CN113683526B - Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor - Google Patents
Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor Download PDFInfo
- Publication number
- CN113683526B CN113683526B CN202110923794.9A CN202110923794A CN113683526B CN 113683526 B CN113683526 B CN 113683526B CN 202110923794 A CN202110923794 A CN 202110923794A CN 113683526 B CN113683526 B CN 113683526B
- Authority
- CN
- China
- Prior art keywords
- chloro
- packed bed
- nitroaniline
- bed reactor
- reaction
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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 belongs to the field of chemical synthesis, and relates to a method for preparing parachloroo-nitroacetanilide by using a packed bed reactor, which comprises the following specific steps: after dissolving p-chloro-o-nitroaniline by toluene, adding diketene into a reaction system, and uniformly stirring for standby; pumping the reaction liquid into a packed bed reactor filled with a solid acid catalyst from the upper end at a constant flow rate through a pump, and allowing the reaction liquid to flow out from the bottom and enter a reaction liquid collector; and after the detection is qualified, removing most of the solvent under negative pressure, cooling, crystallizing, and performing suction filtration and drying to obtain a product. Compared with the prior art, the invention can realize the repeated use of the catalyst due to the use of the acid cation exchange resin catalyst, thereby achieving continuous production; meanwhile, the catalyst has large specific surface area and high catalytic activity, so that the reaction period is shortened, the impurity control is facilitated, the product purity is high (98%), and the yield is high (98%).
Description
Technical Field
The invention relates to the field of chemical synthesis, and in particular provides a method for preparing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor.
Background
Quizalofop-p-ethyl is also called quizalofop-p-ethyl, leisure hoe. Is an improved product after the removal of the inactive optical isomer (L-isomer) during the synthesis of quizalofop-p-ethyl. Quizalofop-p-ethyl is a novel dry land stem and leaf treating agent with high selectivity, has high selectivity between gramineous weeds and dicotyledonous crops, and has good control effect on gramineous weeds in broadleaf crop fields.
Para-chloro-ortho-nitroacetoacetanilide, chinese aliases are acetoacetyl-para-chloro-ortho-nitroaniline, N- (4-chloro-2-nitrophenyl) -3-oxo-butyramide. The p-chloro-o-nitroacetanilide is an intermediate for synthesizing quizalofop-p-ethyl, the main raw materials for synthesizing the p-chloro-o-nitroacetanilide at present are p-chloro-o-nitroaniline and diketene, and the reaction equation is as follows:
reaction mechanism:
the relatively mature route for synthesizing the parachloroo-nitroacetoacetanilide mainly comprises the following steps: on one hand, the diketopentanitroaniline is easy to undergo self-polymerization reaction in an alkaline environment, the requirements on workshop equipment and reaction conditions are high, the production safety is poor, impurities in the product are large, and the purity of the product is low; on the other hand, the catalyst is difficult to recycle and has high production cost. The applicant has proposed to replace diketene with a raw material with low toxicity and high safety to prepare the p-chloro-o-nitroacetanilide, but as diketene is still the most commonly used raw material in the prior art, how to improve the preparation method using diketene as the raw material is still the research direction in the field, and how to provide a synthetic method of p-chloro-o-nitroacetanilide with simple operation, high production safety, low cost, high purity and high yield based on the research direction is a problem to be solved urgently.
Disclosure of Invention
Aiming at a plurality of problems existing in the technology, the invention provides a method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor, which comprises the following steps of filling an acidic cation exchange resin catalyst in a packed bed, introducing a reaction solution into the packed bed at a certain flow rate, and realizing catalytic reaction and substance transfer under a certain reaction condition, wherein the method comprises the following more specific reaction steps: dissolving p-chloro-o-nitroaniline with toluene, adding diketene into the system, and uniformly stirring for later use; pumping the reaction liquid into a packed bed reactor filled with a solid acid catalyst from the upper end at a constant flow rate through a pump, and allowing the reaction liquid to flow out from the bottom and enter a reaction liquid collector; and after the detection is qualified, removing most of the solvent under negative pressure, cooling, crystallizing, and performing suction filtration and drying to obtain a product. Compared with the prior art, the invention can realize the repeated use of the catalyst due to the use of the acid cation exchange resin catalyst, thereby achieving continuous production; meanwhile, the catalyst has large specific surface area and high catalytic activity, so that the reaction period is shortened, the impurity control is facilitated, the product purity is high (98%), and the yield is high (98%).
The specific technical scheme of the invention is as follows:
a method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
firstly, dissolving p-chloro-o-nitroaniline with toluene, adding diketene into a reaction system, and uniformly stirring for later use; pumping the reaction liquid into a packed bed reactor filled with a solid acid catalyst from the upper end at a constant flow rate through a pump, and allowing the reaction liquid to flow out from the bottom and enter a reaction liquid collector;
detecting that residual p-chloro-o-nitroaniline raw materials in the reaction system are less than or equal to 1%, removing most of solvent under negative pressure, cooling, crystallizing, performing suction filtration, drying to obtain a product, and if the detection is unqualified, circularly pumping the reaction liquid into a packed bed until the reaction tracking is qualified;
wherein the mass fraction of the p-chloro-o-nitroaniline toluene solution is 15-40%, preferably 25%;
the mol ratio of the p-chloro-o-nitroaniline to the diketene is 1:1.0-1.5, and the preferable mol ratio is 1:1.15.
The solid acid catalyst is as follows: acidic cation exchange resin (strong acid cation exchange resin, weak acid cation exchange resin), super strong solid acid (C-SO) 3 H、SO 4 2- /ZrO 2 /TiO 2 /Fe 3 O 4 、SO 4 2- /ZrO 2 /Fe 3 O 4 、SO 3 H-PGMA-(Fe 3 O 4 -OA)), hydrogen zeolite molecular sieve (hydrogen ZSM-5 zeolite), acid clay (kaolin, bentonite); preferably a strongly acidic cation exchange resin, more specifically may be selected from D001 macroporous strongly acidic resins or Na 732 cation exchange resins (national pharmaceutical chemicals limited), most preferably Na 732 cation exchange resins are used.
H in the p-chloro-o-nitroaniline and the solid acid catalyst + The molar ratio of (2) is 1:0.1-0.2, preferably 1:0.14. The amount of the charged acidic cation exchange resin in the packed bed reactor is converted based on the molar ratio, and the above requirements are satisfied, wherein one technical scheme that can be implemented is to calculate the molar amount of hydrogen ions contained in 1g of resin according to an acid-base titration method, and then weigh out the corresponding weight of the acidic cation exchange resin to be charged into the packed bed according to the amount of hydrogen ions actually required by the above-defined reaction.
The total feeding speed of the pump is 10-40mL/min, the preferable feeding speed is 25mL/min, and the pump can be one of a peristaltic pump, a constant-flow plunger pump and a high-pressure constant-flow double-plunger pump.
The reaction temperature of the packed bed reactor is 50-100 ℃, and the preferable reaction temperature is 80 ℃.
The temperature reduction crystallization temperature is 0-15 ℃, the preferred crystallization temperature is 0-5 ℃, and then suction filtration and drying are carried out.
Introducing external circulating water into the jacket during the reaction, thereby controlling the reaction temperature;
circularly applying the mother solution obtained by suction filtration until the content of the finally obtained product is lower than 98%, and stopping applying; the mother liquor is used for 1-9 times, and the preferable application time is 8 times; and simultaneously, repeatedly using the resin catalyst until the residual p-chloro-o-nitroaniline in the tracking reaction liquid is more than 1%, and stopping the repeated use of the resin catalyst.
Compared with the prior art, the invention has the main advantages that:
the resin solid catalyst used in the invention has high catalyst load per unit volume and high catalytic efficiency, and simultaneously has extremely high reaction mass transfer efficiency due to the adsorption effect of the resin, so that the reaction time is greatly reduced, the reaction efficiency and the product selectivity are obviously improved, the side reaction and the waste of raw materials are reduced, and the product yield and quality are greatly improved.
Secondly, the acid cation exchange resin packed bed reactor is used, so that the influence caused by mechanical stirring can be avoided, and the use stability of the catalyst is improved.
In conclusion, the method is simple and safe to operate, has little environmental pollution, has the content of more than 98 percent and the yield of more than 98 percent, and is far superior to the traditional synthesis method, thereby obtaining good technical effects.
Drawings
FIG. 1 is a schematic diagram of the preparation process according to the present invention.
Detailed Description
The above-described aspects of the present invention will be described in further detail by way of the following embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples. All techniques realized based on the above description of the present invention are within the scope of the present invention, and the following examples are accomplished by conventional techniques unless otherwise specified.
Example 1
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.5 of the p-chloro-o-nitroaniline to diketene, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to H in p-chloro-o-nitroaniline and hydrogen ZSM-5 zeolite + Filling hydrogen ZSM-5 zeolite molecular sieve into the packed bed according to the molar ratio of 1:0.2;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) Detecting the reaction liquid collected in the collector, and tracking the residual 31.0% of the p-chloro-o-nitroaniline raw material; the hydrogen-type ZSM-5 zeolite has unsatisfactory catalytic effect.
Example 2
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.5 of the p-chloro-o-nitroaniline to diketene, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to H in p-chloro-o-nitroaniline and acid clay kaolin + Filling an acidic clay kaolin catalyst into the packed bed according to the molar ratio of 1:0.2;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) The reaction liquid collected in the detection collector tracks 97.0% of the p-chloro-o-nitroaniline raw material, the acid clay kaolin has poor catalytic effect, and the raw material conversion rate is very low.
Example 3
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.5 of the p-chloro-o-nitroaniline to diketene, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling the D001 acidic cation exchange resin into a packed bed according to the molar ratio of 1:0.14;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) The reaction solution collected in the collector was detected, and the residual amount of the p-chloro-o-nitroaniline raw material was tracked to 7.0%. Compared with hydrogen-type ZSM-5 zeolite and acid clay kaolin, the D001 acid cation exchange resin is used as a catalyst, and has very remarkable improvement.
Example 4
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.0, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling Na 732 acidic cation exchange resin into the packed bed according to the molar ratio of 1:0.2;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) Detecting the reaction liquid collected in the collector, tracking the residual 4.2% of the p-chloro-o-nitroaniline raw material, removing two thirds of the solvent under negative pressure, cooling to 10-15 ℃ by using an ice water bath, maintaining for 30min, and detecting the content of the p-chloro-o-nitroacetanilide to be 97.4% after cold suction filtration and drying, wherein the yield is 93.4%. When Na 732 acid cation exchange resin is used as a catalyst, the residual amount of raw materials is as low as 4.2 percent, and the content of target products is as high as 97.4 percent, so that the catalyst can be industrially applied.
Example 5
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) Preparing 25% of p-chloro-o-nitroaniline toluene solution 250g, adding diketene into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.15 of the p-chloro-o-nitroaniline to diketene, stirring and heating until the solid is completely dissolved to obtain a reaction solution, wherein the temperature of the heating process is controlled below 50 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling Na 732 acidic cation exchange resin into the packed bed according to the molar ratio of 1:0.2;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to be 50 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow speed of 10ml/min so as to enable the reaction liquid to react in the reactor;
(3) The reaction liquid collected in the collector is detected, the residual content of the p-chloro-o-nitroaniline raw material is 15.1%, and the reaction rate is slower when the reaction temperature is too low through the verification of the example.
Example 6
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) Preparing 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 40%, adding diketene into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.3, stirring and heating until the solid is completely dissolved to obtain a reaction solution, wherein the temperature in the heating process is controlled below 85 ℃; according to the P-chloro-o-nitroaniline and H in the resin + The molar ratio of 1:0.1, the Na 732 acid cation exchange resin is filled in the packed bed;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to be 85 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 15ml/min so as to enable the reaction liquid to react in the reactor;
(3) Detecting the reaction liquid collected in the collector, tracking 3.0% of the residual para-chloro-o-nitroaniline raw material, removing two thirds of the solvent under negative pressure, cooling to 5-10 ℃ by using an ice water bath, maintaining for 20min, and detecting 98.3% of the para-chloro-o-nitroacetanilide content after cold suction filtration and drying, wherein the yield is 94.2%.
Example 7
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) Preparing 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 15%, adding diketene into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.5, stirring and heating until the solid is completely dissolved to obtain a reaction solution, wherein the temperature in the heating process is controlled below 70 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling Na 732 acidic cation exchange resin into the packed bed according to the molar ratio of 1:0.2;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to be 70 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 15ml/min so as to enable the reaction liquid to react in the reactor;
(3) And (3) detecting the reaction liquid collected in the collector, removing two thirds of the solvent under negative pressure after the reaction liquid is qualified by tracking, cooling to 0-5 ℃ by using an ice water bath, keeping for 10min, and detecting the content of the parachloroo-nitroacetoacetanilide to be 98.2% and the yield to be 93.2% after cold suction filtration and drying.
Example 8
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.15, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling Na 732 acidic cation exchange resin into the packed bed according to the molar ratio of 1:0.14;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to be 100 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 40ml/min so as to enable the reaction liquid to react in the reactor;
(3) And detecting the reaction liquid collected in the collector, removing two thirds of the solvent under negative pressure after tracking is qualified, cooling to 0-5 ℃ by using an ice water bath, maintaining for 20min, and detecting the content of the parachloroo-nitroacetoacetanilide to be 97.8% and the yield to be 92.1% after cold suction filtration and drying.
The above examples prove that the catalytic effect of the acid resin catalyst is obviously better than that of hydrogen ZSM-5 zeolite and acid clay kaolin, and the catalytic effect of Na-type acid resin in the acid resin catalyst is optimal;
in addition, the reaction temperature, the raw material ratio, the feeding speed, the usage amount of the solid catalyst and the like have obvious influence on the reaction.
From the above examples, the inventors determined the best preparation process as in example 9 below.
Example 9
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.15, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + Filling Na 732 acidic cation exchange resin into the packed bed according to the molar ratio of 1:0.14;
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) And detecting the reaction liquid collected in the collector, removing two thirds of the solvent under negative pressure after tracking is qualified, cooling to 0-5 ℃ by using an ice water bath, keeping for 10min, and detecting the content of the parachloroo-nitroacetoacetanilide to be 99.2% and the yield to be 96.4% after cold suction filtration and drying.
The example shows that under the reaction condition, the product content is high, and the yield is high; this reaction condition will be used as the preferred condition for the mother liquor jacket verification and the resin catalyst continuous use verification in the two subsequent examples.
Example 10
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) Preparing 250g of p-chloro-o-nitroaniline toluene (mother liquor of example 9 is continuously applied for 8 times, and the rest is complemented by toluene), adding diketene into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.15, stirring and heating until the solid is completely dissolved to obtain a reaction solution, wherein the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + The molar ratio is 1:0.14, and the Na 732 acid cation exchange resin is filled in the packed bed (3 times of continuous use);
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) And (3) detecting the reaction liquid collected in the collector, removing two thirds of the solvent under negative pressure after the reaction liquid is qualified by tracking, cooling to 0-5 ℃ by using an ice water bath, maintaining for 10min, performing cold suction filtration, drying, and detecting the content of the parachloroo-nitroacetoacetanilide with the yield of 98.9%.
The example proves that the mother liquor is applied for 8 times, the content of the parachloroo-nitroacetoacetanilide is still higher than 98 percent, and the product content is lower than 98 percent after 9 times of application.
| Experiment number | Number of mother liquor applications/times | Product content/% | Product yield/% |
| 1 | New throw | 99.2 | 96.4 |
| 2 | 1 | 99 | 100.1 |
| 3 | 2 | 99.1 | 98.2 |
| 4 | 3 | 98.8 | 98.4 |
| 5 | 4 | 98.6 | 99.0 |
| 6 | 5 | 98.6 | 98.7 |
| 7 | 6 | 98.4 | 98.6 |
| 8 | 7 | 98.2 | 98.1 |
| 9 | 8 | 98.1 | 98.9 |
| 10 | 9 | 97.5 | 98.0 |
Example 11
A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor comprises the following specific steps:
(1) 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% is prepared, diketene is added into the p-chloro-o-nitroaniline toluene solution according to the mol ratio of 1:1.15, the mixture is stirred and heated until the solid is completely dissolved to obtain a reaction solution, and the temperature in the heating process is controlled below 80 ℃; according to the P-chloro-o-nitroaniline and H in the resin + The molar ratio is 1:0.14, and the Na 732 acid cation exchange resin is filled in the packed bed (10 times of continuous use);
(2) Starting a heating circulation device, setting the temperature of the packed bed reactor to 80 ℃, and pumping the reaction liquid into the reactor by using a peristaltic pump according to the flow rate of 25ml/min so as to enable the reaction liquid to react in the reactor;
(3) Detecting the reaction liquid collected in the collector, tracking the residual 1.8% of the p-chloro-o-nitroaniline raw material, removing two thirds of the solvent under negative pressure, cooling to 0-5 ℃ by using an ice water bath, keeping for 10min, and detecting the content of the p-chloro-o-nitroacetanilide to be 98.2% after cold suction filtration and drying, wherein the yield is 95.3%.
The example verifies that the acidic resin catalyst is continuously used for 10 times, and after the feed liquid flows through the packed bed for one time, the raw material of the chloro-nitroaniline is remained unqualified, and the catalyst treatment is needed.
Comparative example
The method for preparing the p-chloro-o-nitroacetoacetanilide by the conventional reaction comprises the following specific steps:
(1) Preparing 250g of p-chloro-o-nitroaniline toluene solution with the mass fraction of 25% into a 500mL four-necked flask according to the mol ratio of 1:1.3 of the p-chloro-o-nitroaniline to the diketene, and adding 14% (mol%/p-chloro-o-nitroaniline) hydrochloric acid;
(2) Slowly heating the system to 80 ℃, preserving heat for 2 hours, then carrying out liquid phase tracking detection, and if the detection is unqualified (the residual content of the p-chloro-o-nitroaniline raw material is less than or equal to 1%), continuing the heat preservation reaction;
(3) And after the reaction system is tracked to be qualified, removing two thirds of the solvent under negative pressure, cooling to 0-5 ℃ by using an ice water bath, keeping for 10min, and detecting the content of the parachloroo-nitroacetoacetanilide to be 96.0% after cold suction filtration and drying, wherein the yield is 88.5%.
The verification of the example shows that the conventional kettle-type reaction is used, the product content is low, and the yield is low.
Claims (9)
1. A method for preparing p-chloro-o-nitroacetanilide by using a packed bed reactor is characterized in that: the method comprises the following specific steps:
firstly, dissolving p-chloro-o-nitroaniline with toluene, adding diketene into a reaction system, and uniformly stirring for later use; pumping the reaction liquid into a packed bed reactor filled with a solid acid catalyst from the upper end at a constant flow rate through a pump, and allowing the reaction liquid to flow out from the bottom and enter a reaction liquid collector;
detecting that the residual content of the p-chloro-o-nitroaniline raw material in the reaction system is less than or equal to 1%, removing most of the solvent under negative pressure, cooling, crystallizing, and performing suction filtration and drying to obtain a product; if the detection is unqualified, the reaction liquid is circularly pumped into a packed bed until the reaction tracking is qualified;
wherein the mass fraction of the p-chloro-o-nitroaniline toluene solution is 15-40%;
the mol ratio of the p-chloro-o-nitroaniline to the diketene is 1:1.0-1.5;
the solid acid catalyst is D001 macroporous strong acid resin or Na type 732 cation exchange resin; h in the p-chloro-o-nitroaniline and the solid acid catalyst + The molar ratio of (2) is 1:0.14;
the reaction temperature of the packed bed reactor is 80-100 ℃.
2. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: the mass fraction of the p-chloro-o-nitroaniline toluene solution is 25%; the molar ratio of the p-chloro-o-nitroaniline to the diketene is 1:1.15.
3. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: the reaction temperature of the packed bed reactor is set to be 80 ℃.
4. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: the temperature of the cooling crystallization is 0-15 ℃, and then the filtering and drying are carried out.
5. The method for producing p-chloro-o-nitroacetoacetanilide according to claim 4, wherein: the temperature of the cooling crystallization is 0-5 ℃.
6. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: the pump is one of peristaltic pump, constant-flow plunger pump and high-pressure constant-flow double-plunger pump, and the total feeding speed is 10-40 mL/min.
7. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: the pump used is a peristaltic pump.
8. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 1, wherein: circularly applying the mother solution obtained by suction filtration until the content of the finally obtained product is lower than 98%, and stopping applying; meanwhile, the acid resin catalyst is repeatedly used until the residual quantity of the p-chloro-o-nitroaniline in the tracking reaction liquid is more than 1%, and the repeated use is stopped.
9. The method for producing p-chloro-o-nitroacetoacetanilide by using a packed bed reactor according to claim 8, wherein: the application time of the mother solution is 8 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110923794.9A CN113683526B (en) | 2021-08-13 | 2021-08-13 | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110923794.9A CN113683526B (en) | 2021-08-13 | 2021-08-13 | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113683526A CN113683526A (en) | 2021-11-23 |
| CN113683526B true CN113683526B (en) | 2023-06-30 |
Family
ID=78579541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110923794.9A Active CN113683526B (en) | 2021-08-13 | 2021-08-13 | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113683526B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715896A (en) * | 1951-08-27 | 1954-09-22 | Distillers Co Yeast Ltd | Production of acetoacetic acid amides |
| DE3731912A1 (en) * | 1987-02-25 | 1988-09-08 | Hoechst Ag | METHOD FOR PRODUCING ACETOACETYLARYLAMIDES OR -HETEROARYLAMIDES OF DISABLED AROMATS |
| CN101177404A (en) * | 2007-11-30 | 2008-05-14 | 山东金城医药化工有限公司 | Method for preparing high-purity p-chloro-m-nitroacetoacetanilide |
| CN103408452A (en) * | 2013-08-19 | 2013-11-27 | 江苏隆昌化工有限公司 | Green synthesis process for p-chloro-o-nitroacetoanilide |
| CN107652199A (en) * | 2017-09-21 | 2018-02-02 | 南通醋酸化工股份有限公司 | A kind of preparation method of crystal type N AAAs |
| CN111470995A (en) * | 2020-05-21 | 2020-07-31 | 京博农化科技有限公司 | High-safety synthesis method of p-chloro-o-nitro-acetoacetanilide |
| CN112961069A (en) * | 2021-02-08 | 2021-06-15 | 山东京博生物科技有限公司 | Preparation method of p-chloro-o-nitro-acetoacetanilide |
-
2021
- 2021-08-13 CN CN202110923794.9A patent/CN113683526B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715896A (en) * | 1951-08-27 | 1954-09-22 | Distillers Co Yeast Ltd | Production of acetoacetic acid amides |
| DE3731912A1 (en) * | 1987-02-25 | 1988-09-08 | Hoechst Ag | METHOD FOR PRODUCING ACETOACETYLARYLAMIDES OR -HETEROARYLAMIDES OF DISABLED AROMATS |
| CN101177404A (en) * | 2007-11-30 | 2008-05-14 | 山东金城医药化工有限公司 | Method for preparing high-purity p-chloro-m-nitroacetoacetanilide |
| CN103408452A (en) * | 2013-08-19 | 2013-11-27 | 江苏隆昌化工有限公司 | Green synthesis process for p-chloro-o-nitroacetoanilide |
| CN107652199A (en) * | 2017-09-21 | 2018-02-02 | 南通醋酸化工股份有限公司 | A kind of preparation method of crystal type N AAAs |
| CN111470995A (en) * | 2020-05-21 | 2020-07-31 | 京博农化科技有限公司 | High-safety synthesis method of p-chloro-o-nitro-acetoacetanilide |
| CN112961069A (en) * | 2021-02-08 | 2021-06-15 | 山东京博生物科技有限公司 | Preparation method of p-chloro-o-nitro-acetoacetanilide |
Non-Patent Citations (1)
| Title |
|---|
| 固体酸催化制备乙酰乙酸乙酯的工艺研究;巩新伟;崔广平;高超;葛晓萍;;化工科技;第23卷(第02期);第47-50页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113683526A (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100813368B1 (en) | Method of purifying amino acid | |
| KR101787961B1 (en) | Process for manufacturing succinic acid | |
| NO137188B (en) | VELOVABLE LIFTING DEVICE. | |
| EP2987785B1 (en) | Method for the production of 3-(methylthio)propanal | |
| SU505357A3 (en) | Method for preparing 3-methyl mercaptopropionic aldehyde | |
| JP2006503021A (en) | Method and apparatus for producing formate formate and use thereof | |
| CN104672310A (en) | Preparation method of vancomycin hydrochloride | |
| CN100364947C (en) | Method of continuous and high-yield separating and extracting 1,3-dihydroxypropane from fermentation liquid | |
| CN113683526B (en) | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor | |
| CN110845323A (en) | Preparation method of hydroxylamine formate | |
| CN107445869A (en) | A kind of synthetic method of Metformin hydrochloride | |
| KR20230153332A (en) | Method for Continuous Production of Anhydrosugar Alcohols | |
| US4150241A (en) | Process for the production of pure racemic acid and mesotartaric acid and separation of maleic acid from synthetic tartaric acid | |
| CN100369882C (en) | Technological process of purifying and refining glyoxylic acid | |
| CN103890184A (en) | Method for separating and purifying 1,4-diaminobutane from fermented solution | |
| CN108947870B (en) | Preparation method of bromosartanbiphenyl | |
| CN106892840A (en) | A kind of method of refined para-Phthalonitrile | |
| BR112021001332B1 (en) | PROCESS FOR PREPARING ANILINE OR AN ANILINE CONVERSION PRODUCT | |
| CN111470963A (en) | Method for preparing phenoxyacetic acid and 2, 4-dichlorophenoxyacetic acid | |
| CN106008326A (en) | Synthetic method for hydronopyl pyridine quaternary ammonium salts | |
| CN116410130A (en) | Crystallization and purification process of 2-cyanopyridine | |
| CN115073459A (en) | Continuous flow synthesis method of avibactam sodium intermediate | |
| EP2998285B1 (en) | Extraction of carboxylic acids from a dilute aqueous stream | |
| CN116574071A (en) | Synthesis method of 2, 5-dihydrofuran | |
| DE1543555B2 (en) | Process for the continuous production of cyclic glycol carbonates |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Applicant after: Shandong Jingbo Agrochemical Technology Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Applicant before: JINGBO AGROCHEMICALS TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |