CN101560396A - Method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal - Google Patents
Method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal Download PDFInfo
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Abstract
The invention discloses a method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal; in the method, bromobenzene and magnesium are selected to carry out Grignard reaction; then the reactants are coupled and hydrolyzed with alkyl cyclohexanone; dehydration, hydrogenation, transformation and iodization are carried out to synthesize alkyl cyclohexyl iodide; the Grignard reaction is carried out on fluorobromobenzene and magnesium, then low temperature coupling is carried out to synthesize p-fluoropheyl boric acid; finally, coupling reaction is carried out to synthesize the target compound; the method of the invention has the characteristics of use of highly active load catalyst, high yield, low production cost, little discharge of three wastes, reduction of generation of isomers and improvement of selectivity and yield of the target compound.
Description
Technical field
The invention belongs to the fine chemical technology field, especially relate to a kind of synthetic method of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal.
Background technology
Drive the develop rapidly of liquid-crystal display (TFT-LCD) technology along with supertwist nematic liquid crystal (STN-LCD) and thin film transistor (TFT) array, both have occupied high-grade monitor markets such as console display and portable notebook computer greatly in recent years, wherein TFT-LCD is owing to adopt thin film transistor (TFT) array directly to drive liquid crystal molecule, eliminated the monkey chatter effect, therefore shown that information content is big.Just need be used low viscous liquid crystal material this moment, bigger raising response speed, and then reach the needs that satisfy the video image demonstration.Fluorine-containing trans cyclohexyl biphenyl class 4-(4-alkyl-cyclohexyl)-4 '-fluoro-1,1 '-biphenyl liquid crystal has good characteristics such as higher dielectric anisotropy (Δ ε), lower viscosity, medium optical anisotropy (Δ n), high electric charge conservation rate, has exactly satisfied the TFT-LCD display requirement.In addition such liquid crystal material also possesses outstanding advantages such as good light, electricity, heat and chemical stability, so it is widely used among high-grade colored STN-LCD and the TFT-LCD; Have the stability of biphenyls liquid crystal, the low viscosity of dicyclic hexane liquid crystal and the good characteristics such as fast, the suitable moment of dipole of demonstration response speed of fluoro liquid crystals.
This type of liquid crystal monomer is generally by alkyl-cyclohexyl iodobenzene and synthetic or synthetic by alkyl-cyclohexyl phenylo boric acid and p-Fluoro bromo benzene to fluorobenzoic boric acid.Its reaction principle is as follows:
Route A:
Route B:
Annotate: R is expressed as alkyl, represents ethyl respectively, propyl group, butyl, amyl group.
In above-mentioned two kinds of synthetic routes, alkyl-cyclohexyl iodobenzene and alkyl-cyclohexyl phenylo boric acid all will use important intermediate---alkyl-cyclohexyl benzene, and its synthetic route is:
Route i:
Annotate: R is expressed as alkyl, difference represent methylidene, ethyl, propyl group, butyl.
Route ii:
Annotate: R is expressed as alkyl, represents ethyl respectively, propyl group, butyl, amyl group.
In the synthesis of alkyl phenylcyclohexane, route i is the method for early using, and the impurity that generates in this production method is more, and the purifying difficulty is bigger, makes product yield low, about 30～40%.Alkyl acyl chloride and aluminum trichloride (anhydrous) water breakthrough easily decompose and the generation hydrogen chloride gas aborning; Tetrahydrobenzene easily produces superoxide, can cause combustion explosion danger; The toxicity of benzene is maximum in aromatic hydrocarbon; Huang Min-lon reduction temperature of reaction higher (more than 180 ℃), equal potential safety hazards that causes operator and production facility in various degree, because above these drawbacks, this method is often used at present.
Adopt route ii synthetic route, the impurity of generation is few, and product is easy to the yield height (about 80～94%) of purifying and product, and the danger of reactant and reaction conditions are all gentle, therefore generally use this method.But in the product dehydration, in transition, the reaction times is long and the reaction node is wayward, and aftertreatment trouble and three waste discharge are more; In synthetic, because the reactant molecule active sites is more, very easily produce isomers, these isomerss can not produce mesomorphic phase, and their appearance not only influences the product yield, cost is risen, and be objectionable impurities in the target compound, greatly influencing the LCD performance, must remove, but the physicochemical property of they and target compound are extremely approaching, and ordinary method is not easily separated.
In route B, though the alkyl-cyclohexyl phenylo boric acid relatively easily obtains, it is that expensive Pd (0) makees catalyzer that this method is used, and this catalyzer very difficult preservation in routine experimentation, production environment, is unfavorable for very much industrial production requirement in this; And this coupling method yield is not very desirable, about 67%.
Summary of the invention
The objective of the invention is to improve the deficiency of prior art and provide a kind of and use high-efficient carrier catalyzer, high yield, production cost is low, three waste discharge is few, reduce the synthetic method that isomer generated, improved the fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal of the selectivity of target compound and yield.
The object of the present invention is achieved like this, a kind of synthetic method of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal, be to select bromobenzene and magnesium to carry out grignard reaction, then with alkyl cyclohexanone coupling and hydrolysis, again through dehydration, hydrogenation, transition, iodo synthesis of alkyl cyclohexyl iodobenzene; P-Fluoro bromo benzene and magnesium carry out grignard reaction, and the low temperature coupling is synthetic has then synthesized target compound by linked reaction at last again to fluorobenzoic boric acid, and its synthetic route is as follows:
Wherein I is 4-alkyl-1-phenylcyclohexanol, and II is 4-alkyl-1-benzyl ring hexene, and III is an alkyl-cyclohexyl benzene, IV is trans alkyl-cyclohexyl benzene, and V is trans alkyl-cyclohexyl iodobenzene, and VI is to fluorobenzoic boric acid, VII is 4-(4-alkyl-cyclohexyl)-4 ',-fluoro-1-1 ' ,-biphenyl, R is expressed as alkyl, represent ethyl respectively, propyl group, butyl, amyl group.
The preparation of described I is to add tetrahydrofuran (THF) 107g and 6.9g magnesium powder in the 500ml there-necked flask, be heated to backflow 10min, close heating, the mixing liquid that contains 37.7g bromobenzene and 87g toluene of dropping 10% in reaction flask, in system, add 0.2g iodine by the prolong upper end again, after the initiation, continue to be added dropwise to remaining mixed liquid in the reaction flask, heat up after finishing in 55～65 ℃ of insulation reaction 2 hours, change the water-bath temperature regulating device then into, with the mixing liquid of 33.6g ethyl cyclohexanone and 87g toluene, be added dropwise in the system under in the time of 30 ℃, stirring, and the control dropping temperature is in 30～35 ℃, add the back in this temperature insulation 30 minutes, reaction finishes reaction solution with containing the 200g trash ice and 300g10% hydrochloric acid is hydrolyzed, and hydrolysis is told water after finishing, water extracts 3 times with toluene, use toluene 43.5g at every turn, and be washed to neutrality, anhydrous magnesium sulfate drying again with the organic phase merging, filter, organic phase is to be drained off.
The preparation of described II: in the 1000ml there-necked flask, add 4-ethyl-1-phenylcyclohexanol organic phase and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 8.2g, reflux divides water to anhydrous changing into again after going out to concentrate toluene and steam half toluene, residual reaction liquid filters out catalyzer, catalyzer is not treated can be recycled and reused for the reaction of this step, treats hydrogenation.
The preparation of described III: in 1000ml high-pressure hydrogenation still, add 4-ethyl-1-benzyl ring hexene and treat hydrogenation reaction solution, and the palladium carbon and the 78.9g ethanol of this product theoretical amount 5%, the palladium carbon of use is 5% palladium content, water content 53%, uses N after vacuumizing
2Air twice in the displacement hydrogenation still is used H again
2Displacement N
2Three times, be forced into 1.5MPa the 4th time, and in 50～60 ℃ of insulation reaction 2 hours, during when pressure during less than 1.3MPa ftercompction to 1.5MPa; Reaction end back emptying filters palladium carbon in the reaction solution, and filter cake is used ethanol 15.8g with heating back ethanol drip washing 2 times at every turn, and leacheate merges with filtrate, concentrates out solvent toluene and ethanol, gets light yellow liquid 42.9g.
The preparation of described IV: in the 250ml there-necked flask, add ethyl phenylcyclohexane 47g, toluene 104.4g and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 16.4g, temperature rising reflux cooling in 4 hours, elimination catalyzer, catalyzer can not treatedly be reused for this step reaction, and with heating back toluene drip washing catalyzer 2 times, use toluene 21.2g, washing lotion merges with organic phase, concentrated solvent toluene at every turn, again the concentrated solution molecular distillation is got the 43.3g white solid, this step yield 92.15%.
The preparation of described V: in the 2000ml there-necked flask, add 13.8% the aqueous sodium hydroxide solution contain 10g sodium hydroxide, stir and add trans ethyl phenylcyclohexane 47g down, ethanol 274g and potassiumiodide 45.7g, ice-water bath is cooled to 0 ℃, drip the clorox 204.9g of 10% available chlorine again by constant pressure funnel, temperature control＜5 ℃ in the whole dropping process, finish the back in 0～5 ℃ of insulation reaction 1 hour, add Sodium Pyrosulfite 2.4 grams then, adding 400g water again stirred 10 minutes, drip the 800g concentrated hydrochloric acid by constant pressure funnel again and be acidified to PH＜1, and control souring temperature＜50 ℃, material after the acidifying is poured in the 5000ml beaker that fills the 252g ethylene dichloride, and restir 5 minutes, tell organic phase, water with the extraction of 252g ethylene dichloride once, merge organic phase, be washed to neutrality, use 10g anhydrous sodium sulfate drying 2 hours, filter out siccative, and, use ethylene dichloride 31.5g with ethylene dichloride drip washing siccative 2 times at every turn, merge organic phase, be concentrated into solvent-freely to go out, to concentrated solution by the 1g product: 1.2g ethanol carries out recrystallization twice, gets the 67.9g white solid through molecular distillation again, this step yield 86.45%.
