- Method for preparing triketone compound through continuous flow
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The invention relates to a method for preparing a triketone compound through continuous flow, which uses substrate acyl chloride and 1, 3 - cyclohexanedione as a raw material and is subjected to esterification. The method is mild in condition, simple to operate, good in stability and high in reliability. Utilize continuous flow can accurate control dwell time, the good characteristics of mass transfer heat transfer, easily realize accurate control, restrain the production of side reaction, and reaction yield is high. The method has remarkable innovation meaning and economic value, is easy for industrialization and has a wide prospect.
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Paragraph 0023-0025
(2021/09/08)
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- Preparation method of mesotrione
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The invention provides a preparation method of mesotrione. The preparation method comprises: S1) carrying out a reaction on 2-nitro-4-methylsulfonylbenzoyl chloride and 1, 3-cyclohexanedione in the presence of an acid-binding agent to obtain an enol ester reaction liquid; and S2) adding a rearrangement agent as shown in a formula (I) into the enol ester reaction liquid, and performing a rearrangement reaction to obtain mesotrione. Compared with the prior art, the method has the advantages that the rearrangement agent containing unsaturated double bonds is adopted, under the synergistic effect of the double bonds, the rearrangement agent has better reactivity and reaction rate in the rearrangement reaction process, and the green and environment-friendly aftertreatment method is simple.
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
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supporting information
p. 433 - 438
(2020/02/13)
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- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
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p. 2991 - 2992
(2020/03/24)
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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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- Synthetic process of methyl sulcotrione
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The invention discloses a synthetic process of methyl sulcotrione. 2-nitro-4-methylsulfony benzoic acid and 1,3-cyclohexanedione are added into a solvent, then, a catalyst and an addition agent are added, temperature is raised to 140-150 DEG C under stirring, and condensation reaction is directly carried out; and then, rearrangement is carried out to obtain the methyl sulcotrione. According to thesynthetic process of the methyl sulcotrione, the catalyst and the addition agent are added for dehydration, so that the condensation reaction is directly carried out on the 2-nitro-4-methylsulfony benzoic acid and the 1,3-cyclohexanedione; and then, the rearrangement is carried out to obtain a methyl sulcotrione product. Due to no adding of thionyl chloride or phosgene for chlorination, reactionsteps are reduced, and meanwhile, tail gas treatment or production safety is further avoided; and in addition, acid-binding agents are not added, and later wastewater treatment is reduced. Therefore,used raw materials are less, and greenness, environmental protection and no pollution are achieved.
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Paragraph 0016; 0017; 0018; 0019; 0020; 0021
(2019/06/11)
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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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- Method for producing mesotrione
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The invention discloses a method for producing mesotrione. The method comprises the following steps: using an organic solvent, adding 2-nitro-4-methylsulfonylbenzoyl chloride and 1,3-cyclohexanedioneinto a reaction kettle, starting stirring, maintaining a certain vacuum degree with a negative pressure, slowly raising the temperature to 15-25 DEG C, carrying out refluxing, preserving the heat for1-3hr, bringing HCl generated by the reaction out of the reaction system in the form of gas through the negative pressure, absorbing tail gas through two stages of water, adding a rearrangement catalyst and adjusting the vacuum degree after an enol ester reaction, controlling the temperature to 25-35 DEG C, carrying out refluxing, preserving the heat for 2-4hr, steaming out the organic solvent after reaction, adding methanol for crystallization, and carrying out filtering to obtain a finished product of mesotrione. The preparation method of the mesotrione, provided by the invention, does not need to add an organic base or an inorganic base acid-binding agent, is simple and convenient to operate, generates less three wastes, is low in production cost, and is suitable for large-scale industrial production.
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Paragraph 0023-0029
(2018/10/11)
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- Preparation method of mesotrione
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The invention provides a preparation method of mesotrione. The preparation method comprises the following steps: taking p-methylsulfonyl o-nitrobenzoic acid as a raw material; after carrying out acylchlorination, carrying out condensation reaction with 1,3-cyclohexanedione to obtain an intermediate 2-nitryl-4-methylsulfonylbenzoic acid-[3'-carbonyl-1'-cyclohexenol]-ester; then carrying out rearrangement of enol ester under a common catalysis effect of inorganic alkali and tertiary amine type organic alkali with relatively strong basicity, so as to obtain an acrylated cyclic 1,3-dicarbonyl compound mesotrione. According to the method provided by the invention, a virulent cyanide catalyst is not used, the reaction temperature is relatively low and the reaction time is short; a solvent can be cyclically used, the total mol yield of a prepared mesotrione product can reach 95 percent and the content is 98.5 percent; the technology is safe and environmentally friendly, has a small amount ofthree wastes and is suitable for industrial production.
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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 0023-0024
(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 0013-0016
(2017/05/18)
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- NOXIOUS ARTHROPOD CONTROL AGENT CONTAINING AMIDE COMPOUND
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An object of the present invention is to provide a compound having the controlling activity on a noxious arthropod, and a noxious arthropod controlling agent containing an amide compound of formula (I): wherein X represents a nitrogen atom or a CH group, p represents 0 or 1, A represents a tetrahydrofuranyl group or the like, R1, R2, R3, R4, R5, R6 and R7 represent a hydrogen atom or the like, n represents 1 or 2, Y represents an oxygen atom or the like, m represents any integer of 0 to 7, and Q represents a C1-8 chain hydrocarbon group optionally having a phenyl group or the like, has the excellent noxious arthropod controlling effect.
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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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- 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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- Synthesis method of mesotrione
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The invention discloses a synthesis method of mesotrione. The method includes the following steps that firstly, acylation is performed, wherein 2-nitro-4-methylsulfonylbenzoic acid and acylating agents are subjected to an acylation reaction under catalysis of depolymerizing agents, acylation reaction liquid is obtained, and the temperature of the acylation reaction is 10-70 DEG C; secondly, esterification is performed, wherein acid binding agents and 1,3-cyclohexanedione are added in esterification reaction liquid, an esterification reaction is performed, the esterification reaction liquid is obtained, the temperature of the esterification reaction is 30-65 DEG C, and the acid binding agents are inorganic acid; thirdly, rearrangement is performed, wherein rearrangement agents are added in the esterification reaction liquid so that a rearrangement reaction can be performed, and coarse product reaction liquid is obtained; fourthly, refining is performed, wherein the coarse product reaction liquid is subjected to alkali liquor reverse extraction, acidification and recrystallization, and mesotrione is obtained. The method is easy to operate, the raw materials are easy to obtain, the reactant conversion rate is high, reaction is thorough, the purity of the product is high, and the synthesis method is applicable to industrial production.
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- PROCESS FOR PREPARING MESOTRIONE
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A process for the preparation of mesotrione enolate is provided. The process comprises providing a solution of mesotrione in an organic solvent and contacting the solution with a moderate base in the presence of water at a pH of from 6 to 8, to form an aqueous mesotrione enolate solution. A process for preparing mesotrione from the products of an enol ester rearrangement of 3-oxocyclohex-1-enyl-4-(methylsulfonyl)-2-nitrobenzoate is also provided. The process comprises contacting the products of the rearrangement reaction with an organic solvent to dissolve mesotrione; and contacting the resulting solution with an aqueous solution of an acid.
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- PROCESS FOR THE CRYSTALLISATION OF MESOTRIONE
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The invention relates to a process for selectively controlling the crystallisation mesotrione [2-(4-methylsulphonyl-2-nitrobenzoyl)cyclohexane-1 ,3-dione] from aqueous solution in which the aqueous mesotrione solution is introduced to a crystalliser containing seed crystals predominantly of the thermodynamically stable polymorph ("Form 1") in a semi-continuous or continuous manner. The invention further relates to a process for converting the metastable polymorph ("Form 2") of mesotrione to Form 1 by introducing an aqueous solution containing the former form to a crystalliser containing seed crystals predominantly of the latter form.
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Page/Page column 9
(2008/06/13)
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- PROCESS FOR THE PREPARATION OF POLYMORPHS OF MESOTRIONE
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A process for selectively controlling the crystallisation of thermodynamically stable Form (1) or kinetically stable Form (2) polymorphs of mesotrione from an aqueous mesotrione solution, said method comprising adjusting the pH of the mesotrione solutions to a value wherein said thermodynamically stable Form (1) or kinetically stable Form (2) mesotrione is ultimately obtained is disclosed.
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Page/Page column 4; 5; 6
(2008/06/13)
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- PROCESS FOR PURIFYING MESOTRIONE
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A method for reducing the cyanide levels in a mesotrione sample, said method comprising: (i) taking an aqueous solution of the mesotrione sample in an aqueous solvent, (ii) adjusting the pH of said aqueous solution to a value of 9.5 or higher, and (iii) crystallising the mesotrione out of solution is disclosed.
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Page/Page column 3-6
(2008/06/13)
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- PROCESS FOR PURIFYING MESOTRIONE
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A process for reducing the levels of undesirable impurities in a mesotrione sample is disclosed, said process comprising the steps of: (i) forming a mesotrione enolate solution in an aqueous solvent, (ii) carrying out one or more purification processes, and (iii) crystallising the purified mesotrione out of solution.
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Page/Page column 1; 8-18
(2008/06/13)
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- Pesticide treatment
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A method of accelerating the decomposition of an isoxazole and/or a dione pesticide by contacting them with halogen and/hypohalite. A crop seed containing a halogen and/or hypohalite within the seed or at its surface or in a coating on the seed.
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- Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds
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A process for preparing a compound of Formula (I); where Q completes an optionally substituted 5-or 6-member saturated carbocyclic ring and R is optionally substituted phenyl or optionally substituted C3-C6 cycloalkyl which comprises the rearrangement of a compound of Formula (II); where Q and R are as defined in relation to Formula (I) in a polar aprotic, dipolar aprotic or aromatic hydrocarbon solvent in the presence of a moderate base and an azole.
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