- Synthesis of 2-Nitro-4-methylsulfonylbenzoic Acid
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2-Nitro-4-methylsulfonylbenzoic acid was synthesized by the oxidation of 2-nitro-4-methylsulfonyl toluene with hydrogen peroxide in the presence of CuO/Al2O3, which was first used in strong acid system. Furthermore, the process of the reaction was thoroughly investigated by varying reactant molar ratio, reaction temperature and the amount of catalyst to obtain the optimum process. Meanwhile, unreacted 2-nitro-4-methylsulfonyl toluene can be recycled after simple treatment. The yield can reach 78.3 %. The method demonstrated the following advantages. Firstly, the oxidant dosage of sulfuric acid and hydrogen peroxide will be reduced greatly. Secondly, unreacted 2-nitro-4-methylsulfonyl toluene can be recycled. Thirdly, this process had good performance on safety. It will be a high-efficiency, energy-saving and environment-friendly technology to produce 2-nitro-4-methylsulfonylbenzoic acid.
- Cheng, Chunsheng,Wei, Zhenyun,Ma, Xiaohua
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- Kinetics and the mechanism of the photocatalytic degradation of mesotrione in aqueous suspension and toxicity of its degradation mixtures
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The photocatalytic degradation of the herbicide mesotrione (0.05 mM) in aqueous suspensions of TiO2 Degussa P25 and ZnO was examined as a function of the different operational parameters. The optimum of the catalyst loading was found to be 2.00 mg mL-1 under UV light at the pH 4.0 (TiO2 Degussa P25) and pH 9.2 (ZnO). In the first stage of the reaction, the photocatalytic degradation of mesotrione followed the pseudo-first order kinetics, in which the heterogeneous catalysis proceeds mainly via ?OH radicals, and partly also via holes. The results showed that the disappearance of mesotrione led to the formation of a number of organic intermediates and ionic byproducts, whereas its complete mineralization occurred after about 4 h. Tentative photodegradation pathways were proposed and discussed as a function of the type of photocatalyst. A comparison of the evolution of toxicity that was evaluated in vitro in the rat hepatoma (H-4-II-E) and human fetal lung (MRC-5) cell lines with the degradation kinetics indicates that the cell growth of both cell lines was only mildly affected by the mixture of mesotrione and its photocatalytic degradation intermediates obtained using TiO2 Degussa P25, and moderately affected by the mixtures obtained using ZnO, whereby at 120 min toxicity decreased.
- ?oji?, Daniela V.,Or?i?, Dejan Z.,?etojevi?-Simin, Dragana D.,Despotovi?, Vesna N.,Abramovi?, Biljana F.
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- Synthetic method for oxidizing 2 - nitro -4 - methylsulfonyl toluene with oxygen to generate 2 - nitro -4 - methylsulfonylbenzoic acid
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The invention relates to the field of fine chemical synthesis, in particular to a method for synthesizing 2 - nitro -4 - methylsulfonyl benzoic acid by oxidizing 2 - nitro -4 - methylsulfonyl toluene with oxygen. In the microchannel reactor, the catalyst is filled, oxygen is introduced, and 2 - nitro -4 - methylsulfonyltoluene is slowly introduced into the alkaline solution, wherein the oxygen is charged into the pressure maintaining 0.2 - 10 mpa, the reaction temperature is controlled to 130 - 200 °C. according to the obtained product content, and high conversion rate can be obtained. High selectivity, high content of continuous products.
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Paragraph 0044-0047
(2021/09/21)
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- Device and method for fully continuously synthesizing 2-nitro-4-methylsulfonylbenzoic acid from 4-methylsulfonyltoluene
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The invention discloses a device for fully continuously synthesizing 2-nitro-4-methylsulfonylbenzoic acid from 4-methylsulfonyltoluene. The device comprises a first storage tank, a second storage tank, a first metering pump, a second metering pump, a first tubular reactor, a second tubular reactor and a collecting kettle. The first storage tank is communicated with a first metering pump, the firstmetering pump is communicated with a first tubular reactor, the first tubular reactor is communicated with a three-way mixer, the first tubular reactor is communicated with the three-way mixer, the second metering pump is communicated with the three-way mixer, the three-way mixer is communicated with a second tubular reactor, and the second tubular reactor is communicated with the collecting kettle. The device also comprises a waste gas absorption kettle communicated with the collecting kettle. The invention also discloses a method for synthesizing 2-nitro-4methylsulfonylbenzoic acid by adopting a tubular reaction mode based on the device. According to the device design and the method based on the device, the target product is synthesized in a tubular reaction mode, and the technical defects that waste acid is difficult to recycle and the pollution amount is large in existing kettle type preparation are overcome.
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Paragraph 0090-0112
(2021/02/10)
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- Preparation method of 2-nitro-4-methylsulfonylbenzoic acid
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The invention relates to a preparation method of 2-nitro-4-methylsulfonylbenzoic acid. Based on a nitric acid oxidation scheme, p-methylsulfonyltoluene is dissolved into a chloroalkane solvent, nitricacid is dropwise added into sulfuric acid with the mass fraction of 80-90wt%, a chloroalkane solution of p-methylsulfonyltoluene and a mixed acid solution are simultaneously and continuously added into a reaction system for a nitration reaction, the sulfuric acid is repeatedly used after the nitration reaction material liquid is treated, the sulfuric acid can be used both in the nitration reaction and the oxidation reaction, the sulfuric acid in the oxidation reaction can be repeatedly used, the total molar yield of the 2-nitro-4-methylsulfonylbenzoic acid can achieve more than 90%, and the content is more than 99%. By means of the method, the amount of waste acid in production of 2-nitro-4-methylsulfonylbenzoic acid can be reduced by 90% or above, the use amount of vanadium pentoxide isreduced by 90% or above, three wastes are greatly reduced, the process is safe and environmentally friendly, the amount of the three wastes is small, and the method is suitable for industrial large-scale production.
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Paragraph 0042-0043; 0050-0056; 0063-0068; 0075-0080
(2020/11/01)
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- 2 - Nitro -4 --methylsulfonyl benzoic acid (by machine translation)
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The invention discloses a 2 - nitro - 4 - P-methylsulfonyl-benzoic acid synthesis method, using 3 - nitrophthalic acid as the substrate of reaction, willimson sulfonated, sulfinyl acidification, [...] and [...]-step chemical reaction, to obtain the 2 - nitro - 4 - P-methylsulfonyl-benzoic acid. The invention can avoid the use of large amount of sulfuric acid, nitric acid, to avoid high-risk oxidation reaction. The invention has the low cost of raw materials, the conversion is high, high production efficiency, pollution is small, and each step of mild reaction conditions, the reaction process is simple and easy to control and the like. The final product purity can be up to 99% or more, the four-step reaction and the total conversion rate can reach 90% or more, all organic solvent can be recycled, the new method is in line with the direction of the green chemical development clean production process. (by machine translation)
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Paragraph 0032; 0039-0041; 0042; 0049-0051
(2019/05/04)
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- Preparation method of mesotrione intermediate
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The invention relates to a preparation method of a mesotrione intermediate. Methylsulfonyl bromobenzene is taken as an initial raw material, and the method comprises the following steps; first, carrying out a nitration reaction with nitric acid, carrying out extraction treatment on the system after reaction with ethyl acetate and a saturated sodium bicarbonate aqueous solution, and removing an organic phase to obtain a product; then, using DMF as a solvent to carry out a cyanidation reaction with cuprous cyanide at a high temperature, removing the solvent in the system, and separating the product by column chromatography; and hydrolyzing and acidifying the product to obtain a final product namely mesotrione intermediate 2-nitro-4-(methylsulfonyl) benzoic acid. Compared with a traditional synthesis method, the method reduces the use of strong oxidants, has mild reaction conditions, increases the operation safety, is easy in reaction treatment of each step, is beneficial to reaction, andhas a higher yield.
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Paragraph 0006; 0021
(2019/01/23)
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- Preparation method of 2-nitro-4-methylsulfonylbenzoic acid
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The invention provides a preparation method of 2-nitro-4-methylsulfonylbenzoic acid. The preparation method comprises the following steps: adding 1.0-2.0 tons of dichloromethane and 0.8-1.6 tons of 4-(methylsulfonyl) toluene to a nitration reactor, performing cooling, starting to adding concentrated nitric acid dropwise, performing middle-control sampling analysis, putting a product into an oxidation reactor after a nitration reaction is finished, performing heating slowly to distill off dichloromethane, supplementing a solvent, adding a catalyst, performing heating, adding 60% nitric acid dropwise for an oxidation reaction, cooling a product to 25 DEG C plus/minus 1 DEG C after the reaction and centrifuging the product, recycling mother liquor to the oxidation reaction, feeding an obtained coarse product to a reaction kettle again, adding water, adding alkali liquor dropwise to regulate alkaline pH to 11, filtering out impurities, then adding dilute sulfuric acid dropwise to the mother liquor to regulate pH, and performing cooling, centrifugation and drying to obtain a refined product. Dichloromethane is used for replacing original concentrated sulfuric acid as the solvent, reaction temperature is mild, safety of the nitration reaction is improved, sulfuric acid as the byproduct of oxidation can be recycled, so that output of byproduct acid is reduced, yield of the product isincreased, and quality of the product is improved.
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Paragraph 0020-0033
(2019/04/04)
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- Synthesis process of mesotrione
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Belonging to the field of herbicide original drug preparation, the invention discloses a synthesis process of mesotrione. The process includes the steps of: (1) catalytic oxidation: taking 2-nitro-4-methylsulfonyl toluene as the raw material, and adopting oxygen as the oxidant to generate 2-nitro-4-methylsulphonylbenzoic acid under the catalysis of a manganese oxide octahedral molecular sieve loaded heteropolyacid-transition metal salt; (2) acyl chlorination: subjecting 2-nitro-4-methylsulphonylbenzoic acid to acyl chlorination to generate 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensation: carrying out condensation reaction on 2-nitro-4-methylsulfonylbenzoyl chloride and 1, 3-cyclohexanedione to obtain an enol ester intermediate reaction solution; (4) rearrangement: subjecting the enol ester intermediate to enol ester rearrangement under the catalysis of a rearrangement catalyst to obtain a crude product reaction solution; and (5) refining: refining the crude product reaction solution to obtain a mesotrione finished product. The process provided by the invention optimizes the reaction conditions, the conversion rate of each step is high, the yield and purity of the product are high, the whole production process does not involve hypertoxic materials, and the safety is high.
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Paragraph 0038-0052; 0057-0065
(2019/10/04)
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- SYNTHESIS OF MESOTRIONE
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The present disclosure relates to a method for the synthesis of mesotrione. The method comprises reacting p-toluene sulfonyl chloride with alkali metal sulphite and alkali metal bicarbonate to obtain p-toluene alkali metal sulfinate. The p-toluene alkali metal sulfinate is reacted with alkali metal salt of monochloroacetic acid to obtain p- methylsulfonyl toluene. Further, p-methylsulfonyl toluene is nitrated to obtain 2-nitro-p- methylsulfonyl toluene. 2-nitro-p-methylsulfonyl toluene is oxidized and then halogenated to obtain 2-nitro-p-methylsulfonylbenzoyl halide. 2-nitro-p-methylsulfonylbenzoyl halide is reacted with alkali metal salt of 1,3-cyclohexanedione to obtain 3-(2-Nitro-p-methyl sulfonyl benzoyloxy) cyclohexane-l-one. 3-(2-Nitro-p-methyl sulfonyl benzoyloxy) cyclohexane-1- one is reacted with base, a third fluid medium and cyanide ion source to obtain an amorphous mesotrione. The present disclosure also discloses the steps of converting the amorphous mesotrione to crystalline mesotrione having purity greater than 99 %. The process of the present disclosure for preparing mesotrione is rapid, economic, and environment friendly.
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- Preparation method of 2-nitryl-4-methanesulfonyl-benzoic acid
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The invention provides a preparation method of 2-nitryl-4-methanesulfonyl-benzoic acid. The preparation method takes 2-nitryl-4-methylsulfonyl toluene as a starting raw material, aliphatic carboxylicacid as a solvent, one or more N-hydroxylamine compounds as a catalyst, one or more of nitric acid, nitrate or nitrite as a co-catalyst, and molecular oxygen as a catalyst to react for 0.5 to 15h under the conditions that the pressure is 0.1 to 5MPa and the temperature is 60 to 180 DEG C, so as to obtain 2-nitryl-4-methanesulfonyl-benzoic acid. According to the method provided by the invention, the defects of an existing industrial production method of 2-nitryl-4-methanesulfonyl-benzoic acid that the amount of three wastes is great, equipment is seriously corroded and the like are overcome andclean production of 2-nitryl-4-methanesulfonyl-benzoic acid is easy to realize.
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Paragraph 0021-0042
(2018/10/11)
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- Preparative method for carboxylic acids
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A preparative method for carboxylic acids is disclosed in the present invention. The method is characterized in that: compounds (II) are reacted in the presence of hydrogen peroxide and base to produce target products (I), as represented by the following reaction scheme: wherein R1 is aryl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, thiadiazolyl, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl and hydrogen; R2 is alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, alkylthiolcarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, aldehyde, carboxyl, nitro, alkyl and hydrogen; R3 is alkoxycarbonyl, alkyl amido carbonyl, aminocarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, carboxyl and nitro. The present invention has the following main benefits: cheap and readily available starting materials, safe processes, high yield, good quality, which facilitates industrial production.
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Paragraph 0031
(2018/02/03)
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- 2-nitro-4-methylsulfonylbenzoylchloride synthesizing process
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The invention discloses a 2-nitro-4-methylsulfonylbenzoylchloride synthesizing process. By means of the process, the yield and product purity are high. The 2-nitro-4-methylsulfonylbenzoylchloride synthesizing process comprises the steps that after concentrated sulfuric acid, methyl p-tolyl sulfone and water are added into a nitration reaction still, nitric acid is dropwise added for a nitratlon reaction within 4-5 hours, and after dropwise adding is completed, the temperature is preserved for 60-70 minutes, so that a nitration solution is obtained; the nitration solution is guided into an oxidation reaction still, then a catalyst, namely V205, is added, then 1240-1290 kg of nitric acid is dropwise added, and the reaction temperature is controlled to be 142-146 DEG C; after dropwise adding is completed, the temperature is preserved for 1-2 hours; after the temperature of a reaction solution is lowered to 100 DEG C, water is added, then the temperature is lowered to 48-50 DEG C, and then filter pressing is conducted, so that an oxidation product is obtained; the oxidation product is rinsed with water cyclically; after being subjected to refinement, the oxidation product is dried at the temperature of 55-70 DEG C, so that 2-nitro-4-methylsulfonyl benzoic acid is obtained; and thionyl chloride is added into an acylating chlorination reaction still, then the 2-nitro-4-methylsulfonyl benzoic acid and DMF are put into the acylating chlorination reaction still so that a temperature-rising backflow reaction can be conducted, and after the reaction lasts for 8-12 hours, thionyl chloride is obtained through distillation, so that 2-nitro-4-methylsulfonylbenzoylchloride is obtained.
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Paragraph 0012-0017; 0018; 0019; 0020
(2017/05/13)
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- Synthesis process of 2-nitro-4-methylsulfonyl benzoyl chloride
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The invention provides a synthesis process of 2-nitro-4-methylsulfonyl benzoyl chloride with high yield and high product purity. The synthesis process comprises the steps of uniformly adding nitric acid drop by drop within 2-3 hours for nitration reaction after concentrated sulfuric acid, methyl p-tolyl sulfone and an oxidized water-containing mother liquid are added into a nitration reaction kettle, and keeping the temperature for 60-70 min after the adding of the nitric acid is finished so as to obtain a nitrated liquid; importing the nitrated liquid into an oxidization reaction kettle and then adding a catalyst V2O5 and a nucleating agent, then adding the nitric acid drop by drop and controlling the reaction temperature at 142-146 DEG C; keeping the heat for 1-2 hours after the adding of the nitric acid is finished; after cooling the reaction liquid to 100 DEG C, adding water to reduce the temperature to 48-50 DEG C and then pressing and filtering to obtain the oxidization product and the oxidized water-containing mother liquid, and rinsing the oxidization product circularly by using water; refining the oxidization product for multiple times and separating out the nucleating agent, and drying the oxidization product after being subjected to multiple times of refining at 55-70 DEG C; and adding sulfoxide chloride in an acylating chlorination reaction kettle, and then adding 2-nitro-4-methylsulfonylbenzoic acid and DMF for heating reflux reaction for 3-4 hours.
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Paragraph 0017-0019
(2017/05/18)
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- A 2 - nitro - P-methylsulfonyl benzoic acid (by machine translation)
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The invention discloses a 2 - nitro - P-methylsulfonyl-benzoic acid synthesis process, including the 2 - nitro - P-methylsulfonyl-benzoic acid production material is P-methylsulfonyl toluene, nitric acid, sulfuric acid, vanadium pentoxide, the invention relates to a 2 - nitro - P-methylsulfonyl benzoic acid, nitric acid and in the presence of oxygen, the catalytic oxidation of the vanadium pentoxide dual function, thereby improving the conversion rate of the reaction and the product 2 - nitro - P-methylsulfonyl-benzoic acid yield; adopts dropping mixed acid substituted single dropwise nitric acid, to prevent a large amount of nitric acid decomposition and volatilization, maintaining the concentration of the nitric acid in the reaction solution is maintained at a certain range, thereby greatly improving the utilization rate of the nitric acid. (by machine translation)
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Paragraph 0020; 0021; 0022; 0023; 0024; 0025; 0026-0058
(2017/03/08)
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- A 2 - nitro - P-methylsulfonyl-benzoic acid nitration process flow (by machine translation)
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The invention discloses a 2 - nitro - P-methylsulfonyl-benzoic acid nitration process flow, comprises the nitration reaction kettle, the 2 - nitro - P-methylsulfonyl-benzoic acid nitration process comprises: (1) first of all the nitration reaction kettle is sequentially added to the methyl P-tolyl sulfone, nitric acid and sulfuric acid, then the stirring reaction to obtain the reactant; (2) then the reactant is put into the filter device in the filter, the filter will get the mother liquor with the product; (3) the final mother solution is dehydration, producing water with sulfuric acid; the water with sulfuric acid and then respectively through the water metering device, return metering device are sequentially added to the nitration reaction kettle. The procedure is simple, through multiple cycle process, can improve the 2 - nitro - P-methylsulfonyl-benzoic acid nitration of efficiency and quality, while at the same time taking advantage of water instead of the fatty acid and methanol solvent, not only greatly reduces the production cost, reduce the corrosion of the apparatus, but also reduces the discharge of acid, in accordance with the clean production, at the same time improves the safety of the in the production process. (by machine translation)
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Paragraph 0016; 0017; 0018; 0019; 0020; 0021; 0022
(2017/04/29)
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- Synthesis process of mesotrione
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The invention discloses a synthesis process of mesotrione. The synthesis process is high in yield and high in product purity and comprises the following steps: adding concentrated sulfuric acid, an oxidation water-containing mother solution and methyl p-tolyl sulfone into a nitration reaction kettle, evenly dropwise adding nitric acid in 2-3 hours to carry out nitratlon reaction, and keeping the temperature for 60-70 minutes after finishing dropwise adding nitric acid to obtain a nitrification solution; introducing the nitrification solution into an oxidation reaction kettle, then adding V2O5 as a catalyst, dropwise adding nitric acid and controlling the reaction temperature to be 142-146 DEG C; keeping the temperature for 1-2 hours after finishing dropwise adding nitric acid; reducing the temperature of a reaction solution to 100 DEG C, then adding water, and then reducing the temperature to 48-50 DEG C, then carrying out pressure filtration to obtain an oxidation product and the oxidation water-containing mother solution, circularly rinsing the oxidation product with water; refining the oxidation product and then drying the oxidation product at 55-70 DEG C to obtain 2-nitryl-4-methylsulfonylbenzoic acid; adding sulfoxide chloride into an acyl chlorination reaction kettle, then adding 2-nitryl-4-methylsulfonylbenzoic acid and DMF for increasing the temperature and carrying out reflux reaction, distilling after reacting for 11-12 hours for separating sulfoxide chloride out, and then carrying out esterification, condensation and rearrangement.
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Paragraph 0021-0022
(2017/05/18)
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- Synthetic process of mesotrione
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The invention relates to a synthetic process of mesotrione. The yield is high and the product purity is high. The synthetic process comprises the following steps: after adding concentrated sulfuric acid and methyl p-methylphenyl sulfone into a nitration reaction kettle, uniformly dropwise adding nitric acid within 4-5 hours for a nitration reaction, and after dropwise addition, preserving the temperature for 60-70 minutes to obtain a nitration liquid; leading the nitration liquid into an oxidation reaction kettle and then adding a catalyst V2O5 and water, then dropwise adding nitric acid and controlling the reaction temperature at 142-146 DEG C; after dropwise addition, preserving the temperature for 1-2 hours; cooling the reaction liquid to 100 DEG C, then adding water and cooling the reaction liquid to 48-50 DEG C, then performing filter pressing to obtain an oxidized product, and cyclically rinsing the oxidized product with water; drying the refined oxidized product to obtain 2-nitryl-4-methylsulfonyl benzoic acid; adding thionyl chloride into an acylating chlorination reaction kettle, then inputting 2-nitryl-4-methylsulfonyl benzoic acid and DMF to perform a temperature-raising reflux reaction, distilling thionyl chloride 11-12 hours after the reaction, then adding dichloromethane and 1,3-cyclohexanedione, and dropwise adding triethylamine for esterified condensation and rearrangement.
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Paragraph 0023-0025
(2017/05/18)
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- Synthesis process of 2-nitro-4-methanesulfonylbenzoyl chloride
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The invention discloses a synthesis process of 2-nitro-4-methanesulfonylbenzoyl chloride with high yield and high product purity. The synthesis process comprises the following steps: adding concentrated sulfuric acid, oxidized aqueous mother liquid and methyl p-tolyl sulfone into a nitration reaction kettle, uniformly dropping nitric acid to implement nitration reaction within 2-3 hours, and implementing heat preservation for 60-70 minutes after the completion of dropping to obtain nitrification liquid; introducing the nitrification liquid to an oxidation reaction kettle, then adding a catalyst V2O5, dropping nitric acid, and controlling the reaction temperature to 142-146 degrees centigrade; implementing heat preservation for 1-2 hours after the completion of dropping; cooling the reaction liquid to 100 degrees centigrade, then adding water to cool the liquid to 48-50 degrees centigrade, implementing filter pressing to obtain oxidation products and the oxidized aqueous mother liquid, and circularly rinsing the oxidization products with water; refining the oxidization products, and then drying the oxidization products at 55-70 degrees centigrade to obtain 2-nitro-4-methylsulfonylbenzoic acid; and then adding thionyl chloride into an acylating chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF to implement heating reflux reaction, and reacting for 11-12 hours to separate thionyl chloride by distillation.
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Paragraph 0021-0022
(2017/06/20)
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- A process for preparing 2 - nitro - 4 - methyl sulfuryl benzoic acid
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The invention discloses a novel method of preparing 2-nitro-4-methylsulfonyl benzoic acid. The target product which is 2-nitro-4-methylsulfonyl benzoic acid is prepared by carrying out reaction by adopting an oxidation reaction device with a self-priming stirrer, wherein 2-nitro-4-methylsulfonyltoluene is used as the raw material, sulfuric acid is used as a reaction medium, a transition metal oxide is used as the catalyst, and oxygen is introduced in the course of reaction. The method provided by the invention has the advantage that the reaction condition is easy to control, the production cost is low, and the amount of the generated three wastes is reduced.
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Paragraph 0010; 0026-0033; 0036-0037
(2017/08/24)
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- Technology for preparation of 2-nitro-4-methylsulfonylbenzoic acid by oxygen catalytic oxidation
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The invention relates to a method of producing 2-nitro-4-methylsulfonylbenzoic acid from 2-nitro-4-methysulfonyl toluene. Specifically, under the conditions of an atmospheric pressure of 4-70 and a temperature of 100-250DEG C, 2-nitro-4-methysulfonyl toluene is adopted as the raw material and air (oxygen-enriched air or oxygen) is taken as the oxidant, in an acidic solution, a multielement catalytic system composed of heteropoly acid, metal oxygen-containing compound and halogen is employed to oxidize 2-nitro-4-methysulfonyl toluene into 2-nitro-4-methylsulfonylbenzoic acid. The technology provided by the invention can overcome the defects of large production of waste gas and wastewater, serious corrosion, low selectivity, high production cost and the like in existing 2-nitro-4-methylsulfonylbenzoic acid production methods, reduces environmental pollution, and achieves clean production of 2-nitro-4-methylsulfonylbenzoic acid.
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Paragraph 0031; 0032; 0033; 0034; 0035; 0036; 0037-0052
(2017/05/18)
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- A catalytic oxidation of 2 - nitro - 4 - methyl P-tolyl sulfone preparing 2 - nitro - 4 - methyl sulfuryl benzoic acid
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The invention provides a novel method for preparing 2-nitro-4-methylsulphonylbenzoic acid by catalytic oxidation of 2-nitro-4-methylsulfonyl toluene, which comprises the following steps: taking 2-nitro-4-methylsulfonyl toluene as an initial raw material, taking one of water, methanol and ethanol or combination of two of water, methanol and ethanol as a solvent, selecting metal phthalocyanine with certain amount or any one or combination for substituting the metal phthalocyanine as a catalyst, in a sodium hydroxide solution with a certain concentration, under 0.01-4.0 MPa of oxygen or air pressure, reacting for 6-24 hours at 25-120 DEG C, and performing regular isolation to obtain the 2-nitro-4-methylsulphonylbenzoic acid. According to the invention, metal phthalocyanine is taken as the catalyst with little usage amount, the oxygen which has the characteristics of cleaning performance and low cost can substitute a chemical oxidizing agent which has the disadvantages of severe three wastes and expensive cost, environment pollution is greatly reduced, production cost is reduced, reaction condition is relatively mild, reaction time is greatly shortened, the method can be popularized to large-scale industrial production, and has important meaning for cleaning production. The synthesis route is shown in the description.
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Paragraph 0046-0047
(2017/08/25)
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- A 2 - nitro - 4 - methylsulfonyl-benzoic acid synthesis process (by machine translation)
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The invention provides a high yield, high purity of the product 2 - nitro - 4 - methylsulfonyl-benzoic acid synthesis process, comprising the steps of: nitration: in the nitration reaction kettle adding concentrated sulfuric acid 1400 - 1500 kg, P-methylsulfonyl toluene 350 - 360 kg and oxidation aqueous mother liquor 600 - 625 kg after, 2 - 3 hours the pumping in the 200 - 210 kg nitric acid nitration, keeping the heat after dropping 60 - 70 minutes, to obtain the nitrification; oxidation: will be introduced into the oxidation reaction of the nitrification after the cauldron, then adding catalyst V2O5 and nucleating agent, then dropwise 1240 - 1290 kg nitric acid, and the reaction temperature is controlled 142 - 146 °C; after dropping insulation 1 - 2 hours; the reaction liquid cooling to 100 degrees, adding water and 800 - 1000 kg and then lowering the temperature to 48 - 50 degrees, then filter to obtain the oxidation product and oxidizing aqueous mother liquor, water 1000 - 1100 kg circulating rinsing oxidation product; the plurality of times of the oxidized product of refining and isolate the nucleating agent, after the plurality of refined oxidation product in 55 - 70 °C lower drying to obtain 2 - nitro - 4 - methylsulfonyl-benzoic acid. (by machine translation)
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Paragraph 0016; 0018
(2017/09/08)
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- Iron(II) and copper(II) phthalocyanine-catalyzed synthesis of 2-nitro-4-methylsulfonylbenzoic acid under mild conditions
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Abstract : A novel method was?developed?to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc). The order of activity for oxidation of NMST was found to be: FePc > CuPc. Meanwhile, major reaction parameters such as concentrations of catalyst and NaOH, reaction temperature and oxygen pressure have been investigated. Through optimization of the reaction parameters, the highest yield of NMSBA and conversion of NMST (up to 53%, 89.3%, respectively) were achieved with oxygen (2.0 MPa), FePc (1.0×10-4molL-1), NaOH (0.6molL-1), in methanol at 55°C for 8 h. A plausible mechanism for this catalytic process is proposed which involved deprotonation and radical pathways. Graphical Abstract: A novel method to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc) has been developed. The reaction parameters and mechanism were studied. The catalytic system will be readily applicable to large-scale production of NMSBA. [Figure not available: see fulltext.].
- Huang, Cheng,Liu, Rui,Zhang, Caiting,Cheng, Qipeng,Zhu, Hongjun
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p. 1587 - 1594
(2017/11/03)
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- A method for preparing of mesotrione
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The invention provides a preparation method of mesotrione. The preparation method comprises is capable of preparing the target product from raw materials such as ortho-nitrotoluene, chlorosulfonic acid, sulfoxide chloride, sodium sulfite, chloroactic acid, 1,3-cyclohexanedione in the presence of a catalyst and acid-base. The preparation method is based on common chemical raw materials, the reaction flow of each step is implemented under conventional operation conditions, the amount of three wastes is low, the total yield is above 61%, the purity of the product is high, the purity of the coarse product of the mesotrione is greater than 98%, and the coarse product of the mesotrione can be further purified; as a result, the preparation method of mesotrione is applicable to large-scale industrial production.
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- Method for refining 2-nito-4-methylsulfonyl benzoic acid and intermediate thereof
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A method for refining a 2-nitro-4-methylsulfonyl benzoic acid and an intermediate thereof are provided, wherein the method includes steps of: using a crude 2-nitro-4-methylsulfonyl benzoic acid (I) as a raw material; using organic amine (II) as a base; synthesizing an intermediate, which is an amine salt (III), in an organic solvent; treating the amine salt (III) with an inorganic base in an aqueous phase to obtain an inorganic metal salt (IV) or an inorganic metal salt (IV′); and acidifying by adding an inorganic acid to obtain a fine 2-nitro-4-methylsulfonyl benzoic acid (I).
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Paragraph 0039
(2016/10/17)
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- 2-nitro-4-methanesulfonyl-benzoic acid refining method and intermediates
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The invention discloses a refining method for 2-nitro-4-methylsulfonyl benzoic acid, and an intermediate thereof. According to the method, an intermediate organic ammonium salt (III) is synthesized in an organic solvent by using a 2-nitro-4-methylsulfonyl benzoic acid (I) crude product as a raw material and organic amine (II) as an alkali; the organic ammonium salt (III) is treated by an inorganic alkali in a water phase to obtain an inorganic metal salt (IV) or inorganic metal salt (IV'); and an inorganic acid is added to acidize the inorganic metal salt to obtain a 2-nitro-4-methylsulfonyl benzoic acid refined product. The beneficial effects of the refining method are mainly embodied in that the content of undesirable impurities can be effectively reduced by refining low-quality 2-nitro-4-methylsulfonyl benzoic acid; the process is stable; three wastes are few; and high-quality raw materials are provided for producing high-quality mesotrione.
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Paragraph 0039
(2016/10/09)
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- A 2-nitro-4-a process for the preparation of sulfone benzoic acid (by machine translation)
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The invention relates to a 2-nitro-4-methyl-sulfonyl benzoic acid preparation method, which belongs to the technical field of organic synthesis. This invention, in order to 2-nitro-4-methyl-P-tolyl sulfone as the raw material, to 70% sulfuric acid as the solvent quality score, V2O5 as the catalyst, the use of a self-suction type stirring, while dripping of nitric acid of oxygen at the same time; the "drip the high concentration of nitric acid at the same time the condensation system to boil off low-concentration nitric acid", "rapid warming up to the reaction temperature", "matching the rate of acceleration and nitric acid droppasses the oxygen"; thereby maintaining the concentration of sulfuric acid of the reaction liquid is not changed, after the completion of the dropping the need to stir the reaction time can be remarkably shortened (only 0.5-1.0h the reaction can be finished); in addition, the low-concentration of nitric acid is fuming nitric acid after compounding can be used repeatedly. (by machine translation)
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Paragraph 0011
(2016/12/16)
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- An ortho-nitro sulfone method for the preparation of benzoic acid
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The invention provides a preparation method of o-nitro sulfuryl benzoic acid, which comprises: in the presence of a catalyst, reacting o-nitro sulfuryl toluene with a structure as shown in formula (1) with an oxidizing agent in a solvent to obtain o-nitro sulfuryl benzoic acid with a structure as shown in formula (2), wherein R1 is H or C1-C5 alkyl, and the catalyst is at least two selected from vanadium compounds, cobalt compounds, copper compounds, iron compounds, manganese compounds, tungsten compounds, and silver compounds. The method of the invention can increase the conversion rate of o-nitro sulfuryl toluene and the yield of o-nitro sulfuryl benzoic acid.
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Paragraph 0046-0048
(2017/04/08)
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- Production of 2-nitro-4-methoxy benzoic acid sulfone-catalytic process (by machine translation)
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The invention relates to a method for producing 2-nitro-4-methylsulfonylbenzoic acid by adopting 2-nitro-4-methylsulfonyl methylbenzene. The method for producing the 2-nitro-4-methylsulfonylbenzoic acid comprises the steps of oxidizing 2-nitro-4-methylsulfonyl methylbenzene serving as a raw material into 2-nitro-4-methylsulfonylbenzoic acid in a gas-liquid-solid three-phase reaction system which is formed in a reactor at 4-70 atmospheric pressure at the temperature of 100-450 DEG C based on air (oxygen-rich air or oxygen) as an oxidant and aliphatic carboxylic acid as a solvent. The method for producing 2-nitro-4-methylsulfonylbenzoic acid can overcomes the defects of the existing 2-nitro-4-methylsulfonylbenzoic acid production method that massive waste gas and waste water are produced, corrosion is serious, selectivity is low and production cost is high, the selectivity is improved, pollution to the environment is reduced, and clean production of 2-nitro-4-methylsulfonylbenzoic acid is realized.
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Paragraph 0073; 0074; 0075; 0076; 0077; 0078; 0079; 0080
(2019/02/02)
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- Preparation method of triketone compound and triketone compound intermediate
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The present invention discloses a preparation method of a triketone compound and a triketone compound intermediate. The method is as follows: a compound (III) is obtained by nucleophilic substitution reaction of a compound (I) as a raw material and a compound (II) under the action of a base and then oxidation reaction, and the triketone desired product is obtained by acyl chlorination, esterification and rearrangement of the compound (III). The beneficial effects are mainly reflected as follows: the method is mild in reaction conditions, simple in process, high in yield, good in product quality, low in production costs, less in three-waste, and suitable for industrial production.
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Paragraph 0004; 0049; 0050
(2016/11/09)
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- The photo-degradation of mesotrione, a triketone herbicide, in the presence of CuII ions
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The study focuses first on the complexation of CuII ions with mesotrione. Experimental absorption spectra combined with quantum chemical calculations highlight that CuII ions bind to the molecule in bidentate mode between O1 and O7 atoms. The calculated electronic transitions of the complex show that three of them are mostly ligand-to-ligand electron transfer while the lowest-energy one involves a ligand-to-metal charge transfer (LMCT). The second aim of this work is to explore the effect of CuII complexation on the photo-degradation of mesotrione. The kinetics and mechanisms of the reactions are proposed on the basis of the experimental results. The effect of different parameters such as the irradiation wavelength, the oxygen concentration and the pH of the mixture and also the production of reactive species such as hydroxyl radicals is investigated. The photochemical degradation of mesotrione in water arises from the triplet excited state of the molecule and results in a photo-hydrolysis process. For the complex, by exciting mainly in its LMCT absorption band, an electron transfer between copper and mesotrione probably occurs and the mechanism of mesotrione-CuII photo-degradation differs: in addition to the photo-hydrolysis route, a photo-cyclisation process takes place and the oxidation of the ligand is accompanied by the reduction of CuII ions.
- Le Person, Anna?g,Siampiringue, Marie,Sarakha, Mohamed,Moncomble, Aurélien,Cornard, Jean-Paul
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- PROCESS
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The present invention relates to a process for the preparation of 2-nitro substituted benzoic acids of formula (I), wherein the (O)PSO2R1 substituent(s) is in the 3-, 4- and/or 5-position, R1 represents a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; n is zero or an integer from one to three; and p is zero or 1; said process comprising the oxidation of the corresponding compound of formula (II) wherein R1, n and p are as hereinbefore defined, and q is zero, 1 or 2, provided that when p is 1, q is not zero, with hydrogen peroxide in the presence of an acid and a catalyst.
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Page/Page column 4
(2008/06/13)
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- METHOD FOR PRODUCING OPTIONALLY SUBSTITUTED BENZOIC ACIDS
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The invention relates to a method for oxidizing optionally substituted toluols of the formula (I), wherein X, Y and Z independently represent hydrogen, methylsulfonyl, hydroxysulfonyl, nitro, halogen or optionally substituted phenyl, to give the corresponding benzoic acids of formula (II), wherein X, Y and Z are defined as above. Oxidation is carried out in sulfuric acid at a temperature of 40-95 °C, optionally in the presence of a transition metal catalyst with hydrogen peroxide, potassium peroxodisulfate or potassium peroxomonosulfate triple salt.
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Page/Page column 9
(2008/06/13)
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- Preparation of methylsulfonylbenzoic acids
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A process for preparing methylsulfonylbenzoic acids comprises oxidizing the corresponding methylsulfonyltoluenes with nitric acid and air in sulfuric acid in the presence of vanadium or cobalt compounds.
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- Preparation of 2-(chloro, bromo or nitro)-4-(alkyl-sulfonyl)benzoic acids and intermediates
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A process for the preparation of 2-(chloro, bromo or nitro)-4-(alkylsulfonyl)benzoic acid and to intermediates used in the process.
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