The preparation of described VI: in the 500ml there-necked flask, add 89g tetrahydrofuran (THF) and magnesium powder 7.3g, reflux is closed heating after 10 minutes, the mixing liquid that contains 41.3g p-Fluoro bromo benzene and 44.5g tetrahydrofuran (THF) by constant pressure funnel dropping 10%, by the prolong 0.2g iodine that in system, adds suitable for reading, after confirming to cause, remaining mixing liquid is splashed in the system under weak backflow then, after finishing, back flow reaction 2 hours is cooled to below 50 ℃, and is stand-by; In another 500ml there-necked flask, add tributyl borate 97.7g and tetrahydrofuran (THF) 89g, liquid nitrogen cooling is to-75 ℃ under stirring, and the Grignard reagent of preparation is added dropwise in the reaction flask by constant pressure funnel, whole dropping process temperature control is in-75～-70 ℃, finishes back reaction 1 hour under this temperature; In the 3000ml there-necked flask, add entry 700g again, stir and add the 300g concentrated hydrochloric acid down, then this reaction solution is slowly added acidification hydrolization in the 3000ml there-necked flask, after finishing, hydrolysis washes away the 500ml there-necked flask at twice with the 280g sherwood oil, and join in the 3000ml there-necked flask, and continue to stir again 30 minutes, left standstill 1 hour, tell behind the water with 105g petroleum ether extraction water, merge organic phase and be washed to neutrality, concentrate organic phase and go out, cool to 50～60 ℃, and concentrated solution is added drop-wise in the 3000ml there-necked flask that fills 1000g water to solvent-free, continue again after adding to stir 1 hour, filter,, press the 1g product: 1.4g sherwood oil reflux 1 hour the filter cake oven dry, reduce to 0 ℃ of filtration, dry once more stand-by, product 27.9g, this step yield 86%.
The preparation of described VII: in the 500ml there-necked flask, add toluene 75g successively, ethanol 60g, distilled water 78g, Tetrabutyl amonium bromide 4g, silicon dioxide carried four triphenylphosphine palladium chloride catalyzer 32g, to fluorobenzoic boric acid 32.5g, trans ethyl cyclohexyl iodobenzene 78.5g, divide and add potassiumphosphate 46.4g altogether three times, added behind each raw material temperature rising reflux 2 hours, stop heating, be cooled to 55 ℃ and left standstill 1 hour, supported catalyst is filtered, and with toluene drip washing catalyzer 2 times, each toluene 44g, this catalyzer of using can continue on for this step reaction, leaves standstill then and tells water, water extracts 2 times with toluene, each toluene 44g that uses merges with organic phase, and organic phase is washed to neutrality, and add anhydrous magnesium sulfate 10g elimination siccative after dry 4 hours, filter cake is used toluene 17g at every turn, and is merged with organic phase with toluene drip washing 2 times, normal pressure is crossed the silica alumina post, press the 1g product: 0.1g silicon-dioxide: the 0.1g aluminum oxide, cross post and finish the back with toluene 44g drip washing pillar, integrate with in the organic phase, organic phase is concentrated into solvent-freely to go out, and, get white solid 55.9g, this step yield 92% to its molecular distillation.
The preparation of silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent: in the 250ml there-necked flask, add 150g distilled water and 30g tosic acid, stirring makes its dissolving, and then adding 90g silicon-dioxide, heat up in 70 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
Silicon dioxide carried four triphenylphosphine palladium chloride Preparation of catalysts: in the 250ml there-necked flask, add 100g distilled water and 5.8g Palladous chloride, stirring makes its dissolving, add 100g silicon-dioxide then, heat up and in 75 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry is standby after 8 hours under the=0.095MPa condition; In the 1000ml there-necked flask, add the silicon dioxide carried Palladous chloride and the 34.2g triphenyl phosphorus of having dried, N
2Protection is temperature rising reflux 24 hours down, reduces to after the room temperature in N
2Protection is filtered down, solid materials is changed in the vacuum drying oven, in 90 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
The present invention at first bromobenzene and magnesium carries out grignard reaction, then with alkyl cyclohexanone coupling and hydrolysis, through dehydration, hydrogenation, transition, iodo synthesis of alkyl cyclohexyl iodobenzene; P-Fluoro bromo benzene and magnesium carry out grignard reaction, and the low temperature coupling is synthetic to fluorobenzoic boric acid then, has finally synthesized target compound by linked reaction again.
In the synthesis of alkyl phenylcyclohexane: use the production method of route i, impurity is more in the feasible product that generates, and the purifying difficulty is bigger, and product yield is low; Raw material alkyl acyl chloride and aluminum trichloride (anhydrous) water breakthrough easily decompose and produce a large amount of hydrogen chloride gas, tetrahydrobenzene and easily produce superoxide, the toxicity that can cause combustion explosion danger, benzene is maximum, Huang Min-lon reduction temperature of reaction higher (more than 180 ℃) in aromatic hydrocarbon, more than these equal in various degree potential safety hazards that cause operator and production facility.Use the production method of route ii, make that the impurity in products that generates is few, be easy to purifying and improve yield (about 80～94%), the danger of raw material and reaction conditions are all gentle; In the product dehydration and in transition, use the high-efficient carrier catalyzer of development voluntarily, make the reaction times be shortened, and the usage quantity, the reaction that have reduced catalyzer are easy to control, react and abandon loaded down with trivial details aftertreatment (filter get final product catalyzer) after the end, and this catalyzer realized being repeatedly used, and three waste discharge obviously reduces.
In alkyl-cyclohexyl iodobenzene synthetic, following two kinds of synthetic routes are arranged:
Route (one):
Route (two):
Annotate: R is expressed as alkyl, represents ethyl respectively, propyl group, butyl, amyl group
Higher acid iodide of price and expensive iodine have been used in the route (), and usage quantity is bigger, cause raw material availability low, isomers is big in the product, make troubles to subsequent purification, increased cost, simultaneously because the characteristic that iodine easily distils, operator are caused certain potential safety hazard, therefore do not use this route to synthesize; Selection schemer of the present invention (two) synthesize, and the raw material potassiumiodide, clorox, sodium hydroxide and the ethanol that use low price to be easy to get come synthesis of alkyl cyclohexyl iodobenzene.Because the reactant molecule active sites is more, very easily produces isomers.These isomerss can not produce mesomorphic phase.Their appearance not only influences the product yield, and cost is risen, and is the objectionable impurities in the target compound, greatly influences the LCD performance, must remove.But the physicochemical property of they and target compound are extremely approaching, and ordinary method is not easily separated.The present invention adopts the accurate location technology of molecule, utilizes " the cage shape effect " of polar solvent molecule that reactant is carried out selective protection, and locating effect is obvious especially, has effectively avoided unnecessary isomer to generate.Itself increased substantially the product yield, simultaneously avoided loaded down with trivial details process for separating and purifying again and the product that causes loses once again, only this item can reduce cost 45%.
In route B, though the alkyl-cyclohexyl phenylo boric acid relatively easily obtains, it is that expensive Pd (0) makees catalyzer that this method is used, and this catalyzer very difficult preservation in routine experimentation, production environment, is unfavorable for very much industrial production requirement in this; And this coupling method yield is not very desirable (67%).The route A synthetic method that the present invention adopts, by using the high-efficient carrier catalyzer of research and development voluntarily, not only yield improves (reaction yield 92%), catalyzer can be repeatedly used, and reduced three waste discharge, progressively stride forward to green compound direction, the present invention has synthesized four liquid crystal monomers respectively according to above reaction principle:
4-(4-ethyl cyclohexyl)-4 ' ,-fluoro-1-1 ' ,-biphenyl are VIIa, total recovery is 62.7% (in ethyl cyclohexanone);
4-(4-propyl group cyclohexyl)-4 ' ,-fluoro-1-1 ' ,-biphenyl are VIIb, total recovery is 65.24% (in the propyl group pimelinketone);
4-(4-butyl cyclohexyl)-4 ' ,-fluoro-1-1 ' ,-biphenyl are VIIc, total recovery is 60.7% (in butyl cyclohexanone);
4-(4-amyl group cyclohexyl)-4 ' ,-fluoro-1-1 ' ,-biphenyl are VIId, total recovery is 63.37% (in the amyl group pimelinketone)
The quality index that the product that adopts the inventive method to produce can reach is as follows:
The present invention uses the high-efficient carrier catalyzer of development voluntarily in dehydration, transition and the coupling process of product, substitute expensive Pd (0) and made catalyzer, yield obviously improves (reaction yield 92%), catalyzer can be repeatedly used, usage quantity, the reaction that has reduced catalyzer is easy to control, react abandons loaded down with trivial details aftertreatment after the end and this catalyzer has been realized being repeatedly used, and three waste discharge obviously reduces; In alkyl-cyclohexyl iodobenzene synthetic,, very easily produce isomers because the reactant molecule active sites is more.These isomerss can not produce mesomorphic phase.Their appearance not only influences the product yield, and cost is risen, and is the objectionable impurities in the target compound, greatly influences the LCD performance, must remove.But the physicochemical property of they and target compound are extremely approaching; ordinary method is not easily separated; the present invention adopts the accurate location technology of molecule; utilize " the cage shape effect " of polar solvent molecule that reactant is carried out selective protection; locating effect is obvious especially, has effectively avoided unnecessary isomer to generate, and has increased substantially the product yield; the product of having avoided loaded down with trivial details process for separating and purifying again simultaneously and having caused loses once again, and only this item can reduce cost 45%.
