CN113527109A - Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology - Google Patents
Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology Download PDFInfo
- Publication number
- CN113527109A CN113527109A CN202110774273.1A CN202110774273A CN113527109A CN 113527109 A CN113527109 A CN 113527109A CN 202110774273 A CN202110774273 A CN 202110774273A CN 113527109 A CN113527109 A CN 113527109A
- Authority
- CN
- China
- Prior art keywords
- aniline
- micro
- reaction
- perfluoroalkyl
- preparing
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing perfluoroalkyl aniline by a micro-flow field reaction technology, which comprises the following steps: dissolving aniline and perfluoroalkyl iodide in an organic solvent to obtain a homogeneous solution; dissolving an initiator and a phase transfer catalyst in an alkaline solution to obtain a homogeneous mixed solution; and respectively pumping the two homogeneous phase solutions into a micro-reaction device for reaction at the same time to prepare a crude product of the perfluoroalkyl aniline. The micro-reaction device comprises a micro-structure mixer, a micro-structure reactor, a pressure control valve and a product collector which are sequentially connected through a pipeline. Compared with the traditional preparation method of perfluoroalkyl aniline, the preparation method has the advantages of short reaction time, high yield, few byproducts, simple operation, small amplification effect and high safety, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing perfluoroalkyl aniline by a micro-flow field reaction technology.
Background
Perfluoroalkyl aniline and its derivatives are fluorine-containing fine chemicals with wide application prospect, and can be widely applied to raw materials or intermediates of medicines, pesticides, surfactants, coatings, rubber and the like. Because fluorine atoms have special chemical and biological characteristics and fluorine-containing organic compounds have higher lipid solubility and hydrophobicity, people introduce fluorine-containing groups or fluorine atoms into organic compounds with biological activity, and can obviously influence the physicochemical properties, the biological activity and the like of the organic compounds, so that the organic compounds containing fluorine play an important role in the fields of medicinal chemistry, pesticide chemistry and the like, the development of fluorine-containing pesticides becomes a creation main body of novel pesticides, and 2-methyl-4-heptafluoro-isopropyl aniline now becomes a key intermediate for synthesizing the novel pesticide flubendiamide. Therefore, the development of a safe, efficient and environment-friendly perfluoroalkyl aniline production process has important economic value.
Patents US2002/198399 and Indian Pat. No. 2010de00753 report that zinc dust causes large pollution, promoted by zinc dust or by light irradiation. In contrast, the perfluoroalkyl aniline derivative method disclosed in the patent CN1257861A of japan pesticide co-pending has a good industrial development prospect, and repeating the above process found that neither the reaction rate nor the selectivity to the target product is expected.
The micro-flow field reaction technology is a process strengthening technology with the characteristic dimension of reaction and dispersion in the hundred micron level, and a core component micro-reactor is a three-dimensional structural element which is manufactured by a special micro-processing technology in a solid matrix and can be used for carrying out chemical reaction. Microreactors generally contain small channel sizes (equivalent diameters less than 500 μm) and channel diversity in which fluids flow and in which the desired reactions are desired to occur. This results in a very large surface area to volume ratio in a micro-structured chemical device. The micro-flow field reaction technology can be used for rapidly increasing the reaction rate, realizing continuous industrial production, miniaturizing the reaction equipment and facilitating automatic control in the reaction process, greatly improving the production safety, simultaneously enhancing the heat and mass transfer, realizing high-efficiency utilization of energy, reducing the material loss and reducing the waste liquid discharge.
However, at present, there is no research on preparation of perfluoroalkyl aniline by using a micro-flow field reaction technology, and how to apply the preparation reaction of perfluoroalkyl aniline to the micro-flow field technology needs further research.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems in the prior art, the invention provides a method for preparing perfluoroalkyl aniline by a micro-flow field reaction technology, which is efficient, safe and environment-friendly.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing perfluoroalkyl aniline by a micro-flow field reaction technology comprises the following steps:
(1) dissolving aniline and perfluoroalkyl iodide (I) in an organic solvent to obtain a homogeneous solution A;
(2) dissolving an initiator and a phase transfer catalyst in an alkaline solution to obtain a homogeneous solution B;
(3) respectively and simultaneously pumping the two homogeneous phase solutions obtained in the step (1) and the step (2) into a micro-reaction device for reaction, and collecting effluent liquid, namely a perfluoroalkyl aniline (II) crude product;
wherein, -RfIs C2～16A perfluoroalkyl group.
Preferably, said-RfSelected from the group consisting of perfluoro-substituted straight-chain alkyl, perfluoro-substituted branched-chain alkyl, or perfluoro-substituted cycloalkyl, more preferably, -RfSelected from-CF (CF)3)2、-(CF2)2CF(CF3)2、-(CF2)2CF3、-(CF2)4CF(CF3)2、-CF2CF3、-CF2CF＝CF(CF3)2、-(CF2)7CF3Or a perfluoro substituted cyclohexane group.
Preferably, in the homogeneous solution A obtained in the step (1), the concentration of aniline is 0.02 g/mL-0.5 g/mL, preferably 0.08g/mL, and the molar ratio of aniline to perfluoroalkyl iodide is controlled to be 1: 1.0-1.5.
Preferably, in step (1), the organic solvent is halogenated alkane, ether, alcohol, ketone, amide, ester or nitrile.
Preferably, in the homogeneous solution B obtained in the step (2), the concentration of the initiator is 0.3 mmol/mL-0.9 mmol/mL, preferably 0.36 mmol/mL; the initiator is sodium hydrosulfite, potassium hydrosulfite, zinc hydrosulfite or zinc-sulfurous acid solution. .
Preferably, in the basic solution in the step (2), the base used is a base which can form a homogeneous solution and is compatible with the catalyst, and comprises an inorganic base and an organic base, and the concentration is preferably 0.72 mmol/mL.
Preferably, in the step (2), the phase transfer catalyst is selected from quaternary ammonium salts, phosphorus salts, polyethylene glycol ethers or crown ethers.
Preferably, in the step (3), the reaction molar ratio of the aniline and the initiator is controlled to be 1: 0.4-1.2, and the preferred molar ratio is 1: 0.6.
Preferably, in the step (3), the reaction temperature is 0-50 ℃, and the reaction residence time is 1-15 min.
Preferably, in the step (3), the pumping speed of the homogeneous solution A is 1.5-2.5mL/min, the pumping speed of the homogeneous solution B is 2.5-3.5mL/min, and the volume of a micro-reactor in the micro-reaction device is 45-55 mL.
Preferably, in the step (3), the micro-reaction device comprises a micro-structure mixer, a micro-structure reactor, a pressure control valve and a product collector which are connected in sequence through a pipeline;
preferably, the microreactor in the microreactor device is an ultrasonic-assisted microreactor. During the reaction, the ultrasonic frequency is set to be 35-45 KHZ.
Preferably, in the step (3), the effluent material is extracted by using a proper organic solvent to obtain an organic phase, the organic phase is sequentially washed by water, alkali or acid, washed by a saturated sodium chloride solution, dried and filtered by anhydrous sodium sulfate, and the organic solvent is evaporated out under reduced pressure to obtain the perfluoroalkyl aniline product.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the preparation method of the perfluoroalkyl aniline adopts a microchannel double-strand feeding method, and has the advantages of simple operation, high reaction rate and high safety;
(2) the preparation method of perfluoroalkyl aniline of the invention adopts a reaction synthesis method of micro-flow field reaction technology, greatly shortens the reaction time to about 10min from about 6h of kettle type reaction, and is energy-saving and efficient;
(3) the preparation method of the perfluoroalkyl aniline adopts the process strengthening technology based on ultrasonic waves, and utilizes the turbulence effect, the perturbation effect and the shock wave effect of the phase interface ultrasonic cavitation collapse to enhance the mass transfer effect of the fluid in the microchannel.
(4) By the preparation method of perfluoroalkyl aniline, the reaction impurities in the microchannel reactor are less (no by-product of 2-position substitution is generated), the conversion rate is high, the purity of the prepared product is more than or equal to 99.0 percent, and the yield is more than or equal to 85 percent.
Drawings
FIG. 1 is a schematic structural diagram of a microchannel reactor according to the present invention.
FIG. 2 Heptafluoroisopropylaniline1H NMR。
FIG. 3 Heptafluoroisopropyl aniline19F NMR。
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The following microchannel reaction device is composed of a material inlet, a micro mixer, a micro reaction pipeline and a material outlet which are sequentially connected through connecting pipes, wherein the concrete assembly is shown in figure 1, two reaction raw material storage tanks are connected with respective feed liquid inlets through the connecting pipes and then are respectively connected with the micro mixer, pumps are respectively arranged on the connecting pipes, the micro mixer is connected with an ultrasonic auxiliary micro reactor through the connecting pipes, the micro reactor is connected with the material outlet through the connecting pipes, a pressure control valve and a corresponding instrument are connected between the micro reactor and the material outlet, a self-made ultrasonic auxiliary micro reactor (an ultrasonic vibrator and a microchannel are combined and provided with a temperature control system) is adopted, and reagents used in the experiment are AR.
In the microchannel reaction device, the raw material tank is a 250mL conical flask, the feeding delivery pump is a high-pressure injection pump, the diameters of connecting pipes are 2mm, the length of a liquid inlet pipe is 15cm, the length of a connecting pipe between a micro mixer and an ultrasonic auxiliary micro reactor is 20cm, the length of a connecting pipe between a micro reaction pipeline and an outlet is 15cm, and the volume of the ultrasonic auxiliary micro reactor is 50 mL.
The reaction formula is as follows:
wherein, -RfIs C2～16Perfluoroalkyl radical
Example 1:
27.9g (0.3mol) of aniline and 106.6g (0.36mol) of heptafluoro isopropyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature was 25 ℃ and the reaction residence time was 10 min. The coarse product collected at the outlet100mL of methyl t-butyl ether was added thereto, and the mixture was allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined, washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution, saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was dried, and distilled under reduced pressure to obtain 73.83g of a product with a yield of 94.23%.1H NMR(400MHz,CDCl3)δ:7.23(m,2H,Ar-H),6.65(m,2H,Ar-H),3.84(br,2H,-NH2)；19F NMR(376MHz,CDCl3)δ:-76.07(m,6F,-CF3),-181.87(m,1F,-CF)。
Comparative example 1
This comparative example differs from example 1 only in that it is a conventional in-reactor reaction. 27.9g (0.3mol,1.0eq) of aniline, 450mL of water, 300mL of methyl t-butyl ether, 31.4g (0.18mol,0.6eq) of sodium dithionite, 38.2g (0.36mol,1.2eq) of anhydrous sodium carbonate, 10.2g (0.03mol,0.1eq) of tetrabutylammonium hydrogen sulfate, and 106.6g (0.3mol,1.2eq) of heptafluoroisopropylaniline were added to a closed reaction vessel, and the mixture was stirred at room temperature (25 ℃ C.) for 6 hours. 100mL of methyl t-butyl ether was added thereto, and the mixture was allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The anhydrous sodium sulfate was dried, filtered, the solvent was dried by evaporation, and distilled under reduced pressure to obtain 64.79g of a product with a yield of 82.69%.
Comparative example 2:
this comparative example differs from example 1 only in that the microreactor was not subjected to ultrasound-assisted mixing. 27.9g (0.3mol) of aniline and 106.6g (0.3mol) of heptafluoro isopropyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, setting the temperature to be 25 ℃, and carrying out ultrasonic-assisted mixing without opening an ultrasonic device. The two streams were mixed and pumped through a micromixer into an ultrasound assisted microreactor, where the organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature was 25 ℃ and the reaction residence time was 10 min. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The anhydrous sodium sulfate was dried, filtered, the solvent was dried by evaporation, and distilled under reduced pressure to obtain 45.29g of a product with a yield of 57.80%. Comparative example 3:
this comparative example differs from example 1 only in that the alkaline solution is NaHCO3And (4) preparing. 27.9g (0.3mol) of aniline and 106.6g (0.3mol) of heptafluoro isopropyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 30.2g (0.36mol) of sodium hydrogencarbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature was 25 ℃ and the reaction residence time was 10 min. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The anhydrous sodium sulfate was dried, filtered, the solvent was dried by spinning, and distilled under reduced pressure to obtain 70.23g of a product with a yield of 89.64%.
Example 2:
27.9g (0.3mol) of aniline and 106.6g (0.36mol) of perfluoroiodopropane are taken, 300mL of methyl tert-butyl ether is added and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature was 25 ℃ and the reaction residence time was 10 min. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The filtrate was dried over anhydrous sodium sulfate, the solvent was dried by evaporation, and distillation was performed under reduced pressure to obtain 73.11g of a product with a yield of 93.31%.
Example 3:
27.9g (0.3mol) of aniline and 91.78g (0.36mol) of pentafluoroethyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary micro-reactor and controlling the temperature to be 10 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min, the aqueous solution was pumped at a flow rate of 3mL/min, and the system pressure was controlled to allow the fluid to flow in liquid form in the tube. The reaction temperature is 10 ℃, and the reaction residence time is 10 min. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The mixture was dried over anhydrous sodium sulfate, filtered, dried over sodium sulfate, and distilled under reduced pressure to obtain 57.28g, a yield of 90.43%.
Example 4:
27.9g (0.3mol) of aniline and 196.55g (0.36mol) of perfluorooctyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature was 25 ℃ and the reaction residence time was 10 min. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The mixture was dried over anhydrous sodium sulfate, filtered, dried over sodium sulfate, and distilled under reduced pressure to obtain 134.77g, a yield of 87.88%.
Example 5:
27.9g (0.3mol) of aniline and 142.54g (0.36mol) of perfluoro-n-amyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature is 25 ℃, the reaction residence time is 10min, and the crude product is collected at the outlet. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed successively with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The anhydrous sodium sulfate was dried, filtered, the solvent was dried by evaporation, and distilled under reduced pressure to obtain 97.12g of a product with a yield of 89.63%.
Example 6:
27.9g (0.3mol) of aniline and 142.54g (0.36mol) of perfluoro isoamyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature is 25 ℃, the reaction residence time is 10min, and the crude product is collected at the outlet. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined, washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution, saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was dried, and distilled under reduced pressure to obtain 95.62g of a product with a yield of 88.25%.
Example 7:
27.9g (0.3mol) of aniline and 142.54g (0.36mol) of perfluoro-isoheptyl iodide are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature is 25 ℃, the reaction residence time is 10min, and the crude product is collected at the outlet. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The mixture was dried over anhydrous sodium sulfate, filtered, dried over sodium sulfate, and distilled under reduced pressure to obtain 119.23g, a yield of 86.17%.
Example 8:
27.9g (0.3mol) of aniline and 96.17g (0.36mol) of 1-iodoperfluoro (4-methyl-5-pentene) are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 25 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature is 25 ℃, the reaction residence time is 10min, and the crude product is collected at the outlet. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined and washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution and saturated brine. The mixture was dried over anhydrous sodium sulfate, filtered, the solvent was dried by rotation, and distilled under reduced pressure to obtain 96.16g of a product with a yield of 85.90%.
Example 9:
27.9g (0.3mol) of aniline and 146.86g (0.36mol) of undecyliodocyclohexane are added into 300mL of methyl tert-butyl ether and mixed evenly to obtain a homogeneous organic solution; 31.4g (0.18mol) of sodium dithionite, 10.2g (0.03mol) of tetrabutylammonium hydrogen sulfate as a phase transfer catalyst, and 38.2g (0.36mol) of anhydrous sodium carbonate were dissolved in 450mL of water to obtain a homogeneous aqueous solution. And respectively pouring the prepared two materials into corresponding raw material tanks, starting an ultrasonic device of the ultrasonic auxiliary microreactor, and setting the temperature to be 20 ℃. The two materials are mixed and pumped into an ultrasonic auxiliary micro-reactor through a micro-mixer, and the frequency is set to be 40 KHZ. The organic solution was pumped at a flow rate of 2mL/min and the aqueous solution was pumped at a flow rate of 3 mL/min. The reaction temperature is 20 ℃, the reaction residence time is 10min, and the crude product is collected at the outlet. The crude product collected at the outlet was added to 100mL of methyl t-butyl ether and allowed to stand for liquid separation. The organic phase is separated off and the aqueous phase is extracted with 100ml of methyl tert-butyl ether. The organic phases were combined, washed with 0.2mol/L hydrochloric acid solution, 5% sodium carbonate solution, saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was dried, and distilled under reduced pressure to give 95.66g of product in 85.45% yield.
The reaction results of examples 1 to 9 are shown in Table 1 below
Table 1 table of reaction results of examples
While the invention has been described with respect to a number of specific embodiments and methods, it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made without departing from the scope and spirit of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A method for preparing perfluoroalkyl aniline by a micro-flow field reaction technology is characterized by comprising the following steps:
(1) dissolving aniline and perfluoroalkyl iodide (I) in an organic solvent to obtain a homogeneous solution A;
(2) dissolving an initiator and a phase transfer catalyst in an alkaline solution to obtain a homogeneous solution B;
(3) respectively and simultaneously pumping the two homogeneous phase solutions obtained in the step (1) and the step (2) into a micro-reaction device for reaction, and collecting effluent liquid, namely a perfluoroalkyl aniline (II) crude product;
wherein, -RfIs C2～16A perfluoroalkyl group.
2. The method for preparing perfluoroalkyl aniline by using the micro-flow field reaction technology as claimed in claim 1, wherein the concentration of aniline in the homogeneous solution A obtained in step (1) is 0.02 g/mL-0.5 g/mL, and the molar ratio of aniline to perfluoroalkyl iodide is controlled to be 1: 1.0-1.5.
3. The method for preparing perfluoroalkylaniline according to claim 1, wherein in step (1), the organic solvent is halogenated alkane, ether, alcohol, ketone, amide, ester or nitrile.
4. The method for preparing perfluoroalkyl aniline according to the micro-flow field reaction technology of claim 1, wherein the concentration of the initiator in the homogeneous solution B obtained in the step (2) is 0.3 mmol/mL-0.9 mmol/Ml; the initiator is sodium hydrosulfite, potassium hydrosulfite, zinc hydrosulfite or zinc-sulfurous acid solution. .
5. The method for preparing perfluoroalkylaniline according to claim 1, wherein in the step (2), the base used in the alkaline solution is a base which can form a homogeneous solution and is compatible with the catalyst.
6. The method for preparing perfluoroalkylaniline according to claim 1, wherein in step (2), the phase transfer catalyst is selected from quaternary ammonium salts, phosphorus salts, polyethylene glycol ethers or crown ethers.
7. The method for preparing perfluoroalkyl aniline according to claim 1, wherein the reaction molar ratio of aniline and initiator in step (3) is controlled to 1: 0.4-1.2.
8. The method for preparing perfluoroalkylaniline according to claim 1, wherein in the step (3), the reaction temperature is 0-50 ℃ and the reaction residence time is 1-15 min.
9. The method for preparing perfluoroalkylaniline according to claim 1, wherein in step (3), the pumping speed of the homogeneous solution A is 1.5-2.5mL/min, the pumping speed of the homogeneous solution B is 2.5-3.5mL/min, and the volume of a microreactor in the microreactor device is 45-55 mL.
10. The method for preparing perfluoroalkylaniline according to the micro-flow field reaction technology of claim 1, wherein in the step (3), the microreactor in the micro-reaction device is an ultrasonic-assisted microreactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110774273.1A CN113527109A (en) | 2021-07-08 | 2021-07-08 | Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110774273.1A CN113527109A (en) | 2021-07-08 | 2021-07-08 | Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113527109A true CN113527109A (en) | 2021-10-22 |
Family
ID=78127158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110774273.1A Pending CN113527109A (en) | 2021-07-08 | 2021-07-08 | Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113527109A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115738986A (en) * | 2022-11-01 | 2023-03-07 | 南京先进生物材料与过程装备研究院有限公司 | Intensive mixing internal member and method for preparing perfluoroalkyl aniline by using same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731317A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Preparation method of perfluorinated alkyl aniline derivative |
| CN102731321A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Method for preparing 2-methyl-4-(1,1,1,2,3,3,3-heptafluoro-2-propyl) aniline |
| CN104923137A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院大连化学物理研究所 | Method for enhancing fluid mixing in micro-reactor |
| CN106748807A (en) * | 2017-01-16 | 2017-05-31 | 衢州学院 | A kind of sevoflurane isopropyl amine preparation method of 2 methyl of high-purity 4 |
| CN110681332A (en) * | 2018-07-25 | 2020-01-14 | 中国科学院大连化学物理研究所 | Modular temperature control type ultrasonic microreactor |
| CN111132549A (en) * | 2017-09-20 | 2020-05-08 | 三井化学Agro株式会社 | Long-acting control agent for ectoparasites of animals |
| CN112266355A (en) * | 2020-10-26 | 2021-01-26 | 南京先进生物材料与过程装备研究院有限公司 | Method for synthesizing C-5 trifluoromethylated 8-aminoquinoline by using microchannel reaction device under visible light |
-
2021
- 2021-07-08 CN CN202110774273.1A patent/CN113527109A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731317A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Preparation method of perfluorinated alkyl aniline derivative |
| CN102731321A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Method for preparing 2-methyl-4-(1,1,1,2,3,3,3-heptafluoro-2-propyl) aniline |
| CN104923137A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院大连化学物理研究所 | Method for enhancing fluid mixing in micro-reactor |
| CN106748807A (en) * | 2017-01-16 | 2017-05-31 | 衢州学院 | A kind of sevoflurane isopropyl amine preparation method of 2 methyl of high-purity 4 |
| CN111132549A (en) * | 2017-09-20 | 2020-05-08 | 三井化学Agro株式会社 | Long-acting control agent for ectoparasites of animals |
| CN110681332A (en) * | 2018-07-25 | 2020-01-14 | 中国科学院大连化学物理研究所 | Modular temperature control type ultrasonic microreactor |
| CN112266355A (en) * | 2020-10-26 | 2021-01-26 | 南京先进生物材料与过程装备研究院有限公司 | Method for synthesizing C-5 trifluoromethylated 8-aminoquinoline by using microchannel reaction device under visible light |
Non-Patent Citations (1)
| Title |
|---|
| MONTEIRO, JULIA L.: "Continuous Flow Homolytic Aromatic Substitution with Electrophilic Radicals: A Fast and Scalable Protocol for Trifluoromethylation", 基于上述理由，本申请的独立权利要求以及从属权利要求都不具备【新颖性】/【创造性】/【新颖性或创造性】，同时说明书中也没有记载其他任何可以授予专利权的实质性内容，因而即使申请人对权利要求进行重新组合和／或根据说明书记载的内容作进一步的限定，本申请也不具备被授予专利权的前景。如果申请人不能在本通知书规定的答复期限内提出表明本申请具有新颖性和创造性的充分理由，本申请将被驳回。, vol. 23, no. 1, pages 176 - 186, XP071842685, DOI: 10.1002/chem.201604579 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115738986A (en) * | 2022-11-01 | 2023-03-07 | 南京先进生物材料与过程装备研究院有限公司 | Intensive mixing internal member and method for preparing perfluoroalkyl aniline by using same |
| CN115738986B (en) * | 2022-11-01 | 2024-09-10 | 南京先进生物材料与过程装备研究院有限公司 | Reinforced mixing inner member and method for preparing perfluoroalkyl aniline by using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11618727B2 (en) | Method for preparing 3-chloro-4-oxopentyl acetate using fully continuous-flow micro-reaction system | |
| US11555008B2 (en) | Method for preparing L-carnitine using micro-reaction system | |
| CN101664657B (en) | Carboxylate gemini surfactant and preparation method thereof | |
| US20190119496A1 (en) | Totally bio-based vegetable oil polyol and preparation method and use thereof | |
| US9624176B2 (en) | Method for preparing caprolactam by using a microreactor under lewis acid catalysis | |
| CN111233884B (en) | Method for synthesizing gamma-butyrolactone containing spiro 1, 3-indandione structure by using microchannel reaction device | |
| CN113527109A (en) | Method for preparing perfluoroalkyl aniline by micro-flow field reaction technology | |
| CN201692802U (en) | Device for continuously producing hexafluoro propylene oxide | |
| CN115650825A (en) | Method for synthesizing dihydric alcohol monovinyl ether | |
| CN218795951U (en) | Intensive mixed inner member, reaction tube and tubular reactor | |
| JP2002273206A (en) | Synthetic reaction device and synthetic reaction method using the same | |
| KR101874776B1 (en) | Method for preparation of n-butyl nitrite | |
| CN111892532A (en) | Method for synthesizing 3-Cl propionyl substituted heterocyclic compound containing N by using micro-reaction device | |
| CN109574892B (en) | Method for preparing 3-iodine-N- (1, 1-dimethyl-2-methylthioethyl) o-carbamoylbenzoic acid by microchannel reaction | |
| CN107814691B (en) | Method for synthesizing ethylguaiacol | |
| CN106831661B (en) | Method for preparing epoxypropane by using micro-reaction device | |
| CN106588669B (en) | Method for continuously preparing nitrobenzyl ether by using microchannel reaction system | |
| CN115738986B (en) | Reinforced mixing inner member and method for preparing perfluoroalkyl aniline by using same | |
| CN108794307B (en) | Micro-reaction system and method for synthesizing 4-bromo-3-methylanisole by solvent method | |
| CN104211652B (en) | A kind of method preparing Plerixafor | |
| CN107522638A (en) | Prepare the microreactor and method of o-methyl formate benzene sulfonamide | |
| CN113845495A (en) | Continuous synthesis method of two-stage glycidyl neodecanoate | |
| CN1126731C (en) | Process for preparing unsaturated quaternary ammonium salt | |
| US11920017B2 (en) | Preparation method of polyurethane foam | |
| CN114573478A (en) | Method for preparing bromoxynil octanoate |
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 |