CN106967443A - The preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds - Google Patents
The preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds Download PDFInfo
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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Abstract
The invention discloses a kind of preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds, it is used with anti-4（4 alkyl-cyclohexyls）Bromobenzene prepares anti-4 with metal organolithium reagent, borating agent to react（4 alkyl-cyclohexyls）Phenyl boric acid, then with to halogenated benzonitrile, using palladium complex as major catalyst, adding part and co-catalyst, forming good Suzuki coupling reaction systems, carry out Suzuki coupling reactions, prepare target compound alkyl cyclohexyl biphenyl nitrile { trans 4（4 alkyl-cyclohexyls）[1,1 biphenyl] 4 formonitrile HCNs）}.The raw material used is easy to get, and synthesis step simplifies, and the synthetic route of innovation reduces time cost, and efficiency is improved, and the cost of product declines, and quality-improving makes product competitiveness in the market significantly be lifted.
Description
Technical field
The present invention relates to a kind of alkyl cyclohexyl biphenyl nitrile { chemical name：Trans -4-（4- alkyl-cyclohexyls）- [1,1-
Biphenyl] -4- formonitrile HCNs liquid-crystal compounds novel preparation method, belong to liquid-crystal compounds preparing technical field.
Background technology
Liquid crystal material is to constitute liquid crystal display（LCD）One of several big critical materials, also, along with display pattern
Difference, required liquid crystal material is also different.In order to meet the individual features required for various liquid crystal display devices, usually to need to mix
Conjunction is balanced using the liquid-crystal compounds of 10 several different performances and optimizes its performance, to meet the property required by the display pattern
Energy.
Alkyl cyclohexyl biphenyl nitrile { chemical name：Trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs }
Liquid-crystal compounds has larger electrical anisotropy because of it（Δε）, big optical anisotropy（Δn）, big elastic constant
Ratio（K33/K11,K22/K11；K33-- bend elastic constant, K22-- distortion elastic constant, K11-- splay elastic constant）, phase in version
The features such as temperature range is very wide, is widely used in TN-LCD, STN-LCD, HTN-LCD liquid crystal display material；And relative to biography
For system display device, in PDLC PDLC（Polymer Dispersed Liquid Crystal）Field should
It is more extensive with market and prospect.Wherein, pentyl cyclohexyl biphenyl nitrile { chemical name：Trans -4-（4- n-pentyl hexamethylenes
Base）- [1,1- biphenyl] -4- formonitrile HCNs }, CAS：68065--81--6 ；N-propyl cyclohexyl biphenyl nitrile { chemical name：Trans -4-
（4- n-propyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs }, CAS：94412--40--5, is such monomer liquid crystal compound again
Two kinds of middle accounting maximum.
The synthetic method of pentyl cyclohexyl biphenyl nitrile is disclosed in patent CN101811985, is obtained by following course of reaction
Arrive：
This preparation process is existed：1. synthetic route length, step are too many；The reaction of 9 steps is prepared into end step by step from one end, comprehensive
Total recovery is very low, uneconomical；The synthetic route of design is unreasonable；2. two step hydrogenation reaction step, a step is high-pressure hydrogenation, safety
Risk is high, is unfavorable for industrialized production；3. the impurity introduced is more, and purification difficult, quality are difficult to ensure；4. costliness has been used
Iodine, acid iodide, moreover, iodide reaction yield is not high；5. cuprous cyanide has been used in cyanogen solution reaction, pollutes environment, and potential safety hazard is big, with
Current implementation environmental protection production is runed counter to；Therefore, it is poor that many drawbacks of, result in product quality, and product cost is high, lacks competition
Power, is unfavorable for large-scale production.
The content of the invention
To overcome defect present in above-mentioned prior art, alkyl-cyclohexyl connection is prepared it is an object of the invention to provide one kind
The new method of cyanophenyl class liquid-crystal compounds --- using the variation route docked from two ends to centre, this method is easily purchased with the market
Product is raw material, and raw material is easy to get, and step is short, and rationally, prepared by modularization for highway route design, and product yield is high, quality is excellent, and cost is significantly
Reduction, product competitiveness enhancing, is conducive to large-scale production.
To achieve the above object, the present invention is adopted the following technical scheme that：
The present invention prepares alkyl cyclohexyl biphenyl nitrile { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid
The formula of crystallization compound（Ⅰ）：
Synthetic route of the present invention is：
Wherein：
R is C1-C14Alkyl group；Further R is preferably C2-C10Straight chained alkyl；More preferably R is C2-C7Straight chain alkane
Base；Most preferably R is n- propyl group, n- butyl, n- amyl groups, n- heptyl；1,4- cyclohexyl used is anti-configuration.
The raw material used is to halogenated benzonitrile（To Brominal, to 6-chlorophenyl nitrile）With trans- 4-（4- alkyl-cyclohexyls）Bromobenzene
（Ⅱ）All it is very easy buying, maturity very high raw material on domestic market.Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）It is to adopt
Prepared with following route：
Formula of the present invention（Ⅰ）Shown alkyl cyclohexyl biphenyl nitrile { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4-
Formonitrile HCN）Liquid-crystal compounds, its preparation method is：Using trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）Tried with metal organolithium
Agent, borating agent react to prepare trans- 4-（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）, then with to halogenated benzonitrile, with palladium complex
For major catalysts, Suzuki coupling reactions are carried out, target compound is prepared --- alkyl cyclohexyl biphenyl nitrile { trans -4-
（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds（Ⅰ）.
Alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds（Ⅰ）Specific preparation method it is as follows：
A. trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）Preparation：
a1. Dry organic solvent I is added into reactor, and inert gas protection device is installed on reactor, dress is added dropwise
Put and heat sink, then into it, logical inert gas empties air in kettle, keeps pressure-fired, then is passed through liquid nitrogen cooling, works as temperature
Degree is when being down to -60 DEG C~-110 DEG C of cryogenic temperature, starts to be added dropwise metal organolithium reagent, rate of addition with meet -60 DEG C~-
110 DEG C of cryogenic temperature requirements are defined, and after completion of dropping, then under this cryogenic temperature, trans- 4- is added dropwise（4- alkyl-cyclohexyls）Bromobenzene
（Ⅱ）With the mixed solution of organic solvent II, rate of addition is defined by the cryogenic temperature requirement for meeting -60 DEG C~-110 DEG C；
a2.Again in a low temperature of -60 DEG C~-110 DEG C, it is added dropwise after borating agent, completion of dropping, at this low temperature insulation reaction,
After completion of the reaction, it is allowed to be warming up to room temperature；
a3. The hydrochloric acid solution that concentration is 8%~12% is added into container, by a2The reaction solution of middle acquisition is slowly added into container,
Temperature is controlled below 20 DEG C, it is stirring while adding complete to hydrolyzing, then, carry out after a point liquid, standing, separate water layer, be washed with water
To neutral, merge organic layer, organic layer is transferred in cucurbit by branch vibration layer, steam after solvent to the greatest extent, then distilled, until steaming
In the water gone out without oil reservoir untill；
a4. By a3In obtained crude product smash pulverize after be fitted into beaker, add non-polar solven I, be heated to after micro-boiling, stand
Cooling, then carries out suction filtration, compresses, when extremely being dripped without big quantity of fluid, then rinsed with non-polar solven I, after draining, take out production
Product, after hanging, are placed in cleaning oven, after drying, obtain white or shallow white solid：Trans -4-（4- alkyl-cyclohexyls）Benzene boron
Acid（Ⅲ）, after measured, HPLC >=98%, yield >=90%；
B. alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）}
（Ⅰ）Preparation：
b1Trans -4- is added into reaction bulb（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）, to halogenated benzonitrile, organic solvent
IIIth, water, and sealing stirring instrument and spherical condensation tube are installed on reaction bulb, buffer balloon, Ran Hou on the set of condenser pipe upper end
Stirring is lower to be added after alkali, fill repeatedly, denitrogen gas to reaction bulb without air, then under nitrogen protection, add palladium complex main catalytic
Agent, forms good Suzuki coupling reaction systems, and heating carries out catalytic reaction to reaction and finished；
b2Stop heating stirring, after cooling, carry out after a point liquid, standing, separate water layer, be washed with water to neutrality, divide and remove water
Layer, organic layer is distilled, steamed after organic solvent, crude product is obtained；
b3By b2In the obtained crude product dissolving of non-polar solven II, cross the chromatographic column containing adsorbent and carry out post purification, finally
Reusable heat non-polar solven II is rinsed to be added after polar solvent, heating for dissolving in pillar, the solution of excessively complete post, is freezed, weight
After crystallization, dry, then, then dissolved with non-polar solven II, after the chromatographic column containing adsorbent in clean vacuum drying oven
Exquisite purification is carried out, that is, obtains alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds.
In step a of the present invention a1In, it is described that " organic solvent I " is tetrahydrofuran, methyltetrahydrofuran, methyl- tert
Any of butyl ether, ether, preferably tetrahydrofuran.
Step a of the present invention a1In, described " metal organolithium reagent " is any in n- butyl lithiums, s-butyl lithium
Kind.
Step a of the present invention a1In, the adding proportion of described metal organolithium reagent and organic solvent I is generally：
1mol metals organolithium reagent 500ml~1500ml organic solvent I.
Step a of the present invention a1In, after metal organolithium reagent completion of dropping, then trans- 4- is added dropwise（4- alkyls
Base）Bromobenzene（Ⅱ）With the mixed liquor of organic solvent II, it is added dropwise dosage and calculated as follows：Trans- 4-（4- alkyl-cyclohexyls）
Bromobenzene is with metal organolithium reagent mol ratio：Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene/metal organolithium reagent=1/ (1.1~
1.15)。
Step a of the present invention a1In, it is described with trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）Form mixed solution
Organic solvent II is any of tetrahydrofuran, methyltetrahydrofuran, methyl tertiary butyl ether(MTBE), ether, and it is preferably tetrahydrochysene
Furans.Described trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）Calculated as follows with the mixed proportion of organic solvent II：
1kg trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）With 1000ml~1500ml organic solvent II.
Step a of the present invention a1In, described " inert gas " is at least one of nitrogen, argon gas, helium, and its is preferred
For nitrogen, argon gas.
Step a of the present invention a1In, pressure-fired is preferably maintained in after air in logical inert gas emptying kettle into reactor,
Pressure is：0.105MPa~0.115MPa is advisable.
Step a of the present invention a1In, described " cryogenic temperature " control is quite strict, crucial, and typical temperature is -60 DEG C
~-110 DEG C, be preferably -70 DEG C~-100 DEG C, more preferably -75 DEG C~-90 DEG C, be most preferably -77 DEG C~-83 DEG C.
Step a of the present invention a2In, described " borating agent " is the isobutyl ester of boric acid three, butyl borate, boric acid front three
Any of ester, triethyl borate, triproylborate, be preferably：The isobutyl ester of boric acid three, trimethylborate.The boron being added dropwise
The addition for changing reagent is calculated as follows：Trans- 4-（4- alkyl-cyclohexyls）The mol ratio of bromobenzene and borating agent is：It is trans-
4-（4- alkyl-cyclohexyls）Bromobenzene/borating agent=1/ (1.2~1.35).
Step a of the present invention a2In, the insulation reaction after described dropwise addition " borating agent " is complete preferably in 1h~10h
Into preferably 2h~8h, more preferably 2h~6h, most preferably 1.0h~2.0h.
