CN101607868B - Method for synthesizing liquid crystal material intermediate having methlcyclohexanol structure - Google Patents
Method for synthesizing liquid crystal material intermediate having methlcyclohexanol structure Download PDFInfo
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- CN101607868B CN101607868B CN200810116912XA CN200810116912A CN101607868B CN 101607868 B CN101607868 B CN 101607868B CN 200810116912X A CN200810116912X A CN 200810116912XA CN 200810116912 A CN200810116912 A CN 200810116912A CN 101607868 B CN101607868 B CN 101607868B
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Abstract
The invention discloses a method for synthesizing a liquid crystal material intermediate having a methlcyclohexanol structure, which comprises the following steps: firstly, reacting saturated alkyl or alkyl dicyclohexyl formic acid and an alcohol to form saturated alkyl or alkyl dicyclohexyl formate; and using a reducer to reduce the saturated alkyl or alkyl dicyclohexyl formate into a corresponding alcohol by hydrogenation. The method for synthesizing the liquid crystal material intermediate having the methlcyclohexanol structure avoids the strict conditions and dangers of the conventional method. In addition, the method uses cheap potassium borohydride and anhydrous lithium chloride reducers for reduction. The has the advantages that: the reducers are easy to store; the batch charging method is simple; the reaction yield is ideal; the cost is low; and the operation is safe.
Description
Technical field
The present invention relates to the compound method of compound, one type of compound method that contains hexanaphthene methylol structure liquid crystal material intermediate specifically, this compound is ethane class and the ethene liquid crystal material important intermediate in synthetic, is mainly used in liquid-crystal display.
Technical background
Since nineteen seventies; Along with liquid crystal optics, liquid crystal chemistry; And the development of large-scale integrated circuit and liquid crystal material, the application of liquid crystal aspect demonstration obtained the development of advancing by leaps and bounds, and successively experienced TN-LCD, STN-LCD, TFT-LCD three phases.Its typically used has wrist-watch, counter, instrument, and MP3 afterwards, MP4, now in the LCD TV large-scale application.Liquid-crystal display has advantages such as panelized, in light weight, less energy-consumption, low radiation, and complete processing is constantly perfect, cost constantly reduces, and its popularity rate improves rapidly.
The liquid crystal material that is used for liquid-crystal display need have following characteristics:
1. wide nematic phase temperature (particularly having the high and low temperature performance);
2. certain optics, electricity anisotropy;
3. reasonable chemicalstability, thermostability and light stability (particularly the UV irradiation down);
4. LV;
5. resistivity is high, preferably the electric charge conservation rate;
6. solvability preferably.
It is almost nil that a kind of compound meets the display requirement possibility fully in practical application, realizes with forming compsn after several kinds of compound usually.
It is low, stable high, good with other mesomorphic phase capacitives that ethane class liquid crystal has viscosity, and especially chemicalstability and anti-ultraviolet radiation performance are good.Be the necessary component of the high-grade multichannel driving display spare of matrix, like the TFT-LCD mixed liquid crystal.The vinyl liquid crystal is owing to have high K
33/ k
11Therefore value is widely used in the STN-LCD mixed liquid crystal.
The structural formula of the liquid crystal material midbody that the present invention relates to is:
Wherein, R is saturated alkyl or saturated alkyl cyclohexyl.
The method of reducing that is directly prepared alcohol by acid is more, but its condition is harsh, and cost is higher.The basic metal that utilizes as reporting among J.O.C vol44:2180 and the Org Syn Coll Vol2:372 reduces in liquefied ammonia, and this method operational condition is harsh; J.A.C.S.Vol69:1197 and Org SynVol63:140 report select for use tetrahydrochysene lithium aluminium to do catalyst reduction, and this method tetrahydrochysene lithium aluminium operational danger is big, unsuitable large-scale industrial production; All report at J.O.C vol47:4702, vol56:4706 and J.A.C.S.Vol111:3382 and to select for use lithium borohydride as catalyst reduction, this method lithium borohydride price is more expensive, and cost price is high.
Summary of the invention
The objective of the invention is to provides a kind of synthetic compound method that contains hexanaphthene methylol structure liquid crystal material intermediate to above-mentioned deficiency.This method can strengthen the industrialization production feasibility of synthetic said liquid crystalline cpd, reduces danger and cost.
The present invention at first is converted into ester with acid, restores to obtain alcohol, and its synthetic route is following:
Wherein, R is saturated alkyl or saturated alkyl cyclohexyl, is preferably the saturated alkyl or the saturated alkyl cyclohexyl that contain 1-15 carbon atom, and R ' is a saturated alkyl, is preferably the saturated alkyl that contains 1-15 carbon atom.
Obtaining formula (II) compound through formula (I) compound and alcohol are carried out esterification, is that the reaction of second step is prepared.The esterification here can be carried out according to ordinary method well-known to those skilled in the art.
The present invention optimizes synthetic route steps (2).The present invention adopts the reductive agent of the mixture of POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) composition as formula (II) compound reduction reaction, and wherein POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) are 1: 0.8～2 in molar ratio, be preferably 1: 0.9～and 1.2, more preferably 1: 1.The amount that reductive agent adds should adapt with the amount of formula (II) compound, is 1.5～3: 1 according to the mol ratio of POTASSIUM BOROHYDRIDE 97MIN and formula (II) compound, is preferably 1.7～2.5: 1, and more preferably 2: 1.
Those skilled in the art are to be understood that above-mentioned being reflected in the appropriate solvent carry out, for example THF, absolute ethyl alcohol, or they arbitrarily than mixture, temperature of reaction is the reflux temperature of solvent.
The present invention has abandoned tradition by the direct method for preparing alcohol (formula (III) compound) of acid (formula (I) compound); And adopt acid (formula (I) compound) is changed into ester (formula (II) compound); Repeated hydrogenation is reduced into alcohol (formula (III) compound), has avoided traditional method exacting terms and danger like this.The present invention also selects for use cheap POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) to accomplish synthetic second step of containing hexanaphthene methylol structure liquid crystal material intermediate as the reductive agent of formula (II) compound; This reductive agent is easy to preserve; Feeding method is simple; The yield of reaction is comparatively desirable, and cost is low, operational safety.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.Under the situation that does not deviate from the present invention's spirit and essence, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.
Embodiment 1:
This example is the first step of building-up reactions, with compound (1) and ethanol synthesis, obtains compound (2):
300g (1) and 900ml absolute ethyl alcohol are mixed, drip the 100ml vitriol oil then.After adding fully, reaction mixture was heated to back flow reaction 5 hours.In reaction solution, add the 2L deionized water, 500ml petroleum ether and stirring 10 minutes is separated organic phase and with petroleum ether extraction water twice, is merged organic phase, is washed till neutrality with deionized water, drying, and removal of solvent under reduced pressure gets colourless transparent liquid (2).
Yield: 340g (theoretical value 100%), GC (purity): 99.62%.According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl dicyclohexyl ethyl formate,
It is trans-4-butyl dicyclohexyl ethyl formate,
Trans-4-amyl group dicyclohexyl ethyl formate.
Embodiment 2:
This example is second step of building-up reactions, and the compound (2) that embodiment 1 is obtained obtains compound (3) through reduction reaction:
With the 130g POTASSIUM BOROHYDRIDE 97MIN, 102g Lithium chloride (anhydrous) and 1000ml THF mix, and the cooling of external application frozen water drips the 340g (2) and the 300ml tetrahydrofuran solution that obtain among the embodiment 1.After adding fully, reaction mixture is heated to backflow, reacts 8～20 hours, and the monitoring raw material reaction is complete.With slowly pouring in the reaction solution in 2kg trash ice and the 1L deionized water, add 500ml toluene again and stirred 10 minutes, separate organic phase and, merge organic phase with extracted in toluene water twice, be washed till neutrality with deionized water, drying, removal of solvent under reduced pressure.With 600ml sherwood oil recrystallization, solution is cooled to-20 ℃ and spends the night, and suction strainer goes out sedimentary crystal, obtains title product (3) with sherwood oil drip washing and vacuum-drying.
Yield: 270g (theoretical value 95%), GC:99.75%, fusing point: 126.7 ℃.
According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl dicyclohexyl methyl alcohol,
It is trans-4-butyl dicyclohexyl methyl alcohol,
Trans-4-amyl group dicyclohexyl methyl alcohol.
Carry out as stated above, only change the proportion of composing of reductive agent and the amount of interpolation, its result is following:
| POTASSIUM BOROHYDRIDE 97MIN (gram) | Lithium chloride (gram) | Output (gram) | Yield (%) | GC(％) |
| 97.5 | 153.0 | 243 | 85.5 | 98.85 |
| 110.5 | 103.8 | 255 | 89.8 | 99.00 |
| 162.5 | 127.5 | 267 | 94.0 | 99.65 |
| 195 | 122.4 | 272 | 95.6 | 99.70 |
Embodiment 3:
This example is the first step of building-up reactions, with compound (4) and ethanol synthesis, obtains compound (5):
170g (4) and 600ml absolute ethyl alcohol are mixed, drip the 100ml vitriol oil then.After adding fully, reaction mixture was heated to back flow reaction 5 hours.In reaction solution, add the 2L deionized water, 500ml petroleum ether and stirring 10 minutes is separated organic phase and with petroleum ether extraction water twice, is merged organic phase, is washed till neutrality with deionized water, drying, and removal of solvent under reduced pressure gets colourless transparent liquid (5).
Yield: 198g (theoretical value 100%), GC:99.70%.According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl cyclohexyl ethyl formate,
It is trans-4-butyl cyclohexyl ethyl formate,
Trans-4-amyl group cyclohexyl ethyl formate.
Embodiment 4:
This example is second step of building-up reactions, and the compound (5) that embodiment 3 is obtained obtains compound (6) through reduction reaction:
With the 108g POTASSIUM BOROHYDRIDE 97MIN, 85g Lithium chloride (anhydrous) and 800ml THF mix, and the cooling of external application frozen water drips the 198g (5) and the 200ml tetrahydrofuran solution that obtain among the embodiment 3.After adding fully, reaction mixture is heated to backflow, reacts 8～20 hours, and the monitoring raw material reaction is complete.With slowly pouring in the reaction solution in 2kg trash ice and the 1L deionized water, added the 500ml petroleum ether and stirring again 10 minutes, separate organic phase and, merge organic phase with petroleum ether extraction water twice, be washed till neutrality with deionized water, drying, removal of solvent under reduced pressure.Underpressure distillation gets colourless transparent liquid (6).
Yield: 146g (theoretical value 94%), GC:99.40%.
According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl hexahydrobenzyl alcohol,
It is trans-4-butyl hexahydrobenzyl alcohol,
Trans-4-amyl group hexahydrobenzyl alcohol.
Embodiment 5:
This example is the first step of building-up reactions, with compound (1) and propyl carbinol reaction, obtains compound (7):
252g (1) and 740g propyl carbinol are mixed, and the stirring heating reflux water-dividing does not generate to there being the globule, monitors no raw material residue.Propyl carbinol is removed in decompression, gets colourless transparent liquid (7), and the propyl carbinol that wherein steams is recyclable to be applied mechanically.
Yield: 308g (theoretical value 100%), GC:99.6%.
According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl dicyclohexyl n-buty formate,
It is trans-4-butyl dicyclohexyl n-buty formate,
Trans-4-amyl group dicyclohexyl n-buty formate.
Embodiment 6:
With the 108g POTASSIUM BOROHYDRIDE 97MIN, 85g Lithium chloride (anhydrous) and 800ml THF mix, and the cooling of external application frozen water drips the 308g (7) and the 200ml tetrahydrofuran solution that obtain among the embodiment 5.After adding fully, reaction mixture is heated to backflow, reacts 8～20 hours, and the monitoring raw material reaction is complete.With slowly pouring in the reaction solution in 2kg trash ice and the 1L deionized water, add 500ml toluene again and stirred 10 minutes, separate organic phase and, merge organic phase with extracted in toluene water twice, be washed till neutrality with deionized water, drying, removal of solvent under reduced pressure.With 600ml sherwood oil recrystallization, solution is cooled to-20 ℃ and spends the night, and suction strainer goes out sedimentary crystal, obtains title product (3) with sherwood oil drip washing and vacuum-drying.
Yield: 146g (theoretical value 94%), GC:99.40%.
According to above-mentioned similarity method, can obtain following compounds:
It is trans-4-ethyl dicyclohexyl methyl alcohol,
It is trans-4-butyl dicyclohexyl methyl alcohol,
Trans-4-amyl group dicyclohexyl methyl alcohol.
Claims (7)
1. synthetic method that contains the liquid crystal material midbody of hexanaphthene methylol structure comprises that formula (I) compound and alcohol are carried out esterification obtains formula (II) compound:
And the mixture that uses POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) to form is reductive agent, and the mode that adds reductive agent is under with frozen water refrigerative condition; Formula (II) compound is joined in the reductive agent; The solvent of reduction reaction is a THF, with formula (II) compound hydrogenating reduction accepted way of doing sth (III) compound
Wherein, R is saturated alkyl or saturated alkyl cyclohexyl, and R ' is a saturated alkyl.
2. the method for claim 1 is characterized in that, said R is saturated alkyl or the saturated alkyl cyclohexyl that contains 1-15 carbon atom, and R ' is for containing the saturated alkyl of 1-15 carbon atom.
3. the method for claim 1 is characterized in that, the mol ratio of POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) is 1: 0.8～2.
4. method as claimed in claim 3 is characterized in that, the mol ratio of POTASSIUM BOROHYDRIDE 97MIN and Lithium chloride (anhydrous) is 1: 1.
5. the method for claim 1 is characterized in that, the mol ratio of POTASSIUM BOROHYDRIDE 97MIN and formula (II) compound is 1.5～3: 1 in the said reductive agent.
6. method as claimed in claim 5 is characterized in that, the mol ratio of POTASSIUM BOROHYDRIDE 97MIN and formula (II) compound is 2: 1 in the said reductive agent.
7. the method for claim 1 is characterized in that, temperature of reaction is the reaction solvent reflux temperature.
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| CN113024375B (en) * | 2021-01-18 | 2023-06-13 | 阜阳欣奕华材料科技有限公司 | Preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer |
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Non-Patent Citations (3)
| Title |
|---|
| 王德才.3 5-二羟基苯甲醇的简便合成方法.《精细化工》.1997 |
| 王德才.3,5-二羟基苯甲醇的简便合成方法.《精细化工》.1997,第14卷(第6期), * |
| 蔡良珍.NaBH4/Lewis 酸体系室温下还原反式环己基羧酸及酯的反应.《液晶与显示》.2007,第22卷(第6期), * |
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Address after: 100085 Building No. 2, building 1, ten Street, Haidian District, Beijing, 2013 Patentee after: Beijing Bayi Space LCD Materials Technology Co., Ltd. Address before: 100085 No. 5, building 1, East Road, Haidian District, Beijing, 701 Patentee before: Beijing Bayi Space LCD Materials Technology Co., Ltd. |
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