CN112125788A - Preparation method of liquid crystal monomer compound containing difluoromethyl ether bridge bond - Google Patents
Preparation method of liquid crystal monomer compound containing difluoromethyl ether bridge bond Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
The invention relates to the technical field of liquid crystal monomer compound synthesis, and particularly discloses a preparation method of a liquid crystal monomer compound containing a difluoromethyl ether bridge bond. The compound containing a polyfluoro structure shown in the formula I is used as a raw material, imidazole basic ionic liquid shown in the formula II is used as a catalyst, the conversion rate of the polyfluoro structure raw material is effectively improved, the purity and the yield of a target product are further improved, the HPLC content of the prepared liquid crystal monomer compound containing the difluoromethyl ether bridge bond is more than 99.9%, the total yield of the product is more than 85%, meanwhile, the process flow for preparing the liquid crystal monomer compound containing the difluoromethyl ether bridge bond is shortened, the use cost of a butyl lithium reagent with high cost is avoided, and further the problem that the use cost of the butyl lithium reagent is high is avoidedThe method has the advantages of ultralow temperature reaction, low requirement on equipment, reduction in process difficulty and environmental friendliness, and is a novel process for preparing the liquid crystal monomer compound containing the difluoromethyl ether bridge bond, which is green and environment-friendly and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of liquid crystal monomer compound synthesis, in particular to a preparation method of a liquid crystal monomer compound containing difluoromethyl ether bridged bonds.
Background
With the continuous expansion of the application of wide temperature liquid crystal display (AM-LCD), people put higher demands on the performance of liquid crystal materials, and the characteristics required by the liquid crystal materials become very diversified. Researchers from Merck, Germany, first reported having-CF in 19892An O-bridged compound. The research shows that the fluorine-containing polymer contains difluoromethyl ether bridge bonds (-CF)2The O-) high-end liquid crystal monomer not only has the characteristics of low viscosity and high dielectric anisotropy, but also has the advantages of good compatibility with other compounds and the like, is particularly suitable to be used as a raw material of a liquid crystal display, and receives wide attention and application in recent years.
5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] methyl ester]Difluoromethoxy group]-1,2, 3-trifluorobenzene is a typical difluoromethyl ether bridge (-CF)2O-) high-end liquid crystal monomer, the existing synthesis process mostly adopts the following route, the synthesis route has the disadvantages of long synthesis route, low production efficiency, use of expensive butyl lithium reagent in the synthesis process, low temperature reaction equipment, great process difficulty, and most importantly, the preparation of the high-end liquid crystal monomer in the process of preparation
In the process of (2), there are by-products
The selectivity is poor, the highest effective conversion rate can reach about 70 percent, and the purity and the yield of the prepared target product are low. Therefore, the research and development of the preparation method of the liquid crystal monomer compound which has mild reaction conditions and high yield and purity and is suitable for industrial production has very important significance.
Disclosure of Invention
Aiming at the problems of low yield, low purity and harsh reaction conditions in the prior art for preparing the liquid crystal monomer compound containing the difluoromethyl ether bridge bond, the invention provides a preparation method of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing a liquid crystal monomer compound containing difluoromethyl ether bridge bonds, comprising the following steps:
a, taking magnesium metal and a compound shown in a formula I as raw materials, and taking imidazole basic ionic liquid shown in a formula II as a catalyst to perform a Grignard reaction to obtain a compound shown in a formula III;
b, carrying out addition and hydrolysis reaction on the compound shown in the formula III and the compound shown in the formula IV to obtain a compound shown in the formula V;
step c, carrying out dehydration, hydrogenation and transposition reactions on the compound shown in the formula V to obtain a liquid crystal monomer compound shown in the formula VIII and containing a difluoromethyl ether bridge bond;
wherein R is C1-C4 straight-chain alkyl; x is BF4Or PF6；R1、R2、R3Is H or F, and R1、R2、R3At least two of which are F; r4、R5Is H or F, and R4、R5At least one is F; r6Is C2-C5 straight chain alkyl;
the compound shown in the formula I contains a plurality of F atoms in the structure, and the F atoms are strong electron-withdrawing groups, so that the para Br activity is high, the direct preparation of the Grignard reagent is easy to have the Wutz reaction, macromolecular impurities which are not easy to remove are generated, the yield of a target product is particularly low, and the compound has no practical application value. Preparation of Grignard reagents by Grignard exchange reactions using compounds of formula I
In the process, the Wutz reaction is very easy to occur, macromolecular impurities which are not easy to remove are generated, although the product yield and the purity are higher than those of a method for directly preparing the Grignard reagent, the purity of a target product cannot meet the application requirement of the purity of the liquid crystal monomer, particularly, the post-treatment is very complex, and the product with the purity of more than 99.9 percent is difficult to obtain through simple purification. Therefore, the compound shown in the formula I is adopted as a raw material, and the Grignard reagent with high yield and high purity is difficult to obtain in the step of preparing the Grignard reagent, so that a target product meeting the application requirement of the liquid crystal monomer is difficult to prepare after subsequent multi-step reaction.
The preparation method of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond selects the compound containing the polyfluoro structure as shown in the formula I as the raw material, the imidazole basic ionic liquid shown in the formula II is used as a catalyst, the selected catalyst can lead the activity of Br in the compound shown in the formula I to be inactive, and the Wutz reaction is avoided when the Grignard reagent is prepared, so that the conversion rate of the raw material with the polyfluoro structure is effectively improved, further improves the purity and yield of the target product, shortens the process flow for preparing the liquid crystal monomer compound containing the difluoromethyl ether bridge bond, avoids using butyl lithium reagent with high cost, further avoids ultralow temperature reaction, the method has low requirement on equipment, reduces the process difficulty, is environment-friendly, and is a novel process for preparing the liquid crystal monomer compound containing the difluoromethyl ether bridge bond, which is green and environment-friendly and is suitable for industrial production.
The preparation method of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond has the advantages of high yield, high purity and low production cost, the HPLC content of the prepared liquid crystal monomer compound containing the difluoromethyl ether bridge bond is more than 99.9%, the total product yield is more than 85%, the application requirements of liquid crystal monomers are completely met, the raw materials are easy to obtain, the operation is simple, the safety is high, and the industrial production of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond is favorably realized.
Preferably, the imidazole basic ionic liquid is one or two of 1- (N, N-diethylaminoethyl) -3-methylimidazole tetrafluoroborate and 1- (N, N-diethylaminoethyl) -3-methylimidazole hexafluorophosphate.
The optimized catalyst can effectively reduce the activity of Br in the compound containing the polyfluoro structure shown in the formula I, thereby reducing impurities generated in the reaction for preparing the Grignard reagent, improving the conversion rate of a target product and being beneficial to obtaining the target product with high purity and high yield.
The preparation method of the basic ionic liquid can adopt the preparation method of the ionic liquid conventional in the field. The halogenated imidazole salt precursor ionic liquid can be synthesized by quaternization reaction of 1-methylimidazole and halogenated N, N-diethylaminoethane, and then the precursor and corresponding salt (such as tetrafluoroborate and hexafluorophosphate) are subjected to anion exchange reaction in a solvent to synthesize the basic ionic liquid.
Preferably, the preparation method of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond specifically comprises the following steps:
under the protection of inert gas, adding a compound shown as a formula I, imidazole basic ionic liquid shown as a formula II and metal magnesium into a first organic solvent, and carrying out a Grignard reaction at 0-80 ℃ to obtain a reaction solution containing a compound shown as a formula III;
dissolving a compound shown as a formula IV in a second organic solvent to obtain a compound solution shown as a formula IV; adding a compound solution shown as a formula IV into a reaction solution containing a compound shown as a formula III under the protection of inert gas, uniformly mixing, carrying out addition reaction at 40-100 ℃, adding the reaction solution into an acid solution after the reaction is finished, and carrying out hydrolysis reaction at 0-30 ℃ to obtain a reaction solution containing the compound shown as the formula V;
adding a dehydrating agent and a third organic solvent into a reaction solution containing the compound shown in the formula V, and performing dehydration reaction at the temperature of 80-140 ℃ to obtain a compound shown in the formula VI;
step four, adding the compound shown in the formula VI and a hydrogenation catalyst into a fourth organic solvent, uniformly mixing, and carrying out hydrogenation reaction under the conditions of 0.1-1 MPa and 20-80 ℃ to obtain a compound shown in the formula VII;
and step five, adding the compound shown in the formula VII and a transposition catalyst into a fifth organic solvent, and carrying out transposition reaction at the temperature of minus 40-20 ℃ to obtain the liquid crystal monomer compound shown in the formula VIII and containing the difluoromethyl ether bridge bond.
The equation for the above reaction is as follows:
optionally, the magnesium metal in the present invention includes, but is not limited to, magnesium powder, magnesium strip or magnesium chip.
The inert gas in the present invention may be an inert gas conventional in the art, such as nitrogen, argon, etc.
Preferably, in the first step, the first organic solvent is at least one of tetrahydrofuran, dioxane, methyl tert-butyl ether, toluene, benzene or petroleum ether.
Preferably, in the second step, the second organic solvent is at least one of tetrahydrofuran, dioxane, methyl tert-butyl ether, toluene, benzene or petroleum ether.
Preferably, in the third step, the third organic solvent is at least one of cyclohexane, toluene or xylene.
Preferably, in the fourth step, the fourth organic solvent is at least one of methanol, ethanol, petroleum ether, n-heptane, n-hexane or toluene.
Preferably, in the fifth step, the fifth organic solvent is at least one of dichloromethane, dichloroethane, toluene or xylene.
The optimized solvent is beneficial to fully mixing reaction raw materials, improving the utilization rate of the raw materials and reducing the occurrence of side reactions, and is also beneficial to dissolving products prepared by each step of reaction in a reaction system, thereby ensuring the smooth proceeding of the next step of reaction.
Preferably, the dehydrating agent is p-toluenesulfonic acid.
Preferably, the hydrogenation catalyst is a ruthenium carbon catalyst.
Preferably, the translocation catalyst is trifluoroacetic acid.
Preferably, in the first step, the molar ratio of the compound shown in the formula I to the metal magnesium is 1: 1.2-2.
Preferably, in the first step, the mass-to-volume ratio of the compound represented by the formula i to the first organic solvent is 1: 3-6, wherein the unit of mass is gram, and the unit of volume is milliliter.
Preferably, in the first step, the amount of the imidazole basic ionic liquid shown in the formula II is 5-10 wt% of the compound shown in the formula I.
Preferably, in the step one, the reaction time is 1-8 h.
Preferably, in the second step, the molar ratio of the compound shown in the formula I to the compound shown in the formula IV is 1: 1.0-1.2.
Preferably, in the second step, the mass-to-volume ratio of the compound represented by the formula IV to the second organic solvent is 1: 1-5, wherein the unit of mass is gram, and the unit of volume is milliliter.
Preferably, in the second step, the time of the addition reaction is 5-7 h, and the time of the hydrolysis reaction is 20-40 min.
Optionally, in step two, the acid used for hydrolysis is an inorganic acid or an organic acid as is conventional in the art. The mass concentration of the acid in the acid solution is preferably 10-50 wt%, and the molar amount of the acid is 1-3 times of the amount of the metal magnesium substance.
Preferably, in the third step, the addition amount of the dehydrating agent is 4-6 wt% of the theoretical yield of the compound shown in the formula V.
Preferably, in the third step, the volume of the third organic solvent added is 3-5 times of the theoretical yield of the compound represented by the formula v, wherein the volume is ml, and the theoretical yield is g.
Preferably, in the third step, the reaction time is 4-8 h.
Preferably, in the fourth step, the volume of the fourth organic solvent is 3-5 times of the theoretical yield of the compound shown in the formula VI, wherein the volume unit is milliliter, and the theoretical yield unit is gram.
Preferably, in the fourth step, the addition amount of the hydrogenation catalyst is 4-6% of the theoretical yield of the compound shown in the formula VI.
Preferably, in the fourth step, the reaction time is 2-6 h.
Preferably, in the fifth step, the volume of the fifth organic solvent added is 3-6 times of the theoretical yield of the compound represented by the formula VII, wherein the volume is milliliter, and the theoretical yield is gram.
Preferably, in the fifth step, the addition amount of the transposition catalyst is 8-12% of the theoretical yield of the compound shown in the formula VII.
Preferably, in the fifth step, the reaction time is 3-5 h.
The preferable proportion among the reactants, the reaction temperature and the reaction time can improve the utilization rate of raw materials, thereby improving the yield and the purity of the target product.
According to the preparation method of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond, provided by the invention, the used raw materials are common reagents, the production cost is low, the reaction condition is mild, the operation is simple, the safety is high, the preparation method is environment-friendly, the HPLC content of the prepared liquid crystal monomer compound containing the difluoromethyl ether bridge bond is more than 99.9%, the total yield is more than 85%, the defects of long reaction route, low production efficiency, high process difficulty and poor selectivity of the original preparation of the liquid crystal monomer compound containing the difluoromethyl ether bridge bond are overcome, and the preparation method is suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene comprises the following steps:
step one, adding 77.8g (0.20mol) of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene (the structural formula is shown in formula 1) into 200mL of tetrahydrofuran to obtain a raw material solution; putting 5.85g (0.24mol) of magnesium chips into a 1000mL three-necked bottle, adding 50mL of tetrahydrofuran and 5.12g of 1- (N, N-diethylaminoethyl) -3-methylimidazolium tetrafluoroborate (the structural formula is shown in formula 2), stirring and dropwise adding the raw material solution under the protection of nitrogen in a water bath at 40 ℃, and reacting for 2 hours from the beginning of dropwise adding the raw material solution to obtain a tetrahydrofuran solution of 5- [ (2, 6-difluoro-4-magnesium bromide phenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, wherein the tetrahydrofuran solution is marked as a first reaction solution;
step two, weighing 28g (0.2mol) of 4-propylcyclohexanone, and dissolving in 60mL of toluene to obtain a 4-propylcyclohexanone solution; dropwise adding the 4-propylcyclohexanone solution into the first reaction solution under the nitrogen protection stirring condition, starting timing from dropwise adding the 4-propylcyclohexanone solution, reacting at 50 ℃ for 7 hours, then dropwise adding the reaction solution into a hydrochloric acid solution (50mL of concentrated hydrochloric acid dissolved in 200mL of water), hydrolyzing at 10 ℃ for 30min, after the reaction is finished, extracting by 200mL of toluene, and washing by water to obtain a toluene solution of 5- [ [2, 6-difluoro-4- (4-propylcyclohexanol) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, and marking as a second reaction solution;
step three, adding 4.50g of p-toluenesulfonic acid and 300mL of toluene into the second reaction solution, performing dehydration reaction at 110 ℃ for 6h, extracting, washing with water, and performing rotary evaporation after the reaction is finished to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexene) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 1;
step four, dissolving the intermediate product 1 in 300mL of ethanol, adding 4.34g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 3 hours at 50 ℃ under 0.3MPa, and after the reaction is finished, filtering and carrying out rotary evaporation to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 300mL of dichloromethane, adding 8.76g of trifluoroacetic acid, performing transposition reaction at-20 ℃ for 4h, and after the reaction is finished, recrystallizing to obtain 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene (the structural formula is shown in formula 3), white crystals and 75.9g of white crystals.
Based on the molar amount of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, the total yield of five steps was 87.6%, and the content by HPLC was 99.99%.
The detection conditions of HPLC are as follows: c18 column, 250mm 160mm, 5 μm, detection wavelength 254nm, mobile phase acetonitrile (chromatogram pure), flow rate 1.0mL/min, column temperature 35 ℃.
Example 2
A preparation method of 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1, 3-difluorobenzene comprises the following steps:
step one, adding 74.2g (0.2mol) of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1, 3-difluorobenzene (the structure is shown in a formula 4) into 250mL of dioxane to obtain a raw material solution; putting 7.52g (0.31mol) of magnesium chips into a 1000mL three-necked bottle, adding 100mL of dioxane and 3.85g of 1- (N, N-diethylaminoethyl) -3-methylimidazolium hexafluorophosphate (the structure is shown in formula 5), stirring and dropwise adding the raw material solution under the conditions of water bath 80 ℃ and nitrogen protection, and reacting for 1h from the beginning of dropwise adding the raw material solution to obtain a dioxane solution of 5- [ (2, 6-difluoro-4-magnesium bromide phenyl) difluoromethoxy ] -1, 3-difluorobenzene, wherein the dioxane solution is marked as a first reaction solution;
step two, weighing 32g (0.23mol) of 4-propylcyclohexanone, and dissolving in 40mL of dioxane to obtain a 4-propylcyclohexanone solution; dropwise adding the 4-propylcyclohexanone solution into the first reaction solution under the nitrogen protection stirring condition, starting timing from dropwise adding the 4-propylcyclohexanone solution, reacting at 70 ℃ for 6 hours, then dropwise adding the reaction solution into a hydrochloric acid solution (50mL of concentrated hydrochloric acid dissolved in 200mL of water), hydrolyzing at 20 ℃ for 30min, after the reaction is finished, extracting by 200mL of cyclohexane, and washing by water to obtain a cyclohexane solution of 5- [ [2, 6-difluoro-4- (4-propylcyclohexanol) phenyl ] difluoromethoxy ] -1, 3-difluorobenzene, and marking as a second reaction solution;
step three, adding 3.50g of p-toluenesulfonic acid and 260mL of cyclohexane into the second reaction solution, performing dehydration reaction at 80 ℃ for 8 hours, extracting, washing and rotary evaporating after the reaction is finished to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexene) phenyl ] difluoromethoxy ] -1, 3-difluorobenzene, and marking as an intermediate product 1;
dissolving the intermediate product 1 in 360mL of petroleum ether, adding 3.35g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 6 hours at 80 ℃ under 0.1MPa, and after the reaction is finished, filtering and carrying out rotary evaporation to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1, 3-difluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 400mL of dichloroethane, adding 6.85g of trifluoroacetic acid, performing transposition reaction at-20 ℃ for 4h, and after the reaction is finished, recrystallizing to obtain 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1, 3-difluorobenzene (the structure is shown in formula 6), white crystals and 72.13g of mass.
Based on the molar amount of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1, 3-difluorobenzene, the total yield in five steps was 86.7%, and the HPLC content was 99.99%.
Example 3
A preparation method of 5- [ [ 2-fluoro-4- (trans-4-butylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene comprises the following steps:
step one, adding 74.2g (0.2mol) of 5- [ (2-fluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene (the structure is shown in a formula 7) into 300mL of toluene to obtain a raw material solution; putting 8.56g (0.36mol) of magnesium chips into a 1000mL three-necked bottle, adding 145mL of toluene and 6.75g of 1- (N, N-diethylaminoethyl) -3-ethylimidazole hexafluorophosphate (the structure is shown in formula 8), dropwise adding the raw material solution under stirring at 0 ℃ in an ice water bath under the protection of nitrogen, timing from the dropwise adding of the raw material solution, and reacting for 8 hours to obtain a toluene solution of 5- [ (2-fluoro-4-magnesium bromide phenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as a first reaction solution;
step two, weighing 37g (0.24mol) of 4-butylcyclohexanone, and dissolving in 130mL of toluene to obtain a 4-butylcyclohexanone solution; dropwise adding the 4-butylcyclohexanone solution into the first reaction solution under the condition of nitrogen protection and stirring, starting timing from dropwise adding the 4-butylcyclohexanone solution, reacting at 60 ℃ for 5 hours, then dropwise adding the reaction solution into a hydrochloric acid solution (50mL of concentrated hydrochloric acid is dissolved in 200mL of water), hydrolyzing at 0 ℃ for 40min, extracting by 200mL of toluene, and washing to obtain a toluene solution of 5- [ [ 2-fluoro-4- (4-butylcyclohexanol) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, and marking as a second reaction solution;
step three, adding 5.50g of p-toluenesulfonic acid and 460mL of toluene into the second reaction solution, performing dehydration reaction at 110 ℃ for 6h, extracting, washing and rotary evaporating after the reaction is finished to obtain a crude product of 5- [ [ 2-fluoro-4- (4-butylcyclohexene) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 1;
step four, dissolving the intermediate product 1 in 350mL of toluene, adding 4.15g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 5 hours at 40 ℃ under 0.4MPa, and after the reaction is finished, filtering and carrying out rotary evaporation to obtain a crude product of 5- [ [ 2-fluoro-4- (4-butylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 430mL of toluene, adding 10.12g of trifluoroacetic acid, performing transposition reaction at-40 ℃ for 5 hours, and after the reaction is finished, recrystallizing to obtain 5- [ [ 2-fluoro-4- (trans-4-butylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene (the structure is shown in formula 9), white crystals and 73.44g of mass.
Based on the molar amount of 5- [ (2-fluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, the total yield in five steps is 85.4%, and the content of HPLC is 99.95%.
Example 4
A preparation method of 4- [ [ 2-fluoro-4- (trans-4-pentylcyclohexyl) phenyl ] difluoromethoxy ] -1, 2-difluorobenzene comprises the following steps:
step one, adding 70.5g (0.20mol) of 4- [ (2-fluoro-4-bromophenyl) difluoromethoxy ] -1, 2-difluorobenzene (the structure is shown as a formula 10) into 300mL of tetrahydrofuran to obtain a raw material solution; putting 9.56g (0.40mol) of magnesium chips into a 1000mL three-necked bottle, adding 60mL of toluene and 7.08g of 1- (N, N-diethylaminoethyl) -3-ethylimidazole tetrafluoroborate (the structure is shown as formula 11), stirring and dropwise adding the raw material solution under the protection of nitrogen in a water bath at 30 ℃, and reacting for 4 hours from the beginning of dropwise adding the raw material solution to obtain a solution containing 4- [ (2-fluoro-4-magnesium bromide phenyl) difluoromethoxy ] -1, 2-difluorobenzene, wherein the solution is marked as a first reaction solution;
step two, weighing 38g (0.23mol) of 4-pentylcyclohexanone, and dissolving in 190mL of toluene to obtain a 4-pentylcyclohexanone solution; dropwise adding the 4-pentylcyclohexanone solution into the first reaction solution under the condition of nitrogen protection and stirring, starting timing from dropwise adding the 4-pentylcyclohexanone solution, reacting for 7 hours at 40 ℃, then dropwise adding the reaction solution into a hydrochloric acid solution (50mL of concentrated hydrochloric acid dissolved in 200mL of water), hydrolyzing for 40min at 10 ℃, extracting by 200mL of toluene, and washing to obtain a toluene solution of 4- [ [ 2-fluoro-4- (4-pentylcyclohexanol) phenyl ] difluoromethoxy ] -1, 2-difluorobenzene, and marking as a second reaction solution;
step three, adding 5.2g of p-toluenesulfonic acid and 365mL of toluene into the second reaction solution, performing dehydration reaction for 6h at 110 ℃, extracting, washing and performing rotary evaporation after the reaction is finished to obtain a crude product of 4- [ [ 2-fluoro-4- (4-pentylcyclohexene) phenyl ] difluoromethoxy ] -1, 2-difluorobenzene, which is marked as an intermediate product 1;
dissolving the intermediate product 1 in 455mL of n-heptane, adding 5.48g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 2 hours at 1.0MPa and 60 ℃, and after the reaction is finished, filtering and performing rotary evaporation to obtain a crude product of 4- [ [ 2-fluoro-4- (4-pentylcyclohexyl) phenyl ] difluoromethoxy ] -1, 2-difluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 545mL dichloromethane, adding 10.92g trifluoroacetic acid, performing transposition reaction at 0 ℃ for 3.5h, and after the reaction is finished, recrystallizing to obtain 4- [ [ 2-fluoro-4- (trans-4-pentylcyclohexyl) phenyl ] difluoromethoxy ] -1, 2-difluorobenzene (the structure is shown in formula 12), white crystals and 74.2g of mass.
Based on the molar amount of 4- [ (2-fluoro-4-bromophenyl) difluoromethoxy ] -1, 2-difluorobenzene, the total yield in five steps was 87.1%, and the content by HPLC was 99.96%.
Example 5
A preparation method of 5- [ [2, 6-difluoro-4- (trans-4-ethylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene comprises the following steps:
step one, adding 77.8g (0.20mol) of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene (the structure is shown in formula 1) into 200mL of tetrahydrofuran to obtain a raw material solution; putting 7.15g (0.30mol) of magnesium chips into a 1000mL three-necked bottle, adding 135mL of tetrahydrofuran and 5.76g of 1- (N, N-diethylaminoethyl) -3-propylimidazolium tetrafluoroborate (the structure is shown as formula 13), stirring and dropwise adding the raw material solution under the conditions of water bath 50 ℃ and nitrogen protection, timing from the dropwise adding of the raw material solution, and reacting for 5 hours to obtain a tetrahydrofuran solution of 5- [ (2, 6-difluoro-4-magnesium bromide phenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, wherein the tetrahydrofuran solution is marked as a first reaction solution;
step two, weighing 30g (0.24mol) of 4-ethylcyclohexanone, and dissolving in 100mL of dioxane to obtain a 4-ethylcyclohexanone solution; dropwise adding the 4-ethylcyclohexanone solution into the first reaction solution under the nitrogen protection and stirring conditions, starting timing from dropwise adding the 4-ethylcyclohexanone solution, reacting for 5 hours at 100 ℃, then dropwise adding the reaction solution into a hydrochloric acid solution (50mL of concentrated hydrochloric acid is dissolved in 200mL of water), hydrolyzing for 30min at 10 ℃, extracting by 200mL of xylene, and washing to obtain a xylene solution of 5- [ [2, 6-difluoro-4- (4-ethylcyclohexanol) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, and marking as a second reaction solution;
step three, adding 4.25g of p-toluenesulfonic acid and 345mL of xylene into the second reaction solution, performing dehydration reaction at 140 ℃ for 4 hours, extracting, washing and rotary evaporating after the reaction is finished to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-ethylcyclohexene) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 1;
dissolving the intermediate product 1 in 325mL of methanol, adding 4.13g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 4 hours at 50 ℃ under 0.5MPa, and after the reaction is finished, filtering and carrying out rotary evaporation to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-ethylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 482mL of dichloromethane, adding 9.95g of trifluoroacetic acid, performing transposition reaction at 20 ℃ for 3h, and after the reaction is finished, recrystallizing to obtain 5- [ [2, 6-difluoro-4- (trans-4-ethylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene (the structure is shown in formula 14), white crystals and 75.3g of white crystals.
Based on the molar amount of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, the total yield in five steps is 89.6%, and the HPLC content is 99.97%.
In examples 1 to 5, the molar amount of acid added dropwise is 1 to 3 times the amount of the magnesium metal, and the corresponding intermediate can be sufficiently hydrolyzed to obtain the corresponding compound represented by formula V.
The same technical effects as in examples 1 to 5 of the present invention can be achieved as long as the organic solvent, the reaction temperature, the time, the addition amount of each substance, and the acid hydrolysis solution are within the preferable ranges of the present invention.
Comparative example 1
This comparative example provides a process for the preparation of 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene (grignard exchange) comprising the steps of:
step one, adding 31.4g (0.4mol) of isopropyl chloride into 100mL of tetrahydrofuran to obtain an isopropyl chloride solution; adding 77.8g (0.2mol) of 5- [ (2, 6-difluoro-4-bromophenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene into 200mL of tetrahydrofuran to obtain a raw material solution;
under the protection of nitrogen, 5.85g (0.24mol) of magnesium chips and 50mL of tetrahydrofuran are added into a 1000mL three-necked bottle; then dropwise adding an isopropyl chloride solution, after dropwise adding, dropwise adding the raw material solution in a water bath at 40 ℃, timing from the dropwise adding of the raw material solution, and reacting for 2 hours to obtain a tetrahydrofuran solution containing 5- [ (2, 6-difluoro-4-magnesium chloride phenyl) difluoromethoxy ] -1,2, 3-trifluorobenzene, and marking as a first reaction solution;
step two, weighing 28g (0.2mol) of 4-propylcyclohexanone, and dissolving in 60mL of toluene to obtain a 4-propylcyclohexanone solution; dropwise adding a 4-propylcyclohexanone solution into the first reaction solution under the condition of nitrogen protection and stirring, reacting for 7 hours at 50 ℃, then adding a hydrochloric acid solution (50mL of concentrated hydrochloric acid is dissolved in 200mL of water), hydrolyzing for 30 minutes at 10 ℃, extracting by 200mL of toluene, and washing by water to obtain a toluene solution of 5- [ [2, 6-difluoro-4- (4-propylcyclohexanol) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as a second reaction solution;
step three, adding 4.50g of p-toluenesulfonic acid and 200mL of toluene into the second reaction solution, performing dehydration reaction for 6h at 110 ℃, adding a solvent for extraction, washing with water, and performing rotary evaporation to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexene) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 1;
dissolving the intermediate product 1 in 300mL of ethanol, adding 4.34g of ruthenium carbon, uniformly mixing, adding into a hydrogenation reaction kettle, reacting for 3 hours at 50 ℃ under 0.3MPa, filtering, and performing rotary evaporation to obtain a crude product of 5- [ [2, 6-difluoro-4- (4-propylcyclohexyl) phenyl ] difluoromethoxy ] -1,2, 3-trifluorobenzene, which is marked as an intermediate product 2;
step five, dissolving the intermediate product 2 in 300mL of dichloromethane, adding 9.92g of trifluoroacetic acid, performing transposition reaction at-20 ℃ for 4h, and recrystallizing after the reaction is finished to obtain the 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl]Difluoromethoxy group]-1,2, 3-trifluorobenzene (structural formula shown in formula 3), white crystal with mass of 71.8g, yield of 82.9%, purity of 99.15%, and content of impurities generated by Wutz reaction of 0.67%, wherein the impurities are
Comparative example 2
This comparative example provides a 5- [ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] ester]Difluoromethoxy group]-1,2, 3-trifluorobenzene was prepared in exactly the same manner as in example 1, except that the imidazole-based basic ionic liquid catalyst of formula II of Grignard reaction was replaced with
Preparation of the obtained 5-[ [2, 6-difluoro-4- (trans-4-propylcyclohexyl) phenyl ] phenyl]Difluoromethoxy group]The yield of the-1, 2, 3-trifluorobenzene is 36.4 percent, the purity is 87.9 percent,
the content of impurities was 9.37%.
In comparative examples 1 and 2, the HPLC detection method of impurities generated by the Wutz reaction is as follows:
c18 column, 250mm by 160mm, 5 μm, mobile phase: acetonitrile (chromatically pure), detection wavelength: 254nm, flow rate 1.0mL/min, column temperature 35 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a liquid crystal monomer compound containing difluoromethyl ether bridge bonds is characterized by comprising the following steps:
a, taking magnesium metal and a compound shown in a formula I as raw materials, and taking imidazole basic ionic liquid shown in a formula II as a catalyst to perform a Grignard reaction to obtain a compound shown in a formula III;
b, carrying out addition and hydrolysis reaction on the compound shown in the formula III and the compound shown in the formula IV to obtain a compound shown in the formula V;
step c, carrying out dehydration, hydrogenation and transposition reactions on the compound shown in the formula V to obtain a liquid crystal monomer compound shown in the formula VIII and containing a difluoromethyl ether bridge bond;
wherein R is C1-C4 straight-chain alkyl; x is BF4Or PF6；R1、R2、R3Is H or F, and R1、R2、R3At least two of which are F; r4、R5Is H or F, and R4、R5At least one is F; r6Is C2-C5 straight chain alkyl;
2. the method for preparing a liquid crystal monomer compound containing a difluoromethyl ether bridge bond as claimed in claim 1, wherein said imidazole-based ionic liquid is one or both of 1- (N, N-diethylaminoethyl) -3-methylimidazolium tetrafluoroborate and 1- (N, N-diethylaminoethyl) -3-methylimidazolium hexafluorophosphate.
3. The method for producing a liquid crystal monomer compound having a difluoromethyl ether bridge according to claim 1 or 2, comprising the steps of:
under the protection of inert gas, adding a compound shown as a formula I, imidazole basic ionic liquid shown as a formula II and metal magnesium into a first organic solvent, and carrying out a Grignard reaction at 0-80 ℃ to obtain a reaction solution containing a compound shown as a formula III;
dissolving a compound shown as a formula IV in a second organic solvent to obtain a compound solution shown as a formula IV; adding a compound solution shown as a formula IV into a reaction solution containing a compound shown as a formula III under the protection of inert gas, uniformly mixing, carrying out addition reaction at 40-100 ℃, adding the reaction solution into an acid solution after the reaction is finished, and carrying out hydrolysis reaction at 0-30 ℃ to obtain a reaction solution containing the compound shown as the formula V;
adding a dehydrating agent and a third organic solvent into a reaction solution containing the compound shown in the formula V, and performing dehydration reaction at the temperature of 80-140 ℃ to obtain a compound shown in the formula VI;
step four, adding the compound shown in the formula VI and a hydrogenation catalyst into a fourth organic solvent, uniformly mixing, and carrying out hydrogenation reaction under the conditions of 0.1-1 MPa and 20-80 ℃ to obtain a compound shown in the formula VII;
and step five, adding the compound shown in the formula VII and a transposition catalyst into a fifth organic solvent, and carrying out transposition reaction at the temperature of minus 40-20 ℃ to obtain the liquid crystal monomer compound shown in the formula VIII and containing the difluoromethyl ether bridge bond.
4. The method according to claim 3, wherein in the first step, the first organic solvent is at least one of tetrahydrofuran, dioxane, methyl tert-butyl ether, toluene, benzene or petroleum ether; and/or
In the second step, the second organic solvent is at least one of tetrahydrofuran, dioxane, methyl tert-butyl ether, toluene, benzene or petroleum ether; and/or
In the third step, the third organic solvent is at least one of cyclohexane, toluene or xylene; and/or
In the fourth step, the fourth organic solvent is at least one of methanol, ethanol, petroleum ether, n-heptane, n-hexane or toluene; and/or
In the fifth step, the fifth organic solvent is at least one of dichloromethane, dichloroethane, toluene or xylene.
5. The method for producing a liquid crystal monomer compound containing a difluoromethyl ether bridge bond as claimed in claim 3, wherein said dehydrating agent is p-toluenesulfonic acid; and/or
The hydrogenation catalyst is a ruthenium-carbon catalyst; and/or
The translocation catalyst is trifluoroacetic acid.
6. The method for preparing a difluoromethyl ether bridge-containing liquid crystal monomer compound as claimed in claim 3, wherein in step one, the molar ratio of said compound represented by formula I to magnesium metal is 1: 1.2-2; and/or
In the first step, the mass-to-volume ratio of the compound shown in the formula I to the first organic solvent is 1: 3-6, wherein the unit of mass is gram, and the unit of volume is milliliter; and/or
In the first step, the amount of the imidazole basic ionic liquid shown in the formula II is 5-10 wt% of the compound shown in the formula I;
in the first step, the reaction time is 1-8 h.
7. The method for preparing a liquid crystal monomer compound containing a difluoromethyl ether bridge as claimed in claim 3, wherein in step two, the molar ratio of said compound represented by formula I to said compound represented by formula IV is 1: 1.0-1.2; and/or
In the second step, the mass-to-volume ratio of the compound shown in the formula IV to the second organic solvent is 1: 1-5, wherein the unit of mass is gram, and the unit of volume is milliliter; and/or
In the second step, the time of the addition reaction is 5-7 h, and the time of the hydrolysis reaction is 20-40 min.
8. The method for preparing a liquid crystal monomer compound containing a difluoromethyl ether bridge according to claim 3, wherein in step three, the amount of said dehydrating agent added is 4-6 wt% of the theoretical yield of the compound of formula V; and/or
In the third step, the volume of the third organic solvent is 3-5 times of the theoretical yield of the compound shown in the formula V, wherein the volume unit is milliliter, and the theoretical yield unit is gram; and/or
In the third step, the reaction time is 4-8 h.
9. The method according to claim 3, wherein the fourth organic solvent is added in a volume 3 to 5 times the theoretical yield of the compound represented by formula VI, wherein the volume is in ml and the theoretical yield is in g; and/or
In the fourth step, the adding amount of the hydrogenation catalyst is 4-6% of the theoretical yield of the compound shown in the formula VI; and/or
In the fourth step, the reaction time is 2-6 h.
10. The method for producing a liquid crystalline monomeric compound having a difluoromethyl ether bridge bond as claimed in claim 3, wherein in the fifth step, the fifth organic solvent is added in a volume 3 to 6 times the theoretical yield of the compound represented by formula VII, wherein the volume is in ml and the theoretical yield is in g; and/or
In the fifth step, the addition amount of the transposition catalyst is 8-12% of the theoretical yield of the compound shown in the formula VII; and/or
In the fifth step, the reaction time is 3-5 h.
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