CN106496079A - The technique that a kind of Oxygen Catalytic Oxidation produces 2 nitro, 4 thiamphenicol benzoic acid - Google Patents
The technique that a kind of Oxygen Catalytic Oxidation produces 2 nitro, 4 thiamphenicol benzoic acid Download PDFInfo
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- CN106496079A CN106496079A CN201610817189.2A CN201610817189A CN106496079A CN 106496079 A CN106496079 A CN 106496079A CN 201610817189 A CN201610817189 A CN 201610817189A CN 106496079 A CN106496079 A CN 106496079A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C07—ORGANIC CHEMISTRY
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Abstract
The present invention relates to a kind of method for using 2 nitro, 4 methylsulfonyltoluene to produce 2 nitro, 4 thiamphenicol benzoic acid, when tying up to 4 70 atmospheric pressure and 100～250 DEG C, with 2 nitro, 4 methylsulfonyltoluene be raw material, air (oxygen-enriched air or oxygen) be oxidant, in an acidic solution, 2 nitro, 4 methylsulfonyltoluene is oxidized to 2 nitro, 4 thiamphenicol benzoic acid by the multiple catalyzing system constituted with heteropolyacid metal oxycompound halogen.The present invention defect such as big 4 thiamphenicol benzoic acid production method waste gas of existing 2 nitro and waste water yield, seriously corroded, selective low, production cost can be overcome high, reduces environmental pollution, realizes the clean manufacturing of 2 nitro, 4 thiamphenicol benzoic acid.
Description
Technical field
The present invention relates to a kind of technique for producing 2- nitryl-4-thiamphenicol benzoic acids.
Background technology
Mesotrione is a kind of herbicide specially for corn field, with broad weed-killing spectrum, activity is high, miscibilty is strong, toxicity is low,
Environmental friendliness, to succession crop safety, using flexible the advantages of, be a kind of corn field herbicide of wide market.2- nitre
Base -4- methyl sulfonylbenzoic acids are important intermediates of synthesizing methyl sulphur humulone, 2- nitryl-4-thiamphenicol benzoic acids
(NMSBA) also known as adjacent nitro is to thiamphenicol benzoic acid, 2- nitryl-4-thiamphenicol benzoic acids or 4- methylsulfonyl -2- nitrobenzoic acids,
English name is 2-Nitro-4-methylsulfonylbenzoic acid or O-Nitro-P-Methylsulfonyl
Benzoic Acid.Molecular formula is C8H7NO6S, molecular weight are 245.21, are white or light yellow crystalline powder under normal temperature.
2- nitryl-4-thiamphenicol benzoic acids can be obtained by the oxidation of 2- nitro -4- methylsulfonyltoluenes：
2- nitro -4- methylsulfonyltoluenes have two strong electron-withdrawing group group-NO2With-SO2CH3, make the oxidation of methyl on phenyl ring
Extremely difficult.The method for oxidation of 2- nitro -4- methylsulfonyltoluenes can be divided into chemical oxidization method, liquid phase air (oxygen) oxidizing process
Deng.
Sodium dichromate oxidizing process (fine-chemical intermediate, 2005,35 (2)：50-53；CN101921215A, 2010) be with
Sulfuric acid is that solvent, potassium permanganate make catalyst, aoxidizes 2- nitro -4- methylsulfonyltoluenes with strong oxidizer sodium dichromate, 2- nitros -
4- thiamphenicol benzoic acid yields up to 80%, gentle, the simple to operate safety of the method reaction condition, equipment investment is few, but dichromic acid
Salt is expensive, production cost is high, can produce the waste liquid of a large amount of sulfur acids, chromium and manganese, and environmental pollution is serious.
Hydrogen peroxide is Green Oxidant, many document (WO2004058698A1,2004-07-15；
WO2007099450A2,2007-07-09；CN101503383A, 2009；CN102584650A, 2012) report hydrogen peroxide
2- nitro -4- methylsulfonyltoluenes are aoxidized in sulfuric acid, but 2- nitryl-4-thiamphenicol benzoic acid yields are low, and there is peroxidating
Hydrogen consumption is big, production cost is high, the dangerous defect such as big.
The industrial process of 2- nitryl-4-thiamphenicol benzoic acids is in nitration mixture (sulfuric acid and nitric acid) solvent with nitric acid at present
Middle oxidation 2- nitro -4- methylsulfonyltoluenes, report more, such as US 5424481A, 1995-06-13 in the method document；Hebei
Chemical industry, 2005,5:49-50；Hubei agricultural science, 2012,51 (5)：924-926；Zhejiang chemical industry, 2012,43 (1)：12-14；
Zhejiang Polytechnical University's journal, 2009,37 (3)：267-271；CN103073461A,2013.Nitric acid and 2- nitro -4- methylsulfonyl first
Mol ratio of the benzene on stoichiometric equation is 6, and actual production process is far above the value.It is clear that nitric acid oxidation method has many
Defect, such as releases oxides of nitrogen gas, a large amount of acid waste waters of generation, seriously corroded, selective low, production cost high.
Air (oxygen) is a kind of inexpensive, green oxidant, and patent US5591890 proposes to make catalyst with cobalt acetate to exist
Air oxidation 2- nitro -4- methylsulfonyltoluene 2- nitryl-4-thiamphenicol benzoic acids are used in acetic acid；Patent CN102329256A is carried
Go out and catalyst made with methyl alcohol or ethanol as solvent, metalloporphyrin, with air oxidation 2- nitro -4- methylsulfonyltoluene 2- nitros -
4- thiamphenicol benzoic acids.Air (oxygen) oxidation does not consume the chemical oxidizing agent of costliness, does not produce nitrous oxides exhaust gas pollution, but
2- nitro -4- methylsulfonyltoluene conversion ratios are not high, have no that commercial Application is reported.
Content of the invention
It is an object of the invention to provide a kind of produce 2- nitro -4- first using air oxidation 2- nitro -4- methylsulfonyltoluenes
The benzoic method of sulfuryl.
The technical problem to be solved in the invention is to provide one kind 2- nitro -4- methylsulfonyltoluenes production 2- nitro -4-
The method of thiamphenicol benzoic acid, is raw material with 2- nitro -4- methylsulfonyltoluenes, and air (oxygen-enriched air or oxygen) is oxidant,
Acidic aqueous solution makees solvent, in the presence of the multiple catalyzing system that heteropoly acid-metal oxygenate-halide is constituted, by 2-
Nitro -4- methylsulfonyltoluenes are oxidized to 2- nitryl-4-thiamphenicol benzoic acids, overcome nitric acid oxidation method production 2- nitro -4- MSMs
The defect such as yl benzoic acid waste gas and contaminated wastewater are big, seriously corroded, selective low, production cost are high, improves the choosing of target product
Selecting property, reduces environmental pollution, realizes the clean manufacturing of 2- nitryl-4-thiamphenicol benzoic acids.
Idea of the invention is that such：
Heteropoly acid has the advantages that low temperature high activity, high stability, as a kind of multifunction catalyst, homogeneously can urge
Agent, can make heterogeneous catalyst again；Acid catalyst can both be made, can also make oxidation reduction catalyst even phase transfer catalyst.Mirror
There are two strong electron-withdrawing group groups on 2- nitro -4- methylsulfonyltoluenes, the oxidation of methyl is extremely difficult, therefore the present invention intends with miscellaneous
The multiple catalyzing system that polyacid-metal oxygen-containing compound-halide is constituted, using the synergy between multicomponent, reinforcing is urged
Change activity, in acidic aqueous solution, with the gas (air, oxygen-enriched air or oxygen) of molecule-containing keto by 2- nitro -4- methylsulfonyls
Toluene catalytic oxidation is 2- nitryl-4-thiamphenicol benzoic acids.
Heteropoly acid used by the present invention is selected from phosphotungstic acid (H3PWl2O40), silico-tungstic acid (H4SiWl2O40), germanotungstic acid
(H4GeWl2O40), silicomolybdic acid (H4SiMol2O40), germanium molybdic acid (H4GeMol2O40) and phosphomolybdic acid (H3PMol2O40) etc..
Metal oxygen-containing compound used is high price acidic oxide or their corresponding acid or salt, selected from five oxidations two
Vanadium, vanadic acid, vanadate, metavanadic acid, metavanadate, niobium pentaoxide, niobic acid, metaniobate, bismuthic oxide, bismuthic acid, bismuthic acid
Salt etc..
Halide used is selected from four halogen ethane, dihalo- ethane, halogen ethane, hydrogen halides, potassium halide etc., preferably four halogen second
Alkane.Described halogen includes fluorine, chlorine, bromine, iodine.
The present invention is implemented in two steps：
(1) 2- nitros -4- methylsulfonyltoluene catalysis oxidations：By a certain amount of by heteropoly acid, metal oxygen-containing compound, halogenation
The reaction mass of thing and 2- nitro -4- methylsulfonyltoluenes, acid and water composition is put in autoclave, under pressurized nitrogen protection
Temperature of reactor is raised to predetermined value, then is continuously passed through oxygen-containing gas under elevated pressure conditions, by 2- nitro -4- methylsulfonyltoluenes
It is oxidized to 2- nitryl-4-thiamphenicol benzoic acids.
In reactor, the concentration of heteropoly acid is 0.02%～3.0% (quality), and optimum value is 0.08%～1.0% (matter
Amount).
In reactor internal solvent the concentration of metal oxygen-containing compound be 0.005～0.5% (quality), optimum value be 0.01～
0.15% (quality).
In reactor internal solvent, the content of halide is 0.008～0.15% (quality), and optimum value is 0.01～0.05%
(quality).
The present invention is not specially required to 2- nitro -4- methylsulfonyltoluene catalyst oxidation reactors, can be in common bubbling
Carry out in bed, it is recommended that gas/liquid volume flow ratio is 10～100.
The pressure that oxidation reaction is carried out is 4～70 atmospheric pressure, and optimum value is 5～25 atmospheric pressure.
The temperature that oxidation reaction is carried out is 50 DEG C～250 DEG C, and optimum value is 120 DEG C～200 DEG C.
In reactor feed solvent, the concentration of 2- nitros -4- methylsulfonyltoluenes is 2%～55% (quality), and optimum value is
15%～50% (quality).
Reactor inlet gas is air, pure oxygen or oxygen-enriched air, preferably air.
Acidic aqueous solution of the reactor internal solvent for pH0.5-4.5, Optimal pH is 1.0-2.5, and acid used is C1～C6 fat
Aliphatic carboxylic acid, hydrochloric acid or sulfuric acid.
(2) the refined and reactant liquor of 2- nitryl-4-thiamphenicol benzoic acids is circulated：After reaction terminates, temperature lowers, produce
2- nitryl-4-thiamphenicol benzoic acids due to solubility at low temperature very low, can crystalline deposit get off, by filter carry out solid
Liquid is separated.Gained filtrate adds acid to predetermined pH value, adds 2- nitro -4- methylsulfonyltoluenes, is reentered in reactor
Catalysis oxidation is carried out, 2- nitryl-4-thiamphenicol benzoic acids are produced；Gained solids of sedimentation alkali lye is (such as sodium hydroxide solution, carbonic acid
Sodium solution) dissolving, insoluble solid impurity is filtered, gained filtrate is adjusted to pH below 3.0 with sulfuric acid or hydrochloric acid again, crystallizes
The pale yellow precipitate for arriving is refined 2- nitryl-4-thiamphenicol benzoic acids.
The present invention adopt molecular oxygen for oxidant, acidic aqueous solution makees solvent, by heteropoly acid-metal oxygen-containing compound-
Under the polynary gas-liquid catalyst system and catalyzing effect that halide is constituted, 2- nitro -4- methylsulfonyltoluenes are oxidized to 2- nitro -4- methylsulfonyls
Benzoic acid, compares with nitric acid oxidation method, and catalyst, solvent and unreacted raw material can be recycled, and significantly reduces discharging acid
Waste water, reduces cost, and eliminate nitrous oxides exhaust gas pollution, avoid the generation of polynitration thing impurity, improve 2- nitro -4- first
Sulfuryl benzoic acid yield；Compare with other molecular oxygen oxidation methods, with high conversion ratio and selectivity.
Specific embodiment
The present invention is further elaborated with reference to embodiments, but can not limit present disclosure.
Embodiment 1
Test volume for 1000ml stirred autoclave in carry out, plus the dilution heat of sulfuric acid that 680ml pH are 1.5 and
160g 2- nitro -4- methylsulfonyltoluenes, add phosphotungstic acid 1.0g, niobium pentaoxide 0.5g, KI 0.8g, reaction temperature 180
DEG C, pressure 15atm, air mass flow are 1000ml min-1, to react liquid-like liquid-phase chromatographic analysis are taken every 0.5h after starting,
After reaction 2.0h, 2- nitro -4- methylsulfonyltoluenes conversion ratio is up to 92%, 2- nitryl-4-thiamphenicol benzoic acids yield up to 91%.
Reactant liquor is cooled to 5 DEG C, will be precipitated using filter operation and is separated with reactant liquor.
The gained solids of sedimentation sodium hydroxide solution of 400ml l5% (weight) fully dissolves, and filters insoluble solid
Impurity, the filtrate for filtering gained are adjusted to pH 1.0 with sulfuric acid again, and crystalline deposit goes out flaxen 2- nitryl-4-thiamphenicol benzoic acids
161.5 gram.
Gained filtrate, it is 680ml to adjust pH for 1.5, volume with dilute sulfuric acid, adds 160g 2- nitro -4- methylsulfonyl first
Benzene, is reentered in aforesaid reactor, 180 DEG C, pressure 15atm, air mass flow 1000ml min-1Under conditions of, reaction
2.0h, obtains 2- nitro -4- methylsulfonyltoluenes conversion ratio 92%, 2- nitryl-4-thiamphenicol benzoic acid yields with liquid-phase chromatographic analysis
91%.
Embodiment 2
Testing is carried out in reactor of the volume for 600ml, and cocurrent continues through reactor, liquid to gas-liquid two-phase from lower to upper
The flow 5ml/min of body, the flow 1000ml/min of air, in liquid feedstock, 20% (weight of 2- nitro -4- methylsulfonyltoluenes
Amount), phosphomolybdic acid 0.10% (weight), bismuthic oxide 0.08% (weight), KI 0.05% (weight), remaining is pH1.0
Dilute sulfuric acid, 180 DEG C of reaction temperature, pressure 12atm, reactor export liquid liquid-phase chromatographic analysis, 2- nitro -4- methylsulfonyls
It is 91% that toluene conversion is 93%, 2- nitryl-4-thiamphenicol benzoic acids yield.
Embodiment 3
Testing is carried out in stirred autoclave of the volume for 1000ml, plus the aqueous acetic acid 650ml of pH1.6, and 2- nitros-
4- methylsulfonyltoluene 200g, add phosphotungstic acid 0.8g, sodium metavanadate 0.4g, tetrabromoethane 0.5g, 160 DEG C of reaction temperature, pressure
8.0atm, air mass flow are 1000ml min-1, to react and liquid-like liquid-phase chromatographic analysis are taken every 0.5h after starting, react
After 2.0h, 2- nitro -4- methylsulfonyltoluenes conversion ratio is up to 95%, 2- nitryl-4-thiamphenicol benzoic acids yield up to 93%.
Reactant liquor is cooled to 5 DEG C, will be precipitated using filter operation and is separated with reactant liquor.
Methods For Purification of the gained solids of sedimentation as described in embodiment 1, obtains flaxen 2- nitryl-4-thiamphenicol benzoic acids
208.8 gram.
It is that 650ml, pH are 1.6 that gained filtrate adds acetic acid and water to volume, adds 200g 2- nitro -4- methylsulfonyls
Toluene, is reentered in aforesaid reactor, is 1000ml min in 160 DEG C, pressure 8.0atm, air mass flow-1Under conditions of,
Sampling liquid-phase chromatographic analysis, 2- nitro -4- methylsulfonyltoluenes conversion ratio 95% after reaction 2.0h, 2- nitro -4- methylsulfonyl benzene
Carboxylic acid Yield 93%.
Embodiment 4
Testing is carried out in stirred autoclave of the volume for 1000ml, plus pH1.7 dilution heat of sulfuric acid 650ml, 2- nitro -4-
Methylsulfonyltoluene 200g, addition silico-tungstic acid 0.7g, sodium bismuthate 0.6g, hydrogen bromide 0.4g, 170 DEG C of reaction temperature, pressure 9.0atm,
Air mass flow is 1000ml min-1, reaction takes liquid-like liquid-phase chromatographic analysis every 0.5h after starting, after reaction 2.0h, 2-
Nitro -4- methylsulfonyltoluenes conversion ratio is up to 96%, 2- nitryl-4-thiamphenicol benzoic acids yield up to 92%.
Reactant liquor is cooled to 5 DEG C, will be precipitated using filter operation and is separated with reactant liquor.
Methods For Purification of the gained solids of sedimentation as described in embodiment 1, obtains flaxen 2- nitryl-4-thiamphenicol benzoic acids
203.6 gram.
It is that 650ml, pH are 1.7 that gained filtrate adds dilute sulfuric acid and water to volume, adds 200g 2- nitro -4- MSMs
Base toluene, is reentered in aforesaid reactor, is 1000ml min in 170 DEG C, pressure 9.0atm, air mass flow-1Condition
Under, 2.0h is reacted, and 2- nitro -4- methylsulfonyltoluenes conversion ratio 95%, 2- nitro -4- methylsulfonyl benzene first is obtained with liquid-phase chromatographic analysis
Sour yield 92%.
Embodiment 5
Testing is carried out in stirred autoclave of the volume for 1000ml, plus the dilute hydrochloric acid solution 650ml that pH is 0.7,2- nitre
Base -4- methylsulfonyltoluene 200g, add phosphomolybdic acid 0.6g, inclined sodium niobate 0.5g, KBr 0.6g, 150 DEG C of reaction temperature, pressure
7.0atm, is passed through the oxygen-enriched air that oxygen content is 50%, and flow is 500ml/min, and reaction takes liquid-like every 0.5h after starting
With liquid-phase chromatographic analysis, after reacting 2.0h, 2- nitro -4- methylsulfonyltoluenes conversion ratio is up to 92%, 2- nitro -4- methylsulfonyl benzene first
Sour yield is up to 91%.
Reactant liquor is cooled to 5 DEG C, will be precipitated using filter operation and is separated with reactant liquor.
Methods For Purification of the gained solids of sedimentation as described in embodiment 1, obtains flaxen 2- nitryl-4-thiamphenicol benzoic acids
202.3 gram.
It is that 650ml, pH are 0.7 that gained filtrate adds watery hydrochloric acid and water to volume, adds 200g 2- nitro -4- MSMs
Base toluene, is reentered in aforesaid reactor, in 150 DEG C, pressure 7.0atm, is passed through the oxygen-enriched air that oxygen content is 50%,
Flow 500ml/min, reacts 2.0h, obtains 2- nitro -4- methylsulfonyltoluenes conversion ratio 92% with liquid-phase chromatographic analysis, and 2- nitros -
4- thiamphenicol benzoic acids yield 90%.
The principle and its effect of above-described embodiment only illustrative present invention, of the invention not for limiting.Any ripe
The personage for knowing this technology all can carry out modifications and changes to above-described embodiment under the spirit and the scope without prejudice to the present invention.Cause
This, art those having ordinary skill in the art is completed under without departing from disclosed spirit and technological thought such as
All equivalent modifications or change, should be covered by the claim of the present invention.
Claims (10)
1. a kind of method that use 2- nitro -4- methylsulfonyltoluenes produce 2- nitryl-4-thiamphenicol benzoic acids, is characterized in that in reaction
In device, 4-70 atmospheric pressure and when 50～250 DEG C, be raw material with 2- nitro -4- methylsulfonyltoluenes, air (oxygen-enriched air or oxygen)
For oxidant, make solvent with the acidic aqueous solution that pH value is 0.5-4.5, be made up of heteropoly acid-metal oxygenate-halide
Multiple catalyzing system effect under, formed a gas liquid reaction system, by 2- nitro -4- methylsulfonyltoluenes be oxidized to 2- nitros -
4- thiamphenicol benzoic acids；
In described reactor feed solvent, the mass concentration of 2- nitros -4- methylsulfonyltoluenes is 2%～55%；
In described reactor internal solvent, the mass concentration of heteropoly acid is 0.02%～3.0%；
In described reactor internal solvent, the mass concentration of metal oxygen-containing compound is 0.005%～0.5%；
Halide mass concentration in described reactor internal solvent is 0.003%～0.15%；
Contain 10%～100% volume oxygen in described Reactor inlet gas；
Described heteropoly acid is phosphotungstic acid H3PWl2O40, silico-tungstic acid H4SiWl2O40, germanotungstic acid H4GeWl2O40, silicomolybdic acid
H4SiMol2O40, germanium molybdic acid H4GeMol2O40Or phosphomolybdic acid H3PMol2O40；
Described metal oxygen-containing compound is selected from high price acidic oxide or their corresponding acid or salt：Vanadic anhydride, vanadic acid,
Vanadate, metavanadic acid, metavanadate, niobium pentaoxide, niobic acid, metaniobate, bismuthic oxide, bismuthic acid or bismuthates；
Described halide takes from four halogen ethane, dihalo- ethane, halogen ethane, hydrogen halides or potassium halide.
2. the method for claim 1, is characterized in that described reaction pressure is 5～25 atmospheric pressure.
3. the method for claim 1, is characterized in that described reaction temperature is 120 DEG C～200 DEG C.
4. the method for claim 1, is characterized in that described 2- nitro -4- methylsulfonyltoluene oxidation reactor liquid enters
In material, the mass concentration of 2- nitros -4- methylsulfonyltoluenes is 15%～50%.
5. the method for claim 1, is characterized in that described 2- nitro -4- methylsulfonyltoluene oxidation reactor inlet gas
Body is air.
6. the method for claim 1, is characterized in that described 2- nitro -4- methylsulfonyltoluene oxidation reactor internal solvents
PH value be 1.0-2.5.
7. the method for claim 1, is characterized in that the mass concentration of metal oxygen-containing compound in described reactor is
0.01～0.15%.
8. the method for claim 1, is characterized in that halide mass concentration is in described reactor internal solvent
0.005%～0.04%.
9. the method for claim 1, is characterized in that the mass concentration of heteropolyacid catalyst in described reactor is
0.08%～1.0%.
10. the method for claim 1, is characterized in that described reactor is bubbling bed, gas and liquid volume flow
Than for 10～100.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108201894A (en) * | 2016-12-20 | 2018-06-26 | 海利尔药业集团股份有限公司 | A kind of oxidation catalyst for preparing 2- nitryl-4-thiamphenicol benzoic acids |
| CN111254456A (en) * | 2020-03-31 | 2020-06-09 | 青岛科技大学 | Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN111362807A (en) * | 2020-03-30 | 2020-07-03 | 江苏永安化工有限公司 | Preparation method of 3-nitro-2-methylbenzoic acid |
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| CN104016894A (en) * | 2014-06-09 | 2014-09-03 | 中化农化有限公司 | Catalytic technology for producing 2-nitro-4-methylsulfonylbenzoic acid |
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| CN108201894A (en) * | 2016-12-20 | 2018-06-26 | 海利尔药业集团股份有限公司 | A kind of oxidation catalyst for preparing 2- nitryl-4-thiamphenicol benzoic acids |
| CN111362807A (en) * | 2020-03-30 | 2020-07-03 | 江苏永安化工有限公司 | Preparation method of 3-nitro-2-methylbenzoic acid |
| CN111254456A (en) * | 2020-03-31 | 2020-06-09 | 青岛科技大学 | Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid |
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