CN111254456A - 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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- CN111254456A CN111254456A CN202010244373.9A CN202010244373A CN111254456A CN 111254456 A CN111254456 A CN 111254456A CN 202010244373 A CN202010244373 A CN 202010244373A CN 111254456 A CN111254456 A CN 111254456A
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- QNOUABMNRMROSL-UHFFFAOYSA-N 110964-79-9 Chemical compound CS(=O)(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QNOUABMNRMROSL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- OXBDLEXAVKAJFD-UHFFFAOYSA-N 1-methyl-4-methylsulfonyl-2-nitrobenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1[N+]([O-])=O OXBDLEXAVKAJFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000005086 pumping Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011133 lead Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000003115 supporting electrolyte Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 38
- 239000002994 raw material Substances 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000003860 storage Methods 0.000 description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 238000006056 electrooxidation reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- FSDZFKWCTBMYDV-UHFFFAOYSA-N platinum;propan-2-one Chemical compound [Pt].CC(C)=O FSDZFKWCTBMYDV-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005578 Mesotrione Substances 0.000 description 1
- YRPLMRFOYBZORK-UHFFFAOYSA-N [N+](=O)([O-])C1=C(C(=O)O)C=CC(=C1)S(=O)(=O)C.[N+](=O)([O-])C1=C(C(=O)O)C=CC(=C1)S(=O)(=O)C Chemical compound [N+](=O)([O-])C1=C(C(=O)O)C=CC(=C1)S(=O)(=O)C.[N+](=O)([O-])C1=C(C(=O)O)C=CC(=C1)S(=O)(=O)C YRPLMRFOYBZORK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and the like Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
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. In the invention, inert electrodes are adopted, 2-nitro-4-methylsulfonyl toluene is taken as a reaction substrate in a diaphragm-free single-chamber electrolytic cell, a working mode of continuous feeding and continuous discharging is carried out, electrolysis is carried out under the conditions of normal temperature, normal pressure and constant current, and extraction, separation and purification are carried out after the reaction is finished, so that pure 2-nitro-4-methylsulfonylbenzoic acid is obtained. Compared with the traditional chemical oxidation method, the method avoids the use of toxic or dangerous chemical oxidants, catalysts and the like, is more economic and environment-friendly, simple and efficient, and has higher selectivity and yield; in addition, the water phase in the electrolyte can be recycled, thereby reducing the discharge of three wastes and having 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
Concentrated sulfuric acid and water are prepared according to the proportion requirement of 1:3 and pumped into a sulfuric acid solution storage tank 1 by a pump 3, and the raw material 2-nitro-4-methylsulfonyl toluene is prepared according to the proportion requirementPreparing 10 percent (mass percentage, the same below) acetone solution, pumping the acetone solution into a raw material solution storage tank 2 by a pump 4, and pumping the acetone solution and the raw material 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 the water into a sulfuric acid solution storage tank 1 by using a pump 3, preparing a 30% dichloromethane solution by using a raw material 2-nitro-4-methylsulfonyl toluene according to the process requirement, 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 2 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. Stopping the circulating pump after electrolysis, purifying the electrolyte by extraction, reduced pressure distillation, recrystallization and the like to obtain a pure product, and recycling the water phaseWhen the method is used, 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. 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 87.9 percent, the current efficiency 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 starts, the electrolyte in the mixer passes through a circulating pump6 is injected into an electrolytic tank 7 to form a circulation 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 (10)
- The electrochemical synthesis method of the 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) pumping the electrolyte obtained in the step (1) into a diaphragm-free single-chamber electrolytic cell through a circulating pump, and carrying out constant current electrolysis 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.
- 2. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein (1) the volume ratio of concentrated sulfuric acid to deionized water is 1:1 to 1: 6.
- 3. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein in (1), 2-nitro-4-methylsulfonyltoluene is dissolved in an organic solvent to prepare an organic solution with a mass percentage of 5-30%.
- 4. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the organic solvent in (1) is at least one of acetonitrile, acetone, dichloromethane, dichloroethane, chloroform and nitrobenzene.
- 5. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the current density in (2) is controlled to be 200 to 3000 A.m-2。
- 6. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein (2) the intermediate anode is made of a 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.
- 7. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the electrolytic reaction temperature in (2) is controlled to be 10 to 60 ℃.
- 8. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the organic solvent used in the extraction in (3) is any one of dichloroethane, dichloromethane, methyl tert-butyl ether, and cyclohexane.
- 9. 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).
- 10. The electrolytic oxidation synthesis method of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, comprising 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.
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