Embodiment
Embodiment, a kind of synthetic method of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal, be to select bromobenzene and magnesium to carry out grignard reaction, then with alkyl cyclohexanone coupling and hydrolysis, through dehydration, hydrogenation, transition, iodo synthesis of alkyl cyclohexyl iodobenzene, p-Fluoro bromo benzene and magnesium carry out grignard reaction again, and the low temperature coupling is synthetic to fluorobenzoic boric acid then, having synthesized target compound by linked reaction more at last, is that its synthetic route is as follows:
Wherein I is 4-alkyl-1-phenylcyclohexanol, and II is 4-alkyl-1-benzyl ring hexene, and III is an alkyl-cyclohexyl benzene, IV is trans alkyl-cyclohexyl benzene, and V is trans alkyl-cyclohexyl iodobenzene, and VI is to fluorobenzoic boric acid, VII is 4-(4-alkyl-cyclohexyl)-4 ',-fluoro-1-1 ' ,-biphenyl, R is expressed as alkyl, represent ethyl respectively, propyl group, butyl, amyl group; Present embodiment is with 4-(4-ethyl cyclohexyl)-4 ',-fluoro-1-1 ',-biphenyl synthesizes example, the instrument of use: Agilent GC-6820 type gas chromatograph, Tianjin, island LC-10ATvp type high performance liquid chromatograph, TP-531 type determination of resistivity instrument, R-201 type Rotary Evaporators, 2XZ-4 type rotary-vane vaccum pump, DZ-1A type vacuum drying oven, SHB-III type water cycle vacuum pump; The reagent that uses: silicon-dioxide, aluminum oxide, Palladous chloride, propyl carbinol, iodine, magnesium powder, potassiumiodide, sodium hydroxide, potassiumphosphate, Tetrabutyl amonium bromide are AR, tosic acid, tetrahydrofuran (THF), toluene, ethanol, ethylene dichloride, clorox, concentrated hydrochloric acid are technical grade, bromobenzene, ethyl cyclohexanone, p-Fluoro bromo benzene, tributyl borate GC 〉=99.5%; The moisture 53% palladium content 5% of palladium carbon, nitrogen is industrial general nitrogen, hydrogen is industrial general hydrogen, the distilled water self-control; Be specially the preparation of 4-ethyl-1-phenylcyclohexanol: adding tetrahydrofuran (THF) 107g and 6.9g are 0.29mol magnesium powder in the 500ml there-necked flask, be heated to backflow 10min, close heating, in reaction flask, drip 10% the mixing liquid that 37.7g is 0.24mol bromobenzene and 87g toluene that contains, in system, add 0.2g iodine by the prolong upper end again, after the initiation, continue to be added dropwise to remaining mixed liquid in the reaction flask, heat up after finishing in 55～65 ℃ of insulation reaction 2 hours, change the water-bath temperature regulating device then into, mixing liquid with 33.6g 0.24mol ethyl cyclohexanone and 87g toluene under stirring in the time of 30 ℃ is added dropwise in the system, and the control dropping temperature adds the back in this temperature insulation 30 minutes in 30～35 ℃, reaction finishes reaction solution with containing the 200g trash ice and 300g10% hydrochloric acid is hydrolyzed, tell water after hydrolysis is intact, water uses 43.5g toluene with toluene extraction three times at every turn, and merge with organic phase and to be washed to neutrality again, anhydrous magnesium sulfate drying filters, and organic phase is to be drained off; The preparation of 4-ethyl-1-benzyl ring hexene: in the 1000ml there-necked flask, add 4-ethyl-1-phenylcyclohexanol organic phase and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 8.2g, reflux divides water to anhydrous changing into again after going out to concentrate toluene and steam half toluene, residual reaction liquid filters out catalyzer, catalyzer is not treated can be recycled and reused for the reaction of this step, treats hydrogenation; The preparation of ethyl phenylcyclohexane: in 1000ml high-pressure hydrogenation still, add 4-ethyl-1-benzyl ring hexene and treat hydrogenation reaction solution, add palladium carbon (palladium carbon is 5% palladium content, water content 53%) and the 78.9g ethanol of 3.26g, use N after vacuumizing
2Air twice in the displacement hydrogenation still is used H again
2Displacement N
2Three times, be forced into 1.5MPa the 4th time, and in 60 ℃ of insulation reaction 2 hours, during when pressure during less than 1.3MPa ftercompction to 1.5MPa.Reaction end back emptying filters palladium carbon in the reaction solution, and filter cake is used ethanol 15.8g with heating back ethanol drip washing 2 times at every turn, and leacheate merges with filtrate, concentrates out solvent toluene and ethanol, gets light yellow liquid 42.9g, and first three goes on foot reaction yield 95%; The preparation of trans ethyl phenylcyclohexane: adding ethyl phenylcyclohexane 47g in the 250ml there-necked flask is 0.25mol, toluene 104.4g and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 16.4g, temperature rising reflux cooling in 4 hours, the elimination catalyzer, catalyzer can not treatedly be reused for this step reaction, and with heating back toluene drip washing catalyzer 2 times, each toluene 21.2g that uses, leacheate merges with organic phase, concentrated solvent toluene, again the concentrated solution molecular distillation is got the 43.3g white solid, this step yield 92.15%; The preparation of trans ethyl cyclohexyl iodobenzene: in the 2000ml there-necked flask, add 13.8% the aqueous sodium hydroxide solution contain 10g sodium hydroxide, stirring down, the trans ethyl phenylcyclohexane 47g of adding is 0.25mol, ethanol 274g and potassiumiodide 45.7g are 0.25mol, ice-water bath is cooled to 0 ℃, the clorox 204.9g that drips 10% available chlorine by constant pressure funnel is 0.275mol again, temperature control＜5 ℃ in the whole dropping process, finish the back in 0～5 ℃ of insulation reaction 1 hour, adding Sodium Pyrosulfite 2.4 grams then is 0.0126mol, adding 400g water again stirred 10 minutes, drip the 800g concentrated hydrochloric acid by constant pressure funnel again and be acidified to PH＜1, and control souring temperature＜50 ℃, material after the acidifying is poured in the 5000ml beaker that fills the 252g ethylene dichloride, and restir 5 minutes, tell organic phase, water with the extraction of 252g ethylene dichloride once, merge organic phase, be washed to neutrality, with 10g anhydrous sodium sulfate drying 2 hours, filter out siccative, and with twice in ethylene dichloride drip washing siccative, each ethylene dichloride 31.5g that uses, merge organic phase, be concentrated into solvent-freely to go out, to concentrated solution by the 1g product: 1.2g ethanol carries out recrystallization twice, gets the 67.9g white solid through molecular distillation again, this step yield 86.45%; Preparation to fluorobenzoic boric acid: adding 89g tetrahydrofuran (THF) and 7.3g magnesium powder are 0.3mol in the 500ml there-necked flask, reflux is closed heating after 10 minutes, drip 10% by constant pressure funnel and contain the mixing liquid that 41.3g is 0.25mol p-Fluoro bromo benzene and 44.5g tetrahydrofuran (THF), by the prolong 0.2g iodine that in system, adds suitable for reading, after confirming to cause, remaining mixing liquid is splashed in the system under weak backflow then, after finishing, back flow reaction 2 hours is cooled to below 50 ℃, and is stand-by; Adding tributyl borate 97.7g in another 500ml there-necked flask is 0.25mol and tetrahydrofuran (THF) 89g, liquid nitrogen cooling is to-75 ℃ under stirring, and with the preparation Grignard reagent be added dropwise in the reaction flask by constant pressure funnel, whole dropping process temperature control finishes the back and reacted 1 hour under this temperature in-75～-70 ℃; In the 3000ml there-necked flask, add entry 700g again, stir and add the 300g concentrated hydrochloric acid down, then this reaction solution is slowly added acidification hydrolization in the 3000ml there-necked flask, after finishing, hydrolysis washes away the 500ml there-necked flask at twice with the 280g sherwood oil, and join in the 3000ml there-necked flask, and continue to stir again 30 minutes, left standstill 1 hour, tell behind the water with 105g petroleum ether extraction water, merge organic phase and be washed to neutrality, concentrate organic phase and go out, cool to 50～60 ℃, and concentrated solution is added drop-wise in the 3000ml there-necked flask that fills 1000g water to solvent-free, continue again after adding to stir 1 hour, filter,, press the 1g product: 1.4g sherwood oil reflux 1 hour the filter cake oven dry, reduce to 0 ℃ of filtration, dry once more stand-by, product 27.9g, this step yield 86%; 4-(4-ethyl cyclohexyl)-4 ',-fluoro-1-1 ', the preparation of-biphenyl: in the 500ml there-necked flask, add toluene 75g successively, ethanol 60g, distilled water 78g, Tetrabutyl amonium bromide 4g is 0.0125mol, silicon dioxide carried four triphenylphosphine palladium chloride catalyzer 32g are 0.0075mol, to fluorobenzoic boric acid 32.5g is 0.25mol, trans ethyl cyclohexyl iodobenzene 78.5g is 0.25mol, dividing and adding potassiumphosphate 46.4g altogether three times is 0.22mol, added behind each raw material temperature rising reflux 2 hours, stop heating, being cooled to 55 ℃ left standstill 1 hour, supported catalyst is filtered, and, use toluene 44g at every turn with toluene drip washing catalyzer twice, this catalyzer can continue on for this step reaction, leave standstill then and tell water, water toluene extracting twice is used toluene 44g at every turn, merge with organic phase, organic phase is washed to neutrality, and adds anhydrous magnesium sulfate 10g elimination siccative after dry 4 hours, and filter cake is with twice of toluene drip washing, each toluene 17g that uses, and with the organic phase merging, normal pressure is crossed the silica alumina post, presses the 1g product: 0.1g silicon-dioxide: the 0.1g aluminum oxide, crossing post finishes back with 44g toluene drip washing pillar, integrate with in the organic phase, organic phase is concentrated into solvent-freely to go out, and to its molecular distillation, get white solid 55.9g, this step yield 92%, total recovery 62.7% is in ethyl cyclohexanone.
