CN109734566B - Method for continuously preparing liquid crystal compound intermediate by using microreactor - Google Patents
Method for continuously preparing liquid crystal compound intermediate by using microreactor Download PDFInfo
- Publication number
- CN109734566B CN109734566B CN201910089194.XA CN201910089194A CN109734566B CN 109734566 B CN109734566 B CN 109734566B CN 201910089194 A CN201910089194 A CN 201910089194A CN 109734566 B CN109734566 B CN 109734566B
- Authority
- CN
- China
- Prior art keywords
- microreactor
- solution
- reaction
- ethoxy
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of liquid crystal compound intermediate preparation, in particular to a method for continuously preparing a liquid crystal compound intermediate by utilizing a microreactor; the method for continuously preparing the liquid crystal compound intermediate by using the microreactor is used for continuously preparing the liquid crystal compound intermediate by using the microreactor, has very high mass transfer efficiency of the microreactor, is a continuous reaction, can effectively shorten the time consumed by working procedures, and improves the production efficiency. Meanwhile, the invention adopts a microreactor for reaction, and reactants can be fully contacted, thus being beneficial to improving the reaction conversion rate and further improving the product yield. The experimental results of the embodiment show that the yield of the liquid crystal compound intermediate can reach 95% at most by continuously preparing the liquid crystal compound intermediate by using the microreactor, and the time consumed by the process can be shortened to 5-15 min.
Description
Technical Field
The invention relates to the technical field of liquid crystal compound intermediate preparation, in particular to a method for continuously preparing a liquid crystal compound intermediate by utilizing a microreactor.
Background
The liquid crystal compound is widely applied to light and thin display technologies by unique physical, chemical and optical properties, the market share of a liquid crystal panel in flat panel display is over 70 percent, and 1-ethoxy-2, 3-difluoro-4-iodobenzene or 1-ethoxy-2, 3-difluoro-4-boratabenzene is an important liquid crystal compound intermediate, so that the continuous production of the two compounds has important market value.
At present, the two compounds are generally synthesized by a two-step method, 1-ethoxy-2, 3-difluorobenzene and n-butyllithium are firstly mixed in a tetrahydrofuran solution at the temperature of-70 ℃, the solution is milky and viscous after being stirred for 2 hours, then the n-butyllithium and iodine/trimethyl borate are added at the same temperature, the solution is colorless to deep red after being stirred for 1 hour, and the reaction is finished. However, the method is a discontinuous reaction, and the mass transfer efficiency of the stirring reaction is low, so that the production efficiency of the method is low; and the yield of the reaction is low, about 80%.
Disclosure of Invention
The invention aims to provide a method for continuously preparing a liquid crystal compound intermediate by using a microreactor, which can improve the production efficiency and the product yield.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for continuously preparing a liquid crystal compound intermediate by using a microreactor, which comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting an iodine solution or a trimethyl borate solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters an iodine solution or a trimethyl borate solution through a microporous membrane in a second microreactor to carry out a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-iodobenzene or 1-ethoxy-2, 3-difluoro-4-boratabenzene.
Preferably, the solvent of the n-butyllithium solution is petroleum ether and cyclohexane;
the volume ratio of the petroleum ether to the cyclohexane is 1: (0.1 to 10);
the concentration of the n-butyllithium solution is 0.05-10 mol/L.
Preferably, the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is tetrahydrofuran;
the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is 0.05-10 mol/L independently.
Preferably, the solvent of the iodine solution or the trimethyl borate solution is tetrahydrofuran;
the concentration of the iodine solution or the trimethyl borate solution is 0.05-10 mol/L.
Preferably, the flow rate of the n-butyllithium solution or the first reaction material solution is independently 1mL/min to 1L/min;
the flow rate of the 1-ethoxy-2, 3-difluorobenzene solution or the iodine solution or the trimethyl borate solution is independently 1 mL/min-1L/min;
the pore diameter of the microporous membrane in the first microreactor and the pore diameter of the microporous membrane in the second microreactor are independently 2-10 mu m.
Preferably, the molar ratio of the 1-ethoxy-2, 3-difluorobenzene in the 1-ethoxy-2, 3-difluorobenzene solution to the n-butyllithium in the n-butyllithium solution is (0.5-2): 1.
preferably, the molar ratio of the 1-ethoxy-2, 3-difluorobenzene to the iodine or trimethyl borate in the liquid mixture in which the first reaction is carried out is (0.1 to 2): 1.
preferably, the temperature of the first reaction or the second reaction is-80-0 ℃ independently; the first reaction time is 8-12 min; the time of the second reaction is 0.5-2 min.
Preferably, the second reaction further comprises: and mixing the obtained second reaction material, a saturated sodium sulfite aqueous solution and ethyl acetate, standing for layering, taking the upper layer liquid, and drying to obtain a liquid crystal compound intermediate.
Preferably, the volume ratio of the second reaction material to the saturated aqueous sodium sulfite solution is 1: (0.1 to 10);
the volume ratio of the second reaction material to the ethyl acetate is 1: (0.1-10).
The invention provides a method for continuously preparing a liquid crystal compound intermediate by using a microreactor, which comprises the following steps: injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material; injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting an iodine solution or a trimethyl borate solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters an iodine solution or a trimethyl borate solution through a microporous membrane in a second microreactor to carry out a second reaction to obtain a liquid crystal compound intermediate; the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-iodobenzene or 1-ethoxy-2, 3-difluoro-4-boratabenzene.
The method utilizes the microreactor to continuously prepare the liquid crystal compound intermediate, has very high mass transfer efficiency of the microreactor, is a continuous reaction, can effectively shorten the time consumed by working procedures and improve the production efficiency. Meanwhile, the invention adopts a microreactor for reaction, and reactants can be fully contacted, thus being beneficial to improving the reaction conversion rate and further improving the product yield. The experimental results of the embodiment show that the yield of the liquid crystal compound intermediate can reach 95% at most by continuously preparing the liquid crystal compound intermediate by using the microreactor, and the time consumed by the process can be shortened to less than 15 min.
Drawings
FIG. 1 is a flow chart of the present invention for continuously preparing liquid crystal compound intermediates by using a microreactor.
Detailed Description
The invention provides a method for continuously preparing a liquid crystal compound intermediate by using a microreactor, which comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting an iodine solution or a trimethyl borate solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters an iodine solution or a trimethyl borate solution through a microporous membrane in a second microreactor to carry out a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-iodobenzene or 1-ethoxy-2, 3-difluoro-4-boratabenzene.
In the present invention, the solvent of the n-butyllithium solution is preferably petroleum ether and cyclohexane; the volume ratio of petroleum ether to cyclohexane is preferably 1: (0.1 to 10), more preferably 1: (2-8), most preferably 1: (4-6); the concentration of the n-butyllithium solution is preferably 0.05-10 mol/L, more preferably 2-8 mol/L, and most preferably 4-6 mol/L. In the present invention, the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is preferably tetrahydrofuran; the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is preferably 0.05-10 mol/L, more preferably 2-8 mol/L, and most preferably 4-6 mol/L. In the present invention, the solvent of the iodine solution or the trimethyl borate solution is preferably tetrahydrofuran; the concentration of the iodine solution or the trimethyl borate solution is preferably 0.05-10 mol/L, more preferably 2-8 mol/L, and most preferably 4-6 mol/L.
According to the invention, n-butyllithium solution is used as a continuous phase and injected into a lower chamber of a first microreactor, and 1-ethoxy-2, 3-difluorobenzene solution is used as a dispersed phase and injected into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material; in the invention, the flow rate of the n-butyllithium solution is preferably 1mL/min to 1L/min, more preferably 20mL/min to 500mL/min, and most preferably 100 mL/min to 200 mL/min; the flow rate of the 1-ethoxy-2, 3-difluorobenzene solution is preferably 1mL/min to 1L/min, more preferably 20mL/min to 500mL/min, and most preferably 100 mL/min to 200 mL/min. In the invention, the pore diameter of the microporous membrane in the first microreactor is preferably 2-10 μm, more preferably 3-8 μm, and most preferably 4-6 μm. In the invention, the flow rate of the n-butyllithium solution and the 1-ethoxy-2, 3 difluorobenzene solution and the pore diameter of the microporous membrane are controlled so that the molar ratio of the 1-ethoxy-2, 3 difluorobenzene to the n-butyllithium in the mixed solution for the first reaction is (0.5-2): 1, and the molar ratio is more preferably (1 to 1.5): 1.
in the invention, the temperature of the first reaction is preferably-80-0 ℃, more preferably-60-5 ℃, and most preferably-30-10 ℃; the time of the first reaction is preferably 5 to 15min, and more preferably 8 to 12 min. In the invention, after the first reaction of the 1-ethoxy-2, 3-difluorobenzene and n-butyllithium, 1-ethoxy-2, 3-difluoro-4-lithiobenzene is generated.
In the invention, after the first reaction is finished, the obtained first reaction material is directly injected into a second microreactor for a second reaction without post-treatment.
After the first reaction material is obtained, injecting the first reaction material into an upper chamber of a second microreactor as a continuous phase, and injecting an iodine solution or a trimethyl borate solution into a lower chamber of the second microreactor as a dispersed phase; and the first reaction material enters an iodine solution or a trimethyl borate solution through a microporous membrane in the second microreactor to perform a second reaction, so as to obtain a liquid crystal compound intermediate. In the invention, the flow rate of the iodine solution or the trimethyl borate solution is preferably 1mL/min to 1L/min, more preferably 20mL/min to 500mL/min, and most preferably 100 mL/min to 200 mL/min; the flow rate of the first reaction material is preferably 1mL/min to 1L/min, more preferably 20mL/min to 500mL/min, and most preferably 100 mL/min to 200 mL/min. In the invention, the pore diameter of the microporous membrane in the second microreactor is preferably 2-10 μm, more preferably 3-8 μm, and most preferably 4-6 μm. In the invention, the flow rate of the iodine solution or trimethyl borate solution in the first reaction material and the pore diameter of the microporous membrane are controlled so that the molar ratio of 1-ethoxy-2, 3 difluorobenzene in the mixed solution for the first reaction to iodine/trimethyl borate in the mixed solution for the second reaction reaches (0.1-2): 1, the molar ratio is more preferably (0.5 to 1.5): 1.
in the invention, the temperature of the second reaction is preferably-80-0 ℃, more preferably-60-5 ℃, and most preferably-30-10 ℃; the time of the second reaction is preferably 0.5 to 2min, and more preferably 1.0 to 1.5 min. In the invention, after the first reaction material and the iodine solution or the trimethyl borate solution carry out the second reaction, 1-ethoxy-2, 3 difluoro-4 iodobenzene/1-ethoxy-2, 3 difluoro-4 boratabenzene is generated.
After the second reaction is completed, the obtained second reaction material, saturated sodium sulfite aqueous solution and ethyl acetate are preferably mixed, the mixture is kept stand for layering, and the upper layer liquid is taken out and dried to obtain a liquid crystal compound intermediate. In the present invention, the mixing is preferably performed under stirring; in the invention, the stirring time is preferably 5-15 min, and more preferably 8-12 min; the stirring rate is not particularly limited in the present invention, and a stirring rate known to those skilled in the art may be used.
In the present invention, the volume ratio of the second reaction material to the saturated aqueous sodium sulfite solution is preferably 1: (0.1 to 10), more preferably 1: (2-8), most preferably 1: (4-6); the volume ratio of the second reaction mass to ethyl acetate is preferably 1: (0.1 to 10), more preferably 1: (2-8), most preferably 1: (4-6).
In the invention, in the specific process of taking the upper layer liquid for drying, the upper layer liquid and sodium sulfate are mixed until the solution becomes clear. The amount of the sodium sulfate used in the present invention is not particularly limited, and may be an amount known to those skilled in the art.
Fig. 1 is a flow chart of continuously preparing a liquid crystal compound intermediate by utilizing microreactors, wherein a 1-ethoxy-2, 3-difluorobenzene solution is continuously injected into an upper chamber of a first microreactor, an n-butyllithium solution is continuously injected into a lower chamber of the first microreactor, the 1-ethoxy-2, 3-difluorobenzene solution vertically enters the n-butyllithium solution through a microporous membrane of the first microreactor, and the solution stays for 5-15 min for a first reaction to obtain a first reaction material; continuously injecting a first reaction material into an upper chamber of the second microreactor, continuously injecting an iodine solution or a trimethyl borate solution into a lower chamber of the second microreactor, enabling the iodine solution or the trimethyl borate solution to vertically enter the first reaction material through a microporous membrane of the second microreactor, and staying the first reaction material
And (3) carrying out a second reaction for 0.5-2 min to obtain a second reaction material containing the liquid crystal compound intermediate.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing two microreactors as a first microreactor and a second microreactor, wherein the microreactors comprise an upper chamber and a lower chamber, and the upper chamber and the lower chamber are separated by a stainless steel microporous membrane with the aperture of 5 mu m;
continuously injecting a 1-ethoxy-2, 3-difluoro-4-phenylboronic acid solution with the concentration of 1mol/L into an upper chamber of the first microreactor (the flow rate is 40mL/min), continuously injecting a 2mol/L n-butyl lithium solution with the concentration of 20mL/min into a lower chamber of the first microreactor, enabling the 1-ethoxy-2, 3-difluoro-4-phenylboronic acid solution to vertically enter the n-butyl lithium solution through a microporous membrane of the first microreactor, and performing a first reaction for 10min at-30 ℃ to obtain a first reaction material;
continuously injecting the first reaction material into an upper chamber of the second microreactor (the flow rate is 60mL/min), continuously injecting an iodine solution with the concentration of 1mol/L into a lower chamber of the second microreactor (the flow rate is 40mL/min), enabling the iodine solution to vertically enter the first reaction material through a microporous membrane of the second microreactor, and carrying out a second reaction for 1min at-30 ℃ to obtain a second reaction material;
mixing the second reaction material, a saturated sodium sulfite aqueous solution and ethyl acetate according to the volume ratio of 1:1:1, standing for layering, taking the upper layer liquid, adding 5g of sodium sulfate powder, drying until the solution becomes clear, and obtaining the 1-ethoxy-2, 3-difluoro-4-iodobenzene, wherein the yield is 88%, and the conversion rate is 99%.
The working procedure time is 12.5min, based on the time of finishing the continuous injection of the 1-ethoxy-2, 3-difluoro-4-boratabenzene solution (500mL, with the flow rate of 40mL/min) into the upper chamber of the first microreactor, without taking the post-treatment time into account.
Example 2
1-ethoxy-2, 3-difluoro-4-boratabenzene was prepared as in example 1, except that the iodine solution was replaced with a trimethyl borate solution; the yield of the finally obtained 1-ethoxy-2, 3-difluoro-4-boratabenzene is 95 percent, and the conversion rate is 99 percent; the process takes 12.5 min.
Example 3
1-ethoxy-2, 3-difluoro-4-iodobenzene was prepared as in example 1, except that the concentrations of the 1-ethoxy-2, 3-difluoro-4-boratabenzene solution and n-butyllithium solution were changed to 0.5mol/L, 1mol/L and 0.5mol/L, respectively; the yield of the finally obtained 1-ethoxy-2, 3-difluoro-4-iodobenzene is 89%, the conversion rate is 98%, and the process time is 12.5 min.
Example 4
1-ethoxy-2, 3-difluoro-4-boratabenzene was prepared according to the procedure of example 2 except that the flow rates of the 1-ethoxy-2, 3-difluoro-4-boratabenzene solution, the n-butyllithium solution and the iodine solution were changed to 20mL/min, 10mL/min and 20mL/min, respectively; the yield of the finally obtained 1-ethoxy-2, 3-difluoro-4-boratabenzene is 90%, the conversion rate is 98%, and the process time is 25 min.
Comparative example 1
Mixing 1-ethoxy-2, 3-difluorobenzene with the concentration of 1mol/L and n-butyllithium with the concentration of 2mol/L in a tetrahydrofuran solution at-70 ℃, stirring for 2 hours to obtain a milky and viscous solution, adding n-butyllithium and 1mol/L trimethyl iodate at the same temperature, stirring for 1 hour to obtain a colorless to deep red solution, and finishing the reaction. The yield of the reaction under the method is about 80%, and the conversion rate is about 90%.
The post-treatment time is not taken into account, and the process time is 180 min.
According to the embodiments, the liquid crystal compound intermediate is continuously prepared by using the microreactor, the mass transfer efficiency of the microreactor is very high, the microreactor is a continuous reaction, the time consumed by the process can be effectively shortened, and the production efficiency is improved. Meanwhile, the invention adopts a microreactor for reaction, and reactants can be fully contacted, thus being beneficial to improving the reaction conversion rate and further improving the product yield.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for continuously preparing a liquid crystal compound intermediate by using a microreactor comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting an iodine solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters an iodine solution through a microporous membrane in a second microreactor to carry out a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-iodobenzene;
the pore diameter of the microporous membrane in the first microreactor and the pore diameter of the microporous membrane in the second microreactor are 5 micrometers;
the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is tetrahydrofuran, the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is 1mol/L, and the flow rate is 40 mL/min;
the solvent of the n-butyllithium solution is petroleum ether and cyclohexane, and the volume ratio of the petroleum ether to the cyclohexane is 1: (0.1-10), wherein the concentration of the n-butyllithium solution is 2mol/L, and the flow rate is 20 mL/min;
the temperature of the first reaction is-30 ℃, and the time of the first reaction is 10 min;
the flow rate of the first reaction mass is 60 mL/min;
the solvent of the iodine solution is tetrahydrofuran, and the concentration of the iodine solution is 1 mol/L; the flow rate of the iodine solution is 40 mL/min;
the temperature of the second reaction is-30 ℃, and the time of the second reaction is 1 min.
2. A method for continuously preparing a liquid crystal compound intermediate by using a microreactor comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting a trimethyl borate solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters trimethyl borate solution through a microporous membrane in a second microreactor to perform a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-boratabenzene;
the pore diameter of the microporous membrane in the first microreactor and the pore diameter of the microporous membrane in the second microreactor are 5 micrometers;
the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is tetrahydrofuran, the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is 1mol/L, and the flow rate is 40 mL/min;
the solvent of the n-butyllithium solution is petroleum ether and cyclohexane, and the volume ratio of the petroleum ether to the cyclohexane is 1: (0.1-10), wherein the concentration of the n-butyllithium solution is 2mol/L, and the flow rate is 20 mL/min;
the temperature of the first reaction is-30 ℃, and the time of the first reaction is 10 min;
the flow rate of the first reaction mass is 60 mL/min;
the solvent of the trimethyl borate solution is tetrahydrofuran, and the concentration of the trimethyl borate solution is 1 mol/L; the flow rate of the trimethyl borate solution is 40 mL/min;
the temperature of the second reaction is-30 ℃, and the time of the second reaction is 1 min.
3. A method for continuously preparing a liquid crystal compound intermediate by using a microreactor comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting an iodine solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters an iodine solution through a microporous membrane in a second microreactor to carry out a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-iodobenzene;
the pore diameter of the microporous membrane in the first microreactor and the pore diameter of the microporous membrane in the second microreactor are 5 micrometers;
the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is tetrahydrofuran, the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is 0.5mol/L, and the flow rate is 40 mL/min;
the solvent of the n-butyllithium solution is petroleum ether and cyclohexane, and the volume ratio of the petroleum ether to the cyclohexane is 1: (0.1-10), wherein the concentration of the n-butyllithium solution is 1mol/L, and the flow rate is 20 mL/min;
the temperature of the first reaction is-30 ℃, and the time of the first reaction is 10 min;
the flow rate of the first reaction mass is 60 mL/min;
the solvent of the iodine solution is tetrahydrofuran, and the concentration of the iodine solution is 0.5 mol/L; the flow rate of the iodine solution is 40 mL/min;
the temperature of the second reaction is-30 ℃, and the time of the second reaction is 1 min.
4. A method for continuously preparing a liquid crystal compound intermediate by using a microreactor comprises the following steps:
injecting n-butyllithium solution serving as a continuous phase into a lower chamber of the first microreactor, and injecting 1-ethoxy-2, 3-difluorobenzene solution serving as a disperse phase into an upper chamber of the first microreactor; the 1-ethoxy-2, 3-difluorobenzene solution enters an n-butyllithium solution through a microporous membrane in a first microreactor to perform a first reaction to obtain a first reaction material;
injecting the first reaction material serving as a continuous phase into an upper chamber of a second microreactor, and injecting a trimethyl borate solution serving as a dispersed phase into a lower chamber of the second microreactor; the first reaction material enters trimethyl borate solution through a microporous membrane in a second microreactor to perform a second reaction to obtain a liquid crystal compound intermediate;
the liquid crystal compound intermediate is 1-ethoxy-2, 3-difluoro-4-boratabenzene;
the pore diameter of the microporous membrane in the first microreactor and the pore diameter of the microporous membrane in the second microreactor are 5 micrometers;
the solvent of the 1-ethoxy-2, 3-difluorobenzene solution is tetrahydrofuran, the concentration of the 1-ethoxy-2, 3-difluorobenzene solution is 1mol/L, and the flow rate is 20 mL/min;
the solvent of the n-butyllithium solution is petroleum ether and cyclohexane, and the volume ratio of the petroleum ether to the cyclohexane is 1: (0.1-10), wherein the concentration of the n-butyllithium solution is 2mol/L, and the flow rate is 10 mL/min;
the temperature of the first reaction is-30 ℃, and the time of the first reaction is 10 min;
the flow rate of the first reaction mass is 60 mL/min;
the solvent of the trimethyl borate solution is tetrahydrofuran, and the concentration of the trimethyl borate solution is 1 mol/L; the flow rate of the trimethyl borate solution is 20 mL/min;
the temperature of the second reaction is-30 ℃, and the time of the second reaction is 1 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089194.XA CN109734566B (en) | 2019-01-30 | 2019-01-30 | Method for continuously preparing liquid crystal compound intermediate by using microreactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089194.XA CN109734566B (en) | 2019-01-30 | 2019-01-30 | Method for continuously preparing liquid crystal compound intermediate by using microreactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109734566A CN109734566A (en) | 2019-05-10 |
| CN109734566B true CN109734566B (en) | 2020-08-21 |
Family
ID=66366724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910089194.XA Active CN109734566B (en) | 2019-01-30 | 2019-01-30 | Method for continuously preparing liquid crystal compound intermediate by using microreactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109734566B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979688B (en) * | 2021-05-20 | 2022-02-01 | 凯莱英医药集团（天津）股份有限公司 | Preparation method of 2-fluoro-4-trifluoromethylphenylboronic acid |
| CN115121200B (en) * | 2022-07-15 | 2024-02-13 | 浙江大学 | Method for continuously preparing alkylaluminoxane based on micro-membrane reactor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012121301A1 (en) * | 2011-03-10 | 2012-09-13 | 国立大学法人京都大学 | Process for producing fluorine-containing substituted compound, and fluorine-containing substituted compound |
| CN104194800B (en) * | 2014-08-11 | 2016-03-09 | 福建省邵武市永晶化工有限公司 | Fluoric bis(diphenyl)acetylene nematic negative liquid crystal, synthetic method and application |
| CN104479687A (en) * | 2014-12-17 | 2015-04-01 | 石家庄诚志永华显示材料有限公司 | Cycloheptyl-2,3-difluorophenyl negative liquid crystal compound, and preparation method and application thereof |
| CN104774140B (en) * | 2015-04-27 | 2016-08-24 | 芮城县斯普伦迪生物工程有限公司 | A kind of method utilizing micro passage reaction synthesis Pentafluorophenol |
| CN108383682A (en) * | 2018-05-04 | 2018-08-10 | 清华大学 | A method of preparing two fluorobenzyl bromides using microreactor continous way |
-
2019
- 2019-01-30 CN CN201910089194.XA patent/CN109734566B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109734566A (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109734566B (en) | Method for continuously preparing liquid crystal compound intermediate by using microreactor | |
| Luo et al. | Superbase-catalyzed anti-markovnikov alcohol addition reactions to aryl alkenes | |
| Satoh | Oxiranyl anions and aziridinyl anions | |
| CN108559503B (en) | Cs (volatile organic Compounds)2AgBiBr6Double perovskite and preparation method thereof | |
| CN109574851B (en) | Method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under catalysis of ionic liquid | |
| CN103601749B (en) | A kind of synthetic method of 1-alkyl pyrazole-4-pinacol borate | |
| CN106478707B (en) | A method of producing 3- difluoro-methoxy -5- fluorobenzoic boric acids using continuous flow reactor | |
| CN105566671A (en) | Preparation method of organic-inorganic hybrid porous integral material | |
| CN108383682A (en) | A method of preparing two fluorobenzyl bromides using microreactor continous way | |
| CN104513145A (en) | 2,3,5-Trifluoro-4-difluoro(3,4,5-trifluorophenylol)methyl-benzaldehyde, its synthetic method and its application in preparation of liquid crystal compound | |
| CN103193710A (en) | Three-ingredient eutectic ionic liquid and preparation method thereof | |
| CN104804034A (en) | Preparation method of butyltin tris(2-ethylhexanoate) catalyst | |
| TWI807290B (en) | Method for synthesizing oxetane derivative by using microreactor | |
| CN105833909A (en) | (S)-1-(2-hydrox-1-phenethyl)thiourea modified Cr-Anderson heteropolyacid catalyst, and preparation method and application thereof | |
| CN103724275B (en) | 4-nitroimidazole and preparation method thereof | |
| JP2024520288A (en) | Method and catalyst for the synthesis of dimethyl 3-(3-oxo-2-pentyl)cyclopentylmalonate | |
| CN109320522A (en) | A method of preparing isobide | |
| CN106220464B (en) | A kind of method for being catalyzed australene dimerization reaction | |
| CN110591112B (en) | Preparation and application of Cu (I) chiral MOF material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole | |
| CN106699575B (en) | A kind of nitrogenous oxygen tridentate compounds and its preparation method and application | |
| CN114524801A (en) | Method for efficiently producing esomeprazole sodium based on mobile phase | |
| CN104448288B (en) | A kind of method synthesizing Hydrin | |
| CN103030658B (en) | The industrialized preparing process of diisopinocampheylchloroborane | |
| CN105237500A (en) | Macromolecular emulsifying agent suitable for up-hole blasting charge and preparation method thereof | |
| CN101225089A (en) | Process for the preparation of diisopinocampheylchloroborane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |