEG C; insulation dropping DIBAL-H under nitrogen protection, dropping is warming up to 23 DEG C after finishing, insulation reaction 4 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent, selects ethyl acetate to extract after cancellation, and merging organic phase, drying are concentrated to give white solid 3-a-1; yield is 74%, and chromatography of gases purity is 94%；
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of 0 DEG C of dropping 3eq, drip to finish and be warmed to room temperature, react 5 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a, yield is 80%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 3 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
The 4-a-1 preparing embodiment 3 has carried out gas chromatographic detection, as in figure 2 it is shown, it is 99.91% that detection obtains its purity,
Embodiment 4
nullThe flow chart of the preparation method according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1.15eq reactant 1-b-1 is dissolved in a solvent，Add 2eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 2.5h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The preferred 4:3:3 of volume ratio of second alcohol and water，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，Generally 1 gram reactant 1-a-1 correspondence 10ml solvent，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 92%，Gas chromatographic purity is 98.5%；
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to-8 DEG C; insulation dropping DIBAL-H under nitrogen protection, dropping is warming up to 23 DEG C after finishing, insulation reaction 3.5 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent, selects ethyl acetate to extract after cancellation, and merging organic phase, drying are concentrated to give white solid 3-a-1; yield is 76%, and chromatography of gases purity is 91%；
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of 0 DEG C of dropping 4eq, drip to finish and be warmed to room temperature, react 5.5 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a, yield is 78%, gas chromatographic purity is 99.6%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 4 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
Embodiment 5
nullThe flow chart of the preparation method according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1.18eq reactant 1-b-1 is dissolved in a solvent，Add 2.8eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 3.5h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The volume ratio of second alcohol and water selects 1:1:1，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，Generally 1 gram reactant 1-a-1 correspondence 10ml solvent，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 96%，Gas chromatographic purity is 98.6%.
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to-6 DEG C; insulation dropping DIBAL-H under nitrogen protection; dropping is warming up to 22 DEG C DEG C after finishing; insulation reaction 4.5 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent; ethyl acetate is being selected to extract after going out; merge organic phase, drying is concentrated to give white solid 3-a-1; yield is 76%, and chromatography of gases purity is 94%.
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of-4 DEG C of dropping 2eq, drip to finish and be warmed to room temperature, react 4.5 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a-1, yield is 77%, gas chromatographic purity is 99.7%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 5 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
Embodiment 6
nullThe flow chart of the preparation method according to Fig. 1，Initially enter coupling step S1100: 1eq reactant 1-a-1 and 1.05eq reactant 1-b-1 is dissolved in a solvent，Add 2.5eq sodium acid carbonate，The lower tetrakis triphenylphosphine palladium adding catalytic amount of nitrogen protection，It is heated to return stirring reaction 2.5h，It is down to extraction after room temperature、Cross silicagel column and obtain compound 2-a-1，Wherein toluene selected by solvent、The mixed solvent of second alcohol and water，Toluene、The preferred 4:3:3 of volume ratio of second alcohol and water，Its cumulative volume is adjusted according to the amount of reactant 1-a-1，Generally 1 gram reactant 1-a-1 correspondence 10ml solvent，The preferred tetrakis triphenylphosphine palladium of catalyst，During extraction, preferred toluene is as extractant，Cross the preferred toluene of silicagel column to elute，The 2-a-1 obtaining is white solid，Yield is 92%，Gas chromatographic purity is 98.5%；
Enter reduction step S1200 afterwards: 1eq compound 2-a-1 is dissolved in a solvent; it is down to-7 DEG C; insulation dropping DIBAL-H under nitrogen protection; dropping is warming up to 23 DEG C DEG C after finishing; insulation reaction 3.5 hours; it is concentrated to give compound 3-a-1 with saturated aqueous ammonium chloride cancellation, extraction, drying; wherein anhydrous tetrahydro furan selected by solvent; ethyl acetate is selected to extract after cancellation; merge organic phase, drying is concentrated to give white solid 3-a-1; yield is 75%, and chromatography of gases purity is 91%；
Finally enter alkenyl step S1300: 1eq compound 3-a-1 is dissolved in a solvent, it is cooled to the reactant 3-b-1 of-2 DEG C of dropping 2eq, drip to finish and be warmed to room temperature, react 3 hours, add water cancellation, extraction, concentrated silicagel column, recrystallize to obtain end-product 4-a-1, wherein solvent is anhydrous tetrahydro furan, add water after cancellation, extract with ethyl acetate, merge organic phase, it is dried and concentrate, obtain crude product, concentrate is dissolved in toluene, cross silicagel column to decolour, elute with toluene, after collecting eluent and solvent being evaporated off, recrystallize with absolute ethyl alcohol, obtain white needle-like crystals 4-a-1, yield is 76%, gas chromatographic purity is 99.8%, so far step S1300 terminates, preparation method completes.
The 4-a-1 preparing embodiment 6 has done nucleus magnetic hydrogen spectrum, and nucleus magnetic hydrogen spectrum resolves as follows:1HNMR (300Hz, DMSO): (0.96, t, 3H)；(1.25-1.33, m, 4H)；(1.40-1.50, m, 5H)；(1.70-1.80, m, 4H)；(2.70-2.75, m, 1H)；(6.82, d, 1H)；(6.94, s, 2H)；(7.13, d, 2H)；(7.26, d, 1H)；(7.34, d, 2H).
The preparation method of 1-6 according to embodiments of the present invention, has all obtained above-claimed cpd, and the synthetic route changing this preparation method is simple, reaction condition is gentle, controllability is strong, post-processing step is simple, and yield is high, is suitable for industrialized production, reduces production cost.
Obviously, those skilled in the art the present invention can be carried out various change and modification without departing from the spirit and scope of the present invention.So, if these modifications of the present invention and modification belong to the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these changes and modification.
Claims (15)
1. a compound, it is characterised in that this compound shown in formula I:
Wherein,
L1、L2And L3Be each independently selected from: singly-bound ,-CH=CH-,-COO-,-OOC-and
-CF=CF-；
R1And R2It is each independently selected from: hydrogen atom, there is the alkyl of 1-15 carbon atom and there is 1-15
The alkoxyl of individual carbon atom；
A1、A2、A3And A4The one being each independently selected from following radicals:
A, b and c are each independently selected from: the 0th, the 1st, 2 and 3, and a+b+c≤5.
2. compound as claimed in claim 1, it is characterised in that in described alkyl and/or alkoxyl
One and/or multiple-CH2-independently of one another by-CH=CH-,-C ≡ C-,-COO-,-OOC-, cyclobutane
Or-O-substitutes.
3. compound as claimed in claim 1, it is characterised in that in described alkyl or alkoxyl
Individual or multiple hydrogen is independently of one another by Cl, F, CN, OCN, OCF3、CF3、CHF2、OCHF2、
SCN, NCS or SF5Replace.
4. compound as claimed in claim 1, it is characterised in that this compound is:
5. compound as claimed in claim 1, it is characterised in that this compound is:
6. compound as claimed in claim 1, it is characterised in that this compound is:
7. compound as claimed in claim 1, it is characterised in that this compound is:
8. compound as claimed in claim 1, it is characterised in that this compound is:
9. compound as claimed in claim 1, it is characterised in that this compound is:
10. compound as claimed in claim 1, it is characterised in that this compound is:
11. as described in claim 4-10 is arbitrary compound, it is characterised in that
R1It is selected from: hydrogen, carbon number are the straight chained alkyl of 1-10 or the straight chain alkane that carbon number is 1-10
Epoxide；
R2It is selected from: hydrogen, Cl, F, CN, OCF3、CF3,、SCN、CHF2、OCHF2, carbon atom
Number is the straight chained alkyl of 1-10 or the unbranched alkoxy that carbon number is 1-10；
-(F) represents there is fluorine atom substituent on phenyl ring or is hydrogen.
The preparation method of 12. 1 kinds of compounds as claimed in claim 10, it is characterised in that the method bag
Include:
Coupling step (S1100): compound 1-a and compound 1-b coupling are converted into compound 2-a；
Reduction step (S1200): it is compound 3-a that the ester group of described compound 2-a is reduced to convert aldehyde groups；
Alkenyl step (S1300): described compound 3-a reacts with compound 3-b and is converted into compound 4-a；
Wherein, described 1-a, 1-b, 2-a, 3-a, 3-b and 4-a are as follows:
13. preparation methods as claimed in claim 12, it is characterised in that described coupling step (S1100)
For:
1eq compound 1-a, 1～1.2eq compound 1-b and 1～3eq sodium acid carbonate are added in solvent, nitrogen
Gas shielded adds catalytic amount tetrakis triphenylphosphine palladium, purifies to obtain compound 2-a after back flow reaction 2～4h.
14. preparation methods as claimed in claim 12, it is characterised in that described reduction step (S1200)
For:
Adding 1eq compound 2-a in solvent, nitrogen protection drips DIBAL-H at-10 DEG C～0 DEG C,
20 DEG C～25 DEG C reaction 3～5 hours after purify to obtain compound 3-a.
15. preparation methods as claimed in claim 12, it is characterised in that alkenyl step (S1300)
For:
1eq compound 3-a is dissolved in a solvent, the compound 3-b of-5 DEG C～0 DEG C dropping 1～5eq, room temperature
Compound 4-a is purified to obtain after reacting 4～6 hours.
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| CN101302145A (en) * | 2006-12-11 | 2008-11-12 | 默克专利股份有限公司 | Stilbene derivatives, liquid crystal mixture and electrooptical display |
| CN102031120A (en) * | 2010-11-17 | 2011-04-27 | 上海天问化学有限公司 | Fluorine-containing liquid crystal of 4-(2,3,5,6-tetrafluo-R substituent phenethyl) benzoic acid-4'-fluo-4-biphenyl ester |
| CN102153454A (en) * | 2011-01-28 | 2011-08-17 | 上海天问化学有限公司 | Ultrahigh-fluorine-substituted liquid crystal compound with CF2O bridge bond, synthetic method and application |
| CN102329198A (en) * | 2010-04-17 | 2012-01-25 | 默克专利股份有限公司 | Liquid crystalline compounds and liquid crystalline media |
| CN103328458A (en) * | 2011-01-25 | 2013-09-25 | 默克专利股份有限公司 | Liquid-crystalline compounds and liquid-crystalline media |
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| CN101302145A (en) * | 2006-12-11 | 2008-11-12 | 默克专利股份有限公司 | Stilbene derivatives, liquid crystal mixture and electrooptical display |
| CN102329198A (en) * | 2010-04-17 | 2012-01-25 | 默克专利股份有限公司 | Liquid crystalline compounds and liquid crystalline media |
| CN102031120A (en) * | 2010-11-17 | 2011-04-27 | 上海天问化学有限公司 | Fluorine-containing liquid crystal of 4-(2,3,5,6-tetrafluo-R substituent phenethyl) benzoic acid-4'-fluo-4-biphenyl ester |
| CN103328458A (en) * | 2011-01-25 | 2013-09-25 | 默克专利股份有限公司 | Liquid-crystalline compounds and liquid-crystalline media |
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