Gradient energy plasma gas phase reactor and method of use

Abstract

The application discloses a kind of gas phase reactors of gradient energy plasma and use method.This gas phase reactor includes microwave plasma generating device, liquid collection barrel, outlet pipeline, inlet pipeline, concentric atomizer, gas path joint, spherical reaction chamber, main support plate, cooling cup, peristaltic pump, microwave plasma generating device is installed on the top of main support plate, the central embedding of main support plate is equipped with spherical reaction chamber, concentric atomizer is inserted in the top of spherical reaction chamber, outlet pipeline in the top of concentric atomizer is connected with the liquid collection barrel below main support plate through peristaltic pump and inlet pipeline, and circulation flow path is formed.The microwave plasma of the application is used to participate in organic synthesis reaction with energy gradient, without adding additional catalyst, reduce chemical use and discharge, reduce synthesis cost, promote the reaction of reactant and gas in solution, increase reaction dimension, device is small, energy is adjustable, suitable for laboratory and desktop micro chemical industry condition application.

Description

Technical Field

[0001] This invention relates to the field of plasma synthesis, specifically to a gas-phase reactor for gradient energy plasma and its method of use. Background Technology

[0002] In recent years, organic chemical synthesis has been developing towards greener, more economical, more efficient, and more selective directions, giving rise to a series of new reaction devices and equipment. Among them, plasma synthesis equipment is a novel synthesis method that has gradually developed since the late 20th century, often possessing advantages such as energy saving, environmental friendliness, and low emissions. The discharge forms of plasma synthesis include: radio frequency discharge, dielectric barrier discharge, corona discharge, glow discharge, and electrostatic discharge. Many successful cases utilize dielectric barrier discharge, primarily targeting small gaseous molecules with a mass number of less than 150, or some degradation and dissociation reactions. However, plasma reaction devices for gas-liquid and liquid-liquid systems are relatively rare. Microwave plasma, with its high energy, absence of exposed electrodes, and stable operation, is well-suited for the design of plasma reaction devices. With the emergence of the concept of desktop micro-chemistry, there is an urgent need for various portable novel plasma reaction devices to improve the efficiency of organic synthesis, reduce the use of catalysts, and compensate for the shortcomings of traditional organic reaction devices. Summary of the Invention

[0003] This invention provides a gradient energy plasma gas-phase reactor and its usage method. It employs a continuously variable power microwave plasma torch coupled with a concentric atomizer, and utilizes a peristaltic pump to circulate the reaction. This device uses high-energy electrons and metastable ions generated by the microwave plasma beam to break down the potential barriers of organic reactions, enabling rapid, catalytic-free reactions of some organic molecules. Simultaneously, through energy-controlled plasma bombardment, heterolytic rearrangement reactions that are difficult to occur in liquid-phase synthesis systems can be achieved. Furthermore, gas-phase molecules activated by the plasma torch can participate in the organic reaction, achieving rapid gas-liquid two-phase reactions. The device is compact and portable, with its main body dimensions compressible to within 20×10×30cm.

[0004] The technical solution adopted in this invention is as follows:

[0005] This device provides a gradient energy plasma gas-phase reactor, comprising a microwave plasma generator, a liquid collection tank, an outlet pipe, an inlet pipe, a concentric atomizer, a gas path connector, a spherical reaction chamber, a main support plate, a cooling cup, and a peristaltic pump. The main support plate has a central circular through-hole, into which the spherical reaction chamber is embedded. Below the main support plate is the liquid collection tank, whose upper end extends upward through a through-hole at the bottom of the spherical reaction chamber and is installed within the bottom of the chamber. The lower end of the liquid collection tank is located in the cooling cup. The cooling cup, the bottom of the spherical reaction chamber, and the liquid collection tank are coaxially nested from the outside in. During actual operation, a suitable amount of cold water is filled between the cooling cup and the liquid collection tank to ensure product cooling and deposition, reducing collection losses. Furthermore, the cold water in the cooling cup can absorb small amounts of chemicals released during the reaction, reducing chemical emissions.

[0006] The microwave plasma generator is horizontally mounted on the upper surface of one side of the main support plate. The spherical reaction chamber has an opening on one side near the microwave plasma generator. One end of the microwave plasma generator passes through the opening on the side of the spherical reaction chamber and extends into the spherical reaction chamber.

[0007] The concentric atomizer is vertically inserted into the top of the spherical reaction chamber. The concentric atomizer atomizes the reactants into spray droplets. The bottom end of the concentric atomizer extends into the spherical reaction chamber and is perpendicularly spaced from the end of the microwave plasma generator that extends into the spherical reaction chamber. The bottom end of the concentric atomizer faces the center of the spherical reaction chamber. The microwave plasma beam generated by the microwave plasma generator is located directly below the bottom end of the concentric atomizer, so that the reactant spray formed by the concentric atomizer passes through the microwave plasma beam generated by the microwave plasma generator. One side of the top of the concentric atomizer is connected to… The device is equipped with a gas connector for introducing atomizing carrier gas into the concentric atomizer. The top of the concentric atomizer is connected to the outlet of the peristaltic pump via the inlet pipe, and the inlet of the peristaltic pump is connected to the liquid collection tank via the outlet pipe. In actual operation, the peristaltic pump draws the prepared reactant solution into the liquid collection tank through the outlet pipe, and then injects the reactant solution into the concentric atomizer through the inlet pipe. The concentric atomizer atomizes the reactant solution into spray droplets, which pass through the microwave plasma beam and are deposited and collected in the liquid collection tank after reaction, forming a flow path circulation module.

[0008] Furthermore, the peristaltic pump can be replaced with other liquid circulation pumps, including but not limited to syringe pumps, microfluidic pumps, etc.

[0009] The outlet pipe is fixed to the outer wall of the liquid collection tank and extends from the top of the liquid collection tank to the bottom of the liquid collection tank.

[0010] The microwave plasma generator is electrically connected to an external power supply module, which is an adjustable microwave source used to provide microwave signals. The power of the power supply module is adjustable to achieve adjustable plasma energy gradient. The power adjustment range of the power supply module is 60W to 200W. When the power of the power supply module is below 60W, the plasma is difficult to maintain stably. By adjusting the energy gradient to control the plasma ionization energy and temperature, the conditions for the reaction can be controlled. During plasma excitation, working gas is input through the plasma working gas inlet, and electrons are simultaneously supplied through methods such as metal contact.

[0011] The microwave plasma generator is connected to a plasma working gas inlet at the end away from the spherical reaction chamber. The main body of the microwave plasma generator is provided with three concentric nested copper tubes, which are, from the inside out, an inner tube, a central tube, and a microwave input tube. The inner tube is an argon tube and is connected to the plasma working gas inlet. The annular gap between the inner tube and the central tube generates a microwave plasma beam.

[0012] The top of the spherical reaction chamber has a circular opening, and a concentric atomizer bracket is vertically inserted through the opening. The concentric atomizer is movably inserted inside the concentric atomizer bracket, and the concentric atomizer can move vertically up and down continuously inside the concentric atomizer bracket.

[0013] Furthermore, the concentric atomizer can be replaced by one of the following: a piezoelectric atomizer, an ultrasonic atomizer, or an electro-sprayer.

[0014] The main support plate has feet fixedly installed at its four lower corners to support it. A slide rail structure is fixedly installed between the main support plate and the microwave plasma generator for fixing and adjusting the microwave plasma generator. The slide rail is installed on a slotted through hole on the surface of the main support plate, and the track direction of the slide rail is parallel to the microwave plasma generator. In actual operation, coordinating the adjustment of the position parameters of the concentric atomizer and the microwave plasma generator can ensure that the reactant spray and the plasma beam are in full contact.

[0015] The steps for organic synthesis reactions and control methods using the gradient energy plasma gas-phase reactor provided by this device are as follows:

[0016] 1) After installing the gas phase reactor of the gradient energy plasma, prepare the reactants into a reactant solution of appropriate concentration and place it in a liquid collection tank, and inject cold water into the cooling cup;

[0017] 2) Turn on the peristaltic pump to pump the reactant solution into the concentric atomizer, and introduce atomizing carrier gas into the gas line interface. The concentric atomizer atomizes the reactant solution into a spray and sprays it into the spherical reaction chamber.

[0018] 3) Turn on the power module and adjust the appropriate gradient energy by adjusting the power. Inject the working gas into the microwave plasma generator from the plasma working gas inlet. The end of the microwave plasma generator that extends into the spherical reaction chamber generates a microwave plasma beam. The microwave plasma beam comes into full contact with the reactant spray. Under the action of plasma temperature and airflow, the reactant solution loses the solvent and desorbs into a gaseous state, forming gaseous reactant molecules / ions. The gaseous reactant molecules / ions then collide and react with electrons / ions in the microwave plasma. Specifically, the gaseous reactant molecules / ions can collide with high-energy electrons, primary gaseous ions, and high-energy metastable ions, resulting in various gaseous ion reactions.

[0019] 4) After the reaction occurs, the gas-liquid mixture produced settles downwards and condenses under the action of the cooling cup. It then flows down and is collected in the liquid collection tank. After the reaction is completed, the power module and the peristaltic pump are turned off, and the product solution is collected from the liquid collection tank and combined with the liquid in the cooling cup.

[0020] In step 4), the liquid mixture collected in the liquid collection tank is drawn out again by the peristaltic pump through the outlet pipe and pumped back into the concentric atomizer through the inlet pipe, and then circulated through step 3) until the reaction ends.

[0021] In step 1), after the gas phase reactor of the gradient energy plasma is installed, the horizontal distance between the bottom end of the concentric atomizer and the end of the microwave plasma generator that extends into the spherical reaction chamber is adjusted so that the plasma beam and the reactant spray are in full contact before continuing the subsequent steps.

[0022] The organic synthesis reactions include, but are not limited to, oxidation and reduction reactions, addition reactions, proton transfer reactions, elimination reactions, and negative hydrogen migration reactions.

[0023] In step 2), the liquid flow rate in the peristaltic pump is continuously adjustable, ranging from 1 to 13 mL / min.

[0024] In step 2), the atomizing carrier gas in the gas interface includes, but is not limited to, nitrogen, argon, helium, carbon dioxide, etc. Flammable gases are not allowed. The flow rate of the atomizing carrier gas is continuously adjustable from 1L / min to 3L / min.

[0025] In step 3), the working gas introduced into the plasma working gas inlet is argon or helium, and the flow rate of the working gas is continuously adjustable, ranging from 500 to 1000 mL / min.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] 1) This invention innovatively uses microwave plasma with energy gradient to participate in organic reaction synthesis, eliminating the need for additional catalysts, reducing the use and emissions of chemicals, and lowering synthesis costs.

[0028] 2) This invention is based on the collision / energy exchange between gaseous reactant molecules / ions and high-energy electrons, primary gaseous ions, and high-energy metastable ions in plasma as the reaction mechanism, which can realize heterolytic and rearrangement reactions that are difficult or impossible to occur in solution reactions.

[0029] 3) In addition to enabling the reaction of compounds in solution, this invention can also promote the reaction between reactants in solution and gases, thus increasing the reaction dimension.

[0030] 4) The device of this invention is compact and has adjustable energy, unlike large-scale plasma reactions, making it suitable for laboratory and desktop micro-chemical applications. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Figure 1 This is a schematic diagram of the overall structure of the gradient energy plasma gas phase reactor after installation.

[0033] Figure 2 This is a structural diagram of a key component of a gas-phase reactor for a gradient energy plasma.

[0034] Figure 3 This is a schematic diagram of the cross-section of the spherical reaction chamber and the liquid collection tank.

[0035] Figure 4 This is a schematic diagram showing the microwave plasma generator and the concentric atomizer placed orthogonally.

[0036] Figure 5 The mass spectra of the rapid oxidation reaction of thioether compounds are shown, including (a) L-methionine, (b) phenyl benzyl thioether, (c) 4-methoxyphenyl thioether, and (d) pyridyl thioether.

[0037] Figure 6 Mass spectra used to verify the results of the alcohol-to-aldehyde conversion reaction, including (a) benzyl alcohol, (b) 4-methylbenzyl alcohol, (c) 4-chlorobenzyl alcohol, and (d) 4-methoxybenzyl alcohol.

[0038] Figure 7 The total ion current (TIC) spectrum (top) and the ion current chromatogram (bottom) of m / z = 150.09 obtained by the reaction synthesis of phenyl natriuretic acid.

[0039] Figure 8 The mass spectrum of the product synthesized by the reaction of phenyl natriuretic acid at a retention time of 22 min is shown.

[0040] The main components shown in the diagram are: 1. Power module; 2. Microwave plasma generator; 3. Plasma working gas inlet; 4. Stand; 5. Liquid collection tank; 6. Outlet pipe; 7. Microwave plasma beam; 8. Inlet pipe; 9. Concentric atomizer; 10. Gas connection; 11. Concentric atomizer support; 12. Spherical reaction chamber; 13. Main support plate; 14. Cooling cup; 15. Peristaltic pump. Detailed Implementation

[0041] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0042] In the description of this invention, it should be noted that the terms "upper", "lower", "left", "right", "inner", "outer", "middle", "vertical", "horizontal", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or component referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention.

[0043] I. Setup and Operation Methods

[0044] like Figure 1 , 2 As shown, a gradient energy plasma gas phase reactor mainly includes: a microwave plasma generator 2, a liquid collection tank 5, an outlet pipe 6, an inlet pipe 8, a concentric atomizer 9, a gas connection 10, a spherical reaction chamber 12, a main support plate 13, a cooling cup 14, and a peristaltic pump 15.

[0045] A circular through hole is opened in the center of the main support plate 13, and a spherical reaction chamber 12 is installed in the hole. A liquid collection tank 5 is provided below the main support plate 13. The upper end of the liquid collection tank 5 extends upward from the through hole opened at the bottom of the spherical reaction chamber 12 and is installed in the bottom of the spherical reaction chamber 12. The lower end of the liquid collection tank 5 is located in the cooling cup 14. The cooling cup 14, the bottom of the spherical reaction chamber 12 and the liquid collection tank 5 are coaxially nested from the outside to the inside. In actual operation, an appropriate amount of cold water is filled between the cooling cup 14 and the liquid collection tank 5 to ensure that the product is cooled and deposited, reduce collection loss, and the cold water in the cooling cup 14 can absorb a small amount of chemicals that escape during the reaction, reducing the emission of chemicals.

[0046] A microwave plasma generator 2 is horizontally mounted on the upper surface of one side of the main support plate 13. The spherical reaction chamber 12 has an opening on one side near the microwave plasma generator 2. One end of the microwave plasma generator 2 passes through the opening on the side of the spherical reaction chamber 12 and extends into the spherical reaction chamber 12.

[0047] A concentric atomizer 9 is vertically inserted into the top of the spherical reaction chamber 12. The concentric atomizer 9 is used to atomize the reactants into spray droplets. The bottom end of the concentric atomizer 9 extends into the spherical reaction chamber 12, facing the center of the spherical reaction chamber 12 and arranged perpendicularly at a distance from the end of the microwave plasma generator 2 that extends into the spherical reaction chamber 12. The microwave plasma beam 7 generated by the microwave plasma generator 2 is located directly below the bottom end of the concentric atomizer 9, so that the reactant spray formed by the concentric atomizer 9 passes through the microwave plasma beam 7 generated by the microwave plasma generator 2 after being ejected.

[0048] The top of the concentric atomizer 9 is connected to the outlet of the peristaltic pump 15 via the inlet pipe 8. The inlet of the peristaltic pump 15 is connected to the liquid collection tank 5 via the outlet pipe 6. Specifically, the outlet pipe 6 is fixed to the outer wall of the liquid collection tank 5, extending from the top of the liquid collection tank 5 to the bottom. One side of the top of the concentric atomizer 9 is connected to the air passage connector 10, which is used to introduce atomizing carrier gas into the concentric atomizer 9.

[0049] In actual operation, the peristaltic pump 15 draws the reactant solution into the liquid collection tank 5 through the outlet pipe 6, and then injects the reactant solution into the concentric atomizer 9 through the inlet pipe 8. The concentric atomizer 9 atomizes the reactant solution into spray droplets, which pass through the microwave plasma beam 7 and, after reaction, deposit in the liquid collection tank 5, forming a flow path circulation module. The peristaltic pump 15 can be replaced with other liquid circulation pumps, including but not limited to syringe pumps, microfluidic pumps, etc.

[0050] The microwave plasma generator 2 is electrically connected to an external power supply module 1, which is connected to a 220V national standard voltage. Power supply module 1 is an adjustable microwave source used to provide microwave signals. Its output power can be changed to achieve adjustable plasma energy gradient. The power of power supply module 1 is adjustable, with a power adjustment range of 60W to 200W. During plasma excitation, working gas is input through the plasma working gas inlet 3, and electrons are simultaneously supplied via methods such as metal contact.

[0051] The microwave plasma generator 2 has a plasma working gas inlet 3 connected to the end away from the spherical reaction chamber 12. The main body of the microwave plasma generator 2 is equipped with three concentric nested copper tubes, which are, from the inside out, an inner tube, a central tube, and a microwave input tube. The inner tube is an argon tube and is connected to the plasma working gas inlet 3. The annular gap between the inner tube and the central tube generates a conical microwave plasma beam 7 with a diameter of 20-35 mm.

[0052] The top of the spherical reaction chamber 12 is provided with a circular opening, and a concentric atomizer bracket 11 is vertically inserted through the opening. The concentric atomizer 9 is movably inserted into the concentric atomizer bracket 11. The concentric atomizer 9 can be directly inserted into the concentric atomizer bracket 11 and tightly connected. The concentric atomizer 9 can move vertically up and down continuously inside the concentric atomizer bracket 11, with an adjustment range of 0 to 10 mm.

[0053] Furthermore, the concentric atomizer 9 can be replaced with one of the following: a piezoelectric atomizer, an ultrasonic atomizer, or an electro-sprayer.

[0054] The main support plate 13 has multiple through holes and slot structures. The left side of the main support plate 13 has a slot-shaped through hole with a length of about 30mm, which is used to fix and adjust the microwave plasma generator 2. The four corners of the main support plate 13 have circular through holes for fixing the four legs 4. The middle of the main support plate 13 has a circular slot for fixing the spherical reaction chamber 12.

[0055] Furthermore, the main support plate and the spherical reaction chamber 12 can also be machined as a single unit.

[0056] A slide rail structure is fixedly installed between the main support plate 13 and the microwave plasma generator 2 for fixing and adjusting the microwave plasma generator 2. The slide rail is installed on the slot-shaped through hole opened on the upper surface of the main support plate 13. The track direction of the slide rail is parallel to the microwave plasma generator 2. The movement adjustment range of the microwave plasma generator 2 is 0-20mm.

[0057] After the gas phase reactor is installed, such as Figure 4 As shown, the microwave plasma generator 2 and the concentric atomizer 9 are placed orthogonally.

[0058] The steps for the organic synthesis reaction and control method using the gas-phase reactor in this embodiment are as follows:

[0059] 1) After the gas phase reactor of gradient energy plasma is installed, the reactants are prepared into a reactant solution of appropriate concentration and placed in the liquid collection tank 5, and cold water is injected into the cooling cup 14.

[0060] 2) Turn on the peristaltic pump 15 to pump the reactant solution into the concentric nebulizer 9, and introduce the atomizing carrier gas into the gas passage interface 10. The concentric nebulizer 9 atomizes the reactant solution into a spray and sprays it into the spherical reaction chamber 12.

[0061] 3) Turn on the power module 1, adjust the appropriate gradient energy by adjusting the power, and inject the working gas into the microwave plasma generator 2 from the plasma working gas inlet 3. The microwave plasma generator 2 generates a microwave plasma beam 7 at one end that extends into the spherical reaction chamber 12. The microwave plasma beam 7 comes into full contact with the reactant spray. Under the action of plasma temperature and airflow, the reactant solution loses the solvent and desorbs into a gaseous state, forming gaseous reactant molecules / ions. The gaseous reactant molecules / ions then collide and react with electrons / ions in the microwave plasma. Specifically, the gaseous reactant molecules / ions can collide with high-energy electrons, primary gaseous ions, and high-energy metastable ions, resulting in various gaseous ion reactions.

[0062] 4) After the reaction occurs, the gas-liquid mixture produced settles downward and condenses under the action of cooling cup 14. It flows down and is collected in liquid collection tank 5. After the reaction is completed, the power module 1 and peristaltic pump 15 are turned off, and the product solution is collected from liquid collection tank 5 and combined with the liquid in cooling cup 14.

[0063] In step 4), the liquid mixture collected in the liquid collection tank 5 is drawn again by the peristaltic pump 15 through the outlet pipe 6 and pumped back into the concentric atomizer 9 through the inlet pipe 8, and circulated through step 3) until the reaction ends.

[0064] In step 1), after the gas phase reactor of gradient energy plasma is installed, the horizontal distance between the bottom end of the concentric atomizer 9 and the end of the microwave plasma generator 2 that extends into the spherical reaction chamber 12 is adjusted so that the plasma beam 7 is in full contact with the reactant spray. Then the reactant solution is placed into the liquid collection tank 5 and cold water is injected into the cooling cup 14.

[0065] In step 2), the liquid flow rate in the peristaltic pump 15 is continuously adjustable from 1 to 13 mL / min;

[0066] In step 2), the atomizing carrier gas in the gas interface 10 is one or more of nitrogen, argon, helium, and carbon dioxide. Flammable gases are not allowed. The flow rate of the atomizing carrier gas is continuously adjustable from 1L / min to 3L / min.

[0067] In step 3, the working gas introduced into the plasma working gas inlet 3 is argon or helium, and the flow rate of the working gas is continuously adjustable from 500 to 1000 mL / min.

[0068] II. Analysis of Reaction Examples

[0069] (i) Rapid oxidation of thioethers and conversion of alcohols to aldehydes using a gas-phase reactor

[0070] To test the effectiveness of the present invention, the gas-phase reactor device with gradient energy plasma provided above was used to study the rapid non-catalytic oxidation in the device, and the products were analyzed by an LTQ Orbitrap mass spectrometer (Thermo Fisher Scientific, USA).

[0071] 1. Test materials

[0072] The reactant materials tested included:

[0073] Sulfur-containing compounds: L-methionine (Example 1), phenyl benzyl sulfide (Example 2), 4-methoxyphenyl sulfide (Example 3), pyridyl sulfide (Example 4).

[0074] Alcohols: benzyl alcohol (Example 5), 4-methylbenzyl alcohol (Example 6), 4-chlorobenzyl alcohol (Example 7), 4-methoxybenzyl alcohol (Example 8). Weigh them before testing and store them properly in a refrigerator when not testing.

[0075] 2. Experimental conditions

[0076] Weigh 500 mg of reactant sample and dissolve it in 100 mL of acetonitrile:water (3:1). Place the solution in a liquid collection container. Add 200 mL of cold water to the cooling container. Adjust the plasma power supply module to maintain the gradient energy at 100 W. Turn on the peristaltic pump and adjust the flow rate to 3 mL / min. After one cycle of reaction, combine the liquids in the collection container and the cooling container. Add 50 mL of dichloromethane for extraction, retain the organic phase, and rotary evaporate to concentrate it to approximately 5 mL. Analyze the product using mass spectrometry.

[0077] Positive / negative ion detection mode; scanning mode is positive ion full scan; mass spectrometer open; mass spectrometer inlet temperature: 275 degrees Celsius; lens voltage: 110V / -120V; ion transmission tube voltage: 30V / -30V.

[0078] 3. Experimental Results

[0079] The rapid oxidation of various sulfur-containing compounds to sulfoxides without the addition of an oxidizing agent was tested. L-methionine (Example 1) was selected first for the experiment. Figure 5 As shown in (a), L-methionine can be converted to L-methionine sulfide in milliseconds without the addition of any oxide or catalyst, with an initial conversion of approximately 20%. Such compounds can be rapidly oxidized in this device without the addition of an oxidant: four sulfides were detected, including L-methionine (Example 1, ...). Figure 5 (a) ), phenyl benzyl sulfide (Example 2, Figure 5 (b) ), 4-methoxyphenyl sulfide (Example 3, Figure 5 (c) of the example), pyridyl sulfide (Example 4, Figure 5 The results (d) showed that the main oxidation product of almost all sulfides was sulfoxide, with a conversion rate between 5% and 40%.

[0080] Based on this, some common alcohols, including benzyl alcohol (Example 5), were studied. Figure 6 (a) and 4-methylbenzyl alcohol (Example 6, Figure 6 (b) ), 4-chlorobenzyl alcohol (Example 7, Figure 6 (c) , 4-Methoxybenzyl alcohol (Example 8, Figure 6 The conversion of (d) in the middle stage resulted in an oxidation product conversion rate between 10% and 35%. For example... Figure 6 As shown in (a), the product structure was verified to be an aldehyde rather than an ionized product undergoing negative hydrogen migration by passing a mixture of benzyl alcohol and aniline via MPTIR. The peak at m / z 182.0975 (<5 ppm) in the mass spectrum was identified as a Schiff base, the reaction product of benzaldehyde and aniline, proving that benzyl alcohol was indeed oxidized to benzaldehyde.

[0081] (ii) Phenylene ion reaction using a gas-phase reactor

[0082] Phenylacetylamine generates phenyl phenyl ion (PhNH4+) in plasma. + It is an active ion that can react with alcohols, aldehydes, ketones, esters, alkanes, and nitrile compounds. Taking the reaction of phenylhydroxylamine with acetone as an example (Example 9), its gas-phase ion reaction and products were studied, and the analysis was performed using Shimadzu LC-MS-ITTOF.

[0083] 1. Test materials

[0084] Taking the reaction of phenylhydroxylamine with acetone as an example, weigh approximately 0.2 g of phenylhydroxylamine, dissolve it in 20 mL of acetone, and dilute with water to 100 mL to obtain the reaction solution. If a substrate with poor water solubility is used, an additional 20 mL of methanol can be added to promote its dissolution.

[0085] 2. Reaction conditions

[0086] Place the reactant solution into a liquid collection container, control the nitrogen flow rate at approximately 3 L / min, and turn on the peristaltic pump, controlling the liquid flow rate at 2 mL / min. Turn on the power module and microwave plasma generator, adjusting the power module voltage to 120 W. Initially control the gas flow rate at approximately 1 L / min, activate the plasma, and adjust the spray position so that the horizontal distance between its outlet and the plasma beam tip is approximately 5 mm, ensuring sufficient contact between the plasma beam and the reactants. The reaction time is approximately 1 hour, during which the gas flow rate is kept stable to prevent the liquid in the collection container from drying out.

[0087] After the reaction was complete, the liquids in the collection container and cooling vessel were combined, and 50 mL of dichloromethane was added for extraction. The organic phase was retained and concentrated to approximately 5 mL by rotary evaporation. The obtained product was analyzed by Shimadzu LC-MS-ITTOF. Chromatographic conditions: Column: Waters Nova-Pak C18 column, flow rate: 1.0 mL / min, mobile phase: 10% methanol-water solution, analysis time: 45 min.

[0088] 3. Experimental Results

[0089] Phenylacetylamine was detected by LTQ orbitrap high-resolution mass spectrometry under a plasma atmosphere, and the results are as follows: Figure 7 As shown, the generated ion with m / z = 92.05 was determined to be a phenyl naphthol ion (PhNH+). For example... Figure 8 As shown, after plasma beam excitation, the phenylnaphthol ion reacts with acetone to yield an addition product. Comparison by secondary mass spectrometry with products obtained through conventional organic synthesis confirms that the obtained product is the ortho-substituted 2-hydroxy-N-isopropylaniline. Using similar conditions, it can be demonstrated that other ketone compounds react with the phenylnaphthol ion to yield similar ortho-substituted products, exhibiting good substrate universality. This reaction achieves the activation of the ortho-CH bond in the benzene ring, showing great application potential in desktop microchemicals.

[0090] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A gas-phase reactor for gradient energy plasma, characterized in that: The gas phase reactor includes a microwave plasma generator (2), a liquid collection tank (5), an outlet pipe (6), an inlet pipe (8), a concentric atomizer (9), a gas connector (10), a spherical reaction chamber (12), a main support plate (13), a cooling cup (14), and a peristaltic pump (15). The spherical reaction chamber (12) is embedded in the center of the main support plate (13), and the liquid collection tank (5) is located below the main support plate (13). The upper end of the liquid collection tank (5) extends upward and is installed in the bottom end of the spherical reaction chamber (12), and the lower end of the liquid collection tank (5) is located in the cooling cup (14). The cooling cup (14), the bottom end of the spherical reaction chamber (12), and the liquid collection tank (5) are coaxially nested from the outside to the inside. The upper part of the main support plate (13) is located on one side. The microwave plasma generator (2) is installed on the plate. One end of the microwave plasma generator (2) passes through the opening on the side of the spherical reaction chamber (12) and extends into the spherical reaction chamber (12). The concentric atomizer (9) is vertically inserted into the top of the spherical reaction chamber (12). The bottom end of the concentric atomizer (9) extends into the spherical reaction chamber (12) and is arranged perpendicularly and at intervals from the end of the microwave plasma generator (2) that extends into the spherical reaction chamber (12). The gas connector (10) is connected to one side of the top of the concentric atomizer (9). The top of the concentric atomizer (9) is connected to the outlet of the peristaltic pump (15) through the inlet pipe (8). The inlet of the peristaltic pump (15) is connected to the liquid collection tank (5) through the outlet pipe (6). The outlet pipe (6) is fixed on the outer wall of the liquid collection tank (5) and extends from the top of the liquid collection tank (5) to the bottom of the liquid collection tank (5); The microwave plasma generator (2) is electrically connected to an external power supply module (1). The power of the power supply module (1) is adjustable, and the power adjustment range of the power supply module (1) is 60W~200W. The microwave plasma generator (2) has a plasma working gas inlet (3) connected to one end away from the spherical reaction chamber (12). The microwave plasma generator (2) is provided with three concentric nested copper tubes, which are an inner tube, a central tube and a microwave input tube from the inside to the outside. The inner tube is connected to the plasma working gas inlet (3), and the annular gap between the inner tube and the central tube generates a microwave plasma beam (7).

2. The gas-phase reactor for gradient energy plasma according to claim 1, characterized in that: The top of the spherical reaction chamber (12) is vertically provided with a concentric atomizer bracket (11), and a concentric atomizer (9) is movably inserted inside the concentric atomizer bracket (11). The concentric atomizer (9) can move vertically up and down inside the concentric atomizer bracket (11). The main support plate (13) is fixedly installed with brackets (4) at the bottom of the four corners. A slide rail structure is fixedly installed between the main support plate (13) and the microwave plasma generator (2). The slide rail is installed on the slot-shaped through hole opened on the upper surface of the main support plate (13). The track direction of the slide rail is parallel to the microwave plasma generator (2).

3. An organic synthesis reaction and control method using a gas-phase reactor with gradient energy plasma as described in any one of claims 1-2, characterized in that: The steps of the organic synthesis reaction and control method are as follows: 1) After installing the gas phase reactor of the gradient energy plasma, prepare the reactants into a reactant solution and place it in the liquid collection tank (5), and inject cold water into the cooling cup (14); 2) Turn on the peristaltic pump (15). The peristaltic pump (15) pumps the reactant solution into the concentric atomizer (9). The atomizing carrier gas is introduced into the gas connection (10). The atomizing carrier gas and the reactant solution are atomized into a reactant spray by the concentric atomizer (9). 3) Turn on the power module (1), adjust the power, and inject the working gas into the microwave plasma generator (2) from the plasma working gas inlet (3). The microwave plasma generator (2) generates a microwave plasma beam (7) at one end that extends into the spherical reaction chamber (12). The microwave plasma beam (7) comes into full contact with the reactant spray. Under the action of plasma temperature and airflow, the reactant solution loses the solvent and desorbs into a gas phase state, forming gas phase reactant molecules and / or ions. The gas phase reactant molecules and / or ions then collide and react with electrons and / or ions in the microwave plasma. 4) After the reaction occurs, the gas-liquid mixture produced settles downward and condenses under the action of the cooling cup (14). It flows down and is collected in the liquid collection tank (5). After the reaction is completed, the power module (1) and the peristaltic pump (15) are turned off, and the product solution is collected from the liquid collection tank (5).

4. The organic synthesis reaction and control method according to claim 3, characterized in that: In step 4), the liquid mixture collected in the liquid collection tank (5) is drawn again by the peristaltic pump (15) through the outlet pipe (6), and pumped back into the concentric atomizer (9) through the inlet pipe (8) to circulate and react until the reaction ends in step 3).

5. The organic synthesis reaction and control method according to claim 3, characterized in that: In step 1), after the gas phase reactor of the gradient energy plasma is installed, the distance between the bottom end of the concentric atomizer (9) and the end of the microwave plasma generator (2) that extends into the spherical reaction chamber (12) is adjusted, and then the reactant solution is placed into the liquid collection tank (5) to continue the operation of the subsequent steps.

6. The organic synthesis reaction and control method according to claim 3, characterized in that: The organic synthesis reaction is an oxidation reaction, a reduction reaction, an addition reaction, a proton transfer reaction, an elimination reaction, or a negative hydrogen migration reaction.

7. The organic synthesis reaction and control method according to claim 3, characterized in that: In step 2), the liquid flow rate in the peristaltic pump (15) is 1~13 mL / min; In step 2), the atomizing carrier gas in the gas connector (10) is one or more of nitrogen, argon, helium, and carbon dioxide, and the flow rate of the atomizing carrier gas is 1L / min to 3L / min. In step 3), the working gas introduced into the plasma working gas inlet (3) is argon or helium, and the flow rate of the working gas is 500~1000mL / min.

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