Step a of the present invention a2In, after described dropwise addition borating agent insulation reaction is finished, it is preferred that it presses certain liter
Warm speed is warming up to room temperature, and the heating rate can be implemented in relatively wide speed range, usually 1 DEG C/min~10 DEG C/
Min, preferably 2 DEG C/min~8 DEG C/min, more preferably 2 DEG C/min~6 DEG C/min, most preferably 1.0 DEG C/min~2.0 DEG C/
min。
Step a of the present invention a3In, preferably with temperature below 5 °C, the hydrochloric acid solution that concentration is 8%~12%, it adds
It is in highly acid to enter amount to meet the solution after neutralizing, and pH value is 1~3；
Step a of the present invention a3In, it is described by a2The reaction solution of middle acquisition is slowly added into container, and control temperature is at 20 DEG C
Hereinafter, it is stirring while adding complete to hydrolyzing, most handy PH test paper detection, to meet pH value as 1~3.
Step a of the present invention a3In, solvent to the greatest extent is steamed preferably with water-bath normal pressure, is then distilled under reduced pressure again, is steamed
Added water during evaporating, untill in the water steamed without oil reservoir.Described is distilled under " decompression ", and its pressure is generally 0.07
~0.09Mpa.
Step a of the present invention a4In, the non-polar solven I of described recrystallization for 30~60 DEG C petroleum ether, 60~
Any of 90 DEG C of petroleum ether, 90~120 DEG C of petroleum ether, n-hexane, normal heptane, normal octane, it is preferably 90~120
DEG C petroleum ether, 60~90 DEG C of petroleum ether.The addition of non-polar solven I is calculated as follows:The trans- 4- of 1mol（4- alkane
Butylcyclohexyl）Bromobenzene adds the ml of 200ml~500 non-polar solven I.
Step a of the present invention a4In, described use non-polar solven I is rinsed, after draining, take out product, hang, preferably hang to
Without being dried again after obvious petroleum ether taste.
Step a of the present invention a4In, described to be distilled under " decompression ", its pressure is generally 0.07~0.09Mpa.
Step b of the present invention b1In, described palladium complex major catalyst is Pd (PPh3)4 、PdCI2(dppf) 、Pd
(OAc)2, any of Pd/C, preferably Pd (PPh3)4 、Pd(OAc)2.The addition of major catalyst is counted as follows
Calculate：1mol trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）Add 0.0005~0.01mol major catalyst.
Step b of the present invention b1In, the temperature of described catalytic reaction is 50 DEG C~150 DEG C, and the reaction time is generally 3h
~10h.
Step b of the present invention b1In, " part " is also added sometimes, described part is triphenylphosphine, three normal-butyls
Phosphine, tricyclohexyl phosphine, normal-butyl two（1- adamantyls）Phosphine, 2-（Di-t-butyl phosphino-）Biphenyl etc. contains Phosphine ligands and N- heterocycles
At least one of carbenes, imines part, organic amine part, it is preferably tri-n-butyl phosphine, tricyclohexyl phosphine, just
Butyl two（1- adamantyls）Phosphine.The addition of part is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）
Phenyl boric acid（Ⅲ）Add 0~0.05mol part.
Step b of the present invention b1In, " co-catalyst " is also added sometimes, described " co-catalyst " is tetrabutyl phosphonium bromide
Ammonium, tetrabutyl ammonium fluoride, tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tricaprylmethyl chlorination
Any of ammonium, DTAC, tetradecyl trimethyl ammonium chloride, its be preferably TBAB,
Tetrabutylammonium chloride.The addition of co-catalyst is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Benzene boron
Acid（Ⅲ）Add 0~0.2mol co-catalyst.
Step b of the present invention b1In, described addition major catalyst and part, co-catalyst, heating progress are catalyzed instead
Preferably it should be carried out in " certain temperature " and " a period of time "：Generally according to the difference of raw material, the system of selection is different, reaction
Temperature, reaction time are also just different.The general specific requirement according to Suzuki coupling reaction systems is determined, and typical temperature is 50~
150 DEG C, the time is 3~10h.
According to the difference of raw material, the system of selection is different, major catalyst, part, the kind of co-catalyst, the consumption of selection
It is just different, thus reaction temperature, reaction time are also just different.
Step b of the present invention b1In, described organic solvent III is methanol, ethanol, toluene, tetrahydrofuran, DMF, 1,4-
At least one of dioxane, acetone, NMP, DME, DMSO or two kinds of composition, preferably ethanol, toluene, tetrahydrofuran
Any of or any two composition, if using the composition of two kinds of organic solvents III, two kinds of solvents III can be with
Arbitrary proportion is mixed.The addition of organic solvent III is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Benzene
Boric acid（Ⅲ）Add 500ml~3000ml organic solvent III.
Step b of the present invention b1In, described " alkali " is sodium hydroxide, sodium carbonate, potassium carbonate, potassium phosphate, potassium fluoride, vinegar
Any of sour potassium, cesium fluoride, cesium carbonate or any two mixture, it is preferably sodium carbonate, potassium phosphate.If using two
The mixture of alkali is planted, then two kinds of alkali can be mixed with arbitrary proportion.The addition of alkali is calculated as follows：1mol it is trans-
4-（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）Add the mol of 2.0mol~2.5 alkali, then to system or alkali in add
Water, the concentration for making alkali in whole system is 2mol/L.
Step b of the present invention b1In, it is described fill repeatedly, in denitrogen gas to reaction bulb without air, the row of being typically filled with 3-4 times.
Step b of the present invention b2In, described is washed with water neutrality, preferably first with originally washing 2 times, then use deionized water
Wash 3 times, finally reach neutrality.
Step b of the present invention b2In, organic layer is distilled preferably with water-bath decompression method.Described pressure is generally
0.07~0.09Mpa.
Step b of the present invention b3In, the temperature of the pillar used in described column chromatography is 30~90 DEG C, is preferably：45~
60℃.Actual temp is relevant with selected solvent kind.
Step b of the present invention b3In, preferably with more subcrystalline method, i.e.,：By b2In obtained crude product with nonpolar molten
Agent II is dissolved, and is crossed chromatographic column containing adsorbent and is carried out post purification, and reusable heat non-polar solven II rinses pillar, excessively complete post it is molten
Add after polar solvent, heating for dissolving, freezed in liquid, recrystallized, after drying, then the drying in clean vacuum drying oven,
Then, then with non-polar solven II dissolve, carry out exquisite purification after the chromatographic column containing adsorbent, rushed with non-polar solven II
Pillar is washed, merges post liquid, steams after partial solvent, freezed under decompression, recrystallizes, suction filtration is then carried out again, after drying,
Dried using vacuum drying oven, obtain alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds.
Described is evaporated off solvent under " decompression ", and its pressure is generally 0.07~0.09Mpa.
Step b of the present invention b3In, described column chromatography " non-polar solven II " for 30~60 DEG C petroleum ether, 60
Any of~90 DEG C of petroleum ether, 90~120 DEG C of petroleum ether, n-hexane, normal heptane, normal octane or any two combination
Thing, preferably n-hexane, normal heptane and 60~90 DEG C of petroleum ether, if using the composition of two kinds of non-polar solvens II,
Two kinds of non-polar solvens II can be combined with arbitrary proportion.The addition of non-polar solven II is calculated as follows：1kg
Alkyl cyclohexyl biphenyl nitrile { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）}（Ⅰ）Addition 6000ml~
30000ml non-polar solven.
Step b of the present invention b3In, the polar solvent of described recrystallization be ethanol, methanol, acetone, butanone, propyl alcohol,
At least one of ethyl acetate, butyl acetate, toluene and dimethylbenzene, preferably ethanol, acetone, the addition of polar solvent are pressed
Following method is calculated:1kg alkyl cyclohexyl biphenyls nitrile { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）}（Ⅰ）
Add 1000ml~3000ml polar solvent.
Step b of the present invention b3In, the adsorbent used in described column chromatography is silica gel, aluminum oxide, ion exchange resin
Or any of polymer adsorption film or two kinds of mixture, its be preferably silica gel, aluminum oxide, or both mixture.Such as
Fruit uses the mixture of two kinds of adsorbents, then two kinds of adsorbents can be mixed with arbitrary proportion.The consumption of adsorbent is general
Account for the 5%~40% of handled product.
Step b of the present invention b3In, the temperature of described vacuum drying is 50~80 DEG C, 0.07~0.09Mpa of pressure.
Step b of the present invention b3In, described " inert gas " is at least one of nitrogen, argon gas, helium etc., and its is excellent
Elect nitrogen, argon gas as.
The present invention compared with prior art, with following good effect：
1. the present invention is as a result of brand-new design concept, i.e.,：The synthetic route docked from two ends to centre, it is modular
Thinking is prepared, the reaction of 2 steps is reduced to from the 9 steps reaction of prior art.Use with trans- 4-（4- alkyl-cyclohexyls）Bromobenzene
（Ⅱ）Reacted with metal organolithium reagent, borating agent and prepare trans- 4-（4- alkyl-cyclohexyls）Phenyl boric acid（Ⅲ）, then with to halogen
For cyanophenyl, using palladium complex as major catalyst, part and co-catalyst can be also added, good Suzuki coupling reaction bodies are formed
System, carries out Suzuki coupling reactions, prepares target compound --- alkyl cyclohexyl biphenyl nitrile { trans -4-（4- alkyls
Base）- [1,1- biphenyl] -4- formonitrile HCNs）}（Ⅰ）；The raw material used is easy to get, and synthesis step simplifies, the synthetic route of innovation, when making
Between cost reduce, efficiency is improved, and the cost of product declines, and quality-improving makes product competitiveness in the market significantly be lifted.
2. the present invention is used with trans- 4-（4- alkyl-cyclohexyls）Bromobenzene（Ⅱ）Come anti-with metal organolithium reagent, borating agent
Trans- 4- should be prepared（4- alkyl-cyclohexyls）Phenyl boric acid, makes that products obtained therefrom quality is excellent, high income, cost is low, it is to avoid prior art
The existing accessory substance of middle use RMgBr method preparation is more, many drawbacks that yield is low, product quality is poor, cost is high.
3. present invention, avoiding product is produced using high-tension apparatus, production equipment requirement is reduced, safety coefficient is improved,
Be conducive to industrialized production；
4. the present invention creatively make use of Suzuki coupling reactions, according to raw material be to Brominal or to 6-chlorophenyl nitrile not
Together, so that it is determined that using different reaction systems, by major catalyst and Novel Ligands, the reasonable cooperation of co-catalyst with it is excellent
Change, realize very high yield and product quality, realize the purpose for quantifying application, this is that have to Suzuki coupling reactions principle
The development and innovation of body application.
The synthetic route that the present invention is designed is unique, and process route is short, and rationally, modular syntheti c route is saved process conditions
Make an appointment, beneficial to industrialized production, obtained product quality is excellent, the gas chromatographic purity of product is up to more than 99.9%, electricity
Resistance rate is up to 20.0 × 1012More than Ω .cm, are completely adapted to current TN-LCD, STN-LCD, HTN-LCD, PDLC to liquid crystal material
Expect high-quality, high-quality, large-scale needs.
Embodiment
With reference to specific embodiment, the present invention will be further described in detail, however, the embodiment should not be with limit
The mode of system is explained.
Embodiment 1：
To prepare pentyl cyclohexyl biphenyl nitrile { trans -4-（4- pentyl cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid crystal
Compound（I-1）Exemplified by, describe the preparation method of pentylcyclohexyl biphenyl nitrile liquid-crystal compounds in detail：
Step a：Trans -4-（4- pentyl cyclohexyls）Phenyl boric acid（Ⅲ-1）Preparation：
Equipment and charging are installed：The dried tetrahydrofurans of 14L are added into reactor, reactor, nitrogen protection dress is installed
Put（Balloon）, Dropping feeder and heat sink, lead to nitrogen purge 3~4 times, keep pressure-fired, keep the stable standing shape of balloon
State, leads to liquid nitrogen cooling, controls cooling rate, prevents balloon suck-back, about need 1~1.5 hour.
Cooling+dropwise addition 1：When temperature is down to less than -80 DEG C, with nitrogen pressure device by n- butyl lithiums 11mol with stabilization
In speed press-in addition funnel, rate of addition can be slightly fast, observes temperature variations（Temperature is maintained at less than -80 DEG C）If, it is anxious
Play heating should stop being added dropwise immediately, and check reason.
It is added dropwise 2：By the trans- 4- of 3.09kg（4- pentyl cyclohexyls）Bromobenzene（Ⅱ-1）It is dissolved in 3L tetrahydrofurans, nitrogen is protected
Poured under shield in addition funnel, after being finished down every time all should air-discharging 3~4 times, keep stable rate of addition, note temperature and stir
Situation is mixed, control temperature is needed 2~2.5 hours below -80 DEG C, about.
It is stirred for after 45 minutes or so, takes a small amount of sample censorship, is confirmed whether also to contain the trans- 4- of raw material（4- n-pentyl rings
Hexyl）Bromobenzene（Ⅱ-1）, n- butyl lithiums are added if having, if the dropwise addition that next step is carried out without if.
It is added dropwise 3：It is accurate to weigh the isobutyl ester of 2.76kg boric acid three, poured under nitrogen protection in addition funnel, after being finished down every time
All should air-discharging 3~4 times, keep stable rate of addition, note temperature and stirring state, control temperature below -80 DEG C,
After completion of dropping, control temperature is stirred below 40 minutes or so at -80 DEG C.
Temperature control stirring：Heat sink is removed, stirring heating, when rising to -60 DEG C or so, allows it by 1.5 DEG C/min's naturally
Heating rate, untill being warmed to room temperature.
Hydrolysis：2000ml concentrated hydrochloric acids and 4kg mixture of ice and water are added in 50L Plastic Drums, bottom valve is opened, will be anti-
Answer liquid to be put into bucket, put while stirring and mix complete to hydrolysis, control temperature detects PH below 20 DEG C with PH test paper<3 are defined.
Extraction：Hydrolyzate is transferred to 50L points of liquid kettles, and the ethyl acetate for separating water layer 1000ml × 3 or so is extracted, and is associated with
Machine layer, originally washes 3~4 times to neutrality.
Distillation：Branch vibration layer, organic layer is transferred in 50L distillation stills, and water-bath normal pressure steams solvent to the greatest extent, and the 0.5kg that adds water continues to use
Water circulating pump steams, and adds water several times, untill in the water steamed without oil reservoir.
Recrystallization：Crude product is smashed to pieces and is transferred in 10L Aluminum Drums, plus about 1L or so petroleum ether is heated, in heating by bulk
Particle is pulverized, and cooling is stood after micro-boiling.
Suction filtration：Product suction filtration is compressed, is transferred to when being dripped without big quantity of fluid in 10L Aluminum Drums, plus a small amount of petroleum ether is washed 2 times,
Suction filtration again, gained filtrate enters waste liquid barrel.
Drying：Product is hung, after obvious petroleum ether taste, is placed in cleaning oven and is dried 6~8 hours at 65 DEG C, drying
Afterwards, 2.47kg white solids are obtained --- the target product of HPLC >=99.0%（Ⅲ-1）, yield:90%.
Step b：Pentyl cyclohexyl biphenyl nitrile（I-1）Preparation：
1）, crude product prepare：
Equipment and charging are installed：Trans-the 4- of 409g are added in 5L reaction bulbs（4- pentyl cyclohexyls）Phenyl boric acid（Ⅲ-1）、
273g installs sealing stirring, spherical condensation tube and in condenser pipe to Brominal, ethanol 600ml, toluene 1500ml, water 600ml
Upper end puts buffering balloon, and stirring is lower to add natrium carbonicum calcinatum 318g；Denitrogen gas is filled with the air 3~4 times in removing system；Nitrogen
Under gas shielded, Pd (PPh are added3)4 8g, and the entrance of air is prevented, then fill denitrogen gas 3~4 times.
Backflow：Under nitrogen protection, it is heated to reflux 6 hours, stirring should be fast, makes two-phase mixtures uniform.
Divide liquid：Stop heating stirring.After cooling, it is transferred in 5L separatory funnel, after standing, separates water layer, use 1000ml
Running water is washed 2 times, then is washed to neutrality, branch vibration layer with the deionized water of 1000ml × 3.
Distillation：Organic layer is distilled, and toluene is steamed using water-bath decompression, and water is steamed into net, until no solvent steam for
Only, crude product 1 is obtained.
Column chromatography 1：400g silica gel is first added in chromatographic column, pillar is installed；By 90~120 DEG C of the use of crude product 1 3.5L
Petroleum ether is dissolved by heating, and is subsequently poured into during chromatography leans on, control column temperature overheats pillar, finally with 50 DEG C or so at 50 DEG C or so
Hot petroleum ether rushes pillar untill without product（About need 2L or so）.
Recrystallization：The petroleum ether solution for having crossed post adds 0.6L absolute ethyl alcohols, dissolves by heating, and places room temperature, freezing knot
It is brilliant.
Suction filtration and drying：Filter is installed, by crystallization solution suction filtration, is compressed, and is rushed with about 200ml freezing petroleum ethers
Wash once, obtained product is placed in cleaning oven, dried 6~8 hours under the conditions of less than 70 DEG C, obtain 423g white knots
It is brilliant --- crude product 2.
2）, exquisite purification：
Fill post：400g silica gel (mesh of granularity 60~100), 200g aluminum oxide are added in chromatographic column, jiggling makes it fine and close, nothing
Big space, is incubated, and makes it at 60 DEG C or so.
Dissolving：2000g crude products 2 are weighed with dissolving bucket, 24L petroleum ethers are then added（90 DEG C~120 DEG C）, with electric jacket plus
Heat, and glass bar stirring and dissolving is used, notice that temperature does not exceed 70 DEG C during heating.
Column chromatography 2：Lysate is subjected to column chromatography, column temperature is controlled at 60 DEG C or so, outflow solution is connect with clean container
Receive, after product solution is added, silica gel upper strata just without solution when, 60 DEG C or so of 12L oil is now added portionwise to pillar
Ether（90 DEG C~120 DEG C）, allow it to flow through silicon gel column naturally, the 4L petroleum ethers flowed out at first（90 DEG C~120 DEG C）It is molten with product
Liquid merges, and covers lid, remaining uses container reception in addition（Flushing liquor）, separated, otherwise processed.
Freezing：The product solution crossed after pillar is cooled to after room temperature, refrigerator freezing more than 8 hours.
Suction strainer：Suction strainer is carried out with suction funnel or suction strainer bucket, after suction strainer drips to no mother liquor, is stopped.
Drying：In the sealing container that product after suction strainer is put into cleaning, bipyramid drying is carried out, oven temperature is controlled 70
DEG C, Stress control is dried 4 hours in below 0.08Mpa, obtain gas chromatographic purity for >=99.95%, resistivity >=20.0 ×
1012Ω .cm high-quality electron level pentyl cyclohexyl biphenyl nitrile（I-1）Product 1840g, yield:92%.
Experimental result is as follows：Liquid-crystal compounds phase-state change：C95.0℃ N 221.2℃I.
Embodiment 2：
Trans -4-（4- pentyl cyclohexyls）Phenyl boric acid（Ⅲ-1）Preparation：
Preparation process be the same as Example 1, difference is the n- butyl lithiums in step a being substituted for s-butyl lithium, other steps
It is similar, prepare 2.49kg white solids --- the target product of HPLC >=99.0%（Ⅲ-1）, yield:91%.
Embodiment 3：
Trans -4-（4- pentyl cyclohexyls）Phenyl boric acid（Ⅲ-1）Preparation：
Preparation process be the same as Example 1, difference is the isobutyl ester raw material of 2.76kg boric acid three in step a being substituted for
1.250kg trimethylborates, other steps are similar, prepare 2.44kg white solids --- the target product of HPLC >=99.0%
（Ⅲ-1）, yield:89%.
Embodiment 4：
Trans -4-（4- n-propyl cyclohexyl）Phenyl boric acid（Ⅲ-2）Preparation：
Preparation process be the same as Example 1, difference is the trans- 4- in step a（4- pentyl cyclohexyls）Bromobenzene（Ⅱ-1）
Raw material is substituted for trans- 4-（4- n-propyl cyclohexyl）Bromobenzene（Ⅱ-2）, other steps are similar, prepare 2.21kg whites solid
The target product of body --- HPLC >=99.0%（Ⅲ-2）, yield:90%.
Embodiment 5：
Trans -4-（4- propylcyclohexyls）Phenyl boric acid（Ⅲ-2）Preparation：
Preparation process be the same as Example 3, difference is the trans- 4- in step a（4- pentyl cyclohexyls）Bromobenzene（Ⅱ-1）
Raw material is substituted for trans- 4-（4- n-propyl cyclohexyl）Bromobenzene（Ⅱ-2）, other steps are similar, prepare 2.19kg whites solid
The target product of body --- HPLC >=99.0%（Ⅲ-2）, yield:89%.
Embodiment 6：
Pentyl cyclohexyl biphenyl nitrile { trans -4-（4- pentyl cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-2）Preparation method：
Preparation process be the same as Example 1, difference is to be substituted for Brominal raw material in step b to 6-chlorophenyl nitrile, uses
Pd (OAc)2, normal-butyl two（1- adamantyls）Phosphine, potassium phosphate, DMF, the reaction system of water, other steps are similar, prepare
Gas chromatographic purity is >=99.92%, resistivity >=20.0 × 1012Ω .cm target product（I-1）, yield 90%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C95.0℃ N 221.2℃I.
Embodiment 7：
Pentyl cyclohexyl biphenyl nitrile { trans -4-（4- pentyl cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-1）Preparation method：
Preparation process be the same as Example 1, primary raw material is unchanged, and difference is to employ Pd/C、Toluene, ethanol, sodium carbonate, water
Reaction system, other steps are similar, and it is >=99.91%, resistivity >=20.0 × 10 to prepare gas chromatographic purity12Ω.cm
Target product（I-1）, yield 88%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C95.0℃ N 221.2℃I.
Embodiment 8：
Pentyl cyclohexyl biphenyl nitrile { trans -4-（4- pentyl cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-1）Preparation method：
Preparation process be the same as Example 1, primary raw material is unchanged, and difference is to employ Pd (PPh3)4、TBAB,
Potassium carbonate, THF, the reaction system of water, other steps are similar, prepare gas chromatographic purity for >=99.93%, resistivity >=
20.0×1012Ω .cm target product（I-1）, yield 87%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C95.0℃ N 221.2℃I.
Embodiment 9：
N-propyl cyclohexyl biphenyl nitrile { trans -4-（4- n-propyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-2）Preparation method：
Preparation process be the same as Example 1, difference is the trans -4- in step b（4- pentyl cyclohexyls）Phenyl boric acid
（Ⅲ-1）Raw material is substituted for trans -4-（4- n-propyl cyclohexyl）Phenyl boric acid（Ⅲ-2）, other steps are similar, prepare gas phase
Chromatographic purity is >=99.93%, resistivity >=20.0 × 1012Ω .cm target product（I-2）, yield 91%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C 132.0℃ N 231℃I.
Embodiment 10：
N-propyl cyclohexyl biphenyl nitrile { trans -4-（4- n-propyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-2）Preparation method：
Preparation process be the same as Example 6, difference is to be substituted for 6-chlorophenyl nitrile Brominal raw material in step b, other
Step is similar, prepares gas chromatographic purity for >=99.92 %, resistivity >=20.0 × 1012Ω .cm target product（I-
2）, yield：88%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C 132.0℃ N 231℃I.
Embodiment 11：
N-propyl cyclohexyl biphenyl nitrile { trans -4-（4- n-propyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-2）Preparation method：
Preparation process be the same as Example 8, difference is the trans -4- in step b（4- pentyl cyclohexyls）Phenyl boric acid
（Ⅲ-1）Raw material is substituted for the trans -4- of n-propyl cyclohexyl benzene boric acid（4- n-propyl cyclohexyl）Phenyl boric acid（Ⅲ-2）, Qi Tabu
It is rapid similar, gas chromatographic purity is prepared for >=99.91 %, resistivity >=20.0 × 1012Ω .cm target product（I-2）,
Yield：88%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C 132.0℃ N 231℃I.
Embodiment 12：
N-propyl cyclohexyl biphenyl nitrile { trans -4-（4- n-propyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-2）Preparation method：
Preparation process be the same as Example 7, difference is the trans -4- in step b（4- pentyl cyclohexyls）Phenyl boric acid
（Ⅲ-1）Raw material is substituted for trans -4-（4- n-propyl cyclohexyl）Phenyl boric acid（Ⅲ-2）, other steps are similar, prepare gas phase
Chromatographic purity is >=99.90 %, resistivity >=20.0 × 1012Ω .cm target product（I-2）, yield：87%.
Experimental result is as follows：Liquid-crystal compounds phase-state change： C 132.0℃ N 231℃I.
Embodiment 13：
N-heptyl cyclohexyl biphenyl nitrile { trans -4-（4- n-heptyl cyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Liquid-crystal compounds
（I-3）Preparation method：
Preparation process be the same as Example 1, difference is the trans -4- in step b（4- pentyl cyclohexyls）Phenyl boric acid
（Ⅲ-1）Raw material is substituted for trans -4-（4- n-heptyl cyclohexyl）Phenyl boric acid（Ⅲ-3）, other steps are similar, prepare gas phase
Chromatographic purity is >=99.90%, resistivity >=20.0 × 1012Ω .cm target product（I-3）, yield：86%..
Experimental result is as follows：Liquid-crystal compounds phase-state change：C89.1℃ N 216.1℃I.
Presently preferred embodiments of the present invention is the foregoing is only, can not limit to the present invention to understand with this, it is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements done etc. should be included in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds, is used with trans- 4-（4- alkyl-cyclohexyls）Bromine
Benzene reacts to prepare trans- 4- with metal organolithium reagent, borating agent（4- alkyl-cyclohexyls）Phenyl boric acid, then with to halogeno-benzene
Nitrile, using palladium complex as major catalyst, carries out Suzuki coupling reactions, prepares alkyl cyclohexyl biphenyl nitrile LCD compound
Thing.
2. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 1, it is characterized in that pressing
What row step was carried out：
A. trans -4-（4- alkyl-cyclohexyls）The preparation of phenyl boric acid：
a1. Dry organic solvent I is added into reactor, and inert gas protection device is installed on reactor, dress is added dropwise
Put and heat sink, then into it, logical inert gas empties air in kettle, keeps pressure-fired, then is passed through liquid nitrogen cooling, works as temperature
When degree is down to -60 DEG C~-110 DEG C of low temperature, start that metal organolithium reagent is added dropwise, rate of addition will meet -60 DEG C~-110
DEG C cryogenic temperature requirement, then under this cryogenic temperature, trans- 4- is added dropwise（4- alkyl-cyclohexyls）Bromobenzene is mixed with organic solvent II
Solution is closed, rate of addition is defined by the cryogenic temperature requirement for meeting -60 DEG C~-110 DEG C；
a2.Again in a low temperature of -60 DEG C~-110 DEG C, it is added dropwise after borating agent, completion of dropping, at this low temperature insulation reaction, instead
After should finishing, it is allowed to be warming up to room temperature；
a3. The hydrochloric acid solution that concentration is 8%~12% is added into container, by a2The reaction solution of middle acquisition is slowly added into container, control
Temperature processed is stirring while adding complete to hydrolyzing below 20 DEG C, then, carries out after a point liquid, standing, separates water layer, be washed with water to
Neutrality, merges organic layer, and organic layer is transferred in cucurbit by branch vibration layer, and solvent, then under reduced pressure to the greatest extent is steamed using water-bath normal pressure
Distilled, added water during distillation, untill in the water steamed without oil reservoir；
a4. By a3In obtained crude product smash pulverize after be fitted into beaker, add non-polar solven I, be heated to after micro-boiling, stand
Cooling, then carries out suction filtration, compresses, when extremely being dripped without big quantity of fluid, then rinsed with non-polar solven I, after draining, take out production
Product, after hanging, are placed in cleaning oven, after drying, obtain white or shallow white solid：Trans -4-（4- alkyl-cyclohexyls）Benzene boron
Acid；
B. alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds { trans -4-（4- alkyl-cyclohexyls）- [1,1- biphenyl] -4- formonitrile HCNs）}
Preparation：
b1Trans -4- is added into reaction bulb（4- alkyl-cyclohexyls）Phenyl boric acid, to halogenated benzonitrile, organic solvent III, water, and
Sealing stirring instrument and spherical condensation tube are installed on reaction bulb, balloon is buffered on the set of condenser pipe upper end, then adds under agitation
Enter after alkali, fill repeatedly, in denitrogen gas to reaction bulb without air, then under nitrogen protection, add palladium complex major catalyst, formed
Suzuki coupling reaction systems, heating carries out catalytic reaction to reaction and finished；
b2Stop heating stirring, after cooling, carry out after a point liquid, standing, separate water layer, be washed with water to neutrality, branch vibration layer,
Organic layer is distilled, steamed after organic solvent, crude product is obtained；
b3By b2In the obtained crude product dissolving of non-polar solven II, cross the chromatographic column containing adsorbent and carry out post purification, finally
Reusable heat non-polar solven II is rinsed to be added after polar solvent, heating for dissolving in pillar, the solution of excessively complete post, is freezed, weight
After crystallization, dry, then dissolved with non-polar solven II in clean vacuum drying oven, essence is carried out after the chromatographic column containing adsorbent
Purification is caused, that is, obtains alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds.
3. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step a a1In：
It is described added into reactor dry organic solvent I for tetrahydrofuran, methyltetrahydrofuran, methyl tertiary butyl ether(MTBE),
Any of ether；
Described metal organolithium reagent is any of n- butyl lithiums, s-butyl lithium；
Described organic solvent II is any of tetrahydrofuran, methyltetrahydrofuran, methyl tertiary butyl ether(MTBE), ether；
Step a a2In：
Described borating agent is the isobutyl ester of boric acid three, butyl borate, trimethylborate, triethyl borate, triproylborate
Any of；
Step a a4In：
Described non-polar solven I is 30~60 DEG C of petroleum ether, 60~90 DEG C of petroleum ether, 90~120 DEG C of petroleum ether, just
Any of hexane, normal heptane, normal octane；
Step b b1In：
Described palladium complex major catalyst is Pd (PPh3)4 、PdCI2(dppf) 、Pd(OAc)2, any of Pd/C；
Described organic solvent III be methanol, ethanol, toluene, tetrahydrofuran, DMF, 1,4- dioxane, acetone, NMP, DME,
At least one of DMSO or two kinds of combination；
Described alkali is times in sodium hydroxide, sodium carbonate, potassium carbonate, potassium phosphate, potassium fluoride, potassium acetate, cesium fluoride, cesium carbonate
A kind of or any two mixture；
Step b b3In：
Described non-polar solven II for 30~60 DEG C petroleum ether, 60~90 DEG C of petroleum ether, 90~120 DEG C of petroleum ether,
Any of n-hexane, normal heptane, normal octane or any two composition；
The polar solvent of described recrystallization is ethanol, methanol, acetone, butanone, propyl alcohol, ethyl acetate, butyl acetate, first
At least one of benzene, dimethylbenzene.
4. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in Claims 2 or 3, it is characterized in that：
Step a a1In：
The adding proportion of described metal organolithium reagent and organic solvent I is：1mol n- butyl lithiums with 500ml~
1500ml organic solvent I；
After metal organolithium reagent completion of dropping, then trans- 4- is added dropwise（4- alkyl-cyclohexyls）Bromobenzene is mixed with organic solvent II
Liquid is closed, it is added dropwise dosage and calculated as follows：Trans- 4-（4- alkyl-cyclohexyls）The mol ratio of bromobenzene and metal organolithium reagent
For：Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene/metal organolithium reagent=1/ (1.1~1.15)；
Described trans- 4-（4- alkyl-cyclohexyls）The ratio that bromobenzene and organic solvent II are mixed is calculated as follows：1kg's
Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene 1000ml~1500ml organic solvent II；
Step a a2In：
The addition for the borating agent being added dropwise is calculated as follows：Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene and borating agent
Mol ratio be：Trans- 4-（4- alkyl-cyclohexyls）Bromobenzene/borating agent=1/ (1.2~1.35)；
Step a a3In：
Described adds the hydrochloric acid solution that concentration is 8%~12% into container, and its addition will meet the solution after neutralizing in strong
Acidity, pH value is 1~3；
Step a a4In：
The addition of non-polar solven I is calculated as follows:The trans- 4- of 1mol（4- alkyl-cyclohexyls）Bromobenzene addition 200ml~
500 ml non-polar solven I；
Step b b1In：
The addition of described major catalyst is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid
Add 0.0005~0.01mol major catalyst；
The addition of described organic solvent III is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Benzene boron
Acid adds 500ml~3000ml organic solvent III；
The addition of described alkali is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid is added
The mol of 2.0mol~2.5 alkali, then, to system or alkali in add water, the concentration for making alkali in system is 2mol/L；
Step b b3In：
The addition of described non-polar solven II is calculated as follows：1kg alkyl cyclohexyl biphenyls nitrile { trans -4-（4- alkane
Butylcyclohexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Add 6000ml~30000ml non-polar solven；
The addition of described polar solvent is calculated as follows:1kg alkyl cyclohexyl biphenyls nitrile { trans -4-（4- alkyl rings
Hexyl）- [1,1- biphenyl] -4- formonitrile HCNs）Add 1000ml~3000ml polar solvent.
5. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step a a1In, described cryogenic temperature is -77 DEG C~-83 DEG C.
6. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step b b1In：
The temperature of described catalytic reaction is at 50 DEG C~150 DEG C, the reaction time is 3h~10h.
7. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step a a2In, after the completion of the described insulation reaction being added dropwise after borating agent, it is allowed by 1 DEG C/min~10 DEG C/min's
Heating rate is warming up to room temperature.
8. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step b b1In, while adding major catalyst, add part and co-catalyst, described part is triphenylphosphine,
Tri-n-butyl phosphine, tricyclohexyl phosphine, normal-butyl two（1- adamantyls）Phosphine, 2-（Di-t-butyl phosphino-）Biphenyl containing Phosphine ligands and
At least one of N- heterocyclic carbene ligands, imines part, organic amine part, described co-catalyst are tetrabutyl phosphonium bromide
Ammonium, tetrabutyl ammonium fluoride, tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tricaprylmethyl chlorination
Any of ammonium, DTAC, tetradecyl trimethyl ammonium chloride；
The addition of part is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid addition 0~
0.05mol part；
The addition of co-catalyst is calculated as follows：1mol trans -4-（4- alkyl-cyclohexyls）Phenyl boric acid adds 0
~0.2mol co-catalyst.
9. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step b b3In：
The temperature of pillar used in described column chromatography is 30 DEG C~90 DEG C；
Adsorbent used in described column chromatography is any in silica gel, aluminum oxide, ion exchange resin or polymer adsorption film
Kind or two kinds of mixture.
10. according to the preparation method of the alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds described in claim 2, it is characterized in that：
Step b b3In：
The temperature of described vacuum drying is 50~80 DEG C, 0.07~0.09Mpa of pressure.
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