CN113387919A - Method for continuous flow synthesis of piperonyl formaldehyde - Google Patents
Method for continuous flow synthesis of piperonyl formaldehyde Download PDFInfo
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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Abstract
The invention provides a method for continuously synthesizing piperonyl formaldehyde. The method comprises the following steps: (1) dissolving safrole in an organic solvent to obtain a material 1, and introducing the material 1 into a precooler 1; introducing ozone into a precooler 2; introducing the material 1 in the precooler 1 and the ozone in the precooler 2 into a gas-liquid mixing reactor simultaneously for reaction to obtain a material 2; (2) introducing the material 2 into a gas-liquid separator, and collecting separated liquid to obtain a material 3; and (3) introducing the material 3 into a post-treatment module, carrying out post-treatment to obtain a material 4, and concentrating or drying to obtain the piperonyl formaldehyde. The method is safe, efficient, simple to operate, easy for large-scale production, capable of obviously improving the yield and purity of the piperonyl formaldehyde product, and wide in application prospect.
Description
Technical Field
The invention belongs to the field of continuous flow synthesis, and particularly relates to a method for continuously synthesizing piperonyl formaldehyde.
Background
The piperonyl formaldehyde has CAS number of 6543-34-6, its name is 3,4- (methylenedioxy) phenylacetaldehyde, piperonyl formaldehyde, piperonyl aldehyde, and high piperonyl aldehyde, and its molecular formula is C9H8O3The chemical structural formula is as follows:
piper-piper-yl-formaldehyde is an intermediate for synthesizing berberine hydrochloride (berberine hydrochloride), which is a medicine for treating enteroinfection diseases such as gastroenteritis, bacillary dysentery and the like caused by sensitive pathogenic bacteria.
The main methods for synthesizing piperonyl formal currently are (see WO 2009153374): the target product piperonyl formaldehyde is obtained by using piperonal as a raw material through epoxidation and decarboxylation, and the reaction equation is as follows:
the method has the main problems of multiple reaction steps, complex operation, long period and low yield.
Another current method for synthesizing piperonyl formaldehyde is to oxidize safrole with ozone to obtain ozonide, and then decompose the ozonide in the presence of a reducing agent to obtain the target product piperonyl formaldehyde, wherein the reaction equation is as follows:
however, the ozonization reaction is a very dangerous chemical reaction, and the operation is improper, so that the explosion risk is generated, and the method is not suitable for the traditional tank type industrial large-scale production.
The two methods for synthesizing the piperonyl formaldehyde adopt an intermittent process to produce the piperonyl formaldehyde. In the process of intermittent process operation, the composition, temperature and the like of materials (including intermediate products and final products) in a reactor can change along with time, so that the materials are unstable and difficult to control, and the production process and the product quality have great uncertainty. The prior method for producing piperonyl formaldehyde by adopting an intermittent process mainly has the following problems: 1. the intermittent batch operation efficiency is not high, and the reaction time is very long; 2. the ozonization process has extremely high danger and potential safety hazard, and is not suitable for the traditional kettle type industrial large-scale production.
Therefore, it is urgently needed to develop a safe, efficient, simple-to-operate and easy-to-mass-produce method for synthesizing piperonyl formaldehyde.
Disclosure of Invention
The invention aims to solve the technical problems that the intermittent process for producing the piperonyl formaldehyde in the prior art has low yield, high risk and low safety coefficient and is not beneficial to the traditional kettle type industrial large-scale production, and provides a method for continuously synthesizing the piperonyl formaldehyde, which is safe, efficient, simple to operate and easy to produce in a large scale.
The invention provides a method for continuously synthesizing piperonyl formaldehyde, which comprises the following steps:
(1) dissolving safrole in an organic solvent to obtain a material 1, and introducing the material 1 into a precooler 1; introducing ozone into a precooler 2; introducing the material 1 in the precooler 1 and the ozone in the precooler 2 into a gas-liquid mixing reactor simultaneously for reaction to obtain a material 2;
(2) introducing the material 2 into a gas-liquid separator, and collecting separated liquid to obtain a material 3; and (3) introducing the material 3 into a post-treatment module, carrying out post-treatment to obtain a material 4, and concentrating or drying to obtain the piperonyl formaldehyde.
Further, in the step (1), the mass ratio of the safrole to the organic solvent is 1: (0-20); and/or the organic solvent is one or more of methanol, dichloromethane and 1, 2-dichloroethane; and/or the temperature of the precooler 1 is 0-10 ℃, the temperature of the precooler 2 is 0-10 ℃, and the temperature of the gas-liquid mixing reactor is 0-10 ℃; and/or the reaction time is 10-200 s; and/or the flow rate of introducing the material 1 in the precooler 1 into the gas-liquid mixed reactor is 8-500 mL/min.
Further, in the step (1), the mass ratio of the safrole to the organic solvent is 1: (4-8); and/or the organic solvent is a mixed solvent of methanol and dichloromethane; and/or the temperature of the precooler 1 is 5 ℃, the temperature of the precooler 2 is 5 ℃, and the temperature of the gas-liquid mixed reactor is 5 ℃; and/or the reaction time is 60 s; and/or the flow rate of the material 1 in the precooler 1 introduced into the gas-liquid mixed reactor is 10 mL/min.
Further, in the step (1), the mass ratio of the safrole to the organic solvent is 1: 6; and/or the volume ratio of the methanol to the dichloromethane in the mixed solvent of the methanol and the dichloromethane is 1: 5.
further, in the step (1), the ozone is generated by an ozone generator, the oxygen flow in the ozone generator is 4L/min, the ozone discharge power is 0.35KW, and the ozone introduction speed is 200 g/min.
Further, in step (2), the post-treatment module is a liquid containing a reducing agent, and the post-treatment operation is that: and introducing the material 3 into liquid containing a reducing agent for reaction, filtering, collecting filtrate, adjusting the pH value to be neutral, collecting an organic phase, and filtering to obtain a material 4.
Further, in the step (2), the reducing agent is one or more of triphenylphosphine, sodium thiosulfate pentahydrate, sodium thiosulfate, thiourea, sodium metabisulfite, sodium hydrosulfite and zinc powder;
and/or the liquid containing the reducing agent is obtained by mixing the reducing agent and a solvent;
and/or the temperature of the material 3 introduced into the liquid containing the reducing agent is 0-room temperature, and the reaction time is 0.5-2.0 hours.
Further, in the step (2), the molar ratio of the reducing agent to safrole is (0.25-1): 1;
and/or the solvent is one or more of water, methanol, dichloromethane and 1, 2-dichloroethane;
and/or the mass ratio of the reducing agent to the solvent is 1: (6-17);
and/or the temperature of introducing the material 3 into the liquid containing the reducing agent for reaction is 0-15 ℃, and the reaction time is 1.0 hour.
Further, in the step (2), the reducing agent is sodium thiosulfate, and the molar ratio of the reducing agent to the safrole is 0.25: 1, the solvent is a mixed liquid of water and dichloromethane, the volume ratio of the water to the dichloromethane is 1.5:1, and the mass ratio of the reducing agent to the solvent is 1: 16.6.
further, in the step (2), the reducing agent is zinc powder, and the molar ratio of the reducing agent to safrole is 1: 1, the solvent is dichloromethane, and the mass ratio of the reducing agent to the solvent is 1: 6.6.
in the present invention, room temperature means 25. + -. 2 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method for synthesizing piperonyl formaldehyde by continuous flow ozone oxidation saves the production process of a plurality of intermediates, has simple process, can realize continuous flow synthesis, and has high production efficiency and simple operation;
2. the method for synthesizing piperonyl formaldehyde by continuous flow ozone oxidation adopts a continuous flow synthesis process, when the process operation reaches a steady state, the state parameters such as the composition of materials in a reactor, the temperature and the like do not change along with the time, and the reaction is a steady-state process; the synthetic method of the invention has more stable production process and product quality.
3. The oxidation reaction liquid in the synthesis method of the invention does not need to stay, and rapidly enters a reduction system for reduction reaction, thereby avoiding the potential safety hazard existing in oxide storage, avoiding the product from being further oxidized into carboxylic acid, and ensuring high yield.
4. The method for synthesizing piperonyl formaldehyde by continuous flow ozone oxidation further improves the yield and the purity of the obtained piperonyl formaldehyde by controlling the specific reaction solvent, the material-liquid ratio and the specific reducing agent.
In a word, the method for continuously synthesizing piperonyl formaldehyde is safe, efficient, simple to operate, easy for large-scale production, capable of obviously improving the yield and purity of piperonyl formaldehyde products and wide in application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a reaction equation for continuous flow synthesis of piperonyl formaldehyde according to the present invention.
FIG. 2 is a process flow diagram of the continuous flow synthesis of piperonyl formaldehyde in accordance with the present invention.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
Example 1
Mixing and dissolving 200g of safrole as a raw material, 200g of methanol and 1000g of dichloromethane to obtain a liquid material, and sequentially introducing the liquid material into a precooler 1 and a gas-liquid mixing reactor at the flow rate of 10mL/min by using an advection pump, wherein the temperature of the precooler 1 is 5 ℃; ozone is sequentially introduced into a precooler 2 and a gas-liquid mixing reactor by an ozone generator according to the oxygen flow of 4L/min and the ozone discharge power of 0.35KW (introduction speed: 200g ozone/min), and the temperature of the precooler 2 is 5 ℃; and the liquid material in the precooler 1 and the ozone in the precooler 2 are simultaneously introduced into the gas-liquid mixing reactor. The reaction temperature of the gas-liquid mixing reactor is 5 ℃; the liquid material stays in the gas-liquid mixing reactor for 60s and then flows into a gas-liquid separator, and oxygen and reaction liquid are separated out by the gas-liquid separator; collecting the reaction solution, continuously dropwise adding the reaction solution into a suspension prepared by aqueous solution of sodium thiosulfate pentahydrate (76 g of sodium thiosulfate pentahydrate and 760g of water) and 530g of dichloromethane, controlling the temperature to be 0-15 ℃, reacting for 1 hour, then filtering, collecting filtrate, adjusting the pH value of the filtrate to be neutral by using sodium carbonate, separating liquid, filtering by using organic phase pad silica gel, concentrating the filtrate, and drying to obtain 172g of piperonyl formaldehyde, wherein the yield is 85.0%, and the GC purity is 95.5%.
Structural characterization of piperonyl formaldehyde:1HNMR(401MHz,DMSO-d6)δ9.64(t,J＝1.8Hz,1H),6.86(d,J＝7.9Hz,1H),6.81(d,J＝1.7Hz,1H),6.69(dd,J＝7.9,1.7Hz,1H),5.98(d,J＝1.3Hz,2H),3.65(d,J＝2.0Hz,2H)。
example 2
Mixing and dissolving 200g of safrole raw material and 1330g of dichloromethane to obtain a liquid material, and sequentially introducing the liquid material into a precooler 1 and a gas-liquid mixing reactor at the flow rate of 10mL/min by using an advection pump, wherein the temperature of the precooler 1 is 5 ℃; ozone is sequentially introduced into a precooler 2 and a gas-liquid mixing reactor by an ozone generator according to the oxygen flow of 4L/min and the ozone discharge power of 0.35KW (introduction speed: 200g ozone/min), and the temperature of the precooler 2 is 5 ℃; and the liquid material in the precooler 1 and the ozone in the precooler 2 are simultaneously introduced into the gas-liquid mixing reactor. The reaction temperature of the gas-liquid mixing reactor is 5 ℃; the liquid material stays in the gas-liquid mixing reactor for 60s and then flows into a gas-liquid separator, and oxygen and reaction liquid are separated out by the gas-liquid separator; collecting reaction liquid, continuously dropwise adding the reaction liquid into a suspension prepared by aqueous solution of sodium thiosulfate pentahydrate (76 g of sodium thiosulfate pentahydrate and 760g of water) and 530g of dichloromethane, controlling the temperature to be 0-15 ℃, reacting for 1 hour, then filtering, collecting filtrate, adjusting the pH value of the filtrate to be neutral by using sodium carbonate, separating liquid, filtering by using organic phase pad silica gel, concentrating the filtrate, and drying to obtain 157g of piperonyl formaldehyde, wherein the yield is 77.6%, and the GC purity is 95.1%.
Example 3
Mixing and dissolving 200g of safrole as a raw material, 200g of methanol and 945g of 1, 2-dichloroethane to obtain a liquid material, and sequentially introducing the liquid material into a precooler 1 and a gas-liquid mixing reactor at the flow rate of 10mL/min by using an advection pump, wherein the temperature of the precooler 1 is 5 ℃; ozone is sequentially introduced into a precooler 2 and a gas-liquid mixing reactor by an ozone generator according to the oxygen flow of 4L/min and the ozone discharge power of 0.35KW (introduction speed: 200g ozone/min), and the temperature of the precooler 2 is 5 ℃; and the liquid material in the precooler 1 and the ozone in the precooler 2 are simultaneously introduced into the gas-liquid mixing reactor. The reaction temperature of the gas-liquid mixing reactor is 5 ℃; the liquid material stays in the gas-liquid mixing reactor for 60s and then flows into a gas-liquid separator, and oxygen and reaction liquid are separated out by the gas-liquid separator; collecting reaction liquid, continuously dropwise adding the reaction liquid into a suspension prepared from an aqueous solution of sodium thiosulfate pentahydrate (76 g of sodium thiosulfate pentahydrate and 760g of water) and 504g of 1, 2-dichloroethane, controlling the temperature to be 0-15 ℃, reacting for 1 hour, then filtering, collecting filtrate, adjusting the pH value of the filtrate to be neutral by using sodium carbonate, separating the liquid, filtering the organic phase pad silica gel, concentrating the filtrate, and drying to obtain 160g of piperonyl formaldehyde, wherein the yield is 79.1%, and the GC purity is 95.7%.
Example 4
Mixing and dissolving 200g of safrole as a raw material, 200g of methanol and 1000g of dichloromethane to obtain a liquid material, and sequentially introducing the liquid material into a precooler 1 and a gas-liquid mixing reactor at the flow rate of 10mL/min by using an advection pump, wherein the temperature of the precooler 1 is 5 ℃; ozone is sequentially introduced into a precooler 2 and a gas-liquid mixing reactor by an ozone generator according to the oxygen flow of 4L/min and the ozone discharge power of 0.35KW (introduction speed: 200g ozone/min), and the temperature of the precooler 2 is 5 ℃; and the liquid material in the precooler 1 and the ozone in the precooler 2 are simultaneously introduced into the gas-liquid mixing reactor. The reaction temperature of the gas-liquid mixing reactor is 5 ℃; after staying for 60s in the gas-liquid mixing reactor, the liquid material flows into a gas-liquid separator, and oxygen and reaction liquid are separated out by the gas-liquid separator; collecting the reaction solution, continuously dropwise adding the reaction solution into a suspension prepared from 80g of zinc powder and 530g of dichloromethane, controlling the temperature to be 0-15 ℃, reacting for 1 hour, then filtering, collecting filtrate, adjusting the pH value of the filtrate to be neutral by using sodium carbonate, filtering the filtrate by using organic phase pad silica gel, concentrating the filtrate, and drying to obtain 170g of piperonyl formaldehyde, wherein the yield is 84.0%, and the GC purity is 96.5%.
The combination of the examples 1-4 shows that the product purity of the continuous flow synthesis of piperonyl formaldehyde is above 95%, and the yield is as high as 77% -85%, which is higher than the yield (about 50%) of piperonyl formaldehyde produced by the batch process in the prior art. In particular, the yield and purity of the piperonyl formaldehyde are best under the specific process conditions of the examples 1 and 4.
In summary, the present invention provides a continuous flow synthesis method of piperonyl formaldehyde. The method is safe, efficient, simple to operate, easy for large-scale production, capable of obviously improving the yield and purity of the piperonyl formaldehyde product, and wide in application prospect.
Claims (10)
1. A method for continuous flow synthesis of piperonyl formaldehyde is characterized in that: the method comprises the following steps:
(1) dissolving safrole in an organic solvent to obtain a material 1, and introducing the material 1 into a precooler 1; introducing ozone into a precooler 2; introducing the material 1 in the precooler 1 and the ozone in the precooler 2 into a gas-liquid mixing reactor simultaneously for reaction to obtain a material 2;
(2) introducing the material 2 into a gas-liquid separator, and collecting separated liquid to obtain a material 3; and (3) introducing the material 3 into a post-treatment module, carrying out post-treatment to obtain a material 4, and concentrating or drying to obtain the piperonyl formaldehyde.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the safrole to the organic solvent is 1: (0-20); and/or the organic solvent is one or more of methanol, dichloromethane and 1, 2-dichloroethane; and/or the temperature of the precooler 1 is 0-10 ℃, the temperature of the precooler 2 is 0-10 ℃, and the temperature of the gas-liquid mixing reactor is 0-10 ℃; and/or the reaction time is 10-200 s; and/or the flow rate of introducing the material 1 in the precooler 1 into the gas-liquid mixed reactor is 8-500 mL/min.
3. The method of claim 2, wherein: in the step (1), the mass ratio of the safrole to the organic solvent is 1: (4-8); and/or the organic solvent is a mixed solvent of methanol and dichloromethane; and/or the temperature of the precooler 1 is 5 ℃, the temperature of the precooler 2 is 5 ℃, and the temperature of the gas-liquid mixed reactor is 5 ℃; and/or the reaction time is 60 s; and/or the flow rate of the material 1 in the precooler 1 introduced into the gas-liquid mixed reactor is 10 mL/min.
4. The method of claim 3, wherein: in the step (1), the mass ratio of the safrole to the organic solvent is 1: 6; and/or the volume ratio of the methanol to the dichloromethane in the mixed solvent of the methanol and the dichloromethane is 1: 5.
5. the method of claim 1, wherein: in the step (1), the ozone is generated by an ozone generator, the oxygen flow in the ozone generator is 4L/min, the ozone discharge power is 0.35KW, and the ozone introduction speed is 200 g/min.
6. The method according to any one of claims 1 to 5, wherein: in the step (2), the post-treatment module is a liquid containing a reducing agent, and the post-treatment operation is as follows: and introducing the material 3 into liquid containing a reducing agent for reaction, filtering, collecting filtrate, adjusting the pH value to be neutral, collecting an organic phase, and filtering to obtain a material 4.
7. The method of claim 6, wherein: in the step (2), the reducing agent is one or more of triphenylphosphine, sodium thiosulfate pentahydrate, sodium thiosulfate, thiourea, sodium metabisulfite, sodium hydrosulfite and zinc powder;
and/or the liquid containing the reducing agent is obtained by mixing the reducing agent and a solvent;
and/or the temperature of the material 3 introduced into the liquid containing the reducing agent is 0-room temperature, and the reaction time is 0.5-2.0 hours.
8. The method of claim 7, wherein: in the step (2), the molar ratio of the reducing agent to safrole is (0.25-1): 1;
and/or the solvent is one or more of water, methanol, dichloromethane and 1, 2-dichloroethane;
and/or the mass ratio of the reducing agent to the solvent is 1: (6-17);
and/or the temperature of introducing the material 3 into the liquid containing the reducing agent for reaction is 0-15 ℃, and the reaction time is 1.0 hour.
9. The method of claim 8, wherein: in the step (2), the reducing agent is sodium thiosulfate, and the molar ratio of the reducing agent to safrole is 0.25: 1, the solvent is a mixed liquid of water and dichloromethane, the volume ratio of the water to the dichloromethane is 1.5:1, and the mass ratio of the reducing agent to the solvent is 1: 16.6.
10. the method of claim 8, wherein: in the step (2), the reducing agent is zinc powder, and the molar ratio of the reducing agent to safrole is 1: 1, the solvent is dichloromethane, and the mass ratio of the reducing agent to the solvent is 1: 6.6.
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