A reaction kettle for producing and processing kresoxim-methyl raw materials and a green synthesis method of kresoxim-methyl

Abstract

The invention provides a reactor for producing and processing azoxystrobin raw material and a green synthesis method of azoxystrobin. The reactor comprises: a shell, a supporting leg is fixed to the bottom end of the shell, a stirring mechanism is installed on the outer wall of a rotating rod, and a first connecting seat, a first stirring rod, a second connecting seat and other structures are arranged to cooperate so that the angles of the first stirring rod and the second stirring rod are in a parallel state when the hydraulic rod is in a contracted state, so that when the rotating rod is driven to rotate by a starting motor and a reducer, the first stirring rod and the second stirring rod can be driven to stir and synthesize the azoxystrobin raw material in the reactor during rotation, and the hydraulic rod is started to push the first stirring rod and the second stirring rod, so that the angles of the first stirring rod and the second stirring rod are rotated and expanded about the first connecting seat and the fourth connecting seat, so that the vortex generated by the first stirring rod and the second stirring rod during rotation is changed, so that the azoxystrobin raw material in the reactor is synthesized through different stirring modes.

Description

Technical Field

[0001] The embodiments of the present invention relate to the technical field of kresoxim-methyl processing, and in particular to a reactor for producing and processing kresoxim-methyl raw materials and a green synthesis method of kresoxim-methyl. Background Art

[0002] Dioxin inhibits the respiration of fungal mitochondria and acts on the Q of cytochrome b to achieve a bactericidal effect. It has the characteristics of high efficiency, low toxicity, and broad spectrum, and is widely used in the prevention and treatment of crop diseases. In the production process of dioxin, the reactor is the main place for chemical reactions, and its performance directly affects the quality and production efficiency of the product. The design, material, stirring method, heating and cooling system, and control system of the reactor need to be selected and optimized according to the production process requirements of dioxin.

[0003] However, the existing reactor for kresoxim-methyl raw materials still has disadvantages in actual use: that is, it can only stir the kresoxim-methyl raw materials within a fixed range to maintain their activity, and cannot ensure uniform synthesis of the kresoxim-methyl raw materials in the reactor.

[0004] There is currently no better solution to the above problems. Summary of the invention

[0005] The embodiment of the present invention provides a reactor for producing and processing kresoxim-methyl raw materials and a green synthesis method of kresoxim-methyl, so as to at least solve the problem in the related art that the kresoxim-methyl raw materials sink to the bottom and cannot be uniformly stirred during processing.

[0006] According to one embodiment of the present invention, a reactor for producing and processing kresoxim-methyl raw materials is provided, comprising:

[0007] A shell, a supporting leg is fixed to the bottom end of the shell, a feeding port is arranged at the top end of the shell, a reducer is installed at the top end of the shell, a motor is installed at the top end of the reducer, a rotating rod is fixed to the bottom end of the reducer, and a stirring mechanism is installed on the outer wall of the rotating rod;

[0008] The stirring mechanism comprises a first connecting seat, a first stirring rod and a second connecting seat, the first connecting seat is fixed to the outer wall of the rotating rod, the first connecting seat is hingedly connected to the inner wall of the first connecting seat, the bottom end of the first stirring rod is fixed to the second connecting seat, the inner wall of the second connecting seat is hingedly connected to a hydraulic rod, the bottom end of the hydraulic rod is hingedly connected to a third connecting seat, the bottom end of the third connecting seat is fixed to the second stirring rod, and the outer wall of the second stirring rod is hingedly connected to a fourth connecting seat; the first connecting seat and the fourth connecting seat are symmetrically distributed about the central axis of the hydraulic rod, the first connecting seat is provided with a plurality of groups, the first connecting seats are evenly spaced about the central axis of the rotating rod, the fourth connecting seat is fixed to the outer wall of the rotating rod, the The fourth connecting seat is provided with several groups, and the fourth connecting seat is distributed at equal intervals about the central axis of the rotating rod; a reflux mechanism is installed inside the shell, a heating wire is installed on the inner wall of the shell, an explosion-proof mechanism is installed on the outer wall of the shell, and a discharge port is provided at the bottom end of the shell; the reflux mechanism includes a diverter layer, a spiral conveyor disk and a hanging bottom plate, the diverter layer is fixed on the inner wall of the shell, the spiral conveyor disk is fixed on the outer wall of the rotating rod, the bottom end of the rotating rod is fixed with a hanging bottom plate, and the outer wall of the shell is connected with a reflux pipe; the spiral conveyor disk is close to the inner wall of the diverter layer, and the bottom end of the hanging bottom plate is close to the inner wall of the shell, and the hanging bottom plates are provided with several groups, and the hanging bottom plates are symmetrically distributed about the central axis of the rotating rod.

[0009] In an exemplary embodiment, the explosion-proof mechanism includes a first explosion-proof ring, a second explosion-proof ring and fixing bolts, the first explosion-proof ring is installed on the outer wall of the shell, the second explosion-proof ring is arranged on the outer wall of the shell, and the inner wall of the first explosion-proof ring is installed with fixing bolts.

[0010] According to another embodiment of the present invention, a green synthesis method of kresoxim-methyl is provided, which is applied to any of the above-mentioned reactors for producing and processing kresoxim-methyl raw materials, comprising:

[0011] S1. Under nitrogen protection, add o-methylbenzene acetonitrile and methanol in a weight ratio of 1: (1.3-1.5) to a reactor, stir and cool the reactor to 10±2°C, add sodium hydroxide to the reactor in batches and keep warm for 15-20 minutes, add nitrite to the reactor at a temperature of 10-20°C, control the temperature of the reactor to rise to 30±2°C after the addition, keep warm for 2-2.5 hours, then put it into a distillation kettle to distill out the solvent, then add hydrochloric acid to the distillation kettle to adjust the pH value to 1-2, and filter and dry it with a suction pump to obtain material 1 after transferring it out;

[0012] S2, add material 1 and DMF in a weight ratio of 1: (3-3.5) to a reactor, after dissolving, add anhydrous sodium sulfate to the reactor and cool to 10±2°C, add sodium hydroxide to the reactor in batches, stir for 25-35min, control the temperature of the reactor to be cooled to below 10°C, add a catalyst, then dropwise add trimethyl orthoacetate, control the temperature of the reactor to be 10-15°C, react for 2-2.5h, add water, crystallize, filter, and dry to obtain material 2;

[0013] S3, add material 2 and ethylene dichloride in a weight ratio of 1: (3.5-4.5) into a reactor, after material 2 is dissolved, add hydrobromic acid and azobisisobutyronitrile into the reactor and heat to 60-65°C, start to drop hydrogen peroxide into the reactor and keep warm until it fades, recover ethylene dichloride under reduced pressure, and obtain material 3 after cooling;

[0014] S4. Stir and mix acetonitrile and potassium carbonate in a reactor, then dropwise add o-methylphenol dissolved in acetonitrile, stir for 10-15 minutes after the dropwise addition is completed, then dropwise add material three dissolved in acetonitrile, raise the temperature to 45-50°C after the dropwise addition is completed, keep the temperature for reaction for 5-6 hours, then filter, add methanol, heat and dissolve, reflux for 25-30 minutes, cool to minus 5°C, crystallize, filter, and dry to obtain dioxathiocarb.

[0015] In an exemplary embodiment, in step S1, the molar ratio of o-methylbenzeneacetonitrile to sodium hydroxide and nitrite is 1:(1-1.2):(1-1.2).

[0016] In an exemplary embodiment, in step S2, the molar ratio of sodium hydroxide, trimethyl orthoacetate and material one is (1.8-2.2): (2.3-2.8): 1.

[0017] In an exemplary embodiment, the catalyst is dodecyltrimethylammonium chloride and β-cyclodextrin in a weight ratio of 1:1.

[0018] In an exemplary embodiment, in step S2, the β-cyclodextrin is modified β-cyclodextrin, and the modification method of β-cyclodextrin comprises the following steps: mixing β-cyclodextrin and dichloromethane and placing them in an ice water bath, adding chlorosulfonic acid dropwise within two hours, stirring and reacting at room temperature for 2 hours after the addition, and then filtering and washing to obtain sulfonated β-cyclodextrin, and the molar ratio of β-cyclodextrin to chlorosulfonic acid is 1:2.

[0019] The reactor for producing and processing kresoxim-methyl raw materials provided by the present invention has the following beneficial effects:

[0020] 1. By arranging the coordination of the structures such as the splitter layer, the spiral conveyor disk, and the bottom hanging plate, the device can stir the kresoxim-methyl raw material in the kettle through the first stirring rod and the second stirring rod above, and then the kresoxim-methyl raw material can be drained through the splitter layer and fall above the spiral conveyor disk. When the rotating rod rotates to stir and synthesize the kresoxim-methyl raw material, it can synchronously drive the spiral conveyor disk to rotate, so that the spiral conveyor disk pushes the kresoxim-methyl raw material, and the bottom and the top of the shell are connected through the reflux pipe. The spiral conveyor disk pushes the kresoxim-methyl raw material to make it flow back to the top of the shell through the reflux pipe for stirring again, so as to ensure the activity of the kresoxim-methyl raw material, and the bottom hanging plate can be hung on the bottom when it rotates at the bottom end contacting the inside of the shell, so as to prevent the kresoxim-methyl raw material from sinking to the bottom and being unable to be stirred evenly during processing, so as to achieve the purpose of preventing the kresoxim-methyl raw material from sinking to the bottom and reflux stirring by the device.

[0021] 2. By setting up the coordination of the first connecting seat, the first stirring rod, the second connecting seat and other structures, the device can make the angles of the first stirring rod and the second stirring rod parallel when the hydraulic rod is in the retracted state, so that when the rotating rod is driven to rotate by the starting motor and the reducer, the first stirring rod and the second stirring rod can be driven to stir and synthesize the fenoxam-methyl raw material in the kettle during rotation. The hydraulic rod is started to push the first stirring rod and the second stirring rod, so that the angles of the first stirring rod and the second stirring rod are rotated about the first connecting seat and the fourth connecting seat, so that the vortex generated by the first stirring rod and the second stirring rod during rotation is changed, so that the fenoxam-methyl raw material in the kettle is synthesized through different stirring modes, so as to achieve the purpose of facilitating the device to adapt to the synthesis efficiency of the fenoxam-methyl raw material in the kettle in different states by timely changing the stirring mode to produce different degrees of flow mode.

[0022] The green synthesis method of kresoxim-methyl provided by the present invention has the following beneficial effects:

[0023] 1. The kresoxim-methyl obtained by the preparation method of the present application has a high yield, high purity, low production cost, and no high-temperature reaction in the entire production process, thereby reducing the production cost of kresoxim-methyl and fundamentally solving the problem of the need to use hydrochloric acid gas in the prior art. The production process is more green and environmentally friendly, and the on-site environment is greatly improved.

[0024] 2. The preparation method of the present application is simple to operate and has a short production cycle, thereby effectively improving production efficiency.

[0025] 3. The present application uses trimethyl acetate instead of dimethyl sulfate, which makes the reaction process more stable and belongs to a safe and clean production process. At the same time, it reduces the generation of a large amount of salt wastewater and improves the production quality.

[0026] 4. In the present application, the catalyst selected from the mixture of dodecyltrimethylammonium chloride and β-cyclodextrin effectively promotes the reaction rate of trimethyl orthoacetate and material one, and the addition of the catalyst can effectively improve the purity of material two, thereby greatly improving the purity and yield of the finally obtained kresoxim-methyl.

[0027] 5. In the present application, after sulfonation treatment, the β-cyclodextrin is used in combination with dodecyltrimethylammonium chloride, so that the yield of the final obtained kresoxim-methyl can reach 93%, which effectively increases the production of kresoxim-methyl; in addition, the preparation method of the sulfonated β-cyclodextrin in the present application is simple, and it has excellent compatibility with trimethyl orthoacetate, thereby effectively promoting the reaction rate of trimethyl orthoacetate and material one. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic diagram of the overall structure of the present invention;

[0029] Figure 2 It is a schematic diagram of the overall cross-sectional structure of the present invention;

[0030] Figure 3 The overall cross-section of the stirring mechanism of the present invention is a schematic diagram of the storage state structure Figure 1 ;

[0031] Figure 4 The overall cross-section of the stirring mechanism of the present invention is a schematic diagram of the storage state structure Figure 2 ;

[0032] Figure 5 For the present invention Figure 4 A partial cross-section at the center is an enlarged structural diagram;

[0033] Figure 6 For the present invention Figure 4 A schematic diagram of the enlarged structure of the local section at B in the middle;

[0034] Figure 7 It is a schematic diagram of the stirring mechanism structure of the present invention;

[0035] Figure 8 It is a schematic structural diagram of the stirring mechanism of the present invention in an expanded state;

[0036] In the figure: 1. Shell; 2. Support legs; 3. Feed port; 4. Motor; 5. Reducer; 6. Rotating rod; 7. Stirring mechanism; 701. First connecting seat; 702. First stirring rod; 703. Second connecting seat; 704. Hydraulic rod; 705. Third connecting seat; 706. Second stirring rod; 707. Fourth connecting seat; 8. Reflux mechanism; 801. Diversion layer; 802. Screw conveyor plate; 803. Hanging bottom plate; 804. Reflux pipe; 9. Heating wire; 10. Explosion-proof mechanism; 1001. First explosion-proof ring; 1002. Second explosion-proof ring; 1003. Fixing bolt; 11. Discharge port. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments.

[0038] In the following, the terms "first", "second", etc. are used for descriptive purposes only and are not to be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, "plurality" means two or more.

[0039] In addition, in the present application, directional terms such as "up", "down", "left" and "right" may be defined including but not limited to the orientation relative to the schematic placement of the components in the drawings. It should be understood that these directional terms may be relative concepts, which are used for relative description and clarification, and may change accordingly according to the change in the orientation of the components in the drawings.

[0040] In this application, unless otherwise specified or limited, the term "connection" should be understood in a broad sense. For example, "connection" can be a fixed connection, a detachable connection, or an integral connection; it can be a direct connection or an indirect connection through an intermediate medium. In addition, the term "coupling" can be a way of achieving electrical connection for signal transmission.

[0041] As used herein, "about," "substantially," or "approximately" includes the stated value and an average value that is within an acceptable range of variation from the particular value as determined by one of ordinary skill in the art taking into account the measurements in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system).

[0042] like Figures 1 to 8As shown, the present invention provides a reactor for producing and processing kresoxim-methyl raw materials, comprising a shell 1, a supporting leg 2 is fixed to the bottom end of the shell 1, a feeding port 3 is arranged at the top end of the shell 1, a reducer 5 is installed at the top end of the shell 1, a motor 4 is installed at the top end of the reducer 5, a rotating rod 6 is fixed to the bottom end of the reducer 5, a stirring mechanism 7 is installed on the outer wall of the rotating rod 6, a reflux mechanism 8 is installed inside the shell 1, a heating wire 9 is installed on the inner wall of the shell 1, an explosion-proof mechanism 10 is installed on the outer wall of the shell 1, and a discharge port 11 is arranged at the bottom end of the shell 1.

[0043] like Figures 1 to 8 As shown, three groups of support legs 2 are provided, and the support legs 2 are distributed at equal intervals about the central axis of the shell 1 . Several groups of heating wires 9 are provided, and the heating wires 9 are distributed at equal intervals about the central axis of the shell 1 .

[0044] The above scheme is adopted: by providing multiple groups of supporting legs 2, it is possible to ensure that the device is sufficiently stable, thereby ensuring the stability of the processing and synthesis of the fenthion raw material in the kettle, after the fenthion raw material is transported to the inside of the shell 1 through the feed port 3, the motor 4 and the reducer 5 are started to drive the rotating rod 6 to rotate, so that the first stirring rod 702 and the second stirring rod 706 stir the fenthion raw material, and the heating wire 9 is started to heat the internal fenthion raw material to ensure the efficiency and stability of the reaction synthesis, and after the reaction is completed, the electromagnetic valve outside the bottom discharge port 11 is opened to take out the processed fenthion.

[0045] like Figures 1 to 8 As shown, the stirring mechanism 7 includes a first connecting seat 701, a first stirring rod 702 and a second connecting seat 703. The first connecting seat 701 is fixed on the outer wall of the rotating rod 6. The first stirring rod 702 is hinged on the inner wall of the first connecting seat 701. The bottom end of the first stirring rod 702 is fixed with the second connecting seat 703. The inner wall of the second connecting seat 703 is hinged with a hydraulic rod 704. The first connecting seat 701 and the fourth connecting seat 707 are symmetrically distributed about the central axis of the hydraulic rod 704. The first connecting seat 701 is provided with several groups, and the first connecting seats 701 are evenly spaced about the central axis of the rotating rod 6.

[0046] like Figures 1 to 8 As shown, the bottom end of the hydraulic rod 704 is hinged with a third connecting seat 705, the bottom end of the third connecting seat 705 is fixed with a second stirring rod 706, the outer wall of the second stirring rod 706 is hinged with a fourth connecting seat 707, the fourth connecting seat 707 is fixed to the outer wall of the rotating rod 6, and the fourth connecting seat 707 is provided in several groups, and the fourth connecting seats 707 are evenly spaced about the central axis of the rotating rod 6.

[0047] The above scheme is adopted: when the hydraulic rod 704 is in a retracted state, the angles of the first stirring rod 702 and the second stirring rod 706 are in a parallel state, so that when the rotating rod 6 is driven to rotate by the starting motor 4 and the reducer 5, the first stirring rod 702 and the second stirring rod 706 can be driven to stir and synthesize the fenoxam-methyl raw material in the kettle during rotation. The hydraulic rod 704 is started to push the first stirring rod 702 and the second stirring rod 706, so that the angles of the first stirring rod 702 and the second stirring rod 706 are rotated and unfolded about the first connecting seat 701 and the fourth connecting seat 707, so that the vortex generated by the first stirring rod 702 and the second stirring rod 706 during rotation is changed, so that the fenoxam-methyl raw material in the kettle is synthesized through different stirring modes, so as to achieve the purpose of facilitating the device to adapt to the synthesis efficiency of the fenoxam-methyl raw material in the kettle in different states by timely changing the stirring mode to produce different degrees of flow modes.

[0048] like Figures 1 to 8 As shown, the reflux mechanism 8 includes a diverter layer 801, a spiral conveyor plate 802 and a hanging bottom plate 803. The diverter layer 801 is fixed to the inner wall of the shell 1, the spiral conveyor plate 802 is fixed to the outer wall of the rotating rod 6, and the hanging bottom plate 803 is fixed to the bottom end of the rotating rod 6. The spiral conveyor plate 802 is close to the inner wall of the diverter layer 801, and the bottom end of the hanging bottom plate 803 is close to the inner wall of the shell 1. Several groups of hanging bottom plates 803 are arranged, and the hanging bottom plates 803 are symmetrically distributed about the central axis of the rotating rod 6.

[0049] like Figures 1 to 8 As shown, the outer wall of the shell 1 is connected to a return pipe 804, and two groups of return pipes 804 are provided. The return pipes 804 are symmetrically distributed about the central axis of the shell 1, the bottom end of the inner cavity of the shell 1 is connected to the return pipe 804, and the top end of the inner cavity of the shell 1 is connected to the return pipe 804.

[0050] The above scheme is adopted: the kresoxim-methyl raw material in the kettle is stirred by the first stirring rod 702 and the second stirring rod 706 at the top, and then falls onto the top of the spiral conveyor plate 802 through the drainage of the diverter layer 801. When the rotating rod 6 rotates to stir and synthesize the kresoxim-methyl raw material, it can synchronously drive the spiral conveyor plate 802 to rotate, so that the spiral conveyor plate 802 pushes the kresoxim-methyl raw material, and the bottom and the top of the shell 1 are connected through the reflux pipe 804. The kresoxim-methyl raw material is pushed by the spiral conveyor plate 802 to flow back to the top of the shell 1 through the reflux pipe 804 for stirring again, so as to ensure the activity of the kresoxim-methyl raw material, and the bottom can be hung by the hanging bottom plate 803 when it rotates at the bottom end contacting the inside of the shell 1, thereby preventing the kresoxim-methyl raw material from sinking to the bottom and being unable to be processed. The phenomenon of uniform stirring is achieved, so as to facilitate the device to prevent the pyroxithion raw material from sinking to the bottom and to stir it by reflux; in particular, since the first connecting seat 701 and the fourth connecting seat 707 are symmetrically distributed about the central axis of the hydraulic rod 704, and the first connecting seat 701 and the fourth connecting seat 707 are evenly distributed about the central axis of the rotating rod 6, it is helpful for the reflux mechanism 8 to evenly distribute the fluid power generated by stirring, thereby promoting uniform diversion of the diversion layer 801 and avoiding excessive or insufficient local flow; at the same time, the fluid power generated during stirring can more evenly push the substances in the reactor, enhance the stirring efficiency, and ensure that the torque generated by the stirring rod during rotation is evenly distributed, so that the diversion layer 801 distributes the fluid more evenly and reduces the unevenness of the fluid during the diversion process.

[0051] like Figures 1 to 8 As shown, the explosion-proof mechanism 10 includes a first explosion-proof ring 1001, a second explosion-proof ring 1002 and a fixing bolt 1003. The first explosion-proof ring 1001 is installed on the outer wall of the shell 1, the second explosion-proof ring 1002 is arranged on the outer wall of the shell 1, and the inner wall of the first explosion-proof ring 1001 is installed with a fixing bolt 1003. The first explosion-proof ring 1001 and the second explosion-proof ring 1002 are arranged in two groups, and the first explosion-proof ring 1001 and the second explosion-proof ring 1002 are symmetrically distributed about the central axis of the shell 1. Several groups of fixing bolts 1003 are arranged, and several groups of fixing bolts 1003 are evenly spaced about the central axis of the first explosion-proof ring 1001.

[0052] The above scheme is adopted: by sleeve-arranging the first explosion-proof ring 1001 and the second explosion-proof ring 1002 on the outer wall of the shell 1, since the kresoxim-methyl raw material generates gas when reacting in the kettle, the pressure in the kettle is increased, and the first explosion-proof ring 1001 and the second explosion-proof ring 1002 are fixed to the outer wall of the shell 1 by fixing bolts 1003, thereby improving the pressure resistance of the device.

[0053] The working principle and use process of the present invention are as follows: by providing multiple groups of supporting legs 2, the device can be placed stably enough to ensure the stability of the processing and synthesis of the fenthion raw material in the kettle. After the fenthion raw material is transported to the inside of the shell 1 through the feed port 3, the motor 4 and the reducer 5 are started to drive the rotating rod 6 to rotate, so that the first stirring rod 702 and the second stirring rod 706 stir the fenthion raw material, and the heating wire 9 is started to heat the internal fenthion raw material to ensure the efficiency and stability of the reaction synthesis. After the reaction is completed, the bottom discharge port 11 is opened to discharge the fenthion raw material to the outside. The solenoid valve is used to take out the processed fenoxamyl. When the hydraulic rod 704 is in a retracted state, the angles of the first stirring rod 702 and the second stirring rod 706 are in a parallel state, so that when the rotating rod 6 is driven to rotate by the starting motor 4 and the reducer 5, the first stirring rod 702 and the second stirring rod 706 can be driven to stir and synthesize the fenoxamyl raw material in the kettle during rotation. The hydraulic rod 704 is started to push the first stirring rod 702 and the second stirring rod 706, so that the angles of the first stirring rod 702 and the second stirring rod 706 rotate about the first connecting seat 701 and the fourth connecting seat 707. The rotating rod 6 rotates and unfolds, thereby changing the vortex generated by the first stirring rod 702 and the second stirring rod 706 when rotating. The kresoxim-methyl raw material in the kettle is stirred by the first stirring rod 702 and the second stirring rod 706 above, and then falls onto the top of the spiral conveyor plate 802 through the drainage of the diversion layer 801. When the rotating rod 6 rotates to stir and synthesize the kresoxim-methyl raw material, it can synchronously drive the spiral conveyor plate 802 to rotate, so that the spiral conveyor plate 802 pushes the kresoxim-methyl raw material, and the bottom and the top of the shell 1 are connected through the reflux pipe 804, and the spiral conveyor plate 802 pushes the kresoxim-methyl raw material. The ester raw material is pushed so that it can flow back to the top of the shell 1 through the reflux pipe 804 for stirring again to ensure the activity of the kresoxim-methyl raw material, and the bottom can be hung when the bottom end of the shell 1 is rotated by the hanging bottom plate 803. The first explosion-proof ring 1001 and the second explosion-proof ring 1002 are sleeved on the outer wall of the shell 1. Since the kresoxim-methyl raw material generates gas when reacting in the kettle, the pressure in the kettle is increased. The first explosion-proof ring 1001 and the second explosion-proof ring 1002 are fixed to the outer wall of the shell 1 by the fixing bolts 1003 to improve the pressure resistance of the device.

[0054] In addition, the current production method of fenthion uses phthalide as the starting material, and obtains fenthion through high-temperature etherification, chlorination, cyanation, esterification, oximation, and configuration conversion. The total yield is about 60%. Moreover, since a large amount of hydrochloric acid gas is used in the synthesis process, the on-site production environment is poor, the equipment is highly corrosive, and the equipment maintenance cost is high. In addition, the excess hydrochloric acid gas cannot be recycled and can only be made into hydrochloric acid by absorbing the hydrochloric acid gas tail gas with water. However, since there are residual solvents in the hydrochloric acid gas tail gas, the recycled hydrochloric acid also contains a large amount of solvents, which is difficult to handle, resulting in increased environmental pressure.

[0055] In order to solve the above problems, the present invention also provides a green synthesis method of kresoxim-methyl, which is applied to the above-mentioned kresoxim-methyl raw material production and processing reactor, comprising the following synthesis steps:

[0056] S1. Under nitrogen protection, add o-methylbenzene acetonitrile and methanol in a weight ratio of 1: (1.3-1.5) to a reactor, stir and cool the reactor to 10±2°C, add sodium hydroxide to the reactor in batches and keep warm for 15-20 minutes, add nitrite to the reactor at a temperature of 10-20°C, control the temperature of the reactor to rise to 30±2°C after the addition, keep warm for 2-2.5 hours, then put it into a distillation kettle to distill out the solvent, then add hydrochloric acid to the distillation kettle to adjust the pH value to 1-2, and filter and dry it with a suction pump to obtain material 1 after transferring it out;

[0057] S2, add material 1 and DMF in a weight ratio of 1: (3-3.5) to a reactor, after dissolving, add anhydrous sodium sulfate to the reactor and cool to 10±2°C, add sodium hydroxide to the reactor in batches, stir for 25-35min, control the temperature of the reactor to be cooled to below 10°C, add a catalyst, then dropwise add trimethyl orthoacetate, control the temperature of the reactor to be 10-15°C, react for 2-2.5h, add water, crystallize, filter, and dry to obtain material 2;

[0058] S3, add material 2 and ethylene dichloride in a weight ratio of 1: (3.5-4.5) into a reactor, after material 2 is dissolved, add hydrobromic acid and azobisisobutyronitrile into the reactor and heat to 60-65°C, start to drop hydrogen peroxide into the reactor and keep warm until it fades, recover ethylene dichloride under reduced pressure, and obtain material 3 after cooling;

[0059] S4. Stir and mix acetonitrile and potassium carbonate in a reactor, then dropwise add o-methylphenol dissolved in acetonitrile, stir for 10-15 minutes after the dropwise addition is completed, then dropwise add material three dissolved in acetonitrile, raise the temperature to 45-50°C after the dropwise addition is completed, keep the temperature for reaction for 5-6 hours, then filter, add methanol, heat and dissolve, reflux for 25-30 minutes, cool to minus 5°C, crystallize, filter, and dry to obtain dioxathiocarb.

[0060] Preferably, in step S1, the molar ratio of o-methylbenzeneacetonitrile to sodium hydroxide and nitrite is 1:(1-1.2):(1-1.2).

[0061] Preferably, in step S1, the nitrite is any one of isoamyl nitrite, tert-butyl nitrite, n-butyl nitrite, and isopropyl nitrite, and the effects that can be achieved are basically the same, so isopropyl nitrite is used as an example in the embodiments of the present application.

[0062] Preferably, in step S2, the molar ratio of sodium hydroxide, trimethyl orthoacetate and material one is (1.8-2.2):(2.3-2.8):1.

[0063] Preferably, in step S2, the molar ratio of anhydrous sodium sulfate to material one is (0.4-0.6):1.

[0064] Preferably, the catalyst is dodecyltrimethylammonium chloride and β-cyclodextrin in a weight ratio of 1:1.

[0065] Preferably, the β-cyclodextrin is modified β-cyclodextrin, and the modification method of the β-cyclodextrin comprises the following steps: mixing β-cyclodextrin and dichloromethane and placing in an ice water bath, adding chlorosulfonic acid dropwise within two hours, stirring and reacting at room temperature for 1.5-2.5 hours after the addition, and then filtering and washing to obtain sulfonated β-cyclodextrin, and the molar ratio of β-cyclodextrin to chlorosulfonic acid is 1:2.

[0066] Preferably, in step S3, the molar ratio of hydrobromic acid, hydrogen peroxide and material 2 is (1-1.2):(1.3-1.6):1.

[0067] Preferably, in step S4, before dissolution, the molar ratio of o-methylphenol to material three and potassium carbonate is 1:1:(2.2-2.6).

[0068] Preferably, the weight ratio of methanol to material three in step S4 is (1.4-1.6):1.

[0069] In the examples of this application, only the synthesis process of each step of Example 1 is listed.

[0070] Preparation Example 1

[0071] The preparation method of sulfonated β-cyclodextrin comprises the following preparation steps:

[0072] 5.67 g (5 mmol) of β-cyclodextrin and 30 mL of dichloromethane were added to a 100 mL three-necked flask and placed in an ice-water bath. Then, 1.16 g (10 mmol) of chlorosulfonic acid was added dropwise within 2 hours. After the addition was completed, the reaction was stirred at room temperature for 2 hours. The resulting mixture was then filtered, washed with methanol several times, and finally dried to obtain sulfonated β-cyclodextrin. Example 1

[0073] A green synthesis method of kresoxim-methyl comprises the following synthesis steps:

[0074] The synthesis process of material 1 in step S1 is as follows:

[0075] ;

[0076] S1.1. Under nitrogen protection, add 2800g methanol and 2000g (15.25mol) o-methylbenzene acetonitrile (i.e., the weight ratio of o-methylbenzene acetonitrile to methanol is 1:1.4) into a dry 50L reactor, stir and lower the reactor temperature to 10±2℃;

[0077] S1.2, add 670g (16.775mol) of sodium hydroxide to the reactor in batches and keep warm for 15-20min, start to drop 1500g (16.775mol) of nitrite (isopropyl nitrite) into the reactor at a temperature of 10-20℃, control the addition to be completed within 3 hours, raise the temperature of the reactor to 30±2℃ after the addition, keep warm for 2h, that is, the molar ratio of o-methylbenzeneacetonitrile to sodium hydroxide and nitrite is 1:1.1:1.1;

[0078] S1.3, add 5400g water and 670g sodium hydroxide, heat and distill out methanol under normal pressure until the temperature of the reactor reaches 100-105°C, reflux and keep warm for 3 hours, then cool to 15°C, add 30wt% concentrated hydrochloric acid dropwise to adjust the pH to 2;

[0079] S1.4, cool to 10℃ and keep warm for 2h to crystallize, filter with a suction pump to obtain a wet product, and then dry at 60℃ to obtain material 1;

[0080] The synthesis process of material 2 in step S2 is as follows:

[0081] ;

[0082] S2.1. Under nitrogen protection, add 2.7 kg (15 mol) of material 1 and 8.1 kg of DMF to a dry 50L reactor and stir to dissolve, that is, the weight ratio of material 1 to DMF is 1:3, then add 1 kg of anhydrous sodium sulfate and cool to 10±2°C, add 1.2 kg (30 mol) of sodium hydroxide to the reactor in batches, control the temperature of the reactor below 20°C during the addition, stir for 25 minutes after the addition, and the molar ratio of anhydrous sodium sulfate to material 1 is 0.5:1;

[0083] S2.2, cool down to below 10℃, add 0.23kg catalyst dodecyltrimethylammonium chloride, add 4.51kg (37.5mol) trimethyl orthoacetate dropwise, the adding time is not less than 5 hours, react at a temperature of 10-15℃ for 2-2.5h, the molar ratio of sodium hydroxide, trimethyl orthoacetate to material 1 is 2:2.5:1;

[0084] S2.3, after cooling to below 5°C, add 25 kg of water dropwise, control the temperature to be below 15°C, then crystallize at 5-10°C for 1 hour, filter, dry at 60°C, dissolve with dichloroethane, filter and concentrate to obtain material 2;

[0085] The synthesis process of material three in step S3 is as follows:

[0086] ;

[0087] S3.1. In a reactor, dissolve 100g (0.5mol) of material 2 in 400g of dichloroethane, i.e., the weight ratio of material 2 to dichloroethane is 1:4, then add 92.7g (0.55mol) of hydrobromic acid with a concentration of 48% and 2.5g of azobisisobutyronitrile, raise the temperature to 60°C, and start to drop 127.54g (0.75mol) of hydrogen peroxide with a concentration of 20%, control the dropping temperature within 75°C, and keep warm until it fades after the dropping is completed, wherein the molar ratio of hydrobromic acid, hydrogen peroxide and material 2 is 1.1:1.5:1;

[0088] S3.2, cool to room temperature, stand and separate, wash the organic phase once with 10% sodium carbonate, then wash twice with water, recover dichloroethane under reduced pressure at 50°C to obtain a light yellow oil, and cool to obtain material 3;

[0089] The synthesis process of step S4 is as follows:

[0090] ;

[0091] S4.1. Add 30g of acetonitrile and 12.1g of potassium carbonate to the reactor and stir magnetically to mix. Then, drop 3.78g (0.035mol) of o-methylphenol dissolved in acetonitrile (calculated based on the amount before dissolution). Stir for 15min after the addition is complete. Then, drop 10g (0.035mol) of material three dissolved in acetonitrile (calculated based on the amount before dissolution). After the addition is complete, heat to 45°C, keep warm for 5h and filter. Rinse the filter cake with acetonitrile, collect the filtrate, and recover the acetonitrile at 40°C to obtain a crude product, in which the molar ratio of o-methylphenol to material three and potassium carbonate is 1:1:2.5.

[0092] S4.2. Add 15 g of methanol to the crude product, heat it up to dissolve, and then reflux for 30 min. Cool it down to -5°C, crystallize it for 2 h, filter it, and dry it at 50°C to obtain kresoxim-methyl. The gas chromatogram test result of kresoxim-methyl is as follows: Figure 1 As shown, the purity of kresoxim-methyl was 99.7% and the yield was 87.6%. Example 2

[0093] A green synthesis method of kresoxim-methyl comprises the following synthesis steps:

[0094] S1.1. Under nitrogen protection, add 2600 g methanol and 2000 g (15.25 mol) o-methylbenzene acetonitrile (i.e., the weight ratio of o-methylbenzene acetonitrile to methanol is 1:1.3) into a dry 50 L reactor, stir and cool to 10±2°C;

[0095] S1.2. Add 610 g (15.25 mol) of sodium hydroxide to the reactor in batches and keep warm for 15-20 min. Start to drop 1358.6 g (15.25 mol) of nitrite (isopropyl nitrite) at a temperature of 10-20 ° C. The addition is completed within 3 hours. After the addition is completed, the temperature is raised to 30 ± 2 ° C and the reaction is kept warm for 2.5 hours. That is, the molar ratio of o-methylbenzene acetonitrile to sodium hydroxide and nitrite is 1:1:1.

[0096] S1.3, add 5400g water and 670g sodium hydroxide, heat and distill out methanol under normal pressure until the temperature of the reactor reaches 100-105°C, reflux and keep warm for 3 hours, then cool to 15°C, add 30wt% concentrated hydrochloric acid dropwise to adjust the pH to 1;

[0097] S1.4, cool to 10℃ and keep warm for 2h to crystallize, filter to get wet product, and then dry at 60℃ to get material 1;

[0098] S2.1. Under nitrogen protection, add 2.7 kg (15 mol) of material 1 and 9 kg of DMF to a dry 50L reactor and stir to dissolve, that is, the weight ratio of material 1 to DMF is 1:3.3, then add 0.852 kg of anhydrous sodium sulfate and cool to 10±2°C, add 1.08 kg (27 mol) of sodium hydroxide in batches, control the temperature below 20°C during the addition, stir for 35 minutes after the addition is completed, and the molar ratio of anhydrous sodium sulfate to material 1 is 0.4:1;

[0099] S2.2, cool down to below 10℃, add 0.23kg of catalyst dodecyltrimethylammonium chloride, add 4.15kg (34.5mol) of trimethyl orthoacetate dropwise, the adding time is not less than 5 hours, react at a temperature of 10-15℃ for 2h, the molar ratio of sodium hydroxide, trimethyl orthoacetate to material 1 is 1.8:2.3:1;

[0100] S2.3, after cooling to below 5°C, add 25 kg of water dropwise, control the temperature to be below 15°C, then crystallize at 5-10°C for 1 hour, filter, dry at 60°C, dissolve with dichloroethane, filter and concentrate to obtain material 2;

[0101] S3.1. Dissolve 100g (0.5mol) of material 2 in 350g of dichloroethane, i.e., the weight ratio of material 2 to dichloroethane is 1:3.5, then add 84.28g (0.5mol) of hydrobromic acid with a concentration of 48%, 2.5g of azobisisobutyronitrile, raise the temperature to 65°C, start to drop 110.53g (0.75mol) of hydrogen peroxide with a concentration of 20%, control the dropping temperature within 75°C, and keep warm until it fades after the dropping is completed, wherein the molar ratio of hydrobromic acid, hydrogen peroxide and material 2 is 1:1.3:1;

[0102] S3.2, cool to room temperature, stand and separate, wash the organic phase once with 10% sodium carbonate, then wash twice with water, recover dichloroethane under reduced pressure at 60°C to obtain a light yellow oil, and cool to obtain material 3;

[0103] S4.1. Add 30g acetonitrile and 10.6g potassium carbonate to the reactor and stir magnetically to mix. Then, drop 3.78g (0.035mol) of o-methylphenol dissolved in acetonitrile (calculated based on the amount before dissolution). Stir for 10min after the addition is complete. Then, drop 10g (0.035mol) of material three dissolved in acetonitrile (calculated based on the amount before dissolution). After the addition is complete, heat to 50°C, keep warm for 6h and filter. Rinse the filter cake with acetonitrile and collect the filtrate. Recover the acetonitrile at 40°C to obtain a crude product. Collect the filtrate, in which the molar ratio of o-methylphenol to material three and potassium carbonate is 1:1:2.2.

[0104] S4.2. Add 14 g of methanol to the crude product, heat up to dissolve, and reflux for 25 min. Cool down to -5°C, crystallize for 1 h, filter, and dry at 55°C to obtain oxathiocarb-methyl. The purity of oxathiocarb-methyl is 99.1%, and the yield is 86.9%. Example 3

[0105] A green synthesis method of kresoxim-methyl comprises the following synthesis steps:

[0106] S1.1. Under nitrogen protection, add 3000 g methanol and 2000 g (15.25 mol) o-methylbenzeneacetonitrile (i.e., the weight ratio of o-methylbenzeneacetonitrile to methanol is 1:1.5) into a dry 50 L reactor, stir and cool to 10±2°C;

[0107] S1.2. Add 732 g (18.3 mol) of sodium hydroxide to the reactor in batches and keep the temperature for 20 min. Start to drop 2630 g (18.3 mol) of nitrite (isopropyl nitrite) at a temperature of 10-20 ° C. The addition is completed within 3 hours. After the addition is completed, the temperature is raised to 30 ± 2 ° C. The temperature is kept for 2.5 hours. That is, the molar ratio of o-methylbenzene acetonitrile to sodium hydroxide and nitrite is 1:1.2:1.2.

[0108] S1.3, add 5400g water and 670g sodium hydroxide, heat and distill out methanol under normal pressure until the temperature of the reactor reaches 100-105°C, reflux and keep warm for 3 hours, then cool to 15°C, add 30wt% concentrated hydrochloric acid dropwise to adjust the pH to 1;

[0109] S1.4, cool to 10℃ and keep warm for 2h to crystallize, filter to get wet product, and then dry at 60℃ to get material 1;

[0110] S2.1. Under nitrogen protection, add 2.7 kg (15 mol) of material 1 and 9.45 kg of DMF to a dry 50L reactor and stir to dissolve, that is, the weight ratio of material 1 to DMF is 1:3.5, then add 1.278 kg of anhydrous sodium sulfate and cool to 10±2°C, add 1.320 kg (33 mol) of sodium hydroxide in batches, control the temperature below 20°C during the addition, stir for 35 minutes after the addition is completed, and the molar ratio of anhydrous sodium sulfate to material 1 is 0.6:1;

[0111] S2.2, cool down to below 10℃, add 0.23kg of catalyst dodecyltrimethylammonium chloride, add 5.05kg (42mol) of trimethyl orthoacetate dropwise, the adding time is not less than 5 hours, react at a temperature of 10-15℃ for 2.5h, the molar ratio of sodium hydroxide, trimethyl orthoacetate to material 1 is 2.2:2.8:1;

[0112] S2.3, after cooling to below 5°C, add 25 kg of water dropwise, control the temperature to be below 15°C, then crystallize at 5-10°C for 1 hour, filter, dry at 60°C, dissolve with dichloroethane, filter and concentrate to obtain material 2;

[0113] S3.1. Dissolve 100g (0.5mol) of material 2 in 450g of dichloroethane, i.e., the weight ratio of material 2 to dichloroethane is 1:4.5, then add 101.13g (0.6mol) of hydrobromic acid with a concentration of 48%, 2.5g of azobisisobutyronitrile, raise the temperature to 65°C, start to drop 136.04g (0.8mol) of hydrogen peroxide with a concentration of 20%, control the dropping temperature within 75°C, and keep warm until it fades after the dropping is completed. The molar ratio of hydrobromic acid, hydrogen peroxide and material 2 is 1.2:1.6:1;

[0114] S3.2, cool to room temperature, stand and separate, wash the organic phase once with 10% sodium carbonate, then wash twice with water, recover dichloroethane under reduced pressure at 60°C to obtain a light yellow oil, and cool to obtain material 3;

[0115] S4.1. Add 30g acetonitrile and 12.58g potassium carbonate to the reactor and stir magnetically to mix. Then, drop 3.78g (0.035mol) of o-methylphenol dissolved in acetonitrile (calculated based on the amount before dissolution). Stir for 15min after the addition is complete. Then, drop 10g (0.035mol) of material three dissolved in acetonitrile (calculated based on the amount before dissolution). After the addition is complete, heat to 50°C, keep warm for 6h and filter. Rinse the filter cake with acetonitrile and collect the filtrate. Recover the acetonitrile at 40°C to obtain a crude product. Collect the filtrate, in which the molar ratio of o-methylphenol to material three and potassium carbonate is 1:1:2.6.

[0116] S4.2. Add 16 g of methanol, heat up to dissolve, and reflux for 30 min. Cool down to -5°C, crystallize for 2 h, filter, and dry at 50°C to obtain diastereoisomer-methyl. The purity of diastereoisomer-methyl is 99.6%, and the yield is 87.2%. Example 4

[0117] A green synthesis method of kresoxim-methyl is disclosed, which is different from that of Example 1 in that an equal amount of β-cyclodextrin is used as a catalyst in step S2.2, and the rest are the same as those of Example 1. The purity of kresoxim-methyl obtained is 99.5%, and the yield is 87.9%. Example 5

[0118] A green synthesis method of kresoxim-methyl, which is different from that of Example 1 in that the catalyst in step S2.2 is a mixture of dodecyltrimethylammonium chloride and β-cyclodextrin in a weight ratio of 1:1, and the rest are the same as those in Example 1. The purity of kresoxim-methyl finally obtained is 99.8%, and the yield is 91.6%. Example 6

[0119] A green synthesis method of kresoxim-methyl is disclosed, which is different from Example 5 in that β-cyclodextrin adopts sulfonated β-cyclodextrin obtained in Preparation Example 1, and the rest is the same as Example 5. The purity of kresoxim-methyl obtained is 99.8%, and the yield is 93.1%. Example 7

[0120] A green synthesis method of kresoxim-methyl, which is different from that of Example 5 in that the catalyst in step S2.2 is a mixture of tetrabutylammonium bromide and β-cyclodextrin in a weight ratio of 1:1, and the rest are the same as those in Example 1. The purity of the kresoxim-methyl finally obtained is 99.4%, and the yield is 89.5%. Example 8

[0121] A green synthesis method of kresoxim-methyl, which is different from that of Example 5 in that the catalyst in step S2.2 is a mixture of trioctylmethylammonium chloride and β-cyclodextrin in a weight ratio of 1:1, and the rest are the same as those in Example 1. The purity of kresoxim-methyl finally obtained is 99.5%, and the yield is 89.7%. Comparative Example 1

[0122] A green synthesis method of kresoxim-methyl is disclosed, which is different from that of Example 1 in that no catalyst is added in step S2.2, and the rest is the same as that of Example 1. The purity of kresoxim-methyl finally obtained is 99.8%, and the yield is 81.7%. Comparative Example 2

[0123] A green synthesis method of kresoxim-methyl is disclosed, which is different from that of Example 1 in that no catalyst is added in step S2.2, and the same molar amount of dimethyl sulfate is used instead of trimethyl orthoacetate, and the rest are the same as those of Example 1. The purity of kresoxim-methyl obtained is 97.6%, and the yield is 80.1%. Comparative Example 3

[0124] A green synthesis method of kresoxim-methyl is different from that of Example 1 in that the molar ratio of o-methylbenzeneacetonitrile to sodium hydroxide and isopropyl nitrite is 1:1.1:1.5, that is, o-methylbenzeneacetonitrile is 15.25 mol, sodium hydroxide is 16.775 mol, and isopropyl nitrite is 22.875 mol. The rest are the same as those of Example 1. The purity of kresoxim-methyl finally obtained is 98.3%, and the yield is 83.4%. Comparative Example 4

[0125] A green synthesis method of kresoxim-methyl is different from that of Example 1 in that the molar ratio of sodium hydroxide, trimethyl orthoacetate and material one is 2:3:1, i.e., 30 mol of sodium hydroxide, 15 mol of material one and 45 mol of trimethyl orthoacetate, and the rest are the same as those of Example 1. The purity of kresoxim-methyl finally obtained is 98.5%, and the yield is 83.7%. Comparative Example 5

[0126] A green synthesis method of kresoxim-methyl is different from that of Example 1 in that the molar ratio of sodium hydroxide, trimethyl orthoacetate and material one is 2:2:1, i.e., 30 mol of sodium hydroxide, 15 mol of material one and 30 mol of trimethyl orthoacetate, and the rest are the same as those of Example 1. The purity of kresoxim-methyl finally obtained is 98.5%, and the yield is 82.2%.

[0127] It can be seen from the above examples of the present application that the fenthrin obtained in the present application is not only of high purity, but also of a yield of more than 86%. In particular, after the catalyst of a mixture of dodecyltrimethylammonium chloride and β-cyclodextrin is used in step S2.2, the yield of fenthrin is significantly increased, and after further modification of β-cyclodextrin, the yield of fenthrin can reach up to 93.1% (Example 6), indicating that after the catalyst is a mixture of dodecyltrimethylammonium chloride and β-cyclodextrin, the reaction rate of trimethyl orthoacetate and material one is effectively promoted, and the addition of the catalyst can effectively improve the purity of material two, thereby greatly improving the purity and yield of the fenthrin obtained in the end; in addition, after changing the disadvantage of the traditional process of using high-concentration hydrochloric acid gas to prepare fenthrin, the present application greatly increases the yield of fenthrin, and since there is no high-temperature reaction in the whole process, the production cost is greatly reduced and the on-site environment is greatly improved.

[0128] Compared with Example 1, after the catalyst dodecyltrimethylammonium chloride was not added, the yield of kresoxim-methyl obtained in Comparative Example 1 was significantly lower than that in Example 1. It can be seen that the use of a single catalyst dodecyltrimethylammonium chloride can also effectively promote the reaction rate of trimethyl orthoacetate and material 1, thereby improving the final yield of kresoxim-methyl.

[0129] Compared with Example 1, in Comparative Example 2, under the condition of not adding the catalyst dodecyltrimethylammonium chloride, dimethyl sulfate in the traditional process is used to replace trimethyl orthoacetate. The yield of kresoxim-methyl obtained in Comparative Example 1 is significantly lower than that in Example 1, and the yield of kresoxim-methyl in Comparative Example 2 is also lower than that in Comparative Example 1. It can be seen that after trimethyl orthoacetate replaces the toxic dimethyl sulfate, not only can the production process be made safer and more environmentally friendly, but the coordination between trimethyl orthoacetate and the catalyst and other reaction raw materials can also improve the yield of kresoxim-methyl.

[0130] Compared with Example 1, when the addition ratio of isopropyl nitrite exceeds the range specified in the present application or the addition ratio of trimethyl acetate exceeds the range specified in the present application, the purity of the chlorpyrifos obtained in Comparative Examples 3-5 is lower than that in Example 1, and the yield of chlorpyrifos is significantly lower than that in Example 1. The reason may be that when isopropyl nitrite is added in excess, certain impurities will be generated in the reaction system, resulting in a decrease in the purity of the material one, thereby reducing the yield and purity of the chlorpyrifos obtained in the end; and when the amount of trimethyl acetate added is too little, the reaction of step S2 is insufficient, more by-products and impurities will be generated, resulting in a decrease in the purity and yield of the material two. When the amount of trimethyl acetate added is too much, not only waste is caused, but also the occurrence of side reactions leads to the generation of impurities in the material two, reducing the yield and purity of the material two, thereby reducing the purity and yield of the chlorpyrifos obtained in the end.

[0131] In summary, the green synthesis method provided by the present invention has the following effects:

[0132] 1. The kresoxim-methyl obtained by the preparation method of the present application has a high yield, high purity, low production cost, and no high-temperature reaction in the entire production process, thereby reducing the production cost of kresoxim-methyl and fundamentally solving the problem of the need to use hydrochloric acid gas in the prior art. The production process is more green and environmentally friendly, and the on-site environment is greatly improved.

[0133] 2. The preparation method of the present application is simple to operate and has a short production cycle, thereby effectively improving production efficiency.

[0134] 3. The present application uses trimethyl acetate instead of dimethyl sulfate, which makes the reaction process more stable and belongs to a safe and clean production process. At the same time, it reduces the generation of a large amount of salt wastewater and improves the production quality.

[0135] 4. In the present application, the catalyst selected from the mixture of dodecyltrimethylammonium chloride and β-cyclodextrin effectively promotes the reaction rate of trimethyl orthoacetate and material one, and the addition of the catalyst can effectively improve the purity of material two, thereby greatly improving the purity and yield of the finally obtained kresoxim-methyl.

[0136] 5. In the present application, after sulfonation treatment, the β-cyclodextrin is used in combination with dodecyltrimethylammonium chloride, so that the yield of the final obtained kresoxim-methyl can reach 93%, which effectively increases the production of kresoxim-methyl; in addition, the preparation method of the sulfonated β-cyclodextrin in the present application is simple, and it has excellent compatibility with trimethyl orthoacetate, thereby effectively promoting the reaction rate of trimethyl orthoacetate and material one.

[0137] The above contents are only specific implementation methods of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions within the technical scope disclosed in the present application shall be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A green synthesis method of kresoxim-methyl, applied to a reactor for the production and processing of kresoxim-methyl raw materials, characterized in that: include: S1. Under nitrogen protection, add o-methylbenzene acetonitrile and methanol in a weight ratio of 1: (1.3-1.5) to a reactor, stir and cool the reactor to 10±2°C, add sodium hydroxide to the reactor in batches and keep warm for 15-20 minutes, add nitrite to the reactor at a temperature of 10-20°C, control the temperature of the reactor to rise to 30±2°C after the addition, keep warm for 2-2.5 hours, then put it into a distillation kettle to distill out the solvent, then add hydrochloric acid to the distillation kettle to adjust the pH value to 1-2, and filter and dry it with a suction pump to obtain material 1 after transferring it out; S2, add material 1 and DMF in a weight ratio of 1: (3-3.5) to a reactor, after dissolving, add anhydrous sodium sulfate to the reactor and cool to 10±2°C, add sodium hydroxide to the reactor in batches, stir for 25-35min, control the temperature of the reactor to be cooled to below 10°C, add a catalyst, then dropwise add trimethyl orthoacetate, control the temperature of the reactor to be 10-15°C, react for 2-2.5h, add water, crystallize, filter, and dry to obtain material 2; S3, add material 2 and ethylene dichloride in a weight ratio of 1: (3.5-4.5) into a reactor, after material 2 is dissolved, add hydrobromic acid and azobisisobutyronitrile into the reactor and heat to 60-65°C, start to drop hydrogen peroxide into the reactor and keep warm until it fades, recover ethylene dichloride under reduced pressure, and obtain material 3 after cooling; S4, in a reaction kettle, acetonitrile and potassium carbonate were stirred and mixed, and then o-methylphenol dissolved in acetonitrile was added dropwise, and stirred for 10-15 minutes after the addition was completed, and material three dissolved in acetonitrile was added dropwise, and the temperature was raised to 45-50° C. after the addition was completed, and the reaction was kept warm for 5-6 hours, and then filtered, methanol was added, the temperature was raised to dissolve, and then refluxed for 25-30 minutes, and the temperature was lowered to minus 5° C., crystallized, filtered, and dried to obtain kresoxim-methyl; Wherein, in step S1, the molar ratio of o-methylbenzeneacetonitrile to sodium hydroxide and nitrite is 1:(1-1.2):(1-1.2); In the step S2, the catalyst is dodecyltrimethylammonium chloride and β-cyclodextrin in a weight ratio of 1:1; In step S2, the β-cyclodextrin is modified β-cyclodextrin, and the modification method of β-cyclodextrin comprises the following steps: mixing β-cyclodextrin and dichloromethane and placing in an ice water bath, adding chlorosulfonic acid dropwise within two hours, stirring and reacting at room temperature for 2 hours after the addition, and then filtering and washing to obtain sulfonated β-cyclodextrin, wherein the molar ratio of β-cyclodextrin to chlorosulfonic acid is 1:2; Wherein, the reactor for producing and processing the kresoxim-methyl raw material comprises: A shell (1), a supporting leg (2) is fixed to the bottom end of the shell (1), a feed port (3) is arranged at the top end of the shell (1), a reducer (5) is installed at the top end of the shell (1), a motor (4) is installed at the top end of the reducer (5), a rotating rod (6) is fixed to the bottom end of the reducer (5), and a stirring mechanism (7) is installed on the outer wall of the rotating rod (6); The stirring mechanism (7) comprises a first connecting seat (701), a first stirring rod (702) and a second connecting seat (703); the first connecting seat (701) is fixed to the outer wall of the rotating rod (6); the first stirring rod (702) is hingedly connected to the inner wall of the first connecting seat (701); the second connecting seat (703) is fixedly connected to the bottom end of the first stirring rod (702); a hydraulic rod (704) is hingedly connected to the inner wall of the second connecting seat (703); the bottom end of the hydraulic rod (704) is hingedly connected to a third connecting seat (705); the bottom end of the third connecting seat (705) is fixedly connected to the second stirring rod (702); A stirring rod (706), the outer wall of the second stirring rod (706) is hinged with a fourth connecting seat (707); the first connecting seat (701) and the fourth connecting seat (707) are symmetrically distributed about the central axis of the hydraulic rod (704), the first connecting seat (701) is provided with a plurality of groups, the first connecting seats (701) are distributed at equal intervals about the central axis of the rotating rod (6), the fourth connecting seat (707) is fixed to the outer wall of the rotating rod (6), the fourth connecting seat (707) is provided with a plurality of groups, the fourth connecting seats (707) are distributed at equal intervals about the central axis of the rotating rod (6); A reflux mechanism (8) is installed inside the shell (1), a heating wire (9) is installed on the inner wall of the shell (1), an explosion-proof mechanism (10) is installed on the outer wall of the shell (1), and a discharge port (11) is provided at the bottom end of the shell (1); the reflux mechanism (8) comprises a diverter layer (801), a spiral conveyor plate (802) and a hanging bottom plate (803), the diverter layer (801) is fixed to the inner wall of the shell (1), the spiral conveyor plate ( 802) is fixed to the outer wall of the rotating rod (6), a hanging bottom plate (803) is fixed to the bottom end of the rotating rod (6), and the outer wall of the shell (1) is connected to a return pipe (804); the spiral conveying plate (802) is close to the inner wall of the diversion layer (801), the bottom end of the hanging bottom plate (803) is close to the inner wall of the shell (1), and the hanging bottom plates (803) are provided in a plurality of groups, and the hanging bottom plates (803) are symmetrically distributed about the central axis of the rotating rod (6); The explosion-proof mechanism (10) comprises a first explosion-proof ring (1001), a second explosion-proof ring (1002) and a fixing bolt (1003); the first explosion-proof ring (1001) is mounted on the outer wall of the housing (1); the second explosion-proof ring (1002) is arranged on the outer wall of the housing (1); and the fixing bolt (1003) is mounted on the inner wall of the first explosion-proof ring (1001).

2. The method according to claim 1, characterized in that: In step S2, the molar ratio of sodium hydroxide, trimethyl orthoacetate and material 1 is (1.8-2.2): (2.3-2.8): 1.

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