CN106565556A - Synthetic process of mesotrione - Google Patents
Synthetic process of mesotrione Download PDFInfo
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- CN106565556A CN106565556A CN201610994875.7A CN201610994875A CN106565556A CN 106565556 A CN106565556 A CN 106565556A CN 201610994875 A CN201610994875 A CN 201610994875A CN 106565556 A CN106565556 A CN 106565556A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
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Abstract
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.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of synthesis technique of mesotrione.
Background technology
Mesotrione action target is p-hydroxyphenypyruvate dioxydenase (HPPD), is mainly used in preventing and kill off corn field
Broad leaved weed and grassy weed, with herbicidal spectrum it is wide, Environmental compatibility is good, very low to mammal and aquatic toxicity,
It is fool proof to Semen Maydiss and to rear stubble rotation crop without characteristics such as poisoning, it is front with the very big market demand and good application
Scape.Additionally, mesotrione to prevent and kill off anti-three pyridine especially effective with the weeds of anti-sulfonylureas, weeds are in it and these type herbicides
Between there is no cross resistance, this just provides convenience to herbicide Fruit variety in crop rotation.
At present, mesotrione is typically carried out being condensed rearrangement reaction system by intermediate 2- nitro -4- methylsulphonyl benzoyl chlorides
It is standby.And the synthesis of intermediate 2- nitro -4- methylsulphonyl benzoyl chlorides has various methods.At present, further closed by these methods
Overall reaction yield into mesotrione is preferable, up to 78% or so, but still has larger room for promotion.And product purity is low, very
The rare mesotrione in accordance with prescription, i.e. product purity is poor, while in the conjunction of 2- nitro -4- methylsulphonyl benzoyl chlorides
Cheng Zhong, various nitre compound impurities of generation increased the danger of industrialized production to next step synthesizing methyl sulphur oxadiazon.
The content of the invention
To solve the above problems, the invention provides a kind of synthesis technique of the high mesotrione of high income, product purity.
The synthesis technique of mesotrione provided by the present invention, including step：
Nitrification：In nitration reaction kettle addition 1400～1500kg of concentrated sulphuric acid, to 350～360kg of methylsulfonyltoluene, 4～5 is little
When interior uniform 200～210kg of Deca nitric acid carry out nitration reaction, after completion of dropping be incubated 60～70 minutes, obtain nitrification liquid；
Oxidation：Nitrification liquid is imported and is added after 300～330kg of catalyst V2O5 and water after oxidizing reactor, then Deca
1240～1290kg nitric acid, and controlling reaction temperature is 142～146 DEG C；1-2 hours are incubated after completion of dropwise addition；Reactant liquor is dropped
Temperature is added water and be cooled to again after 800～1000kg 48～50 degree to after 100 degree, and then filter pressing obtains oxidation product, with water 1000
～1100kg circulation rinsing oxidation products；It is dried to obtain 2- nitro -4- first at 55～70 DEG C after oxidation product is refined
Sulfonyl benzoic acid；
Chloride：Thionyl chloride is added in acyl chloride reaction kettle, then puts into 2- nitro -4- methyl sulfonylbenzoic acids, DMF
To carry out temperature rising reflux reaction, separated goes out thionyl chloride after reacting 11～12 hours, obtains 2- nitro -4- mesyl benzene
Formyl chloride；
Condensation is reset：After the 2- nitro -4- methylsulphonyl benzoyl chloride dichloromethane for obtaining is dissolved well, it is cooled to
35～40 DEG C, the 1 of 155～170kg of input, hydroresorcinol, uniform Deca 160～180kg triethylamines in 60～80 minutes
Carry out esterification condensation；5～20kg .alpha.-hydroxyisobutyronitrile .s are added, 150～180kg of Deca triethylamines carry out rearrangement reaction, then add hydrochloric acid
It is 1～2 to be adjusted to pH, point liquid washing, is distilled to reclaim dichloromethane, and then blowing, sucking filtration obtain crude product sulphur oxadiazon；While hot by sucking filtration
In the crude product sulphur oxadiazon input refining reaction kettle for going out, stir 20～40 minutes at 50～55 DEG C, sucking filtration after blowing, mother solution enters first
The distillation of alcohol distillating still is refined to reclaim methanol, mesotrione finished product will be obtained after solid product drying, comminution by gas stream.
Preferably, in the oxidation step, the consumption of catalyst V2O5 is 7～7.5kg.
Preferably, in the oxidation step, in Deca nitric acid, the uniform Deca nitric acid 890 first in 20～22 hours
～920kg, while controlling reaction temperature is 144～146 degree；Uniform Deca 350～370kg nitre in 15.5～17 hours again
Acid, while controlling reaction temperature is 142-144 degree；1～2 hour is incubated after completion of dropwise addition.As such, it is possible to further reduce reaction
By-product, to improve product purity.
Preferably, when the oxidation product is refined, NaOH solution is added to adjust pH value to 8.0～9.0 in oxidation product,
To dissolve oxidation product, temperature is controlled in adition process for 55～60 DEG C；Then blowing centrifugation while hot, Deca hydrochloric acid adjusts pH value
To 1～2, kept for 30～50 minutes in the range of 55～60 DEG C of temperature, centrifugation, rinsing, obtain final product refined 2- after being cooled to 35 DEG C
Nitro -4- methyl sulfonylbenzoic acids.
Specific embodiment
Embodiment 1
In nitration reaction kettle 98% concentrated sulphuric acid 1400kg of addition, to methylsulfonyltoluene 360kg, uniform Deca in 4 hours
68% nitric acid of 200kg carries out nitration reaction, and after completion of dropping 60 minutes are incubated, and obtains nitrification liquid；
Nitrification liquid is imported after adding 7kg catalyst V2O5 and water 330kg after oxidizing reactor, after being warming up to 142 degree,
The uniform nitric acid 920kg of Deca 68% in 20 hours, while controlling reaction temperature is 144 degree；The uniform Deca in 17 hours again
50% nitric acid of 370kg, while controlling reaction temperature is 142 degree；2 hours are incubated after completion of dropwise addition.Reactant liquor is cooled to into 100
After degree, add water and be cooled to again after 800kg 48 degree, then filter pressing obtains oxidation product, produced with water 1000kg circulation rinsing oxidations
Thing；NaOH solution is added to adjust pH value to 8.0 in oxidation product, to dissolve oxidation product, controlling temperature in adition process is
55℃；Then blowing centrifugation while hot, Deca hydrochloric acid adjusts pH value to 1, is kept for 50 minutes at 55 DEG C of temperature, after being cooled to 35 DEG C from
The heart, rinsing, obtain final product refined 2- nitro -4- methyl sulfonylbenzoic acids；It is dried at 70 DEG C；Add in acyl chloride reaction kettle
Enter thionyl chloride, then put into 2- nitro -4- methyl sulfonylbenzoic acids, DMF to carry out temperature rising reflux reaction, react 11～12 hours
Afterwards separated goes out thionyl chloride, obtains 2- nitro -4- methylsulphonyl benzoyl chlorides；
After the 2- nitro -4- methylsulphonyl benzoyl chloride dichloromethane for obtaining is dissolved well, 35～40 DEG C are cooled to,
The 1 of input 155kg, hydroresorcinol, uniform Deca 165kg triethylamine carries out esterification condensation in 60～80 minutes；Add
10kg .alpha.-hydroxyisobutyronitrile .s, Deca 150kg triethylamine carries out rearrangement reaction, then adds hydrochloric acid to be adjusted to pH for 1～2, point liquid washing, distill with
Dichloromethane is reclaimed, then blowing, sucking filtration obtain crude product sulphur oxadiazon；Sucking filtration is gone out crude product sulphur oxadiazon input refining reaction kettle while hot
In, stirring 20～40 minutes at 50～55 DEG C, sucking filtration after blowing, mother solution enters the distillation of methanol distillating still and refines to reclaim methanol,
Mesotrione finished product will be obtained after solid product drying, comminution by gas stream.
The mesotrione product purity for obtaining is 97.33%, and yield is 86.90%.
Embodiment 2
In nitration reaction kettle 98% concentrated sulphuric acid 1500kg of addition, to methylsulfonyltoluene 350kg, uniform Deca in 5 hours
68% nitric acid of 210kg carries out nitration reaction, and after completion of dropping 70 minutes are incubated, and obtains nitrification liquid；
Nitrification liquid is imported after adding 7.5kg catalyst V2O5 and water 300kg after oxidizing reactor, be warming up to 142 degree
Afterwards, the uniform nitric acid 890kg of Deca 68% in 22 hours, while controlling reaction temperature is 146 degree；It is uniform in 15.5 hours again
50% nitric acid of Deca 350kg, while controlling reaction temperature is 144 degree；1 hour is incubated after completion of dropwise addition.Reactant liquor is lowered the temperature
To after 100 degree, add water and be cooled to again after 1000kg 50 degree, then filter pressing obtains oxidation product, rinsed with water 1100kg circulations
Oxidation product；Add NaOH solution to adjust pH value to 9.0 in oxidation product, to dissolve oxidation product, control in adition process
Temperature is 60 DEG C；Then blowing centrifugation while hot, Deca hydrochloric acid is adjusted pH value to 2, is kept for 30 minutes under temperature 60 C, is cooled to 35
Centrifugation, rinsing, obtain final product refined 2- nitro -4- methyl sulfonylbenzoic acids after DEG C；It is dried at 55 DEG C；In acyl chloride reaction
Add thionyl chloride in kettle, then put into 2- nitro -4- methyl sulfonylbenzoic acids, DMF to carry out temperature rising reflux reaction, reaction 11～
Separated goes out thionyl chloride after 12 hours, obtains 2- nitro -4- methylsulphonyl benzoyl chlorides.
Condensation is reset：After the 2- nitro -4- methylsulphonyl benzoyl chloride dichloromethane for obtaining is dissolved well, it is cooled to
35～40 DEG C, the 1 of input 165kg, hydroresorcinol, uniform Deca 175kg triethylamine carries out esterification contracting in 60～80 minutes
Close；15kg .alpha.-hydroxyisobutyronitrile .s are added, Deca 150kg triethylamine carries out rearrangement reaction, then it is 1～2 to add hydrochloric acid to be adjusted to pH, point liquid water
Wash, distill to reclaim dichloromethane, then blowing, sucking filtration obtain crude product sulphur oxadiazon；Sucking filtration is gone out crude product sulphur oxadiazon input while hot
In refining reaction kettle, stir 20～40 minutes at 50～55 DEG C, sucking filtration after blowing, mother solution enter the distillation of methanol distillating still it is refined with
Methanol is reclaimed, mesotrione finished product will be obtained after solid product drying, comminution by gas stream.
The mesotrione product purity for obtaining is 97.65%, and yield is 89.45%.
Embodiment 3
In nitration reaction kettle 98% concentrated sulphuric acid 1450kg of addition, to methylsulfonyltoluene 355kg, uniform Deca in 4.5 hours
68% nitric acid of 205kg carries out nitration reaction, and after completion of dropping 65 minutes are incubated, and obtains nitrification liquid；
Nitrification liquid is imported after adding 7.2kg catalyst V2O5 and water 315kg after oxidizing reactor, be warming up to 142 degree
Afterwards, the uniform nitric acid 900kg of Deca 68% in 21 hours, while controlling reaction temperature is 145 degree；Uniformly dripped in 16 hours again
Plus 350～50% nitric acid of 370kg, while controlling reaction temperature is 143 degree；1.5 hours are incubated after completion of dropwise addition.By reactant liquor
After being cooled to 100 degree, add water and be cooled to again after 900kg 49 degree, then filter pressing obtains oxidation product, floated with water 1050kg circulations
Wash oxidation product；Add NaOH solution to adjust pH value to 8.5 in oxidation product, to dissolve oxidation product, control in adition process
Temperature processed is 57 DEG C；Then blowing centrifugation while hot, Deca hydrochloric acid adjusts pH value to 1.5, is kept for 40 minutes in the range of 57 DEG C of temperature,
Centrifugation, rinsing, obtain final product refined 2- nitro -4- methyl sulfonylbenzoic acids after being cooled to 35 DEG C, and it is dried at 65 DEG C；In acyl
Thionyl chloride is added in chlorinating container, then puts into 2- nitro -4- methyl sulfonylbenzoic acids, DMF to carry out temperature rising reflux reaction,
Separated goes out thionyl chloride after reacting 11～12 hours, obtains 2- nitro -4- methylsulphonyl benzoyl chlorides.
After the 2- nitro -4- methylsulphonyl benzoyl chloride dichloromethane for obtaining is dissolved well, 35～40 DEG C are cooled to,
The 1 of input 170kg, hydroresorcinol, uniform Deca 185kg triethylamine carries out esterification condensation in 60～80 minutes；Add
15kg .alpha.-hydroxyisobutyronitrile .s, Deca 160kg triethylamine carries out rearrangement reaction, then adds hydrochloric acid to be adjusted to pH for 1～2, point liquid washing, distill with
Dichloromethane is reclaimed, then blowing, sucking filtration obtain crude product sulphur oxadiazon；Sucking filtration is gone out crude product sulphur oxadiazon input refining reaction kettle while hot
In, stirring 20～40 minutes at 50～55 DEG C, sucking filtration after blowing, mother solution enters the distillation of methanol distillating still and refines to reclaim methanol,
Mesotrione finished product will be obtained after solid product drying, comminution by gas stream.The mesotrione product purity for obtaining is 97.61%, is received
Rate is 88.74%.
Finally it should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；To the greatest extent
Pipe has been described in detail with reference to foregoing embodiments to the present invention, it will be understood by those within the art that：Its according to
So the technical scheme described in foregoing embodiments can be modified, either which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, do not make the essence disengaging various embodiments of the present invention technology of appropriate technical solution
The scope of scheme.
Claims (4)
1. a kind of synthesis technique of mesotrione, it is characterised in that including step：
Nitrification：In nitration reaction kettle addition 1400～1500kg of concentrated sulphuric acid, to 350～360kg of methylsulfonyltoluene, in 4～5 hours
The nitric acid of 200～210kg of uniform Deca carries out nitration reaction, and after completion of dropping 60～70 minutes are incubated, and obtains nitrification liquid；
Oxidation：Nitrification liquid is imported and is added after 300～330kg of catalyst V2O5 and water after oxidizing reactor, then Deca 1240
～1290kg nitric acid, and controlling reaction temperature is 142～146 DEG C；1-2 hours are incubated after completion of dropwise addition；Reactant liquor is cooled to
After 100 degree, add water and be cooled to again after 800～1000kg 48～50 degree, then filter pressing obtains oxidation product, with water 1000～
1100kg circulation rinsing oxidation products；It is dried to obtain 2- nitro -4- first sulphurs at 55～70 DEG C after oxidation product is refined
Acyl group benzoic acid；
Chloride：Thionyl chloride is added in acyl chloride reaction kettle, then puts into 2- nitro -4- methyl sulfonylbenzoic acids, DMF to enter
Row temperature rising reflux reacts, and separated goes out thionyl chloride after reacting 11～12 hours, obtains 2- nitro -4- methylsulphonylbenzoyls
Chlorine；
Condensation is reset：By the 2- nitro -4- methylsulphonyl benzoyl chloride dichloromethane for obtaining dissolve it is good after, be cooled to 35～
40 DEG C, the 1 of 155～170kg of input, hydroresorcinol, uniform 160～180kg of Deca triethylamines are carried out in 60～80 minutes
Esterification condensation；5～20kg .alpha.-hydroxyisobutyronitrile .s are added, 150～180kg of Deca triethylamines carry out rearrangement reaction, then add hydrochloric acid to be adjusted to
PH is 1～2, point liquid washing, is distilled to reclaim dichloromethane, and then blowing, sucking filtration obtain crude product sulphur oxadiazon；Sucking filtration is gone out while hot
In crude product sulphur oxadiazon input refining reaction kettle, stir 20～40 minutes at 50～55 DEG C, sucking filtration after blowing, mother solution enters methanol steaming
Evaporate kettle distillation refined to reclaim methanol, mesotrione finished product will be obtained after solid product drying, comminution by gas stream.
2. synthesis technique as claimed in claim 1, it is characterised in that in the oxidation step, the consumption of catalyst V2O5
For 7～7.5kg.
3. synthesis technique as claimed in claim 2, it is characterised in that in the oxidation step, in Deca nitric acid, exist first
Uniform Deca 890～920kg of nitric acid in 20～22 hours, while controlling reaction temperature is 144～146 degree；Again 15.5～17
Uniform Deca 350～370kg nitric acid in hour, while controlling reaction temperature is 142-144 degree；Insulation 1～2 is little after completion of dropwise addition
When.
4. synthesis technique as claimed in claim 3, it is characterised in that when the oxidation product is refined, in oxidation product
Add NaOH solution to adjust pH value to 8.0～9.0, to dissolve oxidation product, temperature is controlled in adition process for 55～60 DEG C；So
Blowing centrifugation while hot afterwards, Deca hydrochloric acid adjusts pH value to 1～2, is kept for 30～50 minutes in the range of 55～60 DEG C of temperature, is cooled to
Centrifugation, rinsing, obtain final product refined 2- nitro -4- methyl sulfonylbenzoic acids after 35 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354563A (en) * | 2021-06-07 | 2021-09-07 | 浙江天诺医药科技有限公司 | Method for preparing triketone compound by continuous flow |
| CN115819297A (en) * | 2022-12-09 | 2023-03-21 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354563A (en) * | 2021-06-07 | 2021-09-07 | 浙江天诺医药科技有限公司 | Method for preparing triketone compound by continuous flow |
| CN115819297A (en) * | 2022-12-09 | 2023-03-21 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115819297B (en) * | 2022-12-09 | 2024-03-29 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid |
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