The employed Preparation of catalysts method of present embodiment:
The preparation of silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent: in the 250ml there-necked flask, add 150g distilled water and 30g tosic acid, stirring makes its dissolving, and then adding 90g silicon-dioxide, heat up in 70 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
Silicon dioxide carried four triphenylphosphine palladium chloride Preparation of catalysts: in the 250ml there-necked flask, add 100g distilled water and 5.8g Palladous chloride, stirring makes its dissolving, add 100g silicon-dioxide then, heat up and in 75 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry is standby after 8 hours under the=0.095MPa condition; In the 1000ml there-necked flask, add the silicon dioxide carried Palladous chloride and the 34.2g triphenyl phosphorus of having dried, N
2Protection is temperature rising reflux 24 hours down, reduces to after the room temperature in N
2Protection is filtered down, solid materials is changed in the vacuum drying oven, in 90 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
Claims (10)
1, a kind of synthetic method of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal is characterized in that: select bromobenzene and magnesium to carry out grignard reaction, then with alkyl cyclohexanone coupling and hydrolysis, again through dehydration, hydrogenation, transition, iodo synthesis of alkyl cyclohexyl iodobenzene; P-Fluoro bromo benzene and magnesium carry out grignard reaction, and the low temperature coupling is synthetic has then synthesized target compound by linked reaction at last again to fluorobenzoic boric acid, and its synthetic route is as follows:
Wherein I is 4-alkyl-1-phenylcyclohexanol, and II is 4-alkyl-1-benzyl ring hexene, and III is an alkyl-cyclohexyl benzene, IV is trans alkyl-cyclohexyl benzene, and V is trans alkyl-cyclohexyl iodobenzene, and VI is to fluorobenzoic boric acid, VII is 4-(4-alkyl-cyclohexyl)-4 ',-fluoro-1-1 ' ,-biphenyl, R is expressed as alkyl, represent ethyl respectively, propyl group, butyl, amyl group.
2, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, the preparation that it is characterized in that described I is to add tetrahydrofuran (THF) 107g and 6.9g magnesium powder in the 500ml there-necked flask, be heated to backflow 10min, close heating, the mixing liquid that contains 37.7g bromobenzene and 87g toluene of dropping 10% in reaction flask, in system, add 0.2g iodine by the prolong upper end again, after the initiation, continue to be added dropwise to remaining mixed liquid in the reaction flask, heat up after finishing in 55～65 ℃ of insulation reaction 2 hours, change the water-bath temperature regulating device then into, under in the time of 30 ℃, stirring with the mixing liquid of 33.6g ethyl cyclohexanone and 87g toluene, be added dropwise in the system, and the control dropping temperature is in 30～35 ℃, add the back in this temperature insulation 30 minutes, reaction finishes reaction solution with containing the 200g trash ice and 300g10% hydrochloric acid is hydrolyzed, tell water after hydrolysis is intact, water extracts 3 times with toluene, each toluene 43.5g that uses, and merge with organic phase and to be washed to neutrality again, anhydrous magnesium sulfate drying filters, and organic phase is to be drained off.
3, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described II: in the 1000ml there-necked flask, add 4-ethyl-1-phenylcyclohexanol organic phase and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 8.2g, reflux divides water to anhydrous changing into again after going out to concentrate toluene and steam half toluene, residual reaction liquid filters out catalyzer, catalyzer is not treated can be recycled and reused for the reaction of this step, treats hydrogenation.
4, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described III: in 1000ml high-pressure hydrogenation still, add 4-ethyl-1-benzyl ring hexene and treat hydrogenation reaction solution, and the palladium carbon and the 78.9g ethanol of this product theoretical amount 5%, the palladium carbon that uses is 5% palladium content, water content 53%, uses N after vacuumizing
2Air twice in the displacement hydrogenation still is used H again
2Displacement N
2Three times, be forced into 1.5MPa the 4th time, and in 50～60 ℃ of insulation reaction 2 hours, during when pressure during less than 1.3MPa ftercompction to 1.5MPa; Reaction end back emptying filters palladium carbon in the reaction solution, and filter cake is used ethanol 15.8g with heating back ethanol drip washing 2 times at every turn, and leacheate merges with filtrate, concentrates out solvent toluene and ethanol, gets light yellow liquid 42.9g.
5, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described IV: in the 250ml there-necked flask, add ethyl phenylcyclohexane 47g, toluene 104.4g and silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent 16.4g, temperature rising reflux cooling in 4 hours, the elimination catalyzer, catalyzer can not treatedly be reused for this step reaction, and with heating back toluene drip washing catalyzer 2 times, each toluene 21.2g that uses, washing lotion merges with organic phase, concentrated solvent toluene gets the 43.3g white solid with the concentrated solution molecular distillation again, this step yield 92.15%.
6, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described V: in the 2000ml there-necked flask, add 13.8% the aqueous sodium hydroxide solution contain 10g sodium hydroxide, stir and add trans ethyl phenylcyclohexane 47g down, ethanol 274g and potassiumiodide 45.7g, ice-water bath is cooled to 0 ℃, drip the clorox 204.9g of 10% available chlorine again by constant pressure funnel, temperature control＜5 ℃ in the whole dropping process, finish the back in 0～5 ℃ of insulation reaction 1 hour, add Sodium Pyrosulfite 2.4 grams then, adding 400g water again stirred 10 minutes, drip the 800g concentrated hydrochloric acid by constant pressure funnel again and be acidified to PH＜1, and control souring temperature＜50 ℃, material after the acidifying is poured in the 5000ml beaker that fills the 252g ethylene dichloride, and restir 5 minutes, tell organic phase, water with the extraction of 252g ethylene dichloride once, merge organic phase, be washed to neutrality, with 10g anhydrous sodium sulfate drying 2 hours, filter out siccative, and with ethylene dichloride drip washing siccative 2 times, each ethylene dichloride 31.5g that uses, merge organic phase, be concentrated into solvent-freely to go out, to concentrated solution by the 1g product: 1.2g ethanol carries out recrystallization twice, get the 67.9g white solid through molecular distillation again, this step yield 86.45%.
7, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described VI: in the 500ml there-necked flask, add 89g tetrahydrofuran (THF) and magnesium powder 7.3g, reflux is closed heating after 10 minutes, the mixing liquid that contains 41.3g p-Fluoro bromo benzene and 44.5g tetrahydrofuran (THF) by constant pressure funnel dropping 10%, then by the prolong 0.2g iodine that in system, adds suitable for reading, after confirming to cause, remaining mixing liquid is splashed in the system under weak backflow, after finishing, back flow reaction 2 hours, be cooled to below 50 ℃, stand-by; In another 500ml there-necked flask, add tributyl borate 97.7g and tetrahydrofuran (THF) 89g, liquid nitrogen cooling is to-75 ℃ under stirring, and the Grignard reagent of preparation is added dropwise in the reaction flask by constant pressure funnel, whole dropping process temperature control is in-75～-70 ℃, finishes back reaction 1 hour under this temperature; In the 3000ml there-necked flask, add entry 700g again, stir and add the 300g concentrated hydrochloric acid down, then this reaction solution is slowly added acidification hydrolization in the 3000ml there-necked flask, after finishing, hydrolysis washes away the 500ml there-necked flask at twice with the 280g sherwood oil, and join in the 3000ml there-necked flask, and continue to stir again 30 minutes, left standstill 1 hour, tell behind the water with 105g petroleum ether extraction water, merge organic phase and be washed to neutrality, concentrate organic phase and go out, cool to 50～60 ℃, and concentrated solution is added drop-wise in the 3000ml there-necked flask that fills 1000g water to solvent-free, continue again after adding to stir 1 hour, filter,, press the 1g product: 1.4g sherwood oil reflux 1 hour the filter cake oven dry, reduce to 0 ℃ of filtration, dry once more stand-by, product 27.9g, this step yield 86%.
8, the synthetic method of a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal according to claim 1, it is characterized in that the preparation of described VII: in the 500ml there-necked flask, add toluene 75g successively, ethanol 60g, distilled water 78g, Tetrabutyl amonium bromide 4g, silicon dioxide carried four triphenylphosphine palladium chloride catalyzer 32g, to fluorobenzoic boric acid 32.5g, trans ethyl cyclohexyl iodobenzene 78.5g, divide and add potassiumphosphate 46.4g altogether three times, added behind each raw material temperature rising reflux 2 hours, stop heating, being cooled to 55 ℃ left standstill 1 hour, supported catalyst is filtered, and with toluene drip washing catalyzer 2 times, each toluene 44g that uses, this catalyzer can continue on for this step reaction, leave standstill then and tell water, water is used toluene 44g with toluene extraction 2 times at every turn, merge with organic phase, organic phase is washed to neutrality, and adds anhydrous magnesium sulfate 10g elimination siccative after dry 4 hours, and filter cake is with toluene drip washing 2 times, each toluene 17g that uses, and with the organic phase merging, normal pressure is crossed the silica alumina post, presses the 1g product: 0.1g silicon-dioxide: the 0.1g aluminum oxide, crossing post finishes back with toluene 44g drip washing pillar, integrate with in the organic phase, organic phase is concentrated into solvent-freely to go out, and to its molecular distillation, get white solid 55.9g, this step yield 92%.
9, according to the synthetic method of claim 1 or 3 or 5 described a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystals, it is characterized in that the preparation of silicon dioxide carried Catalyzed by p-Toluenesulfonic Acid agent: in the 250ml there-necked flask, add 150g distilled water and 30g tosic acid, stirring makes its dissolving, and then adding 90g silicon-dioxide, heat up in 70 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
10, according to the synthetic method of claim 1 or 8 described a kind of fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystals, it is characterized in that silicon dioxide carried four triphenylphosphine palladium chloride Preparation of catalysts: in the 250ml there-necked flask, add 100g distilled water and 5.8g Palladous chloride, stirring makes its dissolving, add 100g silicon-dioxide then, heat up and in 75 ℃ of insulated and stirred 6 hours, change reaction mass in R201 Rotary Evaporators evaporate to dryness distilled water, take out solid materials and change in the vacuum drying oven, at 80 ℃ and P
VeryOven dry is standby after 8 hours under the=0.095MPa condition; In the 1000ml there-necked flask, add the silicon dioxide carried Palladous chloride and the 34.2g triphenyl phosphorus of having dried, N
2Protection is temperature rising reflux 24 hours down, reduces to after the room temperature in N
2Protection is filtered down, solid materials is changed in the vacuum drying oven, in 90 ℃ and P
VeryOven dry can be used after 8 hours under the=0.095MPa condition.
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Denomination of invention: Synthesis of a Fluorine Containing Trans alkyl cyclohexyl biphenyl Liquid Crystalline Monomer Effective date of registration: 20220927 Granted publication date: 20120725 Pledgee: China Construction Bank Corporation Laiyang Sub branch Pledgor: SHANDONG SHENGHUA NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980016488 |