CN102796049B - A kind of method preparing benbbensulfuronmethyl - Google Patents
A kind of method preparing benbbensulfuronmethyl Download PDFInfo
- Publication number
- CN102796049B CN102796049B CN201210194721.1A CN201210194721A CN102796049B CN 102796049 B CN102796049 B CN 102796049B CN 201210194721 A CN201210194721 A CN 201210194721A CN 102796049 B CN102796049 B CN 102796049B
- Authority
- CN
- China
- Prior art keywords
- benbbensulfuronmethyl
- formiate
- method preparing
- adjacent methyl
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of method preparing benbbensulfuronmethyl, after adjacent methyl-formiate benzyl sulphonamide is mixed in dimethylbenzene with two (trichloromethyl) carbonic ethers and catalyzer n-butyl isocyanate, first be warming up to 70 DEG C ~ 85 DEG C, then slowly the stage is warming up to 110 DEG C ~ 130 DEG C, slowly superpalite is added again at 110 DEG C ~ 130 DEG C, esterification is carried out again, desolvation and catalyzer after reaction at 110 DEG C ~ 130 DEG C; Neighbour's (methyl-formiate) benzylsulphonyl isocyanic ester esterification obtained adds in condensation reaction solvent; stirring is cooled to 30 DEG C ~ 50 DEG C; continue to add 2-amino-4; 6-dimethoxypyridin; condensation reaction at 50 DEG C ~ 90 DEG C after adding; cooling, oven dry, obtain benbbensulfuronmethyl.The present invention can obtain the benbbensulfuronmethyl of more than 97% content, and its total recovery can reach more than 90%.
Description
Technical field
The invention belongs to pesticide synthesis field, be specifically related to a kind of synthetic method of agricultural chemicals benbbensulfuronmethyl.
Background technology
Benbbensulfuronmethyl (bensulfuron-methyl) sterling is white solid, industrial goods faint yellow solid, is the herbicide for paddy field of a kind of novel, wide spectrum, efficient, low toxicity, safety, belongs to sulfonylurea.This weedicide is atomic on environmental quality impact, to person poultry safety, without teratogenesis, mutagenesis phenomenon, applied widely, both can be used for live field and rice seedling bed, also can be used for moving cutting out field; Consumption is extremely low, about 0.1-0.2g(a.i)/ha dosage, effectively can prevent and kill off most of broadleaf weeds and nutgrass flatsedge material weeds; Both can be alone, also can use with.
Its synthetic method has:
Route 1:
Route 1 is owing to adopting Vinyl chloroformate to be ester exchange agent, and this complex process, wastewater flow rate is large, and the final ethanol produced is difficult to timely removing, and cause the benbbensulfuronmethyl of generation to decompose in reaction system, yield is low.Molar yield 75-85%.
Route 2:
Route 2 adopts carbonyl chloride (another name phosgene) as photochemical dose, and reaction yield can reach 85-90%.
But phosgene is severe poisonous chemicals, the operation of national strict production control device, expressly provide that phosgene does not allow to store, packaging and transport, this has sentenced death penalty to not having the manufacturer of phosgene resource will produce benbbensulfuronmethyl.
Route 3:
The same carbonyl chloride (another name phosgene) of route 3, as photochemical dose, is that 2-amino-4,6-dimethoxy pyrimidine is carried out isocyanation esterification, then carries out condensation with sulphonamide and obtain benbbensulfuronmethyl.This technique carries out isocyanation esterification to 2-amino-4,6-dimethoxy pyrimidine, and reaction yield is low, and intermediate is unstable, and cause the benbbensulfuronmethyl yield of final condensation low, content is low.
Summary of the invention
The object of the invention is to overcome the various shortcomings in existing benbbensulfuronmethyl synthetic route, a kind of benbbensulfuronmethyl synthetic method is provided.
Object of the present invention can be reached by following measures:
Prepare a method for benbbensulfuronmethyl, it comprises the steps:
A, adjacent methyl-formiate benzyl sulphonamide is mixed in dimethylbenzene with two (trichloromethyl) carbonic ethers and catalyzer n-butyl isocyanate after, first be warming up to 70 DEG C ~ 85 DEG C, then slowly the stage is warming up to 110 DEG C ~ 130 DEG C, slowly superpalite is added again at 110 DEG C ~ 130 DEG C, esterification is carried out again, desolvation and catalyzer after reaction at 110 DEG C ~ 130 DEG C;
B, neighbour's (methyl-formiate) benzylsulphonyl isocyanic ester esterification obtained add in condensation reaction solvent; stirring is cooled to 30 DEG C ~ 50 DEG C; continue to add 2-amino-4; 6-dimethoxypyridin; condensation reaction at 50 DEG C ~ 90 DEG C after adding; cooling, oven dry, obtain benbbensulfuronmethyl.
The side of present method answers formula as follows:
In step, be warming up to the stage heating step of 110 DEG C ~ 130 DEG C from 70 DEG C ~ 85 DEG C slow stages, be specially: temperature rise rate 0.5 DEG C ~ 1 DEG C/min, often heat up 10 DEG C ~ 15 DEG C, be incubated 5 ~ 15 minutes, preferably insulation 10 minutes.Which makes reactant slowly decompose, and fully reacts, and ensure that the process of reaction, and is conducive to the carrying out of subsequent reactions.
Common use two (trichloromethyl) carbonic ether and superpalites in the present invention, the two adds reaction with condition in a different manner, can fully make reaction complete, and ensure the purity of sulphonamide isocyanic ester.The mol ratio of adjacent methyl-formiate benzyl sulphonamide and two (trichloromethyl) carbonic ether is 1:0.3 ~ 0.7, is preferably 1:0.45 ~ 0.65, most preferably is 1:0.5 ~ 0.6.The mol ratio of adjacent methyl-formiate benzyl sulphonamide and superpalite is 1:0.01 ~ 0.3, is preferably 1:0.05 ~ 0.2, most preferably is 1:0.1 ~ 0.2.
The reaction of this invention isocyanation esterification uses dimethylbenzene to make solvent, the consumption of solvent is as the criterion with the amount can dissolving raw material or catalyzer, in a kind of preferred version, in the total mass of reactant (comprising adjacent methyl-formiate benzyl sulphonamide, two (trichloromethyl) carbonic ether and superpalites) and catalyzer, the general consumption of dimethylbenzene is 2 ~ 12ml/g, is preferably 4 ~ 10ml/g.The mass ratio of adjacent methyl-formiate benzyl sulphonamide and catalyzer n-butyl isocyanate is 10:1 ~ 4.
In steps A, by underpressure distillation desolvation dimethylbenzene and catalyzer after esterification, generally vacuum about-0.09MPa can be kept.
In stepb, the quality of 2-amino-4,6-dimethoxy pyrimidine is 0.5 ~ 0.7 times of adjacent methyl-formiate benzyl sulphonamide quality.
This invention condensation reaction can use the series such as alkane, nitrile, aromatics or aromatic hydrocarbon solvent to make solvent, as one or more in benzene,toluene,xylene, trimethylbenzene, acetonitrile etc., best use solvent is toluene and acetonitrile, the consumption of solvent is as the criterion with the amount can dissolving raw material, its total consumption is generally every gram of raw material (namely participating in the reactant reacted) and adds 0.5 ~ 5ml, preferably every gram of raw material 1 ~ 3ml.
This invention operational phase temperature-raising method, makes two (trichloromethyl) carbonic ether slowly decompose in temperature-rise period, make reaction temperature and, not easily produce a large amount of phosgene, cause danger and pollution.
This invention uses the purity of two (trichloromethyl) carbonic ether high, impurity is few, reaction should not produce impurity, and the raw material Vinyl chloroformate that other modes use, phosgene are dangerous large, the present invention uses two (trichloromethyl) carbonic ethers and adjacent methyl-formiate benzyl sulphonamide addition method simultaneously, simplifies operation easier.The present invention adds superpalite, fully by complete for adjacent methyl-formiate benzyl sulfuryl amine reaction, can ensure the purity of sulphonamide isocyanic ester.
The present invention can obtain the benbbensulfuronmethyl of more than 97% content, and its total recovery can reach more than 90%.
Embodiment
Embodiment 1
50 grams of (98%) adjacent methyl-formiate benzyl sulphonamide are dropped in 500ml tetra-mouthfuls of reaction flasks, 12 grams of n-butyl isocyanates and 300ml dimethylbenzene and two (trichloromethyl) carbonic ether 35 grams (folding hundred), stir companion and be warming up to 80 DEG C, start to heat up with 0.5 DEG C/min speed, often heat up 10 DEG C, be incubated 10 minutes, when being warming up to 120 DEG C, drip superpalite 7 grams again, be incubated 2 ~ 3 hours again, after insulation terminates, solvent is sloughed in underpressure distillation, vacuum-0.09MPa is kept during distillation, solvent evaporated, add 70ml toluene, be cooled to 40 DEG C, evenly add 31 grams of 2-amino-4, 6-dimethoxypyridin, be warming up to 70 DEG C, stir 1 hour, be cooled to room temperature, high speed centrifugation, oven dry obtains benbbensulfuronmethyl, weight 86.3 grams, mass content 97.2%, molar yield 90.2%.mp:185~188℃.
Embodiment 2
50 grams of (98%) adjacent methyl-formiate benzyl sulphonamide are dropped in 500ml tetra-mouthfuls of reaction flasks, 12 grams of n-butyl isocyanates and 300ml dimethylbenzene and two (trichloromethyl) carbonic ether 37 grams (folding hundred), stir companion and be warming up to 80 DEG C, start to heat up with 0.5 DEG C/min speed, often heat up 10 DEG C, be incubated 10 minutes, when being warming up to 120 DEG C, drip superpalite 5 grams again, be incubated 2 ~ 3 hours again, after insulation terminates, solvent is sloughed in underpressure distillation, vacuum-0.09MPa is kept during distillation, solvent evaporated, add 70ml toluene, be cooled to 40 DEG C, evenly add 30 grams of 2-amino-4, 6-dimethoxypyridin, be warming up to 70 DEG C, stir 1 hour, be cooled to room temperature, high speed centrifugation, oven dry obtains benbbensulfuronmethyl, weight 86.2 grams, mass content 97.1%, molar yield 90.1%.
Embodiment 3
50 grams of (98%) adjacent methyl-formiate benzyl sulphonamide are dropped in 500ml tetra-mouthfuls of reaction flasks, 12 grams of n-butyl isocyanates and 300ml dimethylbenzene and two (trichloromethyl) carbonic ether 37 grams (folding hundred), stir companion and be warming up to 80 DEG C, start to heat up with 0.5 DEG C/min speed, often heat up 10 DEG C, be incubated 10 minutes, when being warming up to 120 DEG C, drip superpalite 5 grams again, be incubated 2 ~ 3 hours again, after insulation terminates, solvent is sloughed in underpressure distillation, vacuum-0.09MPa is kept during distillation, solvent evaporated, add 50ml acetonitrile, be cooled to 40 DEG C, evenly add 29 grams of 2-amino-4, 6-dimethoxypyridin, be warming up to 70 DEG C, stir 1 hour, be cooled to room temperature, high speed centrifugation, oven dry obtains benbbensulfuronmethyl, weight 85.2 grams, mass content 98.0%, molar yield 90.1%.
Embodiment 4
50 grams of (98%) adjacent methyl-formiate benzyl sulphonamide are dropped in 500ml tetra-mouthfuls of reaction flasks, 12 grams of n-butyl isocyanates and 300ml dimethylbenzene and two (trichloromethyl) carbonic ether 35 grams (folding hundred), stir companion and be warming up to 80 DEG C, start to heat up with 0.5 DEG C/min speed, often heat up 10 DEG C, be incubated 10 minutes, when being warming up to 120 DEG C, drip superpalite 5 grams again, be incubated 2 ~ 3 hours again, after insulation terminates, solvent is sloughed in underpressure distillation, vacuum-0.09MPa is kept during distillation, solvent evaporated, add 50ml toluene and 20ml acetonitrile, be cooled to 40 DEG C, evenly add 29 grams of 2-amino-4, 6-dimethoxypyridin, be warming up to 70 DEG C, stir 1 hour, be cooled to room temperature, high speed centrifugation, oven dry obtains benbbensulfuronmethyl, weight 86.0 grams, mass content 97.5%, molar yield 90.5%.
Embodiment 5
50 grams of (98%) adjacent methyl-formiate benzyl sulphonamide are dropped in 500ml tetra-mouthfuls of reaction flasks, 10 grams of n-butyl isocyanates and 300ml dimethylbenzene and two (trichloromethyl) carbonic ether 32 grams (folding hundred), stir companion and be warming up to 80 DEG C, start to heat up with 0.5 DEG C/min speed, often heat up 10 DEG C, be incubated 10 minutes, when being warming up to 120 DEG C, drip superpalite 7 grams again, be incubated 2 ~ 3 hours again, after insulation terminates, solvent is sloughed in underpressure distillation, vacuum-0.09MPa is kept during distillation, solvent evaporated, add 60ml toluene and 5ml acetonitrile, be cooled to 40 DEG C, evenly add 29 grams of 2-amino-4, 6-dimethoxypyridin, be warming up to 70 DEG C, stir 1 hour, be cooled to room temperature, high speed centrifugation, oven dry obtains benbbensulfuronmethyl, weight 85.9 grams, mass content 97.2%, molar yield 90.1%.
Claims (9)
1. prepare a method for benbbensulfuronmethyl, it is characterized in that comprising the steps:
A, adjacent methyl-formiate benzyl sulphonamide is mixed in dimethylbenzene with two (trichloromethyl) carbonic ethers and catalyzer n-butyl isocyanate after, first be warming up to 70 DEG C ~ 85 DEG C, then slowly the stage is warming up to 110 DEG C ~ 130 DEG C, slowly superpalite is added again at 110 DEG C ~ 130 DEG C, esterification is carried out again, desolvation and catalyzer after reaction at 110 DEG C ~ 130 DEG C; Described slow stage heating step is: temperature rise rate 0.5 DEG C ~ 1 DEG C/min, often heats up 10 DEG C ~ 15 DEG C, is incubated 5 ~ 15 minutes; The mol ratio of adjacent methyl-formiate benzyl sulphonamide and two (trichloromethyl) carbonic ether is 1:0.3 ~ 0.7, and the mol ratio of adjacent methyl-formiate benzyl sulphonamide and superpalite is 1:0.01 ~ 0.3; The mass ratio of adjacent methyl-formiate benzyl sulphonamide and catalyzer n-butyl isocyanate is 10:1 ~ 4;
B, neighbour's (methyl-formiate) benzylsulphonyl isocyanic ester esterification obtained add in condensation reaction solvent; stirring is cooled to 30 DEG C ~ 50 DEG C; continue to add 2-amino-4; 6-dimethoxypyridin; condensation reaction at 50 DEG C ~ 90 DEG C after adding; cooling, oven dry, obtain benbbensulfuronmethyl.
2. the method preparing benbbensulfuronmethyl according to claim 1, it is characterized in that in steps A, the mol ratio of adjacent methyl-formiate benzyl sulphonamide and two (trichloromethyl) carbonic ether is 1:0.45 ~ 0.65, and the mol ratio of adjacent methyl-formiate benzyl sulphonamide and superpalite is 1:0.05 ~ 0.2.
3. the method preparing benbbensulfuronmethyl according to claim 2, it is characterized in that in steps A, the mol ratio of adjacent methyl-formiate benzyl sulphonamide and two (trichloromethyl) carbonic ether is 1:0.5 ~ 0.6, and the mol ratio of adjacent methyl-formiate benzyl sulphonamide and superpalite is 1:0.1 ~ 0.2.
4. the method preparing benbbensulfuronmethyl according to claim 1, is characterized in that in steps A, and in the total mass of reactant and catalyzer, the consumption of dimethylbenzene is 2 ~ 12ml/g.
5. the method preparing benbbensulfuronmethyl according to claim 1, is characterized in that in steps A, by underpressure distillation desolvation dimethylbenzene and catalyzer after esterification.
6. the method preparing benbbensulfuronmethyl according to claim 1, is characterized in that in step B, and the quality of 2-amino-4,6-dimethoxy pyrimidine is 0.5 ~ 0.7 times of adjacent methyl-formiate benzyl sulphonamide quality.
7. the method preparing benbbensulfuronmethyl according to claim 1, is characterized in that in step B, and described condensation reaction solvent is selected from alkane, nitrile, aromatic solvents.
8. the method preparing benbbensulfuronmethyl according to claim 7, is characterized in that in step B, and described condensation reaction solvent is selected from aromatic hydrocarbon solvent.
9. the method preparing benbbensulfuronmethyl according to claim 1, is characterized in that in step B, and described condensation reaction solvent is selected from one or more in benzene,toluene,xylene, trimethylbenzene or acetonitrile; The consumption of condensation reaction solvent is every gram of reactant 0.5 ~ 5ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194721.1A CN102796049B (en) | 2012-06-13 | 2012-06-13 | A kind of method preparing benbbensulfuronmethyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194721.1A CN102796049B (en) | 2012-06-13 | 2012-06-13 | A kind of method preparing benbbensulfuronmethyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102796049A CN102796049A (en) | 2012-11-28 |
| CN102796049B true CN102796049B (en) | 2015-09-02 |
Family
ID=47195389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210194721.1A Active CN102796049B (en) | 2012-06-13 | 2012-06-13 | A kind of method preparing benbbensulfuronmethyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102796049B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103053576B (en) * | 2012-12-26 | 2015-05-06 | 山东滨农科技有限公司 | Compound agent and preparation method and application for preventing and killing off aquatic weeds in sea cucumber culture zone |
| CN103483274B (en) * | 2013-09-25 | 2016-03-09 | 江苏快达农化股份有限公司 | A kind of method preparing benbbensulfuronmethyl |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051466A2 (en) * | 1980-11-03 | 1982-05-12 | E.I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
-
2012
- 2012-06-13 CN CN201210194721.1A patent/CN102796049B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051466A2 (en) * | 1980-11-03 | 1982-05-12 | E.I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
Non-Patent Citations (3)
| Title |
|---|
| 新稻田除草剂苄黄隆的合成;孔繁蕾 等;《化学世界》;19901231(第5期);211-213 * |
| 方贤达.氧氯化碳.《氯的含氧化合物生产与应用》.化学工业出版社,2004,64-66. * |
| 氰酸钠法合成磺酰脲类除草剂苄嘧磺隆;王岩 等;《化学世界》;20081231(第11期);685-687 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102796049A (en) | 2012-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hart et al. | Benign coupling of reactions and separations with reversible ionic liquids | |
| EP3436450B1 (en) | Reaction medium containing water-surfactant mixture | |
| CN101357895B (en) | Method for synthesizing methoxamine hydrochloride | |
| CN103739500B (en) | A kind of synthesis of cinacalcet hydrochloride and process for purification | |
| JP2008120825A5 (en) | ||
| CN103333120A (en) | Mesosulfuron-methyl synthetic method | |
| CN102796049B (en) | A kind of method preparing benbbensulfuronmethyl | |
| CN101863858A (en) | Synthetic method of bentazone | |
| CN105254543A (en) | Synthesis method of mesotrione | |
| CN106083722A (en) | A kind of Six Steps prepares the synthesis technique of pyrazoles Fluoxastrobin | |
| CN103130657A (en) | Synthetic method of 2-chloro-4-aminophenol | |
| CN108440352B (en) | Preparation method of mesotrione | |
| CN102827065B (en) | The preparation method of N-phenyl-3-bromine carbazole | |
| CN102219712A (en) | Synthetic method of methyl-4-(trifluoromethoxy) phenyl carbamate | |
| CN104129765A (en) | Reaction-extraction coupling method for preparation of hydroxylamine salt / hydroxylamine | |
| Sahnoun et al. | Cs2CO3 in pyrrolidinone promoted hydration of functionalized (hetero) aryl nitriles under metal-free conditions | |
| CN108084001A (en) | A kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes | |
| CN106366002B (en) | A kind of Boscalid intermediate 4 '-chloro- 2- aminobphenyl synthetic method | |
| CN102432559A (en) | Synthetic method for preparing 2,6-dichlorobenzoxazole by photocuring | |
| CN108892671B (en) | Preparation method of pyroxsulam | |
| CN104086402A (en) | Method for synthesizing 4-chlorobutyryl chloride | |
| WO2020139734A1 (en) | Preparation of sulfonamide herbicide process intermediates | |
| CN106008124B (en) | A method of new is broken green syt amide by quaternary ammonium salt C-N keys | |
| CN102766043B (en) | Preparation method for 3- (2-chloro-4- (trifluoromethyl) phenoxy) -benzoic acid | |
| CN109320510A (en) | Preparation method of Maropitan free base |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |