CN110684010B - Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis - Google Patents
Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis Download PDFInfo
- Publication number
- CN110684010B CN110684010B CN201810726511.XA CN201810726511A CN110684010B CN 110684010 B CN110684010 B CN 110684010B CN 201810726511 A CN201810726511 A CN 201810726511A CN 110684010 B CN110684010 B CN 110684010B
- Authority
- CN
- China
- Prior art keywords
- stirring
- water
- methylenedioxy
- added
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D317/46—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 condensed with one six-membered ring
- 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
- C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by adopting an emulsification catalysis process, which comprises the steps of introducing gas into a reaction system in the processes of preparing mixed acid and emulsifying synthesis, so that a large amount of bubbles are generated in the reaction system, the surface area of reactants is increased, the contact area between the reactants is increased, and the conversion rate and the yield of the reaction can be improved. By utilizing the homogenization of the emulsification process, the piperonyl is uniformly dispersed in the glyoxylic acid in the form of tiny liquid drops, so that the contact efficiency between reactants can be improved, and the purity and yield of the product can be improved. The method of adding phase transfer catalyst in the reaction process improves the affinity of the water phase and the oil phase, further improves the emulsification effect, and further improves the reaction selectivity and yield. The invention also discloses a device for synthesizing 3, 4-methylenedioxy-phenylglyoxylic acid by emulsion catalysis, which can realize a method for synthesizing 3, 4-methylenedioxy-phenylglyoxylic acid by adopting an emulsion catalysis process.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a method and a device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by emulsification catalysis.
Background
3, 4-methylenedioxy-mandelic acid is an intermediate in the synthesis of piperonal. Piperonal is widely used as a flavoring agent for perfumes, fragrances, cherries and vanilla flavors. The long-lasting fragrance is used as a sum fragrance agent and a fixing fragrance agent, is a safe fragrance approved by American perfume extract manufacturing society, and is widely applied to indoor fragrances, soap fragrances, food fragrances and tobacco fragrances. Can also be used in chemical biopharmaceuticals. Is one of the special commodities for the country to carry out export license.
The conventional synthesis method of 3, 4-methylenedioxy-mandelic acid is a method of synthesizing piperonyl and glyoxylic acid under acidic conditions, and the influence of reaction factors such as reaction temperature, reaction time, molar ratio of glyoxylic acid to piperonyl and the like is studied by Shan Shaojun and the like (Shan Shaojun, du Zhenmei. Synthesis research of 3, 4-methylenedioxy-mandelic acid [ J ]. Anhui chemical, 2007,2; 46-47.). Wang Shuai et al (Wang Shuai, li Yaoxian, wang Hengguo. Air catalytic oxidation to heliotropin [ J ]. Applied chemical, 2009, 4:491-493.) and Zhang Kunshui et al (Zhang Kunshui, huanghan, chen Yisheng. Silver nitrate methods for synthesis of medicinal jasmonate [ J ]. Chinese modern pharmaceutical applications. 2008, 2:53-54.) A similar process for preparing 3, 4-methylenedioxy-phenylglycolic acid was also employed in the study of heliotropin synthesis. Hongjuan the influence of factors such as reaction temperature, catalyst concentration, raw material proportion and reaction time is examined, and the action mechanism and possible reaction courses of the sulfuric acid catalyst are discussed (Hongjuan, gao Zhixian, wang Jianguo. Synthesis and characterization of heliotropin intermediate 3, 4-methylenedioxy-benzilic acid [ J ]. Chemical research and application, 2009, 21:396-400.).
The above prior art has the following disadvantages;
because the product 3, 4-methylenedioxy-phenylglycolic acid has high viscosity, poor fluidity in the synthesis process, low mass transfer efficiency, immiscibility between the piperonyl and the glyoxylic acid and small contact area between the two phases, insufficient reaction results in low yield, poor heat transfer non-uniform effect, and easy occurrence of the phenomena of poor selectivity and more byproducts of the reaction
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method and a device for synthesizing 3, 4-methylenedioxy-benzilic acid by emulsification catalysis.
The invention is realized by the following technical scheme:
a method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by emulsion catalysis, which is characterized by comprising the following steps:
step 1, mixing the following components in percentage by mass: 50wt% glyoxylate aqueous solution = 1: stirring the mixture at a constant temperature of 15-20, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 20 ℃ and the stirring speed is 350 rpm-450 rpm;
step 3, continuously stirring for 20-40 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 20 ℃;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, and the stirring time is 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition amount of the stop solution to the water mass in the step 1 is the stop solution: water=15 to 30:1, terminating the reaction to obtain a product;
the process of step 1 to step 7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7-20 times of the volume of the mixture.
In the above technical scheme, in the step 1, the mass ratio of water is as follows: 50wt% glyoxylate aqueous solution = 1: the mixture of 15 to 17 is stirred at constant temperature, the constant temperature stirring temperature is minus 28 ℃ to minus 23 ℃, and the stirring speed is 380rpm to 420rpm.
In the above technical scheme, in the step 4, the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass is 3, 4-methylenedioxy-mandelic acid: water=0.1 to 0.4:1.
in the above technical scheme, in the step 4, the ratio of the amount of added benzyltriethylammonium chloride to the water mass in the step 1 is benzyltriethylammonium chloride: water=0.8 to 1.2:1.
in the technical scheme, in the step 5, the emulsifying speed is 10-12 Kr/min, the pepper ring is added dropwise at the same time during emulsifying, the adding amount per minute is 0.5-0.8 times of the water mass, and the emulsifying time is 5-10 min.
In the above technical scheme, step 6, step 5 is repeated 3-8 times, each time is separated by 3-10 min, and the ratio of the total amount of the added piper ring to the water mass is piper ring: water=10 to 12:1.
in the above technical scheme, in the step 8, the added stop solution is water, and the ratio of the total adding amount of the stop solution to the water mass in the step 1 is the stop solution: water=15 to 25:1.
in the technical scheme, the method comprises the following steps of:
step 1, mixing the following components in percentage by mass: 50wt% glyoxylate aqueous solution = 1: stirring the mixture at a constant temperature of 14-16, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 25 ℃ and the stirring speed is 400rpm;
step 3, continuously stirring for 20-30 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 25 ℃;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, and the stirring time is 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition amount of the stop solution to the water mass in the step 1 is the stop solution: water=15 to 20:1, terminating the reaction to obtain a product;
the process of step 1 to step 7 also comprises the process of blowing air into the solution, wherein the air blowing amount per minute is 12-20 times of the volume of the mixture.
In the above technical scheme, the air-blowing medium adopted in the air-blowing process is nitrogen.
The device for synthesizing the 3, 4-methylenedioxy-phenylglycolic acid by emulsion catalysis comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor emulsified tank, a jacketed distributor product stirred tank, a pepper ring metering tank, a constant temperature tank, a filtering device, a feed pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, the outlet of a circulating liquid of the constant temperature tank is respectively connected with the inlet of the jacketed distributor stirred tank, the inlet of the jacketed distributor emulsified tank and the inlet of the jacketed distributor product stirred tank by pipelines, the inlet of the constant temperature tank circulating liquid is respectively connected with the outlet of the jacketed distributor stirred tank, the outlet of the jacketed distributor stirred tank and the outlet of the jacket distributor stirred tank by pipelines, the outlet of the jacketed distributor stirred tank is connected with an inlet pipeline of the feed pump, and the outlet of the jacketed distributor stirred tank is connected with the inlet of the gas storage tank by pipelines.
In the technical scheme, the outlet pipes of the sulfuric acid metering tank and the pepper ring metering tank are respectively provided with a flowmeter.
In the technical scheme, the sulfuric acid metering tank is arranged above the stirring kettle of the jacketed distributor, and the pepper ring metering tank is arranged above the emulsifying kettle of the jacketed distributor.
In the technical scheme, the liquid flow meters are arranged on the jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle.
In the technical scheme, gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle.
In the technical scheme, the emulsifying device and the wall scraping stirring device are arranged on the jacketed distributor emulsifying kettle.
In the technical scheme, 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle.
In the above technical solution, the filtering device may be a multi-stage filtering device.
In the above technical solution, the filtering device may be a 2-stage filtering device.
In the technical scheme, the temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The invention has the advantages and beneficial effects that:
1. the method for synthesizing 3, 4-methylenedioxy-phenylglyoxylic acid adopts the method for synthesizing in the emulsification catalysis process, and the method is used for introducing gas into a reaction system in the processes of preparing mixed acid and emulsifying synthesis, so that a large number of bubbles are generated in the reaction system, the surface area of reactants is increased, the contact area between the reactants is increased, and the conversion rate and the yield of the reaction can be improved.
2. The invention adopts an emulsification method to synthesize the 3, 4-methylenedioxy-phenylglyoxylic acid, and utilizes the homogenization function of the emulsification process in the synthesis to ensure that the piperonyl is uniformly dispersed in the glyoxylic acid in the form of tiny liquid drops, thereby improving the contact efficiency between reactants and improving the purity and yield of the product.
3. The emulsifier adopted by the invention is 3, 4-methylenedioxy-phenylglycolic acid, and the method uses the product as the emulsifier according to the principle that the 3, 4-methylenedioxy-phenylglycolic acid has both lipophilic and hydrophilic groups, so that a stable emulsifying system can be formed without introducing substances outside a reaction system, and the product separation process is simpler and easier.
4. The invention uses the method of adding phase transfer catalyst in the reaction process to improve the affinity of water phase and oil phase, further improve the emulsification effect, thereby improving the reaction selectivity and yield.
Drawings
FIG. 1 is a schematic flow chart of an emulsion-catalyzed synthesis of 3, 4-methylenedioxy-mandelic acid.
Fig. 2 is a schematic diagram of embodiment 3 of the present invention.
Fig. 3 is a schematic diagram of embodiment 4 of the present invention.
Wherein:
1: jacket formula distributor stirred tank, 2: sulfuric acid metering tank, 3: jacket type distributor emulsifying kettle, 4: pepper ring metering tank, 5: constant temperature tank, 6: filtration device, 7: feed pump, 8: gas holder, 9: a filtrate tank; 12: a jacketed distributor product stirred tank;
6-1: primary filtration equipment, 6-2: secondary filtration device, 10-1: first gas flow meter, 10-2: second gas flowmeter, 10-3: third gas flow meter, 11-1: first liquid flow meter, 11-2: second liquid flow meter, 11-3: a third liquid flow meter.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the person skilled in the art better understand the solution of the present invention, the following describes the solution of the present invention with reference to specific embodiments.
Comparative example
1. 100g of piper ring, 10g of water, 160g of 50% glyoxylate and 140g of 98% concentrated sulfuric acid are weighed.
2. 10g of water and 160g of 50% glyoxylate aqueous solution were charged into a jacketed reactor.
3. The jacketed reactor is connected with a constant temperature tank, the temperature of the constant temperature tank is set to be 5 ℃, and the constant temperature tank is operated to cool for more than half an hour until the temperature of liquid in the jacket reaches 5 ℃.
4. The electric stirrer is connected, and the plastic stirring blade is used for stirring the liquid in the jacketed reactor, and the rotating speed is 400r/min
5. 140g of concentrated sulfuric acid is dropwise added at a constant speed by using a constant pressure funnel, the speed is controlled at 7g/min, and stirring is continued for 30min after the addition. Obtaining the mixed acid.
6. The mixed acid accounting for 70 percent of the total mass of the mixed acid is removed from the jacketed reactor and refrigerated at 5 ℃.
7. 30g of piper nigrum was added dropwise at a constant speed to the jacketed reactor with a constant pressure funnel, the speed being controlled at 3g/min. After the completion of the dropwise addition, stirring was continued for 30 minutes.
8. 70% of the mixed acid removed in step 6 (dropping time: 1 h) and 70g of piper-ring (dropping time: 0.5 h) were dropped into the jacketed reactor at a constant speed by means of a constant pressure funnel.
9. After the dripping is finished, the speed of the stirring equipment is regulated to 500r/min, and the stirring reaction is continued for 35min
10. 200mL of water was added to the jacketed reactor to terminate the reaction.
11. Filtering with 1L filter flask to obtain solid, weighing, drying, and detecting by liquid chromatography.
12. The yield was 71.42%, purity 68.54% and total yield 44.64%.
Example 1
The method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by emulsion catalysis is carried out according to the following steps:
step 1, stirring a mixture of 10g of water and 160g of 50wt% glyoxylate solution at a constant temperature, wherein the constant stirring temperature is-25 ℃, and the stirring speed is 400rpm;
step 3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 25 ℃;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 5 ℃, the stirring speed is 500rpm, and the stirring time is 30min;
step 8, adding 200ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the process of the steps 1 to 7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The purity of the product is 97.60% and the total yield is 91.50%.
Example 2
The method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by emulsion catalysis is carried out according to the following steps:
step 1, stirring a mixture of 10g of water and 200g of 50wt% glyoxylate solution at a constant temperature, wherein the constant temperature stirring temperature is minus 30 ℃, and the stirring speed is 430rpm;
step 3, continuously stirring for 30min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 28 ℃;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 5 ℃, the stirring speed is 600rpm, and the stirring time is 30min;
step 8, adding 200ml of water into the solution after the step 7 is finished, and stopping the reaction to obtain a product;
the process of the steps 1 to 7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 2.5L/min, and the adopted air blowing medium is nitrogen.
The detected purity is 97.53 percent and the total yield is 91.43 percent.
Example 3
The device for emulsifying and catalyzing to synthesize 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor stirred tank, a pepper ring metering tank, a constant temperature tank, a filtering device, a charging pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, a flowmeter is arranged at an outlet pipe of the sulfuric acid metering tank, a circulating liquid outlet of the constant temperature tank is respectively connected with a jacket inlet of the jacketed distributor stirred tank, a jacket inlet of the jacketed distributor stirred tank and a jacket inlet of the jacketed distributor stirred tank, the circulating liquid inlet of the constant temperature tank is respectively connected with a jacket outlet of the jacketed distributor stirred tank, a jacket outlet of the jacketed distributor stirred tank and a jacket outlet of the jacketed distributor stirred tank, the outlet of the jacketed distributor stirred tank is connected with an inlet pipeline of the charging pump, the outlet of the pepper ring metering tank is connected with a jacket distributor emulsified tank pipeline, and the inlet of the gas storage tank is respectively connected with the inlet of the jacket distributor stirred tank, and the inlet of the gas storage tank is connected with the jacket inlet of the gas storage tank. The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle are respectively provided with a liquid flowmeter. Gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle. And 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle. And temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
Example 4
The device for emulsifying and catalyzing to synthesize 3, 4-methylenedioxy-phenylglycolic acid comprises a jacketed distributor stirred tank, a sulfuric acid metering tank, a jacketed distributor stirred tank, a pepper ring metering tank, a constant temperature tank, a two-stage filtering device, a charging pump, a gas storage tank and a filtrate tank, wherein the outlet of the sulfuric acid metering tank is connected with a jacketed distributor stirred tank pipeline, a flowmeter is arranged at an outlet pipe of the sulfuric acid metering tank, a circulating liquid outlet of the constant temperature tank is respectively connected with the inlet of the jacketed distributor stirred tank, the inlet of the jacketed distributor stirred tank is connected with the inlet of the jacketed distributor stirred tank, the inlet of the constant temperature tank is respectively connected with the outlet of the jacketed distributor stirred tank, the outlet of the jacketed distributor stirred tank is connected with the inlet of the gas storage tank, the outlet of the pumped distributor stirred tank is connected with the inlet of the gas storage tank, the inlet of the gas storage tank is connected with the inlet of the gas storage tank, and the liquid phase outlet of the secondary filtering equipment is connected with the inlet of the filtrate tank. The jacket inlet pipe of the jacket type distributor stirring kettle, the jacket inlet pipe of the jacket type distributor emulsifying kettle and the jacket inlet pipe of the jacket type distributor product stirring kettle are respectively provided with a liquid flowmeter. Gas flow meters are arranged on the gas distribution pipe inlet pipe of the jacketed distributor stirring kettle, the gas distribution pipe inlet pipe of the jacketed distributor emulsifying kettle and the gas distribution pipe inlet pipe of the jacketed distributor product stirring kettle. And 2 sets of emulsifying devices and wall scraping stirring devices are arranged on the jacketed distributor emulsifying kettle. And temperature detection instruments are arranged on the jacketed distributor stirring kettle and the jacketed distributor emulsifying kettle.
The primary filter equipment and the secondary filter equipment adopt filter media with different precision, the pore diameter of the filter media adopted on the primary filter equipment is larger, products with larger granularity in a product system can be filtered out, filtrate enters the secondary filter equipment, the pore diameter of the filter media adopted by the secondary filter equipment is smaller, 3, 4-methylenedioxy-phenylglycolic acid which is a final product with smaller granularity can be filtered out, and the product recovery is more sufficient.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (9)
1. A method for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by emulsion catalysis, which is characterized by comprising the following steps:
step 1, the mass ratio is 1: stirring 15-20 parts of water and 50wt% of glyoxylate water solution at a constant temperature, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 20 ℃, and the stirring speed is 350 rpm-450 rpm;
step 2, after stirring is started, 98 weight percent of concentrated sulfuric acid is dropwise added to the mixture, wherein the dropwise adding amount per minute is 0.03-0.1 time of the mass of the mixture, and the ratio of the total 98 weight percent of concentrated sulfuric acid to the mass of water in the step 1 is 12-15: 1, stirring at a temperature of-30 ℃ to-20 ℃;
step 3, continuously stirring for 20-40 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 20 ℃;
step 4, adding 3, 4-methylenedioxy-phenylglycol acid and benzyl triethyl ammonium chloride into the solution after the completion of the step 3, wherein the ratio of the amount of the added 3, 4-methylenedioxy-phenylglycol acid to the mass of the water in the step 1 is 0.1-1: 1, the ratio of the added quantity of the benzyl triethyl ammonium chloride to the water mass in the step 1 is 0.5-1.5: 1, a step of;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 10-15 Kr/min, simultaneously dripping piper ring in the emulsifying process, wherein the dripping amount per minute is 0.1-1 times of the water mass in the step 1, and the emulsifying time is 3-10 min;
step 6, repeating the step 5 for a plurality of times, wherein the interval between each time is 3-10 min, and the ratio of the total added piper ring to the water mass in the step 1 is 10-15: 1, a step of;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, and the stirring time is 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition amount of the stop solution to the water mass in the step 1 is 15-30: 1, terminating the reaction to obtain a product; the added stop solution is water;
the process of step 1 to step 7 also comprises a process of blowing air into the solution, wherein the air blowing amount per minute is 7-20 times of the volume of the mixture.
2. The method for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsion catalysis according to claim 1, wherein in the step 1, the mass ratio is 1: the mixture of 15-17 parts of water and 50wt% of glyoxylate water is stirred at constant temperature, wherein the constant temperature stirring temperature is minus 28 ℃ to minus 23 ℃, and the stirring speed is 380 rpm-420 rpm.
3. The method for the emulsion-catalyzed synthesis of 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 4, the ratio of the amount of 3, 4-methylenedioxy-mandelic acid added to the water mass is 0.1 to 0.4:1.
4. the method for synthesizing 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 4, the ratio of the amount of added benzyltriethylammonium chloride to the water mass in the step 1 is 0.8 to 1.2:1.
5. the method for synthesizing 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 5, the emulsifying speed is 10-12 Kr/min, the pepper ring is added dropwise at the same time during the emulsifying, the adding amount per minute is 0.5-0.8 times of the water mass, and the emulsifying time is 5-10 min.
6. The method for synthesizing 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 6, the step 5 is repeated 3 to 8 times, each time at intervals of 3 to 10 minutes, and the ratio of the total amount of added piper rings to the water mass is 10 to 12:1.
7. the method for synthesizing 3, 4-methylenedioxy-mandelic acid according to claim 1, wherein in the step 8, the added stop solution is water, and the ratio of the total added stop solution to the water in the step 1 is 15-25: 1.
8. the method for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsion catalysis according to claim 1, wherein the method comprises the following steps:
step 1, the mass ratio is 1: stirring the mixture of 14-16 parts of water and 50wt% of glyoxylate water at a constant temperature, wherein the constant temperature stirring temperature is minus 30 ℃ to minus 25 ℃ and the stirring speed is 400rpm;
step 2, after stirring is started, 98 weight percent of concentrated sulfuric acid is dropwise added into the mixture, wherein the dropwise adding amount per minute is 0.03-0.07 time of the mass of the mixture, and the mass ratio of the total 98 weight percent of concentrated sulfuric acid to the water in the step 1 is 12-14: 1, stirring at a temperature of-30 ℃ to-20 ℃;
step 3, continuously stirring for 20-30 min after all the 98wt% concentrated sulfuric acid is added dropwise, wherein the stirring temperature is minus 30 ℃ to minus 25 ℃;
step 4, adding 3, 4-methylenedioxy-phenylglycol acid and benzyl triethyl ammonium chloride into the solution after the step 3 is finished, wherein the mass ratio of the added 3, 4-methylenedioxy-phenylglycol acid to the water in the step 1 is 0.3-0.4: 1, the mass ratio of the added amount of the benzyl triethyl ammonium chloride to the water in the step 1 is 0.8-1: 1, a step of;
step 5, emulsifying the solution after the step 4, wherein the emulsifying speed is 11-12 Kr/min, simultaneously dropwise adding a piper ring in the emulsifying process, wherein the dropwise adding amount per minute is 0.5-0.6 time of the water mass in the step 1, and the emulsifying time is 3-5 min;
step 6, repeating the step 5 for a plurality of times, wherein the interval between each time is 3-10 min, and the mass ratio of the total amount of the added piper ring to the water in the step 1 is 10-11: 1, a step of;
step 7, stirring the solution after the step 6 at a constant temperature, wherein the stirring temperature is 0-10 ℃, the stirring speed is 400-600 rpm, and the stirring time is 20-40 min;
step 8, adding a stop solution into the solution after the step 7 is finished, wherein the ratio of the total addition amount of the stop solution to the water mass in the step 1 is 15-20: 1, terminating the reaction to obtain a product; the added stop solution is water;
the process of step 1 to step 7 also comprises the process of blowing air into the solution, wherein the air blowing amount per minute is 12-20 times of the volume of the mixture.
9. The method for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsion-catalyzed synthesis according to any one of claims 1 to 8, wherein the air-blowing medium used in the air-blowing process is nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726511.XA CN110684010B (en) | 2018-07-04 | 2018-07-04 | Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726511.XA CN110684010B (en) | 2018-07-04 | 2018-07-04 | Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110684010A CN110684010A (en) | 2020-01-14 |
| CN110684010B true CN110684010B (en) | 2023-06-23 |
Family
ID=69106817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810726511.XA Active CN110684010B (en) | 2018-07-04 | 2018-07-04 | Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110684010B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190583A (en) * | 1977-12-07 | 1980-02-26 | Haarmann & Reimer Gmbh | Process for the preparation of 3,4-methylenedioxymandelic acid |
| JPH07330755A (en) * | 1994-06-07 | 1995-12-19 | Ube Ind Ltd | Production of piperonal |
| CN105693688A (en) * | 2016-04-01 | 2016-06-22 | 衢州信步化工科技有限公司 | Reaction treatment method of heliotropin intermediate 3,4-dioxymethylene mandelic acid |
-
2018
- 2018-07-04 CN CN201810726511.XA patent/CN110684010B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190583A (en) * | 1977-12-07 | 1980-02-26 | Haarmann & Reimer Gmbh | Process for the preparation of 3,4-methylenedioxymandelic acid |
| JPH07330755A (en) * | 1994-06-07 | 1995-12-19 | Ube Ind Ltd | Production of piperonal |
| CN105693688A (en) * | 2016-04-01 | 2016-06-22 | 衢州信步化工科技有限公司 | Reaction treatment method of heliotropin intermediate 3,4-dioxymethylene mandelic acid |
Non-Patent Citations (1)
| Title |
|---|
| 单绍军 ; 杜振媚 ; .3,4-亚甲二氧基苯乙醇酸的合成研究.安徽化工.(第02期),第46页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110684010A (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201249783A (en) | Ammoximation reactor for cyclohexanone oxime production | |
| CN106800512B (en) | A kind of preparation method and preparation facilities of 3,5- dinitro o methyl benzoic acid | |
| CN107074789A (en) | Method for preparing benzoxazine | |
| CN113307766B (en) | Method for synthesizing pyridine compound by using microchannel reaction device | |
| CN110684010B (en) | Method and device for synthesizing 3, 4-methylenedioxy-mandelic acid by emulsification catalysis | |
| JP2003504193A (en) | Multistage reactor, its use and method for producing hydrogen peroxide | |
| CN110862369B (en) | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification | |
| CN208414296U (en) | A kind of device of Centrifugical extraction synthesis 3,4- methylene-dioxy mandelic acid | |
| CN105949118A (en) | Preparation method of 2-aryl quinoline derivatives | |
| CN106040108A (en) | Gas-liquid-solid three-phase reactor and method for synthesizing glyphosate through continuous catalytic oxidation | |
| CN110684008B (en) | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process | |
| CN108586250A (en) | A kind of sodium stearyl fumarate auxiliary material and preparation method thereof | |
| CN104250219B (en) | A kind of production method of tert-butyl acrylamide sulfonate | |
| CN110862370B (en) | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing emulsification | |
| CN208632422U (en) | It is a kind of to emulsify the device for catalyzing and synthesizing 3,4- methylene-dioxy mandelic acid | |
| CN208776620U (en) | A kind of device improving emulsification synthesis 3,4- methylene-dioxy mandelic acid | |
| CN208632423U (en) | A kind of device of emulsifying process synthesis 3,4- methylene-dioxy mandelic acid | |
| CN106496538A (en) | A kind of synthetic method of high molecular polycaprolactone | |
| CN104370875B (en) | A kind of preparation method of Ethyl vanillin 1,2- propylene glycol acetals | |
| CN208776619U (en) | A kind of device of enhancing emulsification synthesis 3,4- methylene-dioxy mandelic acid | |
| CN110684009B (en) | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by centrifugal extraction | |
| CN104262197A (en) | Synthesis method of 1-cyclohexenylacetonitrile | |
| Zhang et al. | Preparation of p-hydroxybenzaldehyde by hydrolysis of diazonium salts using rotating packed bed | |
| CN107311829A (en) | The synthetic method of fragrant second aldehyde compound | |
| CN106279114B (en) | A kind of synthetic method of Taladegib |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |