CN111254456B - Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid - Google Patents
Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid Download PDFInfo
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Abstract
本发明属于有机物合成技术领域，具体涉及一种以2‑硝基‑4‑甲砜基甲苯为原料通过直接电解氧化来制备2‑硝基‑4‑甲砜基苯甲酸的方法。本发明中，采用惰性电极，在无隔膜单室电解池中以2‑硝基‑4‑甲砜基甲苯为反应底物，进行连续加料、连续出料的工作方式，于常温常压恒电流条件下进行电解，反应完毕进行萃取、分离纯化，得到纯的2‑硝基‑4‑甲砜基苯甲酸。本发明的方法与传统的化学氧化方法相比，避免了有毒或危险的化学氧化剂、催化剂等的使用，更加经济环保，简单高效，且选择性和收率更高；此外电解液中的水相可循环使用，减少了三废的排放，具有很好的工业前景。
The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing 2-nitro-4-methylsulfonyl benzoic acid by using 2-nitro-4-methylsulfonyltoluene as a raw material through direct electrolytic oxidation. In the present invention, an inert electrode is used, and 2-nitro-4-methylsulfonyl toluene is used as the reaction substrate in a single-chamber electrolytic cell without diaphragm, and the working mode of continuous feeding and continuous discharging is carried out, and the constant current is carried out at normal temperature and normal pressure. The electrolysis is carried out under the conditions, and after the reaction is completed, extraction, separation and purification are carried out to obtain pure 2-nitro-4-methylsulfonylbenzoic acid. Compared with the traditional chemical oxidation method, the method of the invention avoids the use of toxic or dangerous chemical oxidants, catalysts, etc., is more economical, environmentally friendly, simple and efficient, and has higher selectivity and yield; in addition, the water phase in the electrolyte It can be recycled, reduces the discharge of three wastes, and has a good industrial prospect.
Description
Technical Field
The invention belongs to the technical field of organic matter synthesis, and particularly relates to a method for preparing 2-nitro-4-methylsulfonylbenzoic acid by taking 2-nitro-4-methylsulfonyl toluene as a raw material through direct electrolytic oxidation.
Background
2-Nitro-4-methylsulfonylbenzoic acid (2-Nitro-4-methylsulfonylbenzoic acid), NMSBA for short, CAS No.110964-79-9, molecular formula C8H7NO6S, usually white to yellow powdery crystals, melting point 211 and boiling point 497.8 ℃, slightly water-soluble, and soluble in organic solvents such as methanol.
2-nitro-4-methylsulfonylbenzoic acid is an important fine organic intermediate which is widely applied to various fields such as dyes, medicines, pesticides and the like; the main application of the herbicide is to prepare the herbicide mesotrione, and the excellent herbicide is widely applied in the global range. In conclusion, the synthesis thereof is receiving a great deal of attention from researchers.
Because the 2-nitro-4-methylsulfonyl toluene is connected with two strong electron-withdrawing groups, the oxidation difficulty of methyl on an aromatic ring is high, and a strong oxidant and a catalyst are needed to carry out the oxidation reaction. The currently reported methods for preparing 2-nitro-4-methylsulfonylbenzoic acid by oxidizing 2-nitro-4-methylsulfonyltoluene serving as a raw material mainly comprise a chemical oxidation method and an indirect electro-oxidation method.
The traditional chemical oxidation method has the defects of high production cost, large three-waste treatment capacity, strong danger in the operation process, poor product quality and the like.
For example, US 5424481 discloses a nitric acid oxidation process using vanadium pentoxide as a catalyst, which is currently in common use in industry, but the process generates a large amount of three wastes, is difficult to treat, and has serious nitrogen oxide pollution; patent document CN 201610778084 discloses a heavy metal salt oxidizing agent oxidation method, but this method will produce a large amount of metal salt waste water, and the environmental pollution is serious; patent document CN 103787934A, US 5591890 discloses an oxidation method using air, oxygen-enriched air or oxygen as an oxidant in a multi-element catalytic system, but the method needs to be carried out at high temperature and high pressure, has high requirements on equipment, great potential safety hazard and low conversion rate; patent documents CN 104262215A, WO 2007099450a2, CN 102584650a, etc. disclose that the former method prepares 2-nitro-4-methylsulfonylbenzoic acid in the presence of a copper sulfate catalyst by using hydrogen peroxide and concentrated sulfuric acid as oxidants, but the method still cannot avoid the problems of high production cost, low efficiency, poor operation safety, etc.
Although the indirect electrooxidation method solves the problems of multiple unsafe factors, complex post-treatment, poor product quality and the like of the chemical oxidation method, the problem of heavy metal residue cannot be solved, so that the indirect electrooxidation method is limited in use; in addition, the domestic ion exchange membrane technology is not closed, the service life is relatively short, and the energy consumption is larger than that of a diaphragm-free method.
The existing oxidation synthesis method of 2-nitro-4-methylsulfonyl toluene still has the defects of large three-waste amount, difficult treatment, poor selectivity, poor operation condition and safety, high production cost and the like, so that the realization of the simple, high-efficiency, green and environment-friendly preparation process of 2-nitro-4-methylsulfonyl benzoic acid is still a key research point.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for synthesizing 2-nitro-4-methylsulfonylbenzoic acid by direct electrolytic oxidation in a working mode of continuous feeding and continuous discharging, so as to overcome the difficulty in treatment, improve the selectivity, improve the operating conditions and the safety and reduce the cost.
The electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid comprises the following steps:
(1) dissolving a reaction substrate 2-nitro-4-methylsulfonyl toluene in an organic solvent to obtain a mixed solution; preparing supporting electrolyte sulfuric acid into a sulfuric acid solution by using deionized water, and then mixing the mixed solution with the sulfuric acid solution to obtain an electrolyte;
(2) the electrolyte obtained in the step (1) is pumped into a diaphragm-free single-chamber electrolytic cell by a circulating pump, and constant current electrolysis is carried out in a continuous feeding and continuous extracting mode;
(3) after the electrolysis is finished, the electrolyte is extracted, separated and purified to obtain the pure 2-nitro-4-methylsulfonylbenzoic acid.
Preferably, the volume ratio of (1) medium concentrated sulfuric acid to deionized water is 1: 1-1: 6.
(1) in the method, 2-nitro-4-methylsulfonyl toluene is dissolved in an organic solvent to prepare an organic solution with the mass percent of 5-30%.
(1) The organic solvent is at least one of acetonitrile, acetone, dichloromethane, dichloroethane, chloroform and nitrobenzene.
(2) The medium control current density is 200-3000 A.m-2。
(2) The middle anode is made of a polar plate material with high oxygen evolution overpotential;
preferably, the anode is any one of titanium-based lead dioxide, lead and titanium-based platinum;
preferably, the cathode is made of a polar plate material with low hydrogen evolution overpotential;
preferably, the cathode is any one of titanium, lead, nickel and titanium-based platinum.
(2) The temperature of the electrolytic reaction is controlled to be 10-60 ℃.
(3) The organic solvent used for extraction is any one of dichloroethane, dichloromethane, methyl tert-butyl ether and cyclohexane.
(3) After the electrolyte is separated and purified, the water phase can be recycled after extraction and refining.
The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid is characterized by comprising the following steps of (1) dissolving a reaction substrate 2-nitro-4-methylsulfonyltoluene in an organic solvent to obtain an organic solution with the mass percent of 5-30%; preparing sulfuric acid solution from supporting electrolyte sulfuric acid and deionized water according to the volume ratio of 1: 1-1: 6, and mixing the mixed solution and the sulfuric acid solution to obtain electrolyte;
the organic solvent is at least one of acetonitrile, acetone, dichloromethane, dichloroethane, chloroform and nitrobenzene;
(2) the electrolyte is pumped into a diaphragm-free single-chamber electrolytic cell by a circulating pump, and constant current electrolysis is carried out at 10-60 ℃ in a continuous feeding and continuous extracting mode; controlling the current density to 200-3000 A.m-2；
The anode is any one of titanium-based lead dioxide, lead and titanium-based platinum; the cathode is any one of titanium, lead, nickel and titanium-based platinum;
(3) after the electrolysis is finished, extracting, separating and purifying the electrolyte to obtain a pure 2-nitro-4-methylsulfonylbenzoic acid product; the organic solvent used for extraction is any one of dichloroethane, dichloromethane, methyl tert-butyl ether and cyclohexane.
Compared with the prior art, the invention has the following advantages and effects:
(1) the direct electrooxidation method provided by the invention takes electrons as a reagent, realizes the synthesis of 2-nitro-4-methylsulfonylbenzoic acid by the gain and loss of electrons of 2-nitro-4-methylsulfonyltoluene on an electrode, avoids the use of a large amount of strong oxidant, catalyst and the like compared with the existing chemical oxidation method, and reduces the resource waste and environmental pollution; the problems of short service life, high cost, difficult industrialization and the like of the diaphragm in indirect electrooxidation are also solved;
(2) the electrode potential is controlled to make the reaction proceed according to the preset target, thereby greatly improving the selectivity and yield of the product, the purity of the product can reach more than 99 percent, and the current efficiency can reach more than 75 percent.
(3) The harsh conditions of high temperature and high pressure are avoided, the operation is simple, the conditions are mild, stable and efficient, the potential safety hazard is reduced, and the production cost is also reduced; and the water phase can be recycled, so that the environmental protection requirement of the current chemical production process is met.
(4) The continuous feeding and extracting mode can meet the requirement of industrial production, is suitable for industrial scale production and has wide application prospect.
Drawings
FIG. 1 is a schematic flow diagram of a diaphragm-free single-chamber electrolyzer of example 1 of the invention;
in the figure, 1-sulfuric acid solution storage tank, 2-raw material solution storage tank, 3, 4 and 6-electrolyte circulating pump, 5-mixer and 7-diaphragm-free single-chamber electrolytic cell.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and explained below with reference to the specific embodiments and the accompanying drawings.
Example 1
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:3, pumping the concentrated sulfuric acid and the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 10% (mass percentage, the same below) acetone solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, pumping the acetone solution into a raw material solution storage tank 2 by using a pump 4, and pumping the acetone solution and the acetone solution into a mixer 5 for uniform mixing; titanium-based lead dioxide is used as an anode, titanium-based platinum is used as a cathode, and the titanium-based lead dioxide and the titanium-based platinum are respectively connected with the anode and the cathode of a power supply to carry out electrolysis. When the electrolysis starts, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 45 ℃, and the current density is 1000 A.m-2. And after the electrolysis is finished, the circulating pump is stopped, the electrolyte is subjected to extraction, reduced pressure distillation, recrystallization and other purification to obtain a pure product, and the water phase is recycled, so that the yield of the obtained 2-nitro-4-methylsulfonylbenzoic acid is about 92%, the current efficiency is about 74.9%, and the purity can reach about 99.1%.
Example 2
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:1, pumping the concentrated sulfuric acid and water into a sulfuric acid solution storage tank 1 by a pump 3, and taking raw materialsPreparing a 30% dichloromethane solution from the 2-nitro-4-methylsulfonyl toluene according to the process requirements, pumping the dichloromethane solution into a raw material solution storage tank 2 by using a pump 4, and pumping the dichloromethane solution and the raw material solution into a mixer 5 for uniform mixing; lead is used as an anode and titanium is used as a cathode. When the electrolysis starts, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 30 ℃, and the current density is 1000 A.m-2. And after the electrolysis is finished, the circulating pump is stopped, the electrolyte is subjected to extraction, reduced pressure distillation, recrystallization and other purification to obtain a pure product, and the water phase is recycled, so that the yield of the obtained 2-nitro-4-methylsulfonylbenzoic acid is about 90%, the current efficiency is about 81.5%, and the purity can reach about 99.1%.
Example 3
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:6, pumping the concentrated sulfuric acid and the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 10% acetone solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, pumping the acetone solution into a raw material solution storage tank 2 by using a pump 4, and pumping the acetone solution and the raw material into a mixer 5 for uniform mixing; lead is used as an anode and nickel is used as a cathode. When the electrolysis starts, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 60 ℃, and the current density is 1500 A.m-2. And after the electrolysis is finished, the circulating pump is stopped, the electrolyte is subjected to extraction, reduced pressure distillation, recrystallization and other purification to obtain a pure product, the water phase is recycled, the yield of the 2-nitro-4-methylsulfonylbenzoic acid is about 89.3%, the current efficiency is about 70.2%, and the purity can reach about 99.1%.
Example 4
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:4, pumping the concentrated sulfuric acid and the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 20% acetone solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, pumping the acetone solution into a raw material solution storage tank 2 by using a pump 4, and pumping the acetone solution and the raw material into a mixer 5 for uniform mixing; lead is used as an anode and titanium is used as a cathode. When the electrolysis starts, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 10 ℃, and the current density is 800 A.m-2. Stopping the circulating pump after electrolysis, purifying the electrolyte by extraction, reduced pressure distillation, recrystallization and the like to obtain a pure product, recycling the water phase, ensuring that the yield of the 2-nitro-4-methylsulfonylbenzoic acid is about 87.9 percent and the current effect is highThe rate is about 71.4 percent, and the purity can reach about 99.1 percent.
Example 5
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:3, pumping the concentrated sulfuric acid and the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 20% acetonitrile solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, pumping the acetonitrile solution into a raw material solution storage tank 2 by using a pump 4, and pumping the acetonitrile solution and the raw material solution into a mixer 5 for uniform mixing; titanium-based platinum is used as an anode, and titanium is used as a cathode. When the electrolysis starts, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 60 ℃, and the current density is 1000 A.m-2. And after the electrolysis is finished, the circulating pump is stopped, the electrolyte is subjected to extraction, reduced pressure distillation, recrystallization and other purification to obtain a pure product, the water phase is recycled, the yield of the 2-nitro-4-methylsulfonylbenzoic acid is about 85.8 percent, the current efficiency is about 74.5 percent, and the purity can reach about 99.1 percent.
Example 6
Preparing concentrated sulfuric acid and water according to the proportion requirement of 1:2, pumping the concentrated sulfuric acid and the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 10% dichloroethane solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, pumping the dichloroethane solution into a raw material solution storage tank 2 by using a pump 4, and pumping the dichloroethane solution and the water into a mixer 5 for uniform mixing; titanium-based platinum is used as an anode, and nickel is used as a cathode. When the electrolysis is started, the electrolyte in the mixer is pumped into an electrolytic tank 7 through a circulating pump 6 to form a circulating loop, the temperature is controlled at 10 ℃, and the current density is 2000 A.m-2. And after the electrolysis is finished, the circulating pump is stopped, the electrolyte is subjected to extraction, reduced pressure distillation, recrystallization and other purification to obtain a pure product, the water phase is recycled, the yield of the 2-nitro-4-methylsulfonylbenzoic acid is about 80.5%, the current efficiency is about 75.3%, and the purity can reach about 99.1%.
TABLE 1 Performance Table for products of examples 1-6
| Examples | Sulfuric acid concentration/vol% | Raw material concentration/wt% | Electrode material (anode/cathode) | Solvent(s) | Temperature/. degree.C | Current density/A.m-2 | Electrolytic efficiency/%) |
| Example 1 | 25 | 10 | Titanium-based lead dioxide/titanium-based platinum | Acetone (II) | 45 | 1000 | 74.9 |
| Example 2 | 50 | 30 | Lead/titanium | Methylene dichloride | 30 | 1000 | 76.1 |
| Example 3 | 14 | 10 | Lead/nickel | Acetone (II) | 60 | 1500 | 70.2 |
| Example 4 | 20 | 20 | Lead/titanium | Acetone (II) | 10 | 800 | 71.4 |
| Example 5 | 25 | 20 | Titanium-based platinum/titanium | Acetonitrile | 60 | 1000 | 74.5 |
| Example 6 | 33 | 10 | Titanium-based platinum/nickel | Dichloroethane | 10 | 2000 | 75.3 |
Comparative example 1
Adding 45% dilute nitric acid, 70% (mass percentage) sulfuric acid, a raw material and a catalyst vanadium pentoxide into an autoclave, wherein the ratio of the dilute nitric acid to the 2-nitro-4-methylsulfonyl toluene to the sulfuric acid is 2.5:1:0.5:0.008, the vanadium pentoxide is dissolved in the sulfuric acid and then added, and the temperature and the pressure in the autoclave are kept at 140 ℃ and 0.7 MPa. After the reaction is finished, the target product is obtained through cooling crystallization, water washing purification and the like. HPLC analysis found that the product prepared in this example contained 80.2% and the yield was about 84.5%.
Comparative example 2
Mixing concentrated sulfuric acid and 30 mass percent of hydrogen peroxide solution in a ratio of 3:1 uniformly for later use, adding the prepared oxidant, 0.5 percent of copper sulfate aqueous solution and the raw material 2-nitro-4-methylsulfonyl toluene in a ratio (molar ratio) of 7:1:0.03 into a reaction kettle, and controlling the reaction temperature to be 85 ℃. After the reaction is finished, the product is cooled by water, filtered by suction, washed by water and dried to obtain the product 2-nitro-4-methylsulfonylbenzoic acid, and HPLC (high performance liquid chromatography) determination analysis shows that the content of the product prepared in the embodiment is 94.5%, and the yield is about 80.1%.
TABLE 2 product purity and yield for each example
| Examples | Purity/%) | Yield/% |
| Example 1 | 99.1 | 92 |
| Example 2 | 99.1 | 90 |
| Example 3 | 99.1 | 89.3 |
| Example 4 | 99.1 | 87.9 |
| Example 5 | 99.1 | 85.8 |
| Example 6 | 99.1 | 80.5 |
| Comparative example 1 | 80.2 | 84.5 |
| Comparative example 2 | 94.5 | 80.1 |
As can be seen from the comparison of the methods in the above embodiments and comparative examples, the content and yield of the product produced by the conventional chemical oxidation method are significantly lower than those produced by the electrooxidation method of the present invention, and the chemical oxidation method needs to additionally add oxidants such as nitric acid, sulfuric acid, hydrogen peroxide, and the like, and catalysts such as vanadium pentoxide, copper sulfate, etc., and the use of these catalysts not only increases the cost, but also is difficult to solve the problem of three wastes treatment generated in the production process, and does not conform to the concept of environmental protection; compared with the comprehensive performance, the method in the embodiment of the invention is a better choice from the viewpoints of yield, purity and environmental protection and economy.
In addition, the invention uses a single-chamber electrolytic cell and adopts constant current electrolysis, thereby avoiding the use of an ion exchange membrane in indirect electrooxidation and a catalyst in chemical oxidation and reducing the cost; secondly, the organic solvent used in the reaction can be recycled, which is beneficial to realizing atom economy, greatly reduces the production cost, simplifies the operation and is more beneficial to realizing industrial production; most importantly, the electrochemical oxidation method can greatly improve the selectivity of the reaction and reduce the generation of byproducts by controlling the oxidation potential.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (2)
- The electrolytic oxidation synthesis method of the 1.2-nitro-4-methylsulfonylbenzoic acid comprises the following steps:(1) dissolving a reaction substrate 2-nitro-4-methylsulfonyl toluene in an organic solvent to obtain an organic solution with the mass percent of 5-30%; preparing sulfuric acid solution from supporting electrolyte sulfuric acid and deionized water according to the volume ratio of 1: 1-1: 6, and mixing the mixed solution and the sulfuric acid solution to obtain electrolyte;the organic solvent is at least one of acetonitrile, acetone, dichloromethane, dichloroethane, chloroform and nitrobenzene;(2) the electrolyte is pumped into a diaphragm-free single-chamber electrolytic cell by a circulating pump, and constant current electrolysis is carried out at 10-60 ℃ in a continuous feeding and continuous extracting mode; controlling the current density to 200-3000 A.m-2；The anode is any one of titanium-based lead dioxide, lead and titanium-based platinum; the cathode is any one of titanium, lead, nickel and titanium-based platinum;(3) after the electrolysis is finished, extracting, separating and purifying the electrolyte to obtain a pure 2-nitro-4-methylsulfonylbenzoic acid product; the organic solvent used for extraction is any one of dichloroethane, dichloromethane, methyl tert-butyl ether and cyclohexane.
- 2. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the aqueous phase is extracted and purified for recycling after the electrolyte is separated and purified in step (3).
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