- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- The polyhedral nature of selenium-catalysed reactions: Se(iv) species instead of Se(vi) species make the difference in the on water selenium-mediated oxidation of arylamines
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Selenium-catalysed oxidations are highly sought after in organic synthesis and biology. Herein, we report our studies on the on water selenium mediated oxidation of anilines. In the presence of diphenyl diselenide or benzeneseleninic acid, anilines react with hydrogen peroxide, providing direct and selective access to nitroarenes. On the other hand, the use of selenium dioxide or sodium selenite leads to azoxyarenes. Careful mechanistic analysis and 77Se NMR studies revealed that only Se(iv) species, such as benzeneperoxyseleninic acid, are the active oxidants involved in the catalytic cycle operating in water and leading to nitroarenes. While other selenium-catalysed oxidations occurring in organic solvents have been recently demonstrated to proceed through Se(vi) key intermediates, the on water oxidation of anilines to nitroarenes does not. These findings shed new light on the multifaceted nature of organoselenium-catalysed transformations and open new directions to exploit selenium-based catalysis.
- Capperucci, Antonella,Dalia, Camilla,Tanini, Damiano
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supporting information
p. 5680 - 5686
(2021/08/16)
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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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- Method for synthesizing aromatic nitro compound by microchannel reactor
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The invention discloses a method for synthesizing an aromatic nitro compound by a microchannel reactor. The method comprises the following steps: continuously conveying p-methylsulfonyl toluene, sulfuric acid and nitric acid as raw materials into the microchannel reactor for reaction. The micro-channel reactor is used for preparing 2-nitro-4-sulfonyl methyl toluene, the high specific area of the micro-channel reactor can realize rapid heat transfer and keep constant temperature, reaction materials react rapidly during instant mixing, heat can be conducted out in time, local overheating is eliminated, the production risk is reduced, and the production efficiency is greatly improved.
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Paragraph 0034-0062
(2021/06/02)
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- Method for preparing 2-nitro-4-methylsulfonyltoluene by continuous flow
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The invention discloses a method for preparing 2-nitro-4-methylsulfonyltoluene by continuous flow. The method comprises conveying 1-methyl-4-(methylsulfonyl)-benzene, sulfuric acid and nitric acid continuously into a channel reactor, and allowing to react so as to continuously prepare 2-nitro-4-methylsulfonyltoluene, wherein the channel reactor comprises a cooling module, a fluid module and an outlet module which are communicated in sequence. The method of the invention has the advantages of high safety, low byproduct output, high product purity and the like, and also has the advantages of good process simplicity, good operational convenience, high automation level, high preparation efficiency and the like; the method of the invention is suitable for large-scale continuous preparation of 2-nitro-4-methylsulfonyltoluene and has good application value and application prospect.
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Paragraph 0030-0035; 0039-0044
(2019/10/17)
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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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- 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 0016-0017
(2017/09/08)
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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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Paragraph 0052; 0055; 0056
(2017/02/09)
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- Preparation method of 2-nitro-4-methylsulphonyl methylbenzene
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The invention discloses a preparation method of 2-nitro-4-methylsulphonyl methylbenzene. The preparation method includes: in presence of a catalyst, enabling o-nitrosotoluene to react with methylsulphonyl chloride, wherein the catalyst is quaternary ammonium salt type ion liquid loaded on an orderly mesoporous material. The quaternary ammonium salt type ion liquid catalyst catalyzes reaction of o-nitrosotoluene and methylsulphonyl chloride in the orderly mesoporous material, ortho-position thiamphenicol reaction is limited, para-position thiamphenicol reaction is promoted, and the preparation method is high in selectivity and yield and relatively low in synthesis cost.
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Paragraph 0018; 0019
(2017/01/02)
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- Continuous-Flow Process for Selective Mononitration of 1-Methyl-4-(methylsulfonyl)benzene
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An expeditious process for selective nitration of 1-methyl-4-(methylsulfonyl)benzene in a continuous-flow reactor in 98% yield is described. The continuous-flow mononitration ran well in adiabatic condition with 80 wt% sulfuric acid, and residence time was reduced to 5 s. The short residence time can significantly reduce byproducts. Dinitration was also studied for optimization of the mononitration. The spent acid could be reused for several times after concentration in a vacuum.
- Yu, Zhiqun,Zhou, Pengcheng,Liu, Jiming,Wang, Wenzuo,Yu, Chuanming,Su, Weike
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p. 199 - 203
(2016/03/04)
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- Methanesulfonylation of deactivated aromatics with superelectrophilic CH3so2F·3SbF5 and (CH3so2)2O-2CF3so 3H/B(O3SCF3)3 systems
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Methanesulfonylation of various deactivated arenes, including tri- and tetrafluorobenzenes, was achieved in good yield under mild conditions using superelectrophilic CH3SO2F/3SbF5 and (CH3SO2O)2O/2CF3SO 3H-B(O3SCF3)3 reagent systems. 1998 MAHK "Hayka/Interperiodica".
- Olah,Orlinkov,Oxyzoglou,Prakash, G.K. Suria
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p. 1573 - 1578
(2007/10/03)
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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 trisubstituted benzene intermediates
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This invention relates to a process for the preparation of 2-nitro-4-(C1 -C4 alkylsulfonyl) toluene or 2-nitro-4-(C1 -C4 alkylsulfonyl) ethylbenzene by the alkylsulfonylation of 2-nitrotoluene or 2-nitro ethylbenzene.
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