Small reactor for preparing chilo suppressalis pheromone intermediate and application of small reactor

Abstract

The invention belongs to the technical field of synthesis, and particularly relates to a small reactor for preparing a chilo suppressalis pheromone intermediate and application of the small reactor. According to the small reactor, rapid mixing is achieved through a threaded mixing pipe, the introduction amount of a hydrobromic acid solution is controlled in the mixing process, and a reaction from low concentration to unilateral bromination of hydrobromic acid is achieved; meanwhile, a mixed solution obtained after the bromination reaction is mixed with a sodium bicarbonate solution in a spraying mode, the washing neutralization effect is achieved, standing, cooling and layering are formed through pressure release valves arranged in a gradient mode, and finally a methylbenzene solution and an aqueous solution are obtained. The method is mild in reaction condition, short in reaction time, high in reaction efficiency, high in automation degree, low in energy consumption and good in safety, meets the green chemical engineering concept and is easy to industrially apply.

Description

Technical Field

[0001] The invention belongs to the field of synthesis technology, and particularly relates to a small reactor for preparing a pheromone intermediate of a striped stem borer and application thereof. Background Art

[0002] With the advancement of science and technology, the scale of chemical synthesis and chemical processes continues to expand. The resulting environmental pollution problems are becoming more and more serious. As the market development trend continues to stabilize and market demand is relatively stable, green concepts such as safety, high efficiency, energy saving, and environmental protection have become important concerns in the industry. The miniaturization and micro-miniaturization of chemical equipment are becoming more and more important, and have become popular in the industry with advantages such as small footprint, fast reaction speed, low energy consumption, and less waste emissions.

[0003] At present, the industrial synthesis method of the pheromone intermediates of the striped stem borer, 1,10-bromo-1-decanol, 8-bromo-1-octanol, and 1,12-bromo-1-dodecanol, is mainly to prepare a toluene solution containing 1-10-decanediol, heat it up and control the temperature between 78-80°C, add 48% hydrobromic acid solution to the kettle, control the dropping speed, and after the addition of 48% hydrobromic acid, introduce steam to heat it up to 103-105°C, keep it warm for 24 hours, then turn off the heating, cool it down to 45°C, pump the material through a pipeline into another ice water that has been cooled to below 10°C in advance, stir it for 1 hour, let it stand and separate, extract the water layer with toluene twice, combine the toluene layers, neutralize it with sodium bicarbonate aqueous solution to PH=7.5, dry it with anhydrous sodium sulfate, and concentrate it to obtain the product. This method has a long reaction time, strict reaction temperature requirements, great safety hazards, and high energy consumption. Although there is a certain foundation for the research of miniaturized reaction equipment, there is no relevant report on the equipment used for pheromone intermediates of Chilo suppressalis. Summary of the invention

[0004] In view of the problems in the prior art, the present invention provides a small-scale reactor for preparing a pheromone intermediate of the striped stem borer, which solves the shortage of small-scale reactors for the pheromone intermediate of the striped stem borer. A short-range concentration control reaction system is formed by a threaded mixing tube, which effectively controls the progress of the unilateral bromination reaction. The water washing and multiple pressure relief sedimentation effects under the spraying in the separation tube are utilized to achieve stable stratification of toluene liquid and aqueous solution, thereby obtaining the pheromone intermediate of the striped stem borer.

[0005] In order to achieve the above technical objectives, the technical solution of the present invention is:

[0006] A small reactor for preparing a pheromone intermediate of a striped stem borer comprises: a threaded mixing tube and a separation tube, wherein the top of the threaded mixing tube is connected with the top of the separation tube through a spray pipe, and a spray device is arranged at one end of the spray pipe located in the separation tube;

[0007] The bottom of the threaded mixing tube is provided with a toluene feeding tube, which is used to feed the toluene solution, and the side is provided with a feeding tube of the hydrobromic acid solution in parallel, and the feeding tube of the hydrobromic acid solution is provided with several injection tubes at intervals, and the injection tube is provided with an injection valve, which injects the hydrobromic acid solution in the feeding tube into the threaded mixing tube, and the injection valve on the injection tube controls the injection flow. The injection amount of the injection tube 3 is gradually reduced from bottom to top.

[0008] The threaded mixing tube is provided with an axis rod, and continuous threaded blades are provided on the outer circumference of the axis rod from bottom to top, and the outer side surfaces of the threaded blades are close to the inner wall of the threaded mixing tube; when the toluene solution enters the threaded mixing tube from the toluene feed pipe, the threaded blades of the threaded mixing tube can form a spiral upward liquid flow channel in the entire threaded mixing tube; further, a porous composite block is provided on the top of the threaded mixing tube, and the porous composite block has an excellent pore structure.

[0009] A drain pipe is arranged at the bottom end of the separation tube, and a water pipe is arranged at the upper end. A buffer porous plate, a first pressure relief valve and a second pressure relief valve are arranged in sequence from top to bottom in the separation tube. The accommodating space of the first pressure relief valve is 30-40% of the volume of the accommodating space of the second pressure relief valve, and the lower accommodating space of the second pressure relief valve is 3-5 times the accommodating space of the second pressure relief valve. The bottom of the lower accommodating space of the second pressure relief valve is connected to the drain pipe. The buffer porous plate has a porous structure and is located below the spray device and the water pipe.

[0010] The method for preparing a Chilo suppressalis pheromone intermediate in a small reactor comprises the following steps:

[0011] Step 1, toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, thereby obtaining a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 4-7%, and the solute is one of 1,10-decanediol, 1,8-octanediol, and 1,12-dodecanol; the mass concentration of the hydrobromic acid solution is 8-15%; the reaction time is 10-15min; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.1-1.3; the flow distribution of the injection tube from bottom to top is 4:4:2-3:1-2:0.5;

[0012] Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid and the sodium bicarbonate solution in the water pipe are mixed on the buffer porous plate, and are mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 1.5-2.5:1;

[0013] Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and layers it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the water-washing neutralization liquid after cooling and layering to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and layer it; after the water-washing neutralization liquid is completely layered, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution containing 10-bromo-1-decanol, 8-bromo-1-octanol or 12-bromo-1-dodecanol. The space volume ratio of the first pressure relief valve accommodation space, the second pressure relief valve accommodation space and the accommodation space below the second pressure relief valve is 0.3-0.4:1:3-5.

[0014] It can be seen from the above description that the present invention has the following advantages:

[0015] 1. The present invention solves the shortage of small reactors for the intermediates of the pheromone of the striped stem borer, uses a threaded mixing tube to form a short-range concentration control reaction system, effectively controls the progress of the unilateral bromination reaction, and utilizes the water washing and multiple pressure relief sedimentation effects under the spraying in the separation tube to achieve stable stratification of the toluene solution and the aqueous solution, thereby obtaining the intermediates of the pheromone of the striped stem borer.

[0016] 2. The small reactor provided by the present invention has a high degree of automation, a fast reaction flow rate, relatively low energy consumption, good safety, and meets the concept of green chemical industry.

[0017] 3. The preparation method provided by the present invention is based on a small reactor and has the advantages of mild reaction, strong controllability, few side reactions and high reaction rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Schematic diagram of the structure of a small reactor in an embodiment of the present invention. DETAILED DESCRIPTION

[0019] Combination Figure 1 , describes in detail a specific embodiment of the present invention, but does not limit the claims of the present invention.

[0020] like Figure 1As shown, a small reactor for preparing a pheromone intermediate of a striped stem borer comprises: a threaded mixing tube 4 and a separation tube 5, wherein the top of the threaded mixing tube 4 is connected to the top of the separation tube 5 through a spray tube 10, and a spray device 7 is provided at one end of the spray tube 10 located in the separation tube 5;

[0021] A toluene feeding pipe 1 is arranged at the bottom of the threaded mixing tube 4, and the toluene feeding pipe 1 is used for feeding the toluene solution of 1,10-decanediol, 1,8-octanediol or 1,12-dodecyl alcohol. A feeding pipe 1 for a hydrobromic acid solution is arranged in parallel on the side, and the feeding pipe 1 for the hydrobromic acid solution is arranged with a plurality of injection pipes 3 at intervals, and an injection valve 3-1 is arranged on the injection pipe 3. The injection pipe 3 injects the hydrobromic acid solution in the feeding pipe into the threaded mixing tube 4, and the injection valve 3-1 on the injection pipe 3 controls the injection flow rate. And through the injection pipes arranged at intervals, a gradient injection is formed to achieve a low-concentration reaction of the hydrobromic acid solution, thereby greatly improving the reaction rate of the hydrobromic acid solution; during use, the toluene feeding pipe at the bottom can pass 1,10-decanediol, 1,8-octanediol or 1,12-dodecanol into the threaded mixing tube, and form a gradual rise from bottom to top, and the threads in the threaded mixing tube rotate, and the hydrobromic acid solution entering from the injection valve is brought in to form a rapid mix, thereby ensuring a rapid reaction of hydrobromic acid. In order to ensure the amount of hydrobromic acid solution introduced and the reaction requirements, the injection amount of the injection pipe 3 is gradually reduced from bottom to top, ensuring that the toluene solution and the hydrobromic acid solution in the threaded mixing tube maintain a concentration difference for most of the time, thereby improving the stable consumption of the hydrobromic acid solution.

[0022] The threaded mixing tube 4 is provided with an axis 4-3, and the outer circumference of the axis is provided with continuous thread leaves 4-1 from bottom to top, and the outer side of the thread leaves 4-1 is close to the inner wall of the threaded mixing tube 4; when the toluene solution enters the threaded mixing tube from the toluene feeding tube 1, the thread leaves of the threaded mixing tube can form a spiral upward liquid flow channel in the entire threaded mixing tube, and when the hydrobromic acid solution in the injection tube enters, the hydrobromic acid solution is entrained upward by the toluene solution in the liquid flow channel, and it is ensured that the hydrobromic acid forms a contact reaction with 1,10-decanediol, 1,8-octanediol or 1,12-dodecanol in the toluene solution, thereby achieving a small channel reaction; further, the top of the threaded mixing tube 4 is provided with a porous composite The block 4-2, the porous composite block has an excellent pore structure, which can fully mix the mixed liquid after the reaction in the threaded composite tube, not only slowing down the mixed liquid, ensuring that the hydrobromic acid introduced last reacts with the solute in the toluene solution, but also the porous composite block effectively blocks the impact of the liquid in the flow direction, reduces the impact of the liquid flow, and enters the spray pipe 10 in a gentle liquid flow; the toluene solution feed enters the threaded mixing tube in a slow circulation manner, and cooperates with the flow path of the liquid from bottom to top, effectively controlling the bubbles in the entire threaded mixing tube, and through the porous composite block, effectively reducing the flow velocity, while ensuring the filling effect of the liquid in the threaded mixing tube, and also reducing the dead volume in the threaded mixing tube.

[0023] The bottom end of the separation tube 5 is provided with a drain pipe 8, and the upper end is provided with a water pipe 9. The separation tube 5 is provided with a buffer porous plate 6, a first pressure relief valve 5-1 and a second pressure relief valve 5-2 from top to bottom. The accommodating space of the first pressure relief valve is 30-40% of the volume of the accommodating space of the second pressure relief valve, and the lower accommodating space of the second pressure relief valve is 3-5 times the accommodating space of the second pressure relief valve. The bottom of the lower accommodating space of the second pressure relief valve is connected to the drain pipe. The buffer porous plate has a porous structure and is located below the spray device 7 and the water pipe 9. When the spray device sprays the reaction mixture onto the buffer plate, ammonium bicarbonate solution is simultaneously added to the water pipe to form water washing and neutralization. At this time, the buffer porous plate plays a role in liquid phase segmentation, which effectively improves the reaction mixture and The ammonium bicarbonate solution is fully mixed and deposited on the first pressure relief valve through a buffer porous plate to form a water-washing neutralization liquid deposition. When the first pressure relief valve reaches a certain pressure, the water-washing neutralization liquid is deposited on the second pressure relief valve through the first pressure relief valve to form a slow cooling stratification. Based on the fact that the second pressure relief valve accommodating space is much larger than the first pressure relief valve accommodating space, after several pressure relief depositions of the first pressure relief valve, the second pressure relief valve reaches the pressure relief pressure, thereby allowing the water-washing neutralization liquid in the second pressure relief valve accommodating space to enter the accommodating space under the second pressure relief valve. As the deposition time increases, the water-washing neutralization cooling stratification under the second pressure relief valve forms a toluene liquid and an aqueous solution. After the stratification is stable, it is discharged in a gradient manner through a drain pipe to obtain a toluene liquid and an aqueous solution.

[0024] The method for preparing a Chilo suppressalis pheromone intermediate in a small reactor comprises the following steps:

[0025] Step 1, toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, thereby obtaining a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 4-7%, and the solute is one of 1,10-decanediol, 1,8-octanediol, and 1,12-dodecanol; the mass concentration of the hydrobromic acid solution is 8-15%; the reaction time is 10-15min; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.1-1.3; the flow distribution of the injection tube from bottom to top is 4:4:2-3:1-2:0.5;

[0026] Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid and the sodium bicarbonate solution in the water pipe are mixed on the buffer porous plate, and are mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 1.5-2.5:1;

[0027] Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and layers it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the water-washing neutralization liquid after cooling and layering to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and layer it; after the water-washing neutralization liquid is completely layered, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution containing 10-bromo-1-decanol, 8-bromo-1-octanol or 12-bromo-1-dodecanol. The space volume ratio of the first pressure relief valve accommodation space, the second pressure relief valve accommodation space and the accommodation space below the second pressure relief valve is 0.3-0.4:1:3-5.

[0028] The preparation method of the pheromone intermediate of the striped stem borer forms rapid mixing through a threaded mixing tube, and controls the amount of hydrobromic acid solution introduced during the mixing process to achieve a low-concentration hydrobromic acid to unilateral bromination reaction, which not only effectively controls the amount of hydrobromic acid solution used, reduces the residual and pollution of hydrobromic acid, but also effectively shortens the process of the unilateral bromination reaction and improves the reaction efficiency; at the same time, the mixed solution after the bromination reaction is mixed with a sodium bicarbonate solution by spraying to achieve the effect of water washing and neutralization, and a gradient-set pressure relief valve is used to form standing, cooling and stratification, and finally a toluene solution and an aqueous solution are obtained, which are discharged through a gradient discharge pipe to obtain a toluene solution containing 10-bromo-1-decanol, 8-bromo-1-octanol or 12-bromo-1-dodecanol.

[0029] Example 1

[0030] The method for preparing a Chilo suppressalis pheromone intermediate using the small reactor of the above structure comprises the following steps:

[0031] Step 1, a toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and a hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, thereby obtaining a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 4%, and the solute is 1,10-decanediol; the mass concentration of the hydrobromic acid solution is 8%; the reaction time is 10 minutes; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.1; the flow distribution of the injection tube from bottom to top is 4:4:2:1:0.5;

[0032] Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid is mixed with the sodium bicarbonate solution in the water pipe on the buffer porous plate, and is mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 1.5:1;

[0033] Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and layers it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the water-washing neutralization liquid after cooling and layering to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and layer it; after the water-washing neutralization liquid is completely layered, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution of 10-bromo-1-decanol. The space volume ratio of the first pressure relief valve accommodation space, the second pressure relief valve accommodation space, and the accommodation space below the second pressure relief valve is 0.3:1:3.

[0034] The 1,10-bromo-1-decanol prepared in this example has a purity of 95.87% and a yield of 96.01%.

[0035] Example 2

[0036] The method for preparing a Chilo suppressalis pheromone intermediate using the small reactor of the above structure comprises the following steps:

[0037] Step 1, a toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and a hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, thereby obtaining a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 7%, and the solute is 1,8-octanediol; the mass concentration of the hydrobromic acid solution is 15%; the reaction time is 15 minutes; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.3; the flow distribution of the injection tube from bottom to top is 4:4:3:2:0.5;

[0038] Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid and the sodium bicarbonate solution in the water pipe are mixed on the buffer porous plate, and are mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 2.5:1;

[0039] Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and layers it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the water-washing neutralization liquid after cooling and layering to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and layer it; after the water-washing neutralization liquid is completely layered, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution of 8-bromo-1-octanol. The space volume ratio of the first pressure relief valve accommodation space, the second pressure relief valve accommodation space, and the accommodation space below the second pressure relief valve is 0.4:1:5.

[0040] The 8-bromo-1-octanol prepared in this example has a purity of 95.96% and a yield of 96.13%.

[0041] Example 3

[0042] The method for preparing a Chilo suppressalis pheromone intermediate using the small reactor of the above structure comprises the following steps:

[0043] Step 1, toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, so as to obtain a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 4-7%, and the solute is 1,12-dodecanol; the mass concentration of the hydrobromic acid solution is 12%; the reaction time is 13 minutes; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.2; the flow distribution of the injection tube from bottom to top is 4:4:3:1:0.5;

[0044] Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid and the sodium bicarbonate solution in the water pipe are mixed on the buffer porous plate, and are mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 2:1;

[0045] Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and layers it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the water-washing neutralization liquid after cooling and layering to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and layer it; after the water-washing neutralization liquid is completely layered, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution of 12-bromo-1-dodecanol. The space volume ratio of the first pressure relief valve accommodation space, the second pressure relief valve accommodation space, and the accommodation space below the second pressure relief valve is 0.3:1:4.

[0046] The 12-bromo-1-dodecanol prepared in this example has a purity of 96.12% and a yield of 96.94%.

[0047] Comparative Example

[0048] An intermittent reactor-type synthesis of a Chilo suppressalis pheromone intermediate comprises:

[0049] In a 2L three-necked flask, add 100g (0.5737mol) of 1,10-decanediol and 1500ml of toluene solution, heat and control the temperature between 78-80℃, add 48%, 235g (1.16mol) of hydrobromic acid solution to the kettle, control the dropping speed, after the addition of 48% hydrobromic acid is completed, heat and heat to 103-105℃, keep warm for 24 hours, then turn off the heating, cool to 45℃, and pump the material through a pipeline into another ice water that has been cooled to below 10℃ in advance, stir for 1 hour, let it stand and separate, extract the water layer twice with toluene, combine the toluene layers, neutralize with sodium bicarbonate aqueous solution to PH=7.5, dry with anhydrous sodium sulfate, and concentrate to obtain a light yellow oily liquid, i.e., the product 10-bromo-1-decanol 140g, GC external standard detection purity 84.43%, yield 86.8%.

[0050] From the comparison of the data of Examples 1-3 and the comparative example, it can be seen that the present invention adopts a small reactor to synthesize the intermediate of the pheromone of the striped stem borer, which can not only effectively control the amount of the reactants to form a controllable bromination reaction, but also realize stable stratification without stopping the equipment in an automatic deposition manner, and the purity and yield of the obtained product are much higher than those of the intermittent reactor synthesis method.

[0051] It is understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A small reactor for preparing a pheromone intermediate of a striped stem borer, characterized in that: The small reactor comprises: a threaded mixing tube and a separation tube, the top of the threaded mixing tube is connected with the top of the separation tube through a spray pipe, and a spray device is arranged at one end of the spray pipe located in the separation tube; A toluene feeding pipe is arranged at the bottom of the threaded mixing tube, and the toluene feeding pipe is used for feeding the toluene solution of 1,10-decanediol, 1,8-octanediol or 1,12-dodecanol. A feeding pipe for a hydrobromic acid solution is arranged in parallel on the side, and the feeding pipe for the hydrobromic acid solution is arranged with several injection pipes at intervals. A shaft is arranged in the threaded mixing tube, and continuous threaded leaves are arranged on the outer circumference of the shaft from bottom to top; The separation tube is provided with a drain pipe at the bottom end and a water pipe at the upper end. A buffer porous plate, a first pressure relief valve and a second pressure relief valve are sequentially arranged in the separation tube from top to bottom. The bottom of the accommodation space under the second pressure relief valve is connected to the drain pipe.

2. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The injection pipe is provided with an injection valve, which injects the hydrobromic acid solution in the feed pipe into the threaded mixing pipe, and the injection valve on the injection pipe controls the injection flow rate.

3. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 2, characterized in that: The injection amount of the injection pipe decreases gradually from bottom to top.

4. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: A porous composite block is arranged on the top of the threaded mixing tube, and the porous composite block has an excellent pore structure.

5. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The outer side surface of the threaded blade is close to the inner wall of the threaded mixing tube; when the toluene solution enters the threaded mixing tube from the toluene feeding tube, the threaded blade of the threaded mixing tube can form a spiral upward liquid flow channel in the entire threaded mixing tube.

6. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The accommodating space of the first pressure relief valve is 30-40% of the volume of the accommodating space of the second pressure relief valve.

7. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The lower accommodation space of the second pressure relief valve is 3-5 times the accommodation space of the second pressure relief valve.

8. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The buffer porous plate has a porous structure and is located below the spray device and the water pipe.

9. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 1, characterized in that: The method for preparing a Chilo suppressalis pheromone intermediate in a small reactor comprises the following steps: Step 1, toluene solution is introduced into a threaded mixing tube through a toluene solution feeding tube, and hydrobromic acid solution is added into the hydrobromic acid solution feeding tube, and injected into the threaded mixing tube through 5 injection tubes arranged in parallel; the toluene solution and the hydrobromic acid solution are blended in the threaded mixing tube and subjected to a unilateral bromination reaction, thereby obtaining a mixed solution after the reaction; the mass concentration of the solute in the toluene solution is 4-7%, and the solute is one of 1,10-decanediol, 1,8-octanediol, and 1,12-dodecanol; the mass concentration of the hydrobromic acid solution is 8-15%; the reaction time is 10-15min; the molar ratio of the solute in the toluene solution to the hydrobromic acid is 1:1.1-1.3; the flow distribution of the injection tube from bottom to top is 4:4:2-3:1-2:0.5; Step 2, the mixed liquid is fully mixed through the porous composite block and then enters the separation tube through the spray pipe, and is sprayed onto the buffer porous plate by a spray device, and at the same time, the water pipe passes the sodium bicarbonate solution into the separation tube; the sprayed mixed liquid and the sodium bicarbonate solution in the water pipe are mixed on the buffer porous plate, and are mixed and neutralized by water washing in the buffer porous plate, and then deposited on the first pressure relief valve; the volume ratio of the sodium bicarbonate solution to the mixed liquid in the spray pipe is 1.5-2.5:1; Step 3, when a certain volume of water-washing neutralization liquid is deposited in the accommodation space of the first pressure relief valve, the first pressure relief valve deposits the water-washing neutralization liquid to the second pressure relief valve by pressure relief, and cools and stratifies it; when a certain volume is deposited in the accommodation space of the second pressure relief valve, the second pressure relief valve deposits the cooled and stratified water-washing neutralization liquid to the accommodation space below the second pressure relief valve by pressure relief, and continues to stand and stratify it; after the water-washing neutralization liquid is completely stratified, the water-washing neutralization liquid collects the toluene solution and the aqueous solution in the accommodation space below the second pressure relief valve by gradient discharge, thereby obtaining a toluene solution containing 1,10-bromo-1-decanol, 8-bromo-1-octanol or 1,12-bromo-1-dodecanol.

10. The small reactor for preparing the Chilo suppressalis pheromone intermediate according to claim 9, characterized in that: The spatial volume ratio of the first pressure relief valve accommodating space, the second pressure relief valve accommodating space and the second pressure relief valve lower accommodating space in step 3 is 0.3-0.4:1:3-